Chemistry of the Climate System: Volume 2 History, Change and Sustainability [3rd, completely revised and extended Edition] 9783110561340, 9783110559859

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Detlev Möller Chemistry of the Climate System

Also of Interest Chemistry of the Climate System. Volume : Fundamentals and Processes Möller,  ISBN ----, e-ISBN ----

Drinking Water Treatment. An Introduction Worch,  ISBN ----, e-ISBN ----

Biomass and Biowaste. New Chemical Products from Old Balu, García (Eds.),  ISBN ----, e-ISBN ----

Carbon Dioxide Utilization. Volume : Fundamentals ISBN ----, e-ISBN ---- Volume : Transformations ISBN ----, e-ISBN ---- North, Styring (Eds.),  Chemistry for Environmental Scientists. Möller,  ISBN ----, e-ISBN ----

Detlev Möller

Chemistry of the Climate System Volume 2: History, Change and Sustainability 3rd, completely revised and extended Edition

Author Univ.-Prof. Dr. rer. nat. habil. Detlev Möller Brandenburgische Technische Universität Cottbus – Senftenberg Fakultät Umwelt und Naturwissenschaften Siemens-Halske-Ring 8 03046 Cottbus Germany This book has 129 figures and 118 tables.

ISBN 978-3-11-055985-9 e-ISBN (PDF) 978-3-11-056134-0 e-ISBN (EPUB) 978-3-11-055996-5 Library of Congress Control Number: 2019944996 Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.dnb.de. © 2020 Walter de Gruyter GmbH, Berlin/Boston Cover image: shulz / Kollektion:E+ / Getty Images Typesetting: Integra Software Services Pvt. Ltd. Printing and binding: CPI books GmbH, Leck www.degruyter.com

Für Ursula

The history of science is science itself Johann Wolfgang von Goethe (Goethe wrote, “daß die Geſchichte der Wiſſenſchaft die Wiſſenſchaft ſelbſt ſey“. In: Zur Farbenlehre. Erster Band. Cotta, Tübingen 1810, Vorwort, p. XX)

Vielleicht ist nie etwas Erhabeneres gesagt oder als Gedanke erhabener ausgedrückt worden als in jener Aufschrift über dem Tempel des Isis (der Mutter Natur): „Ich bin alles was da ist, was da war und was sein wird, und meinen Schleier hat kein Sterblicher aufgedeckt“.

[Perhaps there has never been a more sublime utterance, or a thought more sublimely expressed, than the inscription upon the Temple of Isis (Mother Nature): “I am all that has been, that is or shall be; no mortal Man hath ever me unveiled”.]

Immanuel Kant (1790) § 49 to Kritik der Urteilskraft [Critique of Judgment]

Preface to the first edition Half a century ago, Christian Junge, the founding “father” of atmospheric chemistry summarized the existing knowledge in his field of research. In 1958, Junge counted only 75 research articles dealing with atmospheric chemistry and radioactivity. Nowadays the publication rate and number of researchers in atmospheric chemistry are orders of magnitude greater. Many major advances have been made since then. For example in the early 1970s, the role of OH radicals in oxidizing gases, leading to their removal from the atmosphere, was discovered. The necessary ingredients to produce OH are ozone, water vapor, and UV-B solar radiation. The catalytic role of NO in producing ozone was also recognized at the beginning of the 1970s. Until then it was generally believed that tropospheric ozone was produced in the stratosphere and transported downward into the troposphere. The feedstocks for the creation of ozone are CO, CH4, and many biogenic gases. Both natural and anthropogenic processes are responsible for their emissions. Although the main photochemical chain reactions are reasonably well known, their quantification needs much further research. They all are parts of the biogeochemical cycles of carbon, nitrogen, and sulfur. They can also play a role in climate, as does particulate matter, which, contrary to the greenhouse gases (CO2, CH4), tends to cool the earth and atmosphere. In his book, Detlev Möller gives a thorough overview of the main chemical processes that occur in the atmosphere, only a few of which have been mentioned above. The novel title of this book Chemistry of the Climate System should direct the attention of the reader to the fact that understanding atmospheric chemistry is incomplete without considering interfacing neighboring reservoirs such as the hydrosphere, the lithosphere, and the biosphere. An overview of the topics treated is provided in the Introduction. It emphasizes that drawing strong borderlines between disciplines makes no sense and this is also valid for the various systems because they overlap and the most important processes can happen at their interfaces. Therefore, Chemistry of the Climate System combines atmospheric with water, soil, and biological chemistry. Another general approach of this book lies in the incorporation of historical facts: despite the orders of magnitude more publications each year nowadays than in past, we should not forget that careful observations were made and serious conclusions drawn by many of our scientific ancestors. The text has its roots in a book written in German, entitled Luft and published by De Gruyter in 2003. Although the text has been entirely rewritten and many sections have been replaced, the main emphasis on regarding the atmosphere as a multiphase system is essentially unchanged. Moreover, by adding interfacial chemistry, the system is enlarged to a multireservoir system, encompassing the climate system. At the end, however, the central focus is chemistry. The author avoids using the term environmental chemistry, emphasizing that substances having specific physical and chemical properties can modify (chemical) systems in various directions depending https://doi.org/10.1515/9783110561340-202

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on the mixture and initial conditions. Specialists in physics, chemistry and biology as well its many subdisciplines need to understand what their disciplines can bring to the subject of climate system chemistry. This book is about fundamental aspects of (chemical) climate change. But this book does not attempt to review all of the research on this topic. At many sites in this book, “Further Reading” is provided referring the reader to more specialized textbooks. The book comprises three large fundamental sections: chemical evolution, physicochemical fundamentals, and substances and chemical reactions. Following the Introduction, the section “Chemical Evolution” gives a brief history from the Big Bang to the Anthropocene, the human influenced earth system. Detlev Möller describes the historical dimension in connecting the past with future developments. Changing chemical air composition is based on three pillars: land use change, burning of fossil fuels and agricultural fertilizing, all caused by the rising global population. The resulting air chemical “episodes” (acid rain, ozone, particulate matter) are fairly well understood and end-of-pipe technologies to control air pollution have been introduced. The remaining future challenge, limiting global warming through reduced emission of CO2, however, can be achieved only by moving the anthroposphere into a solar era, as suggested in Section 2.8.4. Hence, Möller defines global sustainable chemistry as a coupling biogeochemical cycles with anthropogenic matter cycles, almost importantly CO2 cycling. Chapter 4 briefly overviews the physical and chemical principles of transporting and transforming substances in natural reservoirs, again with an emphasis on multiphase and interfacial processes. The texts on chemical reactions, multiphase processes, atmospheric removal, and characteristic timescales are well written and easy to read even for nonchemists. The third main section treats “Substances and Chemical Reactions in the Climate System” according to the elements and their compounds, depending on the conditions of reactions and whether the substance exists in the gaseous or condensed phase. The structure is adapted from “classical,” substance-oriented textbooks in chemistry: hydrogen, oxygen, nitrogen, sulfur, phosphorus, carbon, and halogens. Many excellent figures summarize chemical pathways under different natural conditions and make it easy to understand complex chemical processes. Different appendixes provide useful information on abbreviations, quantities, units, and the earth geological time scale. The respect brought to the history of science is fulfilled by a nice biography including some not so well-known scientists. All together, this well-written and useful book fills a gap in the attempt to provide books written from the perspective of a particular discipline (chemistry) on an interdisciplinary subject (the climate system) for readers and scientists from different disciplines to learn (or teach) some chemistry outside of the laboratory retort or industrial vessel. Paul Crutzen, Mainz 2009 Nobel Prize in Chemistry 1995

Authors preface to the third edition The entire focus in all previous editions of the Chemistry of the Climate System was on a chemical understanding of the climate system in the light of changes, from early times to the present and even into the future. Hence, insights into the evolution (or history) of the Earth and the atmosphere became key for understanding processes under changing conditions. It was the idea of De Gruyter to issue a third edition. Unfortunately, we are living in a time when the infinitesimal period between today and tomorrow is virtually the only thing that interests people. Holding onto the past seems to be a hobby for only a few passionate individuals and looking far into the future is of interest only to a few solitary individuals. Students ask for textbooks that are no older than 2 years, not knowing that (good) textbooks, being decades old, already contain 90% of basic knowledge for understanding natural processes (in chemistry, physics, and biology) today. Nevertheless, books always get better with each new edition, even if only mistakes are corrected. It goes without saying that mistakes have been corrected in the present text as well. My deep gratitude goes to the publishers, who granted me an extension and allowed me to fully restructure the second edition of Chemistry of the Climate System into two volumes, now in the present third edition. Volume 1 now comprises the physical–chemical basics (fundamentals and principles) of the chemistry of the climate system. Volume 2 treats the system with respect to its evolution (or history) and how it has changed, as well as its sustainability. Volume 1 contains carefully corrected, fully restructured, and partly enlarged chapters from the second edition concerning the fundamentals of physics (kinetic gas theory and radiation budget), physicochemistry (thermodynamics, equilibrium, properties of water and solutions, multiphase processes), chemistry (substances and reactions, enlarged by metalloids and metals that are environmentally important), and global cycling in the climate system. All historical remarks are now – more systematically – integrated in Volume 2. The transport and transformation of chemical species are continuous, ongoing processes in the atmosphere. Air constituents (gases, solid, and liquid particles) change perpetually through chemical reactions, transfers among physical states, and transfers to (deposition) and from (emissions) the earth surface. Direct solar radiation and scattered and reemitted radiation interacts with air constituents, resulting in changes to energetic states and photochemical conversions. This volume mainly focuses on the physicochemical fundamentals of the climate system. As I will often mention in this book, we cannot separate chemical and physical processes. Hence, it is inevitable to outline briefly the physical fundamentals in this regard. However, there are many excellent books on atmospheric physics and meteorology on the market, and the reader is referred to them in connection with the following topics: atmospheric physics and thermodynamics (Peixoto and Oort 1992, Andrews 2000, Zdunkowski and Bott 2004, Hewitt and Jackson 2003, Tsonis 2007), atmospheric dynamics (Gill 1982, Holton 2004, Vallis 2006, Marshall and Plumb https://doi.org/10.1515/9783110561340-203

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2007), meteorology (Garratt 1992, Kraus 2004, Wallace and Hobbs 2006, Ackerman and Knox 2006, Ahrens 2007, Lutgens et al. 2009), and radiation (Kyle 1991, Zdunkowski et al. 2007, Wendisch and Yang 2012). Great scientific progress was made in the nineteenth century. The twentieth century saw explosive scientific growth. What do we expect in the present century? The growth of science or “growth of knowledge,” a term coined by Karl Popper (1902–1994), was shown to have “an exponential curve” by the sociologist William Fielding Ogburn (1886–1959) in 19221 (Popper 1962, Ogburn 1922), based on data compiled by Darmstaedter (1908) on discoveries and inventions. Basil Bernstein (1924–2000) said, “the theory, however primitive, has always come before the research. Thus by the time a piece of research was initiated the theory has already been subject to conceptual clarification as it engages with the empirical problem. And by the time it has finished there were further conceptual developments” (Bernstein 2000, p. 93).1 By the evolution of Earth and the climate system, we will simply understand their historical development from earliest times until the present. Theories on how the atmosphere and ocean formed must begin with an idea of how the Earth itself originated (Kasting 1993). An understanding of our atmosphere and the climate system is incomplete without going into the past. “The farther backward you can look the farther forward you can see” (Winston Churchill). “Evolution is God’s, or Nature’s, method of creation. Creation is not an event that happened in 4004 BC; it is a process that began some ten billion years ago and is still under way” (Theodosius Grygorovych Dobzhansky2). “Progress is not an objective fact of nature and cannot therefore be used to justify a normative ethic” (Ruse 1999, p. 221). Despite important achievements in our understanding of key aspects of aerosols, clouds, and precipitation chemistry and physics, clouds and aerosols remain the largest source of uncertainty in the two most important climate change metrics: radiative forcing and climate sensitivity (IPPC 2007, 2013). This uncertainty is the “manifestation of the lack of our understanding of how aerosol-cloudprecipitation processes act in the climate system” (Heintzenberg and Charlson 2009). An understanding of this complex matter requires an interdisciplinary and integrated approach. Contemporary science had to adopt a new way of thinking because of the emergence of a rapid accumulation of knowledge at different levels. It seems, however, that progress in understanding nature is slow and infinite. Wise adages illustrate this predicament: “Nature is simple, but scientists are complicated,” said Spanish cardiologist Francisco Torrent-Guasp (1931–2005), and Jean-Jacques Rousseau (1712–1778) asserted, “Nature never deceives us; it is we 1 Ogburn wrote, “When the material culture was small inventions were few, and now when the material culture is large the inventions are many” or in other words, the greater the number of inventions, the greater the number of new inventions generated. Ogburn’s exponential curve was criticized regularly throughout history; see for example Schmookler (1966). 2 Russian-American biologist (1900–1975).

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who deceive ourselves” (references from Buckberg 2005). Albert Einstein said that “everything should be made as simple as possible, but not simpler.” Stewart and Cohen (1994) also stated: “The role of science is to seek simplicity in a complex world. This is a comfortable picture, which encourages a view of the relation between laws and their consequences – between cause and effect –that might be characterized as ‘conservation of complexity’. That is, simple rules imply simple behavior; therefore complicated behavior must arise from complicated rules.” Today, an innumerable sites devoted to the study of air chemistry exist that are often only active for short periods, with sometimes barely more than a dozen samples collected and analyzed for whatever purpose. Josiah Charles Stamp (1880–1941) wrote: “We are so obsessed with the delight and advantage of discovery of new things that we have no proportionate regard for the problems of arrangement and absorption of the things discovered” (Stamp 1937, p. 60). I hope that this history, at least since the systematic monitoring in the second half of the nineteenth century – which is certainly unknown to most modern air chemists – will not only encourage respect for our scientific predecessors but will also help to avoid many scientifically meaningless studies of the kind that have appeared over the last few decades. The endeavor remains to learn from previous studies to ask the appropriate open questions and draw the right conclusions for further studies. We learn from history that all kinds of people have been interested in our subject from a philosophical perspective or with respect to the application of techniques (engineering) but always motivated by specific problems (e.g., pollution) of their era. We also hold deep respect for our scientific forebears for the brilliant conclusions they drew based on experiments using very simple techniques and limited quantitative measurements. The great interest in historical data from the era before fossil fuel combustion lies also in the deduction of background concentrations, in other words, the natural reference concentrations for assessing human-influenced changes in chemical air composition. On the other hand, recognition of pervasive urban air pollution in the past would also provide a scale for a more realistic assessment of present air pollution, often still referred to as serious by politicians and administrators. English chemist Colin Archibald Russell (1928–2013) wrote, “Science without its history is like a man without a memory. The results of such collective amnesia are dire” [In: Whigs and professionals. Nature (1984) 308, 777–778]. A chemist who has spent 40 years studying atmospheric chemistry and air pollution wrote this book. When I began learning what air chemistry was about, it was the era of sulfur dioxide pollution, the 1970s. It was soon clear to me – and first shown by Junge and Ryan (1958) – that aqueous-phase chemistry dominates in the overall conversion of SO2 to sulfuric acid, that is, chemical reactions in clouds, fog, and raindrops (Möller 1980). Being fascinated from the first publication on complex chemistry in raindrops (Graedel and Weschler 1981), we began to study acid deposition (Marquardt et al. 1984) and to develop the first extensive model on aqueousphase chemistry for raindrops and rain events in Europe (Möller and Mauersberger

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1990, Mauersberger and Möller 1990). Soon after, we learned that chemical conversion in rain is negligible compared to chemistry in clouds in the development of a cloud chemistry model (Möller and Mauersberger 1992). Following the motto of Gottfried Wilhelm Leibniz (1646–1716) “theoria cum praxis” we constructed a mountain cloud chemistry station at Mount Brocken of the Harz Mountains (Möller et al. 1993), in continuous operation until 2010. Now, more than 7 years after my retirement and at the end of my scientific career, I would like to thank more people than just my former staff members (see preface to the second edition). First, I thank history (very special East German circumstances) that I had the freedom to decide in late 1974 to become an atmospheric chemist. It was the time of the so-called cold war, dividing the world into East (former “socialist” countries) and West (“capitalistic” countries), antagonized at all fronts. However, air pollution knows no borders, nor does science. Before the fall of the Wall in late 1989, despite some invitations from Western countries (my special thanks go to Henning Rodhe and Hans-Walter Georgii (†)), my “area of distribution” remained the East before 1990. I am very happy to know all those individuals in the Eastern bloc (the number was limited) who worked at the same time as I did in the field of atmospheric chemistry and air pollution. It also makes me happy that I became one of the very few specialists in the field in the former Eastern bloc in the 1980s. The most renowned scientists from the East at that time, who were also of international repute, I name here: Ernö Mészáros (Budapest), Alexey Ryaboshapko (Moscow), Mark Evseevič Berljand (†), and Rimma Lavrinenko and Valerij Isidirov (Leningrad and St. Petersburg, respectively), and in addition Bedřich Binek (Prague), Dušan Zavodsky (Bratislava), László Horváth, László Bozo, László Haszpra and Gabriella Várhelyi (Budapest), Stefan Godzik (Katowice), Dalia Shopauskine (Vilnius), Zhao Dianwu (Beijing), and a few more with whom I was in constant contact and was engaged in very fruitful discussions. Unfortunately, I never met the great Olga Petrovna Petrenchuk (Leningrad), a pioneer in aerosol and cloud research. Another person I never met owing to his untimely death but whom I hold in the highest regard is Hans Cauer (1899–1962), the German pioneer of chemical climatology – my intellectual father. The dream, however, of establishing a research station at Mount Brocken became a reality only after the fall of the Berlin Wall in early spring 1990. Hence, I would also like to thank many leading West German scientists for supporting me and my project ideas in the early 1990s: Paul Crutzen, Meinrath Andreae, Adolf Ebel, Hans-Walther Georgii (†), Hans Pruppacher, Dieter Kley, Dieter Ehhalt, Ruprecht Jaenicke, Reinhard Zellner, Dieter Klockow (†), Wolfgang Jaeschke, Wolfgang Seiler, Ullrich Schurath, Peter Warneck, Gode Gravenhorst, Peter Winkler, Karl-Heinz Becker, Ulrich Platt, Jürgen Kesselmeier, and many others. I am very happy to have met Christian Junge (†) in 1992. My special thanks go again to Volker Mohnen, who flew me in his Cessna airplane in 1991 from Albany to Lake Placid, New York, visiting the Whiteface Mountain Field Station, which served as the inspiration for my Brocken station. Without the extensive international cooperation or idea exchange in

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the 1990s, the Brocken station and our large mobile measuring equipment (we participated in 12 international field campaigns at many sites throughout Europe between 1990 and 2008 and 13 joint national and 17 institutional field campaigns) would not have been developed to such a sophisticated degree. I would like to thank (in alphabetical order) Hajime Akimoto, Helen ApSimon, Greg Ayers, Len Barrie, Axel Berner, Peter Brimblecombe, Peter Builtjes, Robert Charlson, Nadine Chaumerliac, Tom Choularton, Jeff Collett, Tony Cox, Robert Delmas, Bob Duce, Sandro Fuzzi, Ian Galbally, Hiroshi Hara, Manabu Igawa, Peter Liss, Tony Marsh, John Miller, Stuart Penkett, Pascal Perros, Hans Puxbaum, Robert Rosset, Steve Schwartz, Jack Slanina (†), Chris Walcek, and many others. Last but not the least, I thank my East German colleagues and partners without whom I would not have been able to build my research profile in the 1980s: Karl-Heinz Bernhardt, Hans-Günther Däßler, Wolfgang Rolle (†), Eberhard Renner, Wolfgang Warmbt (†), Uwe Feister, Wolfgang Marquardt (†), Herbert Mohry, Herbert Lux, Günther Flemming, Ulrich Damrath, Manfred Zier, Günter Herrmann, Bernd Schneider, Eberhard Hüttner, Peter Ihle, Christian Hänsel (†), Kurt Schwinkowski, Wolfgang von Hoyningen-Huene, Rudolf Kind, and others. Unfortunately, I never had the opportunity to meet Helmut Mrose (†), a pioneer in air chemistry at Wahnsdorf (DDR) in the early 1950s (in addition to W. Warmbt). I cannot name everyone, but I have forgotten no one. Detlev Möller Berlin, May 2019

Authors preface to the second edition Now, 4 years after the publication of the first edition of Chemistry of the Climate System, we see continued growth in the scientific literature and in particular new insights in the field of atmospheric aerosol (fine PM and especially the role of biological material) but also in HNO2 and OH chemistry; however, it is not my aim to consider them all in the second edition, giving an actual review. My intention is, rather, to provide the reader a monograph textbook for a deeper understanding of physicochemical processes in a very complex system composed of different states of matter (gas, liquid, and solid) within different reservoirs, specifically the atmosphere, hydrosphere, lithosphere, and biosphere (the climate system). Scientific progress is measured in large strides in the fundamental sciences – laboratory and theoretical studies. Nevertheless, studying complex environmental processes by “outdoor” studies (field experiments) – and even extending one reservoir or phase – became extremely complicated and was carried out in the decade or two only in large projects that included many institutes and scientists. Our knowledge also increased and feedback for detailed laboratory work was produced. Better understanding of the climate system acquired by a deeper consideration and coupling of subsystems, most of the entire atmosphere with the oceans (e.g., explaining the discrepancy between a further rise in atmospheric CO2 and stagnant air temperature). In addition, the biosphere was revealed to be much more complex in its feedbacks to atmospheric changes (the still unanswered question of where all the CO2 remains). Unfortunately, controlling our climate system is much more far off compared to our understanding 4 years ago. Economics largely disregards results from climate research. Visible, human-caused catastrophes, such as the Fukushima Daiichi nuclear disaster, did result in any forward-looking changes to the energy mix or a transition to solar technologies but led backward to coal combustion, exacerbating the CO2 problem. Climate change is likely not a catastrophe in a traditional way; rather, it is a slow process with winners and losers (humans, animals, and plants). I hope that this new edition of Chemistry of the Climate System will find new readers who want to learn more about our climate system. Knowledge is the key to sustainable development and to realizing that the benefits accruing to winners will pale by comparison to the penalty the losers will pay. Needless to say, (I hope) all errors have been corrected, information (especially monitoring and emission data) has been updated, many figures have been improved, several paragraphs were rewritten for clarity, and new key knowledge has been added in this edition. Moreover, two new sections on “chemical climatology” have been added: precipitation and cloud chemistry monitoring. The chapter on atmospheric trace species was enlarged to include a discussion of hydrochloric acid, nitrous acid, and nitric acid with its salty PM. Last but not the least, I would like to express my profound gratitude to my coworkers who accompanied me over many years, even decades, in atmospheric chemistry; without them this book would have been impossible [I corrected the https://doi.org/10.1515/9783110561340-204

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periods with this 3rd edition]: Karin Acker (1988–2014), Wolfgang Wieprecht (1982–2019), Günther Mauersberger (1983–2006), Renate Auel (1987–2008), Gisela Hager (1987–1997), Jürgen Hofmeister (1988–2017), and Dieter Kalass (1992–2018). Many others, not named here, were part of my group for “only” a few years. We had a great time, with many highlights in atmospheric chemistry in the 1980s and 1990s. Detlev Möller Berlin, February 2014

Prologue Ten years ago the publishing house De Gruyter asked me to write a book titled Luft (Air), which was published in 2003. Paul Crutzen said that it was written in the wrong language. It was written in German, my mother tongue. I took it as a compliment that they wanted me to reach more international readers. I thank De Gruyter who offered me the opportunity to write another book on air in English about 3 years ago. The German book Air belongs to a planned series on water, air, and soil (the last one has not been written yet), which means that there were certain restrictions and wishes that came from the editor. However, for this new book I had absolute freedom to choose my own content; therefore, I would like to thank De Gruyter. The only wish from the editor was that this book should contribute to the discussion on climate change. This new book is not a (revised) translation of Air – I have only used a few fundamental issues such as physicochemistry and basic air chemistry, which has become fundamental knowledge in any textbook. I am a chemist; my original background is physical chemistry, but for 35 years I have been dealing with air chemistry (and air pollution studies). Chemistry is the science of matter, and matter distributes and cycles through nature. The climate system is a part of this, and the atmosphere is another part. The earth climate system provides a habitable zone. I agree with those scientists who argue that human beings, as a part of nature, have altered the “natural system” to such an extent that we are now unable to reverse the present system back to a preindustrial or even prehuman state. Nevertheless, the key question at present is how to maintain the functioning of our climate system in such a way that enables the sustainable survival of humans. We can state that humans have become a global force in chemical evolution with respect to climate change by interrupting naturally evolved biogeochemical cycles. However, humans also have all the capacities to turn the “chemical revolution” into a sustainable chemical evolution. An understanding of how the climate system works is provided by the natural sciences (physics, chemistry, and biology). This book focuses on the chemistry of the climate system, but differentiating precisely between physics and chemistry makes absolutely no sense when trying to understand that system. However, without an understanding of biological laws – and we could probably include social laws here as well, considering that the biosphere was long ago transformed into the noosphere – we will neither understand climate change nor find solutions to climate control. Maybe this book will provoke people by bridging state-of-the-art textbook knowledge with ideas or opinions beyond “pure” chemistry. Without a paradigm change in the next two to three decades (for example, carbon dioxide cycling), we will have little chance to control climate. My knowledge is limited; therefore, specialists will find gaps and missing pieces in my book. A few weeks ago, I attended a lecture by Professor Norimichi Takenaka (Japan), who studied the decomposition of ammonium nitrite in drying dew droplets by the formation of N2 – a disproportioning and fascinating pathway for atmospheric NH3 and NOx. Unfortunately, I did not know about this reaction, https://doi.org/10.1515/9783110561340-205

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even though it was already known in the nineteenth century, and it is a key example of interfacial chemistry, which is a focus of my book and has been a special interest of mine in the last few years after having studied multiphase chemistry for many years. I believe that interfaces (or heterogeneous systems) at certain places in nature provide special conditions for chemical reactions and therefore result in the turnover of matter. Our knowledge about what happens in atmospheric multiphase chemistry, despite much progress over the last two decades, remains limited (I hope that some of that knowledge is summarized in this book). However, interfacial chemistry may be more important (and almost more interesting) for controlling the climate system at the interfaces between the atmosphere and the earth surface, including, for example, natural waters, soils, plants, and microorganisms. Special thanks go to Professor Volker A. Mohnen, to whom I owe important scientific suggestions over the last 20 years, including the impulse to write this book. Finally, I would like to thank my coworkers who accepted my frequent absence at the institute throughout the last 2 years (and who kept things running smoothly); I wrote this book in my office at my home in Berlin (day and night, weekdays and weekends – special thanks go to my wife Ursula and my family), surrounded by hundreds of books on the chemistry (but also the history, physics, and biology) of the climate system published in the last 200 years (and a few older ones). This book, to my knowledge, is the first ever to be titled Chemistry of the Climate System, and I hope – no, I am sure – that it will not be the last. It stands between “special” and “generic”; it is part textbook, part monograph (and might even appear to be an ecopamphlet). Hence, the book is recommended to any and all who like nature and chemistry or who want to learn more about climate system chemistry. Detlev Möller Berlin and Cottbus, November 2010

Contents Preface to the first edition

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Authors preface to the third edition Authors preface to the second edition Prologue

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1 1.1 1.2 1.2.1 1.2.2

Introduction 1 The human problem: a changing earth system 1 Chemistry: a historic view 5 Definition of chemistry 5 Atmospheric chemistry: a terminological and historical approach 8 1.2.3 A brief history of chemistry 15 1.2.4 Terminology 28 1.2.4.1 On the chemical nomenclature and symbols 28 1.2.4.2 On the origin and meaning of the words air, fog, and smoke 2 2.1

2.1.1 2.1.2 2.1.2.1 2.1.2.2 2.1.3 2.1.3.1 2.1.3.2 2.1.3.3 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.2.6 2.2.7 2.2.7.1 2.2.7.2

History of investigation and understanding the climate system Air and atmosphere before exploring air chemical composition 44 Ancient views: origin of the world 44 Ancient views: air and water 46 Greek philosophers 46 The time after Aristotle 49 The time after 1600 52 Beginning measurements 52 Theories on condensation and evaporation 54 Alchemy: airs and gases 66 Discovery of air chemical composition 73 A brief history of the discovery of gases 73 Carbon dioxide 83 Nitrogen 84 Oxygen 86 Water 87 Argon and the other novel gases 91 Air analysis 92 Determination the goodness of air: eudiometry 92 Analysis of oxygen 95

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2.2.7.3 2.2.8 2.2.8.1 2.2.8.2 2.3 2.3.1 2.3.2 2.4 2.4.1 2.4.2 2.4.3 2.4.4 2.4.5 2.4.6 2.4.6.1 2.4.6.2 2.4.7 2.4.7.1 2.4.7.2 2.4.7.3 2.4.7.4 2.4.8 2.4.8.1 2.4.8.2 2.4.8.3 2.4.8.4 2.4.8.5 2.4.9 2.5 2.5.1 2.5.2 2.5.3 2.5.4 2.5.5 2.5.6

Contents

Carbon dioxide measurements 99 Trace gases 107 Ozone 116 Hydrogen peroxide 128 Understanding interaction between biosphere and atmosphere 137 A brief history of understanding plant growth and photosynthesis 137 Cycling of matter 142 Investigation of atmospheric waters in air 149 Alchemist treatment of atmospheric waters 154 Transmutation of rainwater into earth 162 Colored rain and snow 164 Rainwater studies before 1800 166 Rainwater studies 1813–1863: an analytical approach 174 Rainwater analysis for understanding agricultural chemistry (1851–1950) 183 Agriculture Experimental Stations 183 The “nitrogen period” (1851–1919) 187 Rainwater analysis for understanding air pollution and air chemistry 207 Robert Angus Smith: air and rain (1869–1872) 209 The “sulfur and chlorine period” (1870–1945) 214 The “geochemical and meteorological period” (1945–1960) 227 Precipitation chemistry after 1960: an outlook 233 Fog and cloud water studies 237 Fog water studies before 1900 239 Fog and cloud water studies: understanding condensation nuclei (1925–1955) 241 Fog and cloud water studies: understanding air pollution (1955–1970) 244 Fog and cloud water studies: understanding chemistry (1971–1990) 245 Fog and cloud water studies after 1990: an outlook 249 Dew water studies 252 Investigation of dust (particulate matter) in air 257 A short history of understanding particulate matter in air 258 Soil dust: Ehrenberg’s red dust 265 Dry fog 268 A brief history of town pollution 269 Smoke and fog: smog and the soot plague 273 On sea salt as cloud condensation nuclei 278

Contents

2.6 2.6.1 2.6.2

Climate and climatology: a historic perspective Understanding climate 280 Understanding climate change 288

280

3 History of the climate system: the chemical evolution 293 3.1 The prebiological period 293 3.1.1 Origin of elements, molecules, and the Earth 293 3.1.2 Origin of organic bonded carbon 304 3.1.3 Origin of nitrogen 311 3.2 Evolution of the atmosphere 314 3.2.1 Degassing of the Earth: the formation of the atmosphere 315 3.2.1.1 Volcanic gases 315 3.2.1.2 Occluded and produced gases from rocks 318 3.2.1.3 The prebiological primitive atmosphere 323 3.2.2 Biosphere–atmosphere interaction 329 3.2.2.1 Origin of life 329 3.2.2.2 The rise of oxygen and ozone: biogeochemical evolution 335 3.2.2.3 The carbon and oxygen pools and global cycling 342 3.2.2.4 Life limits by catastrophic events: mass extinction 350 3.2.2.5 Biosphere and the noosphere 352 3.2.2.6 What is the role of life in earth climate system? 357 3.2.3 Abiogenic versus biogenic formation of “fossil fuels” 361 3.3 Climate and climatology: change 362 3.3.1 Climate change in past: paleoclimatology 363 3.3.2 Climate change and variability 364 4 4.1 4.1.1 4.1.2 4.1.3 4.1.4 4.1.5 4.1.6

A changing climate system 373 The Earth’s energy sources 374 Geothermal energy 374 Wind energy 376 Water energy 378 Biomass and energy 379 Solar energy 380 Comparison among Earth’s energy sources – potential for humans 381 4.2 Humans historic perspective 384 4.2.1 From the past into future 384 4.2.2 Energy: fossil fuel use 390 4.2.3 Agriculture: the food problem 401 4.2.4 Land-use change: the population problem 404 4.2.4.1 Deforestation 404 4.2.4.2 Biomass burning 407

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4.2.5 4.2.5.1 4.2.5.2 4.2.5.3 4.2.5.4 4.2.5.5 4.3 4.3.1 4.3.2 4.3.3 4.3.4 4.3.5 4.3.6 4.3.7 4.3.8 4.3.9 4.3.9.1 4.3.9.2 4.3.10 4.4 4.4.1 4.4.2 4.4.3 4.4.3.1 4.4.3.2 4.4.3.3 4.4.3.4 4.4.4 4.4.4.1 4.4.4.2 4.4.5 4.4.6 4.4.7 4.4.7.1 4.4.7.2 4.4.7.3 4.4.7.4 4.4.8 4.4.9 4.4.10

Contents

Eastern German air pollution abatement: a world-wide unique example 413 Change of emissions 416 Change of concentrations in the gas phase 422 Change of concentrations in cloud water at Mt. Brocken 437 Change of concentrations in rainwater at Seehausen 454 Emissions versus concentrations: chemical climatology (summary) 466 Emission of atmospheric substances 473 Introduction: estimation of emissions 474 479 Sulfur dioxide (SO2) 483 Nitrogen oxides (NOx) 484 Carbon dioxide (CO2) 488 Ammonia (NH3) 491 Methane (CH4) 494 Dinitrogen monoxide (N2O) Carbon monoxide (CO) 496 Non-methane volatile organic compounds (NMVOC) 498 Isoprene and monoterpenes 500 Oxygenated volatile organic compounds (OVOC) 502 504 Reduced sulfur compounds (H2S, DMS, COS, CS2) Atmospheric substances: concentrations and trends 507 Fundamentals: why concentration fluctuates? 510 512 SO2, NO2 and dust: classic for local to regional up-scaling 514 CO2: the fossil fuel era challenge 514 The preindustrial CO2 level derived from ice core data 518 The twenties century CO2 increase 521 Timely and latitudinal CO2 variations 523 The city dome CO2 524 CH4 and N2O: permanent agricultural associates 524 Methane (CH4) 527 Dinitrogen monoxide (N2O) Halogenated organic compounds: sit out problem 528 CO: the biomass burning problem 530 533 O3: locally believed to be solved but regional unsolved Ozone trends in troposphere and stratosphere 533 Ozone change with altitude 540 Ozone timely variations 541 Ozone budget: sources versus sinks 543 544 H2O2: mysterious OH: the key oxidant 548 551 H2: light but problematic

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HNO2: volatile acid and OH precursor 552 560 HCl and HNO3 versus chloride and nitrate Particulate matter (dust) 563 Atmospheric substances: impacts on health 567 The basics 570 The problem 576 579 Nitrogen dioxide (NO2) Particulate matter (dust) 585

4.4.11 4.4.12 4.4.13 4.5 4.5.1 4.5.2 4.5.3 4.5.4 5 5.1 5.2 5.2.1 5.2.2 5.2.3 5.3 5.3.1 5.3.2

Climate change mitigation: global sustainable chemistry 591 Growth and steady-state economy 593 The carbon problem: out of balance 596 The carbon budget 597 602 Atmospheric CO2 residence time Direct air capture (DAC) 605 The energy problem: the last industrial revolution 608 609 The carbon economy: CO2 cycling Solar fuels: carbon as a material and energy carrier 615

6

Final remarks

621

Appendix I

List of acronyms and abbreviations found in literature

Appendix II

Quantities, units and some useful numerical values

Appendix III

Earth geological time scale

References

637

Name Index

747

Subject Index Errata to Volume 1

757 773

635

627 631

1 Introduction Out of the recognized complexity of nature arose the three basic sciences: physics, chemistry, and biology. Further progress in understanding of natural processes created numerous subdisciplines and cross-disciplines, termed with a variety of prefixes and combinations, often creating misunderstandings unless careful definitions are used. In order to overcome disciplinary borders, a new super-science was established, earth system science, to study the Earth as a system, with an emphasis on observing, understanding, and predicting global environmental changes involving interactions between biogeochemical compartments (land, atmosphere, water, ice, and biosphere) and anthropogenic compartments (societies, technologies, and economies). We will define the climate system to be a part of the earth system, with emphasis on the atmosphere but involving interactions between land, atmosphere, water, ice, biosphere, societies, and others. Hence, “Chemistry of the Climate System” is neither simply air nor environmental chemistry. Humans – by decoupling their life cycle from natural conditions – have altered “natural” biogeochemical cycles. The Russian geochemist Vladimir Ivanovich Vernadsky understood by noosphere (called anthroposphere by Paul Crutzen) a new dimension of the biosphere, developing under the evolutionary influence of humans on natural processes (Vernadsky 1926); consequently, Crutzen and Stoermer (2000) proposed to name the present epoch Anthropocene. Now it seems that humankind enters a nouveau régime climatique [new climatique regime] according to Bruno Latour (Latour 2015).

1.1 The human problem: a changing earth system In recent decades, humans have become a very important force in the earth system, demonstrating that emissions and land-use change are the causes of many of our environmental issues. These emissions are responsible for the major global reorganization of biogeochemical cycles. With humans as part of nature and the evolution of a man-made changed earth system, we also have to accept that we are unable to remove the present system into a preindustrial or even prehuman state because this means disestablishing humans. The key question is which parameters of the climate system allow the existence of humans under which specific conditions. The chemical composition of air is now contributed by both natural and man-made sources. As will be discussed, large uncertainties in the estimations of global emissions (and subsequent regional gridded emission patterns) remain. Nevertheless, major regional and global environmental issues, such as acid rain, stratospheric ozone depletion, pollution by persistent organic pollutants (POPs), and tropospheric ozone pollution, resulting in adverse effects on human health, plant growth, and ecosystem diversity, were identified and controlled to different extents https://doi.org/10.1515/9783110561340-001

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1 Introduction

by various measures. Some key issues remain unsolved, such as the further increase of greenhouse gases (GHG), most importantly that of CO2. With the growth of “megacities,” local pollution will have a renaissance, and this will inevitably contribute to regional and subsequently global pollution by large plumes, such as “brown clouds.” Thus, it is important to find answers to the following questions: – What is the ratio between natural and man-made emissions? – What are the concentration variations on different timescales? – What are the true trends of species by man-made origin? – What are the concentration thresholds for the effects (concerns different impacts) we cannot tolerate? The chemical composition of air was changing since the settlement of humans. In addition to the scale problem (from local to global), we have to consider the timescale. Natural climate variations (e.g., due to ice ages) had a minimum timescale of 10,000 years. The man-made changes in our atmosphere over the last 2,000 years were relatively small before the 1850s. In the past 150 years (but almost all after 1950), however, the chemical composition has changed drastically. For many atmospheric compounds, anthropogenic emissions have grown to the same or even larger order of magnitude than natural ones. Because of the huge population density, the need (or consumption)3 of materials and energy has drastically forced the earth system. The timescale of adaptation and restoration of natural systems is much larger than the timescale of man-made stresses (or changes) to the climate system. We should not forget that “nature” cannot assess its own condition. In other words, the biosphere will accept all chemical and physical conditions, even worse (catastrophic) ones. Only humans possess the facility to evaluate the situation, accepting it or not, and coming to the conclusion of making it sustainable. Under the aspect of chemical evolution, this volume also briefly outlines the role of humans in forcing the climate system. Let us define a sustainable society as one that balances the environment, other life forms, and human interactions over an indefinite time period. Throughout the entire history of our planet, chemical, physical, and biological processes have changed the composition and structure of its reservoirs. Beginning

3 This is an interesting question: do we need all this consumption? What consumption do we need to realize a cultural life? Of course, we move from natural (earth sciences) to a social and political dimension (life sciences) in answering these questions. But there is a huge potential to economize and save resources in answering these questions and implementing it. Karl Marx wrote: “The philosophers have only managed to interpret the world in various ways. The point is to change it” (this is still fixed in the main hall of the central building of the Humboldt University in Berlin, Germany). However, the key point is how and in which direction we have to change the world to receive sustainability.

1.1 The human problem: a changing earth system

3

with a highly dynamic inner earth 4.6 billion years ago, geochemical and geophysical processes have created the fundamentals for the Earth to become a habitat. With this, the formation of the hydrosphere was the most important precondition for the evolution of living matter. Despite large changes of the chemical composition of the atmosphere, hydrosphere and lithosphere (the geosphere) over the ages, these spheres or reservoirs are well defined concerning these essential parameters as interfaces, volume, mass, and others. The British scientist James Lovelock together with Lynn Margulis developed the hypothesis that the Earth is a self-controlling system (Gaia: the earth goddess in Greek), and proposed that our present atmosphere is far from the chemical equilibrium that is assumed for other planets (Lovelock and Margulis 1974, Crutzen 2002). One expression of this is the difference in the redox potentials between biosphere (reducing medium) and atmosphere (oxidizing medium). It is believed that living organisms are responsible (to a large extent) for the chemical composition of the present atmosphere and, from the opposite point of view, the chemical composition of the atmosphere determines the biota. Remarkably, the composition of the biosphere is similar to that of the present atmosphere. The term evolution4 was used first in the field of biology at the end of the nineteenth century. In the context of biology, evolution is simply the genetic change in populations of organisms over successive generations. Evolution is widely understood as a process that results in greater quality or complexity (a process in which something passes by degrees to a different stage, especially a more advanced or mature stage). However, depending on the situation, the complexity of organisms can increase, decrease, or stay the same, and all three of these trends were observed in biological evolution. At present, the word has a number of different meanings in different fields. Geological evolution is the scientific study of the Earth, including its composition, structure, physical properties, and history; in other terms, the Earth changes over time or the process of how the Earth has changed over time. The term chemical evolution is not well defined and is used in different senses. Chemical evolution is not simply the change and transformation of chemical elements, molecules, and compounds as is often asserted – that is the nature of chemistry itself. It is essentially the process by which increasingly complex molecules, compounds, and matter develop from the simpler chemical elements that were created in the Big Bang. The chemical history of the universe began with the generation of simple chemicals in the Big Bang. Depending on the size and density of the star, the fusion reactions can end with the formation of carbon or they can continue to form all the elements up to iron.

4 From Greek έξελίγμός and έξελίσσω (Latin evolutio and evolvere), to evolve (develop, generate, process, originate, educe).

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1 Introduction

The origin of life is a necessary precursor for biological evolution, but understanding that evolution occurred once organisms appeared and investigating how this happens does not depend on understanding exactly how life began. The current scientific consensus is that the complex biochemistry that makes up life came from simpler chemical reactions, but it is unclear how this occurred. Not much is certain about the earliest developments in life, the structure of the first living things, or the identity and nature of any last universal common ancestor or ancestral gene pool. Consequently, there is no scientific consensus on how life began, but proposals include self-replicating molecules such as RNA, and the assembly of simple cells. Astronomers have recently discovered the existence of complex organic molecules in space. Small organic molecules were found to have evolved into complex aromatic molecules over a period of several thousand years. Chemical evolution is an exciting topic of study because it yields insight into the processes that lead to the generation of the chemical materials essential for the development of life. If the chemical evolution of organic molecules is a universal process, life is unlikely to be a uniquely terrestrial phenomenon and is instead likely to be found wherever the essential chemical ingredients occur. In colloquial contexts, evolution usually refers to development over a long timescale, and the question is not important whether evolution tends toward more complexity. Many definitions tend to postulate or assume that complexity expresses a condition of numerous elements in a system and numerous forms of relationships among the elements. At the same time, what is complex and what is simple is relative and changes with time. Natura non facit saltus (Latin for “nature does not make jumps/leaps”) was a principle of natural philosophy since at least Aristotle’s time used as an axiom by Gottfried Wilhelm Leibniz, Isaac Newton, Charles Darwin, and others. A modern understanding of evolution includes continuing development, but also leaps (catastrophes, see Section 3.2.2.4). This is referred to as “transformation of quantity into quality” (dialectic leap) and may characterize the current discussion on the impacts of climate change. However, it is hard to envisage a physical situation in which a quantifiable parameter can increase indefinitely without a critical condition occurring. Physical processes – starting with the Big Bang – created the first atoms (which form chemical elements) and physical conditions permanently affecting the subsequent chemical and biological evolution. Compared with the Big Bang as the beginning of physical evolution, the creation of molecules and life can be referred to as the starting point of a chemical and biological evolution, respectively. Life became a geological force with oxygenic photosynthesis and created an interactive feedback with chemical and physical evolution. After forming the geosphere and the first atmosphere in the sense of a potentially habitable system, and later the biosphere with the modern atmosphere, a habitable climate system evolved. But life created a further dimension, human intelligence, which becomes another geological force (human evolution – today approaching a critical condition which we call crisis).

1.2 Chemistry: a historic view

5

Human intelligence disengaged humankind from the rigorous necessities of nature and provided unlimited scope for reproduction (at least in the past). Man in all his activities and social organizations is part of, and cannot stand in opposition to or be a detached or external observer of, nature. However, the new dimension (or quality) of human intelligence as a result of biological evolution – without some global ecomanagement – could change the climate system in a direction not providing the internal principle of self-preservation. Mankind converts the biosphere into a noosphere. Chemical evolution is now interloped with human evolution. Changing fluxes and concentrations of chemicals in bio- (or rather noo-) geochemical cycles with a subsequent changing climate system seems to be the creation of a human–chemical evolution.

1.2 Chemistry: a historic view 1.2.1 Definition of chemistry In contrast to physics, chemistry (alchemistry) has been excluded from real sciences until the first half of the eighteenth century. Johann Carl Fischer (1760–1833), who wrote the first “History of Physics” (Fischer 1802, p. 181), states: . . . das noch kein einziger daran gedacht hatte, die Chemie in eine wissenschaftliche Form zu bringen, und die Physiker, welche größthenteils Matematiker waren, noch nicht so einleuchtend erkannten, wie jetzt, was für eine wichtige Rolle die chemischen Operationen in der Natur spielen [. . . that not a single one yet has thought of it, to bring the chemistry in a scientific form, and the physisists which were almost mathematicians, not yet recognized – like right now – what an important role chemical operations play in nature].

In the Encyclopædia Britannica published in Edinburgh in 17715 (shortly before the discovery of the chemical composition of air) chemistry is defined as . . . to separate the different substances that enter into the composition of bodies [analytical chemistry in modern terms]; to examine each of them apart; to discover their properties and relations [physical chemistry in modern terms]; to decompose those very substances, if possible; to compare them together, and combine them with others; to reunite them again into one body, so as to reproduce the original compound with all its properties; or even to produce new compounds that never existed among the works of nature, from mixtures of other matters differently combined [synthesis chemistry in modern terms].

Antoine François Comte de Fourcroy (1755–1809) wrote in his textbook (Fourcroy 1790, pp. 1–2):

5 In Vol. 2, the complete knowledge of the time on chemistry is comprehensively presented on more than 100 pages (pp. 66–180).

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1 Introduction

Chemistry, according to Macquer,6 is a science, the object of which is to discover the nature and properties of all bodies by means of analysis and syntheses. This definition is indisputable the best that has yet been given. . . The chemist cannot attain the knowledge of the properties of bodies without bringing them into contact; . . . Chemistry is that science which explains the intimate mutual action of all natural bodies.

Johann Andreas Buchner (1783–1852) wrote (Buchner 1826, p. 1–2): Was ist Chemie: Die Wissenschaft vom Wesen der natürlichen Dinge heißt Chemie. . . Wesen nennen wir das Bleibende einer Sache, was bei allen Veränderungen der Form und Bewegung das Seyn fortwährend behauptet. . . Indessen liegt der höchste Zweck dieser Wissenschaft nicht im Scheiden und Mischen, sondern vielmehr in der Kenntniß der Elemente und ihrer Kräfte und Gesetze, nach welchen sie sich miteinander verbinden, oder mit anderen Worten: in der Kenntnis der Ursachen, Gesetze und Wirkungen der Stoffwandlungen [What chemistry means: the science of essence of natural things. . . essence we call the permanent of a thing, which constantly maintain the Sein in all changes of shape and movement. . . nevertheless the highest purpose of this science does not consists in separation and mixing, but rather in the knowledge of the elements and its forces and laws, according to which they combine, or in other words: in the knowledge of the causes, laws and effects of chemical changes].

Julius Adolph Stöckhardt wrote in his textbook (Stöckhardt 1851, p. 4) The Principles of Chemistry: “Wherever we look upon our Earth, chemical action is seen taking place, on the land, in the air, or in the depths of the sea”7. Thus, chemistry is a priori the science of mineral, animal, and vegetable matter. The chemistry of the earth system – when not considering life – is geochemistry. The term geochemistry, like many other scientific terms, has variable connotations. If geochemistry means simply the chemical study of the earth or parts of the earth, then geochemistry must be as old as chemistry itself, and dates from the attempts of Babylonian and Egyptian metal-workers and potters to understand the nature and properties of their materials (Tomkeiev 1944). It is self-evident that biochemistry deals with chemical processes in organisms and thus the chemical interaction between organisms occurs via geochemical processes. Consequently, biogeochemistry is the chemistry of the climate system, which I will define as that part of the earth system affecting life. Subdividing the geogenic part of the climate system into “other” systems, we gain the atmosphere, hydrosphere, cryosphere, and lithosphere. Thus atmospheric, aquatic, and soil chemistry are the subdisciplines of geochemistry.

6 Pierre-Joseph Macquer (1718–1884), French chemist; known for his Dictionnaire de chymie (1766), the first chemical encyclopedia, translated into several languages – in German: Macquer (1788). 7 First German edition: Schule der Chemie oder erster Unterricht in der Chemie, versinnlicht durch einfache Versuche. Zum Schulgebrauch und zur Selbstbelehrung, insbesondere für angehende Apotheker, Landwirte, Gewerbetreibende etc. Vieweg, Braunschweig 1846. German original: Wohin wir nur blicken auf unserer Erde, überall gewahren wir chemische Prozesse, auf dem Festlande, in der Luft, wie in den Tiefen des Meeres (1852, p. 2 and 1881, p. 4).

1.2 Chemistry: a historic view

7

The elemental chemical processes occurring in the atmospheric aqueous phase (rain, fog, and cloud) are not different from those described by “water chemistry,” now often also termed aquatic chemistry (e.g., Stumm and Morgan 1981, 1995, Stumm 1990, Sigg and Stumm 1996). However, aquatic chemistry deals with the composition of natural waters and aqueous solutions (or common water, to distinguish it from atmospheric water in the droplet form). In air, the chemistry in droplets is permanent in interaction with the surrounding gas phase chemistry. Hence, the term multiphase chemistry reflects best the processes in the air. Concerning the different phenomenology of atmospheric waters, it is obvious to speak of rain, snow, fog, and cloud as well as dew chemistry in the sense of analyzing the chemical composition of the solution. Analytical chemistry as a subdiscipline of chemistry has the broad mission of understanding the composition of all matter. Much of early chemistry was analytical chemistry since the questions of which elements and chemicals are present in the world around us and what their fundamental nature is are very much in the realm of analytical chemistry (Szabadváry 1966). Before 1800, the German term for analytical chemistry8 was “Scheidekunst” (“separation craft”); in Dutch, chemistry is still generally called “scheikunde.” Before developing reagents to identify substances by specific reactions, simple knowledge about the features of the chemicals (smell, color, flavor, crystalline structure, etc.) was used to “identify” substances. With Lavoisier’s modern terminology of substances (1789) and his law of the conservation of mass, chemists acquired the basis for chemical analysis (and synthesis). The German chemist Carl Remigius Fresenius wrote the first textbook9 on analytical chemistry (in 1841 on qualitative analysis and 1847 on quantitative analysis), which is still generally valid, and rewritten by Gerhard Jander (1892–1961) and

8 In Vol. 1 (p. 142) of the Encyclopædia Britannica (1871), the following definition is given: Analysis, in chemistry, is reducing of an heterogeneous or mixt body, into its original principles or component parts. 9 The first textbook on this issue was written by Johann Friedrich Gmelin (1848–1804), father of Leopold Gmelin, “Chemische Grundsätze der Probier- und Schmelzkunst” [Chemical principals of assaying and the art of melting] (Halle 1786) and soon later by Johann Friedrich August Göttling (1753–1809) entitled “Vollständiges chemisches Probekabinett” [Complete chemical sample cabinet] (Jena 1790), published in a second edition already with a more scientific title “Praktische Anleitung zur prüfenden und zerlegenden Chemie” [Practical instruction for testing and separating chemistry] (Jena 1802). Furthermore, Nicolas Louis Vauquelin (1763–1826) “Manuel de l´essayeur” (Paris 1799), translated into German “Handbuch der Probierkunst“ [handbook of assaying] (Königsberg 1800). Wilhelm August Lampadius (1772–1842) declared in his “Handbuch zur chemischen Analyse der Mineralkörper” [Handbook for chemical analysis of mineral bodies] (Freyberg 1801) the analytical chemistry as an independent discipline; he writes in the preface that the “Analysis der genannten Körper” [analysis of the mentioned bodies] should be named “vorzugsweise analytische Chemie” [preferably analytical chemistry]. Johann Heinrich Kopp (1777–1858), father of Hermann Kopp, wrote “Grundriß der chemischen Analyse mineralogischer Körper” [Fundamentals of chemical analysis of mineral bodies] (Frankfurt/M. 1805) and Johann Friedrich John (1772–1847)

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1 Introduction

Ewald Blasius (1921–1987), normally only called “Jander-Blasius,” is still used at German universities.10

1.2.2 Atmospheric chemistry: a terminological and historical approach Augustus Allen Hayes (1806–1882), Assayer to the Commonwealth of Massachusetts and a prominent but nowadays forgotten American chemist, write in a Paper (Hayes 1851) as first the phrase: The chemistry of our atmosphere has, from the earliest tine, been deemed of high interest, and its connection with the phenomena of animal and vegetable life has led to its study the minds of the most eminent chemical investigators.

“Chemisches Laboratorium, oder Anwendung der chemischen Analyse der Naturalien. Mit einer Vorrede von M. H. Klaproth” (Berlin 1808). Thomas Balthasar Fabricius (1774–1851) “Anleitung zur chemischen Analyse unorganischer Naturkörper” [Treatise to analyse inorganic natural bodies] (Kiel 1810). From the famous “Traité de Chimie élémentaire théorique et pratique” (in four volumes) by Louis Jacques Thénard (1777–1857), Vol. 4 (“Suivi d’un Essai sur la philosophie chimique et d’un Précis sur l’analyse,” Paris 1816) appear as “Anleitung zur chemischen Analyse dem gegenwärtigen Zustand der Wissenschaft gemäss; nach L. J. Thenard´s Handbuch der theoretischen und praktischen Chemie; aus dem Franz. übersetzt und mit Anmerkungen begleitet von Johann Bartholmäus Trommsdorff” (Erfurt 1817). All these books were focused on analysis of mineral matter. The first more general textbook on analytical chemistry was written by Christian Heinrich Pfaff (1753–1852) “Handbuch der analytischen Chemie” [Handbook of analytical chemistry] in two volumes (Altona 1821 and 1822) and soon later “Handbuch der analytischen Chemie” in two volumes (Berlin 1829; in six edns. until 1867) by Heinrich Rose (1795–1864) who first described the separation process (Trennungsgang in German), but very circumstantial; hence, this book by Rose was the reason that Fresenius wrote a more systematic approach of the separation process. Johann Andreas Buchner (1783–1852), German pharmacologist, best comments the fast development in chemisty in that time (Buchner 1826, p. 27) that “the chemical textbooks until beginning of the nineteenth century have mostly only a historic value.” The books of Rose and Fresenius have been translated into English. In UK, the first book on analytical chemistry was written by James Sheridan Muspratt (1821–1871), an Irish-born chemist and teacher, “Chemistry, theoretical, practical and analytical as applied and relating to the arts and manufactures” (in 2 vol. 1858–1860). The German-born chemist Wilhelm (William) Dittmar (1833–1899) published “A manual of qualitative and quantitative chemical analysis” (Manchester 1874) and “Analytical chemistry. A series of laboratory exercise” (London and Edinburgh 1879). William E. Pink and George E. Webster wrote “A course of analytical chemistry, qualitative and quantitative” (London 1874). The first American (very small) textbook is by Henry Trimble (1858–1898) “Practical and analytical chemistry: a complete course in chemical analysis” (Philadelphia 1885). 10 Jander, G. and E. Blasius (1949–1990) Einführung in das anorganisch-chemische Praktikum (Einschließlich der quantitativen Analyse) [Introduction into inorganic chemical practicum (including quantitative analysis)]. Hirzel, Leipzig, and Stuttgardt (1st–13th edns). Jander, G. and E. Blasius (1951–2006) Lehrbuch der analytischen und präparativen anorganischen Chemie (Mit Ausnahme der quantitativen Analyse) [Textbook of analytical and preparative inorganic chemistry (With the exception of quantitative analysis)]. Hirzel, Leipzig and Stuttgardt (1st–16th edns).

1.2 Chemistry: a historic view

9

The term “Die Chemie der Luft” [chemistry of air] appeared for the first time as heading in “Jahresberichte über die Fortschritte auf dem Gesammtgebiete der Agricultur-Chemie” [Annual Reviews on Progresses in the Whole Field of Agriculture Chemistry], Vol. 13–15 for the years 1870–1872 (Berlin 1874); in previous volumes, the first section was entitled “Die Chemie des Ackerbaus” [The chemistry of agriculture] with a subsection “Die Luft” [air]. These chapters presented abstracts of almost all investigations of the chemical composition of the air and rainwater (and meteorological observations). The term “Chemie der Atmosphäre” [chemistry of the atmosphere] was used first by Anton Baumann (1856–1912; chemist at Forstliche Versuchsanstalt, forest experimental station of the University Munich) in 1892 (and later) in the “Jahresberichte,” where the reports were subdivided into atmosphere, water, and soil; “atmosphere” further in “chemistry of the atmosphere” and “physics of the atmosphere.” In 1886, for the first time the heading of that report in “Jahresberichte” was termed “Chemie der Atmosphäre und der atmosphärischen Niederschläge” [chemistry of the atmosphere and atmospheric precipitation] by the rapporteur Richard Hornberger (1849–1918; chemist, professor of mineralogy and soil sciences at Forest Academy in Münden, Germany).11 Sir William Ramsay used in his book “The Gases of the Atmosphere” (Ramsay 1896, p. 18) this term in the following phrase: “Mayow´s contributions to the chemistry of the atmosphere . . . .” In 1897 Henriet´s book12 “Les gaz de l´atmosphére” was published in Paris in a style of a modern monograph on atmospheric chemistry. He also used the term “chimique de l´atmosphére.” In his introduction he started with emphasizing air chemistry monitoring: “ . . . nécessite des recherches qu´il est indispensable de poursuivre pendant un temps très long, afin de ne pas donner l´importance d´une loi à des phénoménes qui peuvent n´être qu´accidentels.” This was likely fully forgotten by “modern” atmospheric chemists and the term “atmospheric chemistry” was used 67 years later again (in German as “atmosphärische Chemie”) by Hans Cauer (1899–1962) in 1949 (Cauer 1949a, b). Similar to Hans Cauer in Germany, in the Soviet Union Evgenij Samojlovitsch Burkser [Евгений Самойлович Бурксер] (1887–1965), first Russian-Ukrainian radiochemist and geochemist in Vernadsky´s tradition,13 introduced the term аэрохимия

11 Hornberger was the director of the agricultural research station Kuschen (1875–1877), where Wollny 1864–1865 analyzed rainwater (see Table 2.21). 12 Henri Henriet (no life data known) published many papers on ozone and other air constituents. In Nature 55 (1897) 579, a fair review appeared: “Les gaz de l´atmosphére by H. Henriet, is an excellent little volume on the chemisty of our atmosphere. The author is chemist at the Montsouris Observatory, and the methods of analysis described by him, as well as the results of investigation into the composition of the air at different places and at different times, make this little book very valuable for meteorologists as well chemists.” 13 Vladimir Ivanovich Vernadsky [Вернадский, Владимир Иванович] (1863–1945): Russian/ Ukrainian geologist. His research ranged from meteorites and cosmic dust to microbiology and migration of microelements via living organisms in ecosystems.

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1 Introduction

[air chemistry]14 as a section of geochemistry of the atmosphere; Burkser studied since the 1920s the atmospheric chemical composition with respect to balneological aptitude (Burkser 1924, 1937, 1940, Burkser and Genet 1939, Burkser and Burkser 1951). It was soon used as the label for a new discipline. The first monograph in the field of this new discipline was written by the German air chemist Christian Junge (1912–1996),15 entitled Air Chemistry and Radioactivity (New York and London 1963), soon after he had published chapters entitled “Atmospheric Chemistry” (Junge 1957, 1958b). The first monograph (photochemistry of air pollution) in the field of this new discipline was written by Philipp Albert Leighton (1897–1983) in 1961, based on the results gained from the Los Angeles Smog studies. Atmospheric chemistry as a scientific discipline using laboratory, field, and (later) modeling studies was vigorously developed after identification of the Los Angeles smog end of the 1940s. The term “atmospheric chemistry” clearly identifies a subdiscipline of chemistry and not meteorology or physics. Atmospheric chemistry is now widely defined as the discipline dealing with the origin, distribution, transformation, and deposition of gaseous, dissolved, and solid substances in air (Möller 2011a). This chain of matter provides the atmospheric part of the biogeochemical cycles. In that sense, atmospheric chemistry (such as for geochemistry) is a part of biogeochemistry. Without any quantification, cycling already was recognized in the middle of the nineteenth century (see Section 2.3.2).

14 After 1960, in the USSR only the term атмохимический [atmochimitscheskij – air chemical] parallel to geochemical, hydrochemical, and so on have been used but never атмохимия [atmochimija – air chemistry], only the Russian equivalent to “atmospheric chemistry” or “chemistry of the atmosphere.” It is interesting that the German synonym Luftchemie was used first in the 1950s in the Meteorological Observatory Wahnsdorf (near Dresden) and later by Junge (1963b) and in 1968 with the establishment of the department Luftchemie at the Max-Planck-Institut in Mainz, headed by Christian Junge until 1979 (successors: Paul Crutzen 1980–2000 and since 2000 Jost Lelieveld). At the beginning of the 1920s, in Schichany (Шиханы), Saratov area (USSR), an air chemical station [аэрохимическая станция] has been established (called object “Tomka”) for investigation of chemical weapons (under participation of Germans), 1928 as part of the 33rd Central Research Institute of the Ministry of Defense (testing institute). The Central Air Chemical Museum was opened in Moscow in 1927 [Центральный аэрохимический музей], later (1941) renamed in museum of aviation. 15 German meteorologist and geophysicist. In 1953–1961 he worked at the Cambridge Air Force Research Center, Bedford, Mass. (USA); in 1962 he returned to Germany, first as Professor of Meteorology and Director of the Meteorological Institute at the University of Mainz (1962–1968), then as Director of the new founded Air Chemistry Department of the Max-Planck-Institut für Chemie (former Otto-Hahn-Institut) from which he retired in 1977; he is one of the founders of modern Atmospheric Chemistry. The Max-Planck-Institut für Chemie was refounded in 1949 in Mainz from the former Kaiser-Wilhelm-Institut für Chemie (founded in Berlin 1911) in line with the refounding of the Kaiser-Wilhelm-Gesellschaft (KWG) into the Max-Planck-Gesellschaft (MPG) with Otto Hahn (1879–1968) as the first president.

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A more general definition, but one that is appealing as a wonderful phrase, is given by Christian Junge: “Air chemistry is defined . . . as the branch of atmospheric science concerned with the constituents and chemical processes of the atmosphere . . . ” (Junge 1963a). In other words, air chemistry is the science concerned with the origin and fate of the components in air. The origin of air constituents concerns all source and formation processes, the chemicals of air itself, but also emissions by natural and man-made processes into the atmosphere. The fate of air constituents includes distribution (which is the main task of meteorology), chemical conversion, phase transfers, and partitioning (reservoir distribution) and deposition of species. Deposition is going on via different mechanisms from gas, particulate, and droplet phases to the earth’s ground surface, including uptake by plants, animals, and humans. Before the 1950s, this “discipline” was called “chemical meteorology.” However, chemical meteorology was mainly looking for the relationship between condensation nuclei, its chemical composition, and the formation of clouds and rain. That term is still in use as a subtitle of the journal Tellus (Series B: Chemical and Physical Meteorology, started in 1982 when Tellus, created in 1949, was split into Series A and B) and for a professorship at the University of Stockholm (Henning Rodhe held the chair from 1980 to 2008, continued by Caroline Leck since 2002), created in 1979 by Bert Bolin (1925–2007).16 Another term, “chemical climatology” came into use with the famous book Air and Rain – The Beginning of a Chemical Climatology (London 1872) by Robert Angus Smith (1817–1884).17 At that time, knowledge of chemical processes in air was still rather limited, hence the book’s focus on the description of concentrations of air constituents in time and space in analogy to physical parameters (“meteorological elements” such as temperature, pressure, and wind). Consequently, meteorology has often been defined as the physics and chemistry of the atmosphere. Hans Cauer must be seen as the German founder of a “chemical climatology” (Cauer 1934)18; he also used the terms chemical meteorology and air chemistry synonymously. In Sweden, Carl-Gustaf Arvid Rossby (1898–1957) and Hans Egnér (1896–1989) first used the term chemical climate for air masses having a characteristic chemical feature (Rossby and Egnér 1955).19

16 Carl-Gustaf Rossby (1898–1957) established the Department of Meteorology at Stockholm University (MISU) in 1947; Bert Rickard Johannes Bolin (1925–2007) took over the leadership in 1957 and hold it for almost 30 years. 17 Robert Angus Smith was a Scottish chemist, who investigated numerous environmental issues. He was a scholar of Liebig and studied the rain chemistry in 1848 in Manchester, at the first time from air pollution point of view. He was appointed Queen Victoria’s first inspector under the Alkali Acts Administration of 1863. For further reading on Smith, see Gibson and Farrar (1974). 18 In 1942, he became the head of the “Institute for Chemical Climatology” in Oberschreiberhau (now Szklarska Poreba Gorna in Poland). 19 Understanding of a chemical climate and hence a chemical climatology is thus in line with Robert Angus Smith (Smith 1872), Hans Cauer (Cauer 1934), Hans Egnér (Egnér 1955), and further developed by Möller (2006).

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1 Introduction

The typical dictionary definition of atmosphere is “the mixture of gases surrounding the Earth and other planets” or “the whole mass of an aeriform fluid surrounding the Earth.” This definition is very close to that given by Robert Boyle (1692, p. 1): BY the Air I commonly understand that thin, fluid, diaphanous, compressible and dilatable Body in which we breathe, and wherein we move, which envelops the Earth on all sides to a great height above the highest Mountains.

It makes even more sense to define the atmosphere being the reservoir (space) surrounding our (and any) planet, and air to be the mixture of substances filling the atmospheric space. With this in mind, the term air chemistry is more adequate than atmospheric chemistry. From a chemical point of view it is possible to say that air is the substrate with which the atmosphere is filled. This is in analogy to the hydrosphere where water is the substance. Furthermore, air is an atmospheric suspension containing different gaseous, liquid (water droplets), and solid (dust and icy particles) substances and therefore it provides a multiphase and multicomponent chemical system. It was air pollution, creating the discipline of atmospheric chemistry. With the discovery of the main chemical composition of air, different disciplines arose that deal with the minor chemical composition of air: – analytical chemistry, – agriculture chemistry, – sanitary chemistry, – pollution chemistry, – atmospheric chemistry. The discovery of main and trace substances in air can be called as the beginning (or fundamentals) of atmospheric chemistry. In the eighteenth century, the interest on natural processes generally expanded. A fundamental interest in biological processes, such as plant growth, nutriation, and respiration, stimulated the study of water cycle and gas exchange between plant and air. Concerns the discovery of CO2, the following scientists must be named: John Mayow (1643–1679) and Joseph Black (1728–1799) as well Stephen Hales (1677–1761), who early in the eighteenth century began his important study on air, absorption of water by plants, and its transpiration to the atmosphere. The discovery of nitrogen is generally attributed to Daniel Rutherford (1749–1819) and that of oxygen to Carl Wilhelm Scheele (1742–1786)20 and Joseph Priestley (1733–1804).21 Based on these findings, Antoine-Laurent de Lavoisier 20 German chemist, born in Stralsund/Pomerania (Sweden at that time), druggist in Gothenburg, Malmö, and Stockholm, member of the Royal Academy of Sweden (1775). 21 English scientist; due to his sympathy with the French revolution he moved to Philadelphia/ USA in 1794; discovered oxygen and many gases in air (parallel to Scheele).

1.2 Chemistry: a historic view

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(1743–1794) recognized the role of oxygen in combustion and established the modern chemistry; he also gave the names of the main air constituents, oxygéne and azote. Henry Cavendish (1731–1810), who never rejected the phlogiston theory and who did not publish his results on air studies until 1783, likely did know nitrogen before Rutherford. Cavendish was the first to study flammable air (H2) in different mixtures with common air to investigate its explosion (1766). In 1781 he sampled atmospheric air at different sites and analyzed it gravimetrically after sorption of water-soluble gases (CO2, NH3, and water vapor). In explosions, in which Cavendish used electric sparks, he found “ . . . liquor in the globe . . . ; it consisted of water united to a small quantity of nitrous acid” (Cavendish 1784). This statement is most remarkable to me; it forms the first evidence of HNOx formation under atmospheric conditions by lightning (note that separation between nitric and nitrous acid was not yet known; “nitrous” was a term for NOx). Finally, Lord Rayleigh (1842–1919) and Sir William Ramsay (1852–1916) identified the novel gases in air between 1882 and 1898. At the end of the nineteenth century, many trace species were known in air (NH3, HCl, NOx, HNOx, SO2, H2S, O3, H2O2, CH4, H2), with a few determinations in gaseous air and more systematically in rain water (namely ammonium, nitrate, chloride, and sulfate). It is important to note that all the trace species mentioned and discovered or assumed to be in air were believed to be natural or, in other words, substances with a (at that time still unknown) special function in nature. Robert Angus Smith was the first who considered sulfur and chlorine also to be of man-made origin from coal combustion and chemical processing (Smith 1872). The assimilation of gases and the uptake of nitrogen dissolved in water by plants and the decomposition of dead biomass as source of gases led to a first understanding of matter cycles by early agricultural chemists (Knop 1868). The 150-years period, 1749–1898, can now be termed as the era of the discovery of main and trace substances in air and hydrometeors; beginning in 1749 with Marggraf´s rainwater study, in 1752 with Black who was the first to detect CO2 in the air of Edinburgh and ending in 1898 with Ramsay’s discovery of He, Ne, and Xe in air. The next 50 years – with the exception of stratospheric O3 studies and beginning accurate tropospheric O3 measurements – were stagnant in further air chemical studies. Air pollution remained a local problem until the 1960s. It was not before the end of the 1970s that scientists recognized the occurrence of global changes. The techniques available to measure trace species, however, were still rather limited. In 1944, plant injuries had been observed in the Los Angeles area, which for the first time were not related to “classical” pollutants (such as SO2 or fluorine compounds). Only a few years later, Arie Jan Haagen-Smit (1900–1977) and coworkers made automobile exhaust gases responsible for surface-near formation of ozone, which then was considered as the impact species. The stimulus of radical reactions was the recognizing of photochemical air pollution in Los Angeles toward the end

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1 Introduction

of the 1940s. Many radicals were proposed during studying atomic reactions in combustion and explosive processes since about 1925 but fast kinetic observations and intermediate detection became possible only in the 1940s with spectroscopic techniques. Scientific literature in the 1950s is full of studies on this topic. A complete description of radical reactions with the citation of original sources can be found in Leighton (1961). Despite some ideas on chemical processes (almost by electrical discharges) in air at the beginning of the nineteenth century, only the formation of ozone under strong UV light had been roughly understood by the 1930s. Before World War II, ozone was believed to be produced only naturally in the stratosphere. In 1924, Gordon Dobson (1889–1975) designed a spectrometer, which became the standard instrument for measuring both total column ozone and the profiles of ozone. With Dobson spectrophotometers Joe Farman and his team on the British Antarctic survey discovered the ozone hole in 1984 (Farman et al. 1985). Summer and winter smog stimulated much of ozone and sulfur chemistry. Junge and Ryan (1958) first pointed out the importance of the atmospheric aqueous phase for SO2 oxidation. Although acidic rain (Smith 1872),22 the bleaching properties of dew (Prout 1834, 1836), and hydrogen peroxide in rain (Meissner 1863, Schöne 1874) were known as phenomena many years ago, atmospheric aqueous phase chemistry has long been ignored compared with gas phase chemistry. Between 1950 and 2000, we can subdivide the atmospheric chemistry research into the following issues (some of them are overlapping): – fundamental research (chemical kinetics and mechanisms; laboratory studies), – research on global cycling (sulfur, chlorine, nitrogen, carbon), – precipitation chemistry (“acid rain”), – plume chemistry (pollutant dispersion and conversion), – cloud and fog chemistry (aqueous-phase and interfacial chemistry), – tropospheric ozone and reactive oxygen species research (photochemistry, “summer smog”), – stratospheric ozone research (ozone depletion, “ozone whole”), – atmospheric aerosol research (heterogeneous chemistry, secondary organic aerosol, and cloud condensation nuclei formation). Beside laboratory reactor studies under defined conditions, monitoring and field experiments were the essential tools. Unfortunately, long-term environmental measurements were underappreciated and underfunded because they are seen neither as basic measurements to test scientific hypothesis nor as challenging high-tech 22 Smith (1872) used the term “acid rain” only twice in his book (on page 444) in connection with effects of the atmosphere on stones and iron: “I was led to attribute this effect to the slow, but constant, action of the acid rain” and “ . . . iron oxidises readily, . . . where the acid rain . . . .” However, the term acid rain was first used in French pluie acide by Ducros (1842), see Section 2.4.5.

1.2 Chemistry: a historic view

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opportunities for profit by commercial interests. Other air pollution studies (such as heavy metals, POPs, and GHGs) included less chemistry but almost physics and toxicology. It is self-evident that with the exception of laboratory fundamental research, physical especially meteorological research is linked with atmospheric chemistry: transport, mixing, and conversion occur simultaneously. Aim of atmospheric chemistry was an understanding of time-spatial dependent and changing toxicity, acidity, oxidation/reduction capacity, composition, and size distribution of particles to explain impacts such as acidification of soils and lakes, plant injures, forest decline, human diseases, climate forcing, and change.

1.2.3 A brief history of chemistry Chemistry, first established as a scientific discipline around 1650 by Robert Boyle (1627–1691), had been a nonscientific discipline (alchemy) until then (Boyle 1680); however, Boyle remained believing on alchemistic transmutation (More 1941). Even until the end of the eighteenth century, some researchers remained in its believing of transmutation, for example, water into salt. Alchemy never employed a systematic approach and because of its “secrets” no public communication existed, which would be essential for scientific progress. In contrast, physics, established as a scientific discipline even earlier, made progress, especially with regard to mechanics, thanks to the improved manufacturing of instruments in the sixteenth century. Boyle first combined in his studies on gases (relation between amount, pressure, and temperature) alchemy with the exact discipline physics. He introduced the scientific terms element, chemical compound, and chemical reaction. The beginning of a modern chemistry as a scientific discipline can be attributed to Antoine-Laurent Lavoisier, also called the founder of modern chemistry who presented his Traité élémentaire de Chimie, présenté dans un ordré nouveau et d´après les découvertes modernes (Paris 1789), soon later translated by Robert Kerr into the “Elements of Chemistry in a new systematic order, containing all the modern discoveries” (Edinburgh 1790).23 The history of chemistry may be divided into periods, as follows (Bauer 1914, 1921); the era since Lavoisier is also named “era of quantitative research” (Kopp 1931): – chemistry of the ancients (until fourth century AD), – era of alchemy (from fourth to sixteenth century), – era of iatrochemistry (sixteenth and seventeenth centuries), – era of phlogiston theory (1700–1774), – era of Lavoisier (1774–1828), and – modern era of chemistry (from 1828 until present).

23 Reprint by Dover Publ. New York, 1965.

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1 Introduction

There are several ideas published on the origin of the term “chemistry” since Hermann Kopp (1817–1892) wrote his “history of chemistry” between 1842 and 1847. Until now, the etymology of the word “chemistry” is still unsolved (Pommerening 2018), but an etymological origin from Egypt is likely. The word “Chemia” is first used by Plutarch (45–127) in his Isis et Osisis (p. 364) in connection with Egypt: Præterea Ægyptum,quæ vel maxime nigram habet terram, tanquamnigram oculi partem, Chemia vocant [Furthermore Egypt, where even the earth is so dark like black olives, is calleed Chemia], cited from Gren (1800, p. 4).

The term (Khem) appears in different relations with ancient Egypt. Letopolis (Greek: Λητοῦς Πόλις) was an ancient Egyptian city, the capital of the second Nome of Lower Egypt; its Egyptian name was Khem (Ḫm), Lichtheim (1980, p. 84). Akhmim (or Achmim) is a city in Upper Egypt located on the east bank of the Nile, referred to by the ancient Greeks as Khemmis, Chemmis, and by the Coptics Chemin. In ancient Egypt, this city was the capital of the province Chemmite. The name of this city is derived from Egypt ḫnt-mnw (Chenet-Min); the Egyptian god Min, however, according to newer interpretations (Pommerening 2018), is not pronounced as “Chem” as proposed by Egyptologist such as Francis Llewellyn Griffith (1862–1934) in the nineteenth century. In the Psalms, Egypt is called Terra Chami (the land of Ham); Ham (Greek Kham) is the youngest son of Noah. Ham was a sun god; Egypt ḫm means “to be hot” (Pommerening 2018). It is without any doubt that the Sun was associated with light and heat (see also Tab. 2.1). Since the seventeenth century, a number of suggestions have been made that relate the word Ham is believed to come from the word Khawm (and chamam), which means “black, hot, and burnt” in Hebrew. Smith (1882) means that the Hebrew word ‫( חמם‬pronunciation khema, or chom according to Modern Hebrew) means “heat” (in modern dictionaries it also means “brown,” pronounced chum). In all probability, the first use of chemistry was for obtaining metals from their ores. Hence, it is likely that the Egyptians used one word to designate the strange phenomena produced in substances by means of heat (e.g., burning, extraction, and distillation). From that it can be derived that χημία was the “Egyptian art,” for more than 2000 years celebrated by temple priest. Another explanation given by Lockemann (1950) that the root of word “black” led to a “black art” (alchemy) is not likely because behind “black art” always religious ceremonies were understood and chemical operations. Nevertheless, there is consensus that χημία was the ancient name for Egypt, meaning “black earth.” Before the New-Platonic, the word Chemia is never mentioned in connection with chemical operations, neither by the Greek nor by the Romans. The word “chemistry” is only known since the fourth century in sense of a “discipline” dealing with substances and its transmutation namely formation of gold and silver from ignoble metals. Julius Maternicus Firmicus (lived under Constantine the

1.2 Chemistry: a historic view

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Great about AD 340) for the first time used the word “Alchemiæ” (cited from Gren 1800, p. 4)24: Si fuerit hæc domus Mercurii, dabit Astronomiam; si Veneris, cantilenas et lætitiam; si Martis, opus armorum et instrumentorum ; si Jovis, divinum cultum, scientiamque in lege; si Saturni, Scientam Alchemiæ.

In fragments of the alchemist and Hermetic philosopher, Zosimos of Panopolis (about 350–420), referring back to the Book of Enoch the word χημεõ “chemeu” (Zosimus Book of Chemeu) is frequently used for the work of metalworker χυμδύτης (metal casters) (Hermann 1954, Fraser 2004). For a long time, for alchemy the meaning χρυσοποϊα (the art of making gold) was used (Thomson 1830, Meyer 1914). Without doubt, the Arabians prefixed their article to the Greek χημία into the Arabic al-kīmīā. Thus, the terms Alchemy, Alchimy, or Alchymy were introduced.25 Olaus Borrichius (Latin) or Ole Borch (1626–1690), a Danish naturalist, likely was the first who used the term Chemiæ in a modern sense in his dissertation (Figure 1.1) because he quoted Zosimus, who said that the term Chemia was never used before of to signify the science of nature. The earliest applications of chemical processes were concerned with the extraction and working of metals and the manufacture of pottery, which were forms of crafts practiced many centuries before the Bronze Age cultures of Egypt and Mesopotamia. It was the practical working life of ancient humans who accumulated knowledge not systematically but by accident. In ancient Egypt, apart from metalworking and pottery, dye works, glassmaking, beer brewing, and preparation of drugs were cultivated on high levels where the knowledge was put into hands of temple priest. Seven metals were known: gold, silver, copper, tin, lead, mercury, and iron in the antiquity and the whole Middle age. Sulfur and carbon were known among the seven metals as the only other elements. Salts were known since ancient time, such as salmiac (Sutton et al. 2008) and saltpeter. The early Greek philosophers (about 600 BC)26 adopted the knowledge from their ancestors but not contributed newer facts because of their rejection of experiments and their mind-set that dirty work is carried out only by lower classes. They 24 Friedrich Albrecht Carl Gren (1760–1798), German chemist, author of Systematische Handbuch der Gesammten Chemie (1787–1790) in three volumes. After Schorlemmer (1882) who stated that other editions of this work have also ”scientia alchimiae.” The manuscript in the library of the Vatican has “chymiæ” and not “alchymiæ” (Schorlemmer 1882). 25 There is no consensus in the literature whether different spelling is due to various translators (among Greek, Arabian, and Latin) or through different original Greek root term such as χημία, χημεία, or χυμία (Kopp 1931, 1869, Schorlemmer 1882); in Latin: Chimia, Chymia. 26 The earliest Greek philosophers all came from one small area on the Ionic coast of Asia Minor (now Turkey). Thales, Anaximander, and Anaximenes lived in the prosperous trading port of Miletus, less than 50 km from Heraclitus’ city, Ephesus. These philosophers all tried to answer the central question: what was the underlying “stuff” of the universe.

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1 Introduction

Fig. 1.1: Cover page of the dissertation of Borrichius or Ole Borch (1668): De Ortu, Et Progressu Chemiæ (on the rise and progress of chemistry). Source: Bayerische Staatsbibliothek.

established theories by a few observations and many speculations only through thinking. The four elements AIR-FIRE-EARTH-WATER were introduced by Anaximander of Milet (611–546 BC) (Figure 1.2). As a consequence of this belief, all substances were transmutable into all others and were contained in each of them. In his book μετεωρολογιχά, Aristotle placed the transformation of four elements (soil, water, air, and fire) in focus. Each of these elements occupies its own region but with the understanding that the matter of άήρ (aër – air) and ϋδωρ (idor – water) cannot be treated separately. The changing states of elements are produced, according to the ancient philosophy, by two forces: heat and cold. Whereas older Greek philosophers treated water (Thales) or air (Anaximenes, Heraclitus) as elementary bodies, Aristotle (and his

1.2 Chemistry: a historic view

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FIRE

hot

dry

EARTH

AIR wet

cold

WATER

Fig. 1.2: The relationships between the four antique elements air, fire, water, and earth.

scholar Platon) did not consider the four elements as different basic materials but as carriers of different properties, belonging to a single primary matter (Meyer 1914). Aristotle attributed to each element paired properties (warm, cold, dry, and wet): water is wet and cold and air wet and warm. However, he deemed the four elements insufficient to explain nature, and therefore, introduced ούδία or αίϑήρ (Aether) as a fifth element, having an ethereal and more spiritual (the quinta essentia in the Middle Ages) property. The doctrine of Aristotle appeared for the next 1,500 years. The idea of a materia prima led later to the assumption of the existence of philosopher’s stone, a tinctura universalis or magno sudarunt elixyre, which would make transmutation processes possible, for example, formation of gold from ignoble metals, and create a drug for live extension and all diseases. In Middle Age, however, only three “elements” (base material) were regarded, namely Sulfur (characterizing the principle of combustibility: flammability), Mercurius (characterizing the principle of metallic properties: volatility and stability), and Sal (salty properties: solidity). Different mixtures of these elements would form the various substances found in nature. The only task of alchemy was the search for philosopher’s stone. It is agreed that “chemical knowledge” was focused in Alexandria until third century. In Baghdad under the caliphate from the eighth century, there is enthusiastic translation and study of Greek scientific texts. Arab alchemists,27 in their pursuit of synthesized gold, make practical advances in techniques of distillation. And they identify several chemical substances. The experimental framework established by the polymath Jābir (Dschabir) ibn Hayyān [ ‫( ]ﺟﺎﺑﺮ ﺑﻦ ﺣﻴﺎﻥ‬about 721–815, born in Persia), also known as Geber,28 influenced alchemists as the discipline migrated through the Islamic world, and then to Europe in the twelfth century.

27 Another great center of alchemical experiments in medieval Asia is China, where alchemical experiments have a slightly different purpose. The quarry is still gold, but as an elixir of eternal life. Daoists make the most startling chemical discovery of the period, gunpowder. 28 Jābir ibn Hayyān is the supposed author of an enormous number and variety of works in Arabic often called the Jabirian corpus. As early as the tenth century, the identity and exact corpus of

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1 Introduction

In the first half of the sixteenth century, at the same time of Reformation, the chemistry (or alchemy) was now used as the exclusive basis for medicine and explanation of processes leading to health and diseases; now called the iatrochemical era. Philippus Aureolus Theophrastus Bombastus von Hohenheim, called Paracelsus (1493–1541) was the main representative of this new direction (Figure 1.3).29 The chemical knowledge, originating from the Arabic world, now together with European findings, was summarized by the German polymath Andreas Libavius (1555–1615) in his work Alchemia (Frankfurt 1597).

Fig. 1.3: Philippus Aureolus Theophrastus Bombastus von Hohenheim, called Paracelsus. After his thesis there were no substances at first in the world; only by god’s world through “fiat” have been created “das corpus und sein geist gemacht worden” (the body and his spirit have been made).

works of Jābir was in dispute in Islamic circles. The authorship of all these works by a single figure, and even the existence of a historical Jabir, is also doubted by modern scholars. Instead, Jābir ibn Hayyan is seen more like a pseudonym to whom “underground writings” by various authors became ascribed. His name was Latinized as “Geber” in the Christian West and in thirteenth-century Europe an anonymous writer, usually referred to as Pseudo-Geber, produced alchemical and metallurgical writings under the pen-name Geber. 29 He is well known due to his phrase “Alle Ding’ sind Gift und nichts ohn’ Gift; allein die Dosis macht, das ein Ding’ kein Gift ist” [All things are poison and nothing without poison; only the dose makes that a thing is no poison], mostly shortened as sola dosis facit venenum. He is also called “father of toxicology.”

1.2 Chemistry: a historic view

21

Although the iatrochemistry is the parent of pharmaceutical chemistry, the close relation between medicine and chemistry, namely the search for the universal drug, inhibited any systematic research in chemistry as a natural science. “All these authors have written on chemistry in a very obscure, confused manner. Though acquainted with some processes of solution, extraction, and purification, their pretensions rose much higher than their knowledge; and scarce any advantages can be derived from a perusal of their work” (Fourcroy 1790, p. 26). The medical chemistry remains dominant until middle of the seventeenth century with the beginning of Boyle’s new understanding of chemistry as a science. However, individual chemists developed important subdisciplines of chemistry such as Georg Agricola30 (1494–1555) the technical chemistry. Apart from Agricola, who contributed pioneering to metallurgy, Bernard Palissy (c. 1510–1590) contributed to advances in ceramic and pottery. Furthermore, major progress in dye works, glassmaking, brandy distillery, and beginning of agriculture chemistry were other characteristics of applied chemistry in the sixteenth century. One of the most important chemists of that time was Johann Baptist (Jan) van Helmont (1577–1644). He rejected Paracelsus idea of the three “elements” (sulfur, mercurius, and sal) and believed that all substances could be reduced to air and water. He was known for many careful observations and experiments and expressed for the first time the ideas of the preservation of substance. Apart from the iatrochemical research, Johann Rudolf Glauber (1604–1668) was the grand technical (or applied) chemist in that period. Whereas many salts, acids, and metals were produced and used in the sixteenth and seventeenth centuries, nothing was known on its chemical composition and systematic relations. The last important exponent of medical chemistry was Herman Boerhaave (1668–1738)31 who summarized the knowledge in his book Elementa Chemiae which is recognized as the first text on chemistry.32 This work is organized into two

30 His German name was Bauer; he wrote the manual De re metallica libri. 31 Boerhaave was variously professor of medicine, botany, and chemistry at the University of Leiden from 1701 until his death in 1738. Prior to the invention of printed textbooks, the professor in a typical medieval university would read his lectures out loud to the students, who would, in turn, carefully transcribe them for their own personal use, a practice reflected in the modern German word for a lecture – Vorlesung – which literally means “to read in front of.” In 1724 an unauthorized edition of Boerhaave’s popular chemical lectures, based on student lecture notes, was published anonymously in Paris under the title of Institutiones et experimenta chemiae. The only way for him to preserve his reputation and prevent further sales of the spurious textbook was for him to publish an official version of his chemical lectures, which he finally did in 1732 under the title of Elementa chemiae (Jensen 2011). As it is known, many works attributed to Boerhaave were actually lecture notes published by former students. 32 Elementa chemiae, que anniversario labore docuit, in publicis, privatisque, scholius, Hermannus Boerhaave, qui continuet operationes chemiacae. In two volumes (896+60 and 538+90 pp.) Leiden 1732; Bâle 1732, 1745, 1747; Tübingen 1732; Venice 1732, 1745, 1749, 1752, 1759, 1777 (J. R. Imhoff);

22

1 Introduction

volumes: Vol. 1 contains Part I (containing the history of chemistry) and Part II (containing the theory of chemistry), and Vol. 2 with Part III (containing the processes or operations of the art, including chemical operation upon vegetables, animals, and minerals). Part II contains a large section “Of Air,” containing subsections of the contents of air, dew in air and clouds whence in air, and a section “Of Water,” containing a subsection “of rainwater.” The time between Boyle and Lavoisier is often named the era of phlogiston theory. However, one man, the first chemist in Russia, who several times criticized wrong ideas of Boyle, must be noted here: Michail Wassiljewitsch Lomonossov [Михаил Васильевич Ломоносов] (1711–1765), a genius, who had many good ideas, and if he had worked them out in detail, might have notably advanced science, but his duties as an academician, his variety of interests, and his irregular mode of life hindered his progress in scientific work (Partington 1961, p. 204). Lomonossov can be regarded as the founder of the science of physical chemistry (Lomonossov 1752).

Londini 1732 (Sumptubus S. K. and J. K.); Lipsiae 1732 (C. Fritsch, 744 + 470 pp.; containing only the theory of chemistry); Paris 1733, 1753 (G. Cavetier, 476+61 and 340+48 pp.). The Latin edition consists of three parts (In Vegetantia, In Animalia, In Fossilia). Other Latin editions: Basileæ 1745, Venitiis 1749, Parisiis 1753. Translated into German (Anfangsgründe der Chemie 1732–1734, 1738, 1762, 1782, 1791), French (Eléments de Chymie, 1748, 1752, 1754, 1755), and English (Elements of Chemistry 1727, 1735, 1741, 1753). In addition there were abridgements in English and German. The first English edition 1727, translated by P. Shaw and E. Chambers, based on the unauthorized edition 1724 from Paris, is entitled “A New Method of Chemistry including the Theory and Practices of that Art: Laid down on Mechanistic Principles and acommodated to the Uses and Life. The whole making a clear and rational System of Chemical Philosophy. A Criticial History of Chemistry and Chemists; from the Origin of the Art to the present Time. Written by the Learned H. Boerhaave, Translated from the Printed Edition by P. Shaw and E. Chamgres, London, Printed for J. Osborn and T. Longman.” A second edition (more careful and quite close to the Latin origin from 1732) in 1741 by Peter Shaw (1694–1736) was entitled “A new Method of Chemistry; including the History, Theory, and Practice of the Art. Translated from the Original Latin of Dr. Boerhaave´s Elementa Chemiæ as published by himself. To which are added, Notes, and an Appendix, showing The Necessary and Utility of Enlarging three Bounds of Chemistry” (Longman, London). With the same title appeared the third corrected edition in 1753. The official translation of Boerhaave’s textbook from 1732 is by Timothy Dallowe (Elements of Chemistry: being the Annual Lectures of Herman Boerhaave, Leiden 1735. Both can be claimed equally to reflect whatever it was Boerhaave’s Latin express (Christie 1994, Knoeff 2002). Volume I (528 pp.) is divided into two parts: Part I comprises a historical survey of chemistry; Part II, description of chemical notions and instruments, including 17 plates with illustrations of the latter. Volume II (376 pp.) is devoted to the description and explanation of 227 experiments (called operations), from which plants are the substrate of 88. In the following I’m citing only from the 1735 edition, Vol. 1. The German edition 1753: Elementa Chemiae, Oder: Anfangs-Gründe der Chymie, Worinnen der Herr Auctor durch 227 Processe gründliche Anweisung gegeben, Auf was Art die natürlichen Cörper können Kunstmäßig analysirt, oder Chymisch aufgeschlossen und daraus heilsame Artzeneyen bereitet werden. Leipzig, M. Blochberger, 1753 in 2 Vol., 1032 pp.

1.2 Chemistry: a historic view

23

The significant development of physics, the growing influence of the inductive method in science, the foundation of academic societies33 in the second half of the seventeenth century with its publications contributed to a propagation of scientific results, benefit chemistry as science. However, still in this era the main focus remains on qualitative description of phenomena. Neglecting the weight ratios in chemical reactions (quantitative description) was the main cause for wide acceptance of the wrong phlogiston doctrine. Nevertheless, this period finally contributed to the elimination of the delusional idea of alchemy. Although physician, John Mayow (1645–1679) is another British genius apart from Boyle, whose earlier death delayed the understanding of combustion processes; doubtless he is called the predecessor of Lavoisier. Mayow assumed that atmospheric air contains a substance (which he called spiritus igno-aereus or nitro-aereus), which combines with metals during calcinations,34 is also present in saltpeter,35 supports breezing, and transforms venous into arterial blood.36 In France, two scholars, but much less important in its scientific contribution, Wilhelm Homberg (1652–1715) and Nicolas Lemery (1645–1715) must be named. Lemery regarded chemistry as a demonstrative science and is one of the fathers of acid–base theory. In Germany, Johann Kunckel (1630–1703) and Johann Joachim Becher (1635–1685) were protagonists between alchemy and modern chemistry. Becher “developed” the idea of Paracelsus further that instead of Mercury, Sal, and Sulfur now all inorganic materials consist of three “elements”: mercurial, glassmaking, and combustible (terra pinguis). When burning substances or calcination37 of metals, terra pinguis escapes. This idea was accepted by Georg Ernst Stahl (1660–1734)38 who explained combustion of material by release of a hypothetical fierily substance, which he named phlogiston, from the Greek word for inflammable.39

33 Academia naturae curiosum in Wien (1652), Accademia del cimento in Florence (1657), Royal Society in London (1660), Académie royale de sciences in Paris (1666), Berliner Akademie (1700); later academic societies where founded in Petersburg (1725), Stockholm (1739), and Copenhagen (1743) . 34 It is CO2. 35 It is NO and/or NO2. 36 It is oxygen. 37 The IUPAC defines calcination as heating to high temperatures in air or oxygen. The process of calcination derives its name from the Latin calcinare (to burn lime) due to its most common application, the decomposition of calcium carbonate (limestone) to calcium oxide (lime) and carbon dioxide. In alchemy, calcination was believed to be one of the 12 vital processes required for the transformation of a substance. 38 German chemist and physician in Weimar, Halle, and Berlin; known for his obsolete phlogiston theory. 39 The word Phlogiston is not by Stahl introduced in the chemical literature (as stated, e.g., in Wikipedia and other sources). Kopp (1869, part III, p. 217, Footnote 462) cites various sources where Phlogiston was used before by van Helmont, Becher, and Sennert. Derived from Greek φλογιστός = burnt. Phlogiston was equalized with caloricum, the matter of caloric or Wärmestoff in German (fire in old terms).

24

1 Introduction

In other words, he stated that every combustible substance contained a universal component of fire (it is still the old element idea of Aristotle). This doctrine was accepted by almost all scientists for the next 120 years until Lavoisier finally rejected this idea. In Stahl´s publications, phlogiston is never identified as a substance that can be prepared; it was a substantial support of a property, the capacity to combust. Conflicts arose from later ideas to regard phlogiston as a preparation such as carbon or hydrogen. Kopp (1869, part III, pp. 222ff.) summarizes Stahl’s ideas on phlogiston that combustion requires the presence of air or something similar, in which phlogiston dispenses (which also comes from rotting) and reached again into plants and from them into animals. Common metals contain phlogiston apart from an earthy component, which can be represented as metallic calces40 or metallic ash. When heating with coal, the phlogiston therein combines with them (carbon) and the metal appears again; hence, the calx is a component of the metal. Another wrong conclusion by Stahl was the idea that sulfur is composed from sulfurous acid and phlogiston. The conclusion that the combustion products must be weightless than the burned body as a composite was neglected. Even the (well-observed) fact that some products are heavier such as metal calces were also neglected. Finally, these observations were the reason for the fall of the phlogiston theory. Stahl’s merit, however, was the creation of a theory what we at present call oxidation–reduction; uptake of phlogiston means reduction, and release of phlogiston is identical with the term oxidation.41 Nonetheless, this wrong theory did not hindered important progress by other chemists such as Joseph Black, Henry Cavendish, Andreas Sigismund Marggraf, Carl Wilhelm Scheele, Torbern Olof Bergman, and Joseph Priestley which all were phlogistians but contributed pioneering to our understanding of air chemical composition or the chemistry of gases. These chemists and their contributions will appear in later chapters. The late era of phlogiston (1770–1790) shows significant progress in (qualitative) analytical chemistry and development of apparatus for gas separations and volume measurements (pneumatic chemistry). With Lavoisier’s work (about 1775) the antiphlogistic system in chemistry developed, the modern understanding of combustion processes arose, namely uptake of oxygen (former escape of phlogiston) characterizes combustion (oxidation) and release of oxygen (former uptake of phlogiston) the inverse process (reduction). The contributions of Lavoisier to the development of a modern chemistry are immense; the interested reader should read special books. Understanding the role of oxygen can be seen to be the imprint benefit of Lavoisier. With the ending of eighteenth century, so many important chemists worked and their number increased continually (to name here the most important: Martin

40 Metallic calces (in German Metallkalk) are oxides, but at that time not separated from its carbonates or mixtures. 41 In Section 2.2.4 on the discovery of oxygen, we go into more details of phlogiston.

1.2 Chemistry: a historic view

25

Heinrich Klaproth, John Dalton, Claude Louis Berthollet, Antoine François Comte de Fourcroy, and Joseph Louis Proust). This time is characterized by the creation of the atomic, equivalent, and radical theory, the base for systematic formulas of chemical compounds, further developed by Sir Humphry Davy, Joseph Louis Gay-Lussac, William Prout, Jöns Jakob Berzelius, Eilhard Mitscherlich, Jean-Baptiste André Dumas, Michael Faraday, Justus von Liebig, Friedrich Wöhler, and others in the early nineteenth century. The acid–base theory and electrochemical theory were developed in early stages. The organic chemistry became an own field. “Organic” compounds were known for centuries but were not distinguished from “inorganic” matter. A systematic classification of chemistry was first done into mineral, vegetable, and animal according to its origin by the French chemist Nicolas Lémery who wrote Cours de chymie (1675, cited after Kopp 1931). According to Walden (1941), the first use of the term “organic chemistry” is now attributed to the Swedish chemist Jöns Jacob Berzelius, who termed it “organisk kemie” in a book published in 1806. It was believed since that time that organic matter (also termed “organized”) could not be synthesized from its elements and that a special force, the vital force, is needed for its production. First, Lavoisier found systematically that vegetable matter is composed from C, H, and O and that in animal matter additionally N and P are present. However, organic molecules can be produced by processes not involving life. Friedrich Wöhler destroyed the theory of vital force by the synthesis of urea in 1828; an event generally seen as the turning point. At that time, the isomerism, that is, substances having the same chemical composition but different properties (because of different chemical structure, what was found much later), was widely proved and accepted. In the middle of the nineteenth century, the theory of types was introduced for classification of organic compounds (by Charles Frédéric Gerhardt, Charles Adolphe Wurtz, August Wilhelm von Hofmann, and Alexander William Williamson) and further developed by August Kekulé. Hermann Kolbe renewed the radical theory in the 1860s. At about the same time, the beginnings of the structural theory proceeded (August Kekulé, Sir Edward Frankland, Arthur Rudolf Hantzsch, Wilhelm Traube, and Johannes Adolf Wislicenus). In the second half of the nineteenth century, many new elements were discovered and finally the periodic system of element created (Lothar Meyer42 and Dmitri Mendelejev). One of the most important developments of modern chemistry was the progress in physical chemistry (François Marie Raoult, Josiah Willard Gibbs, Jacobus Henricus van´t Hoff, Svante August Arrhenius, Friedrich Wilhelm Ostwald, and Walther Nernst) and in the spectral analysis (Robert Wilhelm Bunsen and Gustav Robert Kirchhoff).

42 Julius Lothar Meyer (1830–1895), German chemist.

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1 Introduction

At the turn of the twentieth century, radiochemistry was discovered (Marie Skłodowska Curie, Antoine Henri Becquerel, and Ernest Rutherford). Niels Bohr introduced the concepts of quantum mechanics in 1913, later in the 1920s developed into the quantum chemistry by Louis-Victor Pierre Raymond de Broglie, Wolfgang Ernst Pauli, Erwin Schrödinger, and Werner Karl Heisenberg. With the book Nature of the Chemical Bond (1939) by Linus Pauling, one of the key concepts in classical chemistry was founded that all chemical compounds can be described as groups of atoms bonded together and chemical reactions can be described as the making and breaking of those bonds. The first book on history of chemistry was written by Johann Christian Wiegleb in 1790, soon after Antoine Lavoisier’s revolutionary treatment of chemistry (Lavoisier 1789); books on history of chemistry are listed in Table 1.1. There are many books on chemists on the market but only very few on the history of disciplines of chemistry (e.g., analytical, clinical, and peptide chemistry). The present volume contains to my knowledge for the first time an extended section on the history of atmospheric chemistry.

Tab. 1.1: Books on history of chemistry. yeara

author

title

publisher

/ Johann Christian Wiegleb – Johann F. Gmelin  Johann Bartholomäus Trommsdorff / Thomas Thomson  Jean-Baptiste Dumas – Hermann Kopp

Geschichte des Wachsthums und der Erfindungen in der Chemie in der neueren Zeit ( Vol.)b Geschichte der Chemie ( Vol.)

Fr. Nicolai, Berlin und Stettin

/ Ferdinand Hoefer  Charles Adolphe Wurtz / Hermann Kopp

Historie de la chimie ( Vol.)

Vieweg, Braunschweig Firmin Didot, Paris

A History of Chemical Theory: From the Age of Lavoisier to the Present Time

Macmillan and Co, London

Beiträge zur Geschichte der Chemie ( Vol.)



Les origines de l’alchimie

Vieweg, Braunschweig G. Steinheil, Paris

Marcellin Berthelot

Versuch einer allgemeinen Geschichte der Chemie History of Chemistry ( Vol.) Leçons sur la philosophic chimique Geschichte der Chemie ( Vol.)

Rosenbusch, Göttingen Henning’sche Buchhandlung, Erfurt Colburn and Bentley, London Ebrard, Paris

1.2 Chemistry: a historic view

27

Tab. 1.1 (continued ) yeara

author

title

publisher



Hermann Kopp

Die Alchemie in Älterer und Neuerer Zeit



Introduction à l’étude de la chimie des anciens et du moyen âge Elektrochemie. Ihre Geschichte und Lehre



Marcellin Berthelot Wilhelm Ostwald Ernst v. Meyer

C. Winter, Heidelberg G. Steinheil, Paris



Ernst v. Meyer



Adelbert Rössing Albert Ladenburg Franz Strunz



 



Wilhelm Ostwald

/ Edward Thorpe / Karl Hugo Bauer  Edmund Oskar v. Lippmann  Carl Graebe  Paul Walden / Georg Lockemann – James Riddick Partington  Crosland, Maurice P.  Charles-Albert Reichen  Ferenc Szabadváry  Roman Mierzecki

Geschichte der Chemie von den ältesten Zeiten bis zur Gegenwart A History of Chemistry: From the Earliest Times to the Present Day, Being also an Introduction to the Study of the Science Geschichte der Metalle Vorträge zur Entwicklungsgeschichte der Chemie von Lavoisier bis zur Gegenwart Über die Vorgeschichte und die Anfänge der Chemie. Eine Einleitung in die Geschichte der Chemie des Altertums. Der Werdegang einer Wissenschaft. Sieben gemeinverständliche Vorträge aus der Geschichte der Chemie History of Chemistry ( Vol.) Geschichte der Chemie ( Vol.) Die Entstehung und Ausbreitung der Alchemie Geschichte der organischen Chemie Geschichte der organischen Chemie seit  Geschichte der Chemie ( Vol.) A History of Chemistry ( Vol.) Historical Studies in the Language of Chemistry A History of Chemistry Geschichte der analytischen Chemie The Historical Development of Chemical Concepts Chemists and Chemistry

Veit, Leipzig, Veit & Comp., Leipzig Macmillan & Co. Ltd., London Simon, Berlin Vieweg, Braunschweig Deuticke, Leipzig und Wien Akademische Verlagsgesellschaft, Leipzig Watts & Co., London Sammlung Göschen, Berlin und Leipzig Springer, Berlin Springer, Berlin Springer, Berlin de Gruyter, Berlin Macmillan and Co, London Heinemann, London Hawthorn Books, New York Akadémiai Kiado, Budapest Kluwer, Dordrecht

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1 Introduction

Tab. 1.1 (continued ) yeara

author

title

publisher



John Hudson

The History of Chemistry



David Knight

Ideas in Chemistry: A History of the Science

Chapman & Hall, New York Rutgers University Press

Note: There are much more books on history of special fields in chemistry available such as instrumentation, industry, substances, and regions. a Of first edition (some books appeared in several editions). b Wiegleb cites that the first and oldest history of chemistry is written by Olaus Borrichius (De ortu et progressu chemiae. Dissertation, Hafniae, Matth. Godicchenius, 1668); another earlier history was written by Tobern Bergmann in 1779 (Gradualis de Primordiis Chemiae. Dissertation).

There is no doubt that the discovery of different kinds of airs (gases) and of the main gases in the atmosphere such as carbon dioxide (process of calcination) and oxygen (process of oxidation) was the root of modern chemistry as natural science.

1.2.4 Terminology Antoine Lavoisier, who revolutionized the science of chemistry in the eighteenth century and replaced the mythical “phlogiston” with the term (and concept) of oxygen, clearly understood the importance of accurate definitions. In his words: “We cannot improve the language of any science without at the same time improving the science itself; nor can we, on the other hand, improve a science without improving the language or nomenclature” (Lavoisier 1789). 1.2.4.1 On the chemical nomenclature and symbols In Chapter 2 on history (namely Tables 2.2 and 2.3) different names of gases and substances being relevant to the atmosphere will be mentioned, given already by alchemists, than by the discoverers, and later by following researchers. The knowledge on its chemical constitution was very limited, some compounds were confused, and some terms were used for different substances. A first approach in development of a systematic chemical nomenclature was proposed by the French chemist Gyuton de Morveau (1737–1816)43 that was presented to the public in a joint publication by Morveau, Lavoisier, Bertollet, and Fourcrout in 178744 (Table 1.2). 43 J. Phys. (1782) 19, 310 and Ann. Chim. Phys 1798, 1, 24. 44 Methodé de Nomenclature Chemique. Chez Cuchet, Libraire, Paris, 1787, 314 pp. At least seven French issues and editions, one English, two Germans, one Spain, and one Italian appeared, all of the full work (Duveen and Klickstein 1954). German translation by Karl von Meidinger (1793) Methode

29

1.2 Chemistry: a historic view

Tab. 1.2: New names according to Lavoisier’s New Nomenclature of “simple substances or such as have not hitherto been decompounded” (after Mitchill´s nomenclature of the new chemistry, cited from Duveen and Klickstein 1954, p. 292).a Frenchc

German

English

Lumière Calorique Oxygéne Azote Hydrogène Carbone Soufre Phosphorus

Lichtstoff Wärmestoff Sauerstoff Stickstoffb Wasserstoff Kohlenstoff Schwefel Phosphor

Lightd Caloricd,e Oxygen Nitrogenf Hydrogen Carbon Sulfur Phosphorus

The first attempt to translate the French nomenclature into German was presented in the “Taschenbuch für Scheidekünstler und Apotheker” (11. Jahrgang, 1790, pp. 147–155) and is entitled “Alphabetisches Verzeichnis der neuen französischen Nomenklatur.” The second effort to adopt the new terms to the German language was by Christoph Girtanner (1760–1800) in “Neue chemische Nomenklatur für die deutsche Sprache” (Berlin 1791). Samual Latham Mitchill (1764–1831), American naturalist and chemist, notes “the German words, derived from French, but they are in no way more appropriate for general use than the older ones, and some terms even longer and more cumbersome” (cited from Duveen and Klickstein 1954). b Or Salpeterstoffgas (Girtanner) and Salpeterluft (in Mitchill). c In the French edition, Radical muriatique (chlorine, Cl) has not been taken into other languages. Berzelius (1813b) named it muriatic radical. d Light (Lichtstoff, Lumière) and Caloric (Wärmestoff, Calorique) have been still assumed to be matter. e Matter of heat (old terms: igneous fluid, matter of fire, element of heat). f Berzelius (1813a) termed it nitric radical. a

Jean Henri Hassenfratz (1755–1827) and Pierre August Adet (1763–1832) appended to this publication a system of symbolism to be employed with the new term (but still close to the alchemistic symbols, cf. Figure 1.4). An excellent book Historical Studies in the Language of Chemistry is written by Crosland (1962). John Dalton (1766–1844) was an English meteorologist who switched to chemistry when he saw the applications of chemistry for his ideas about the atmosphere. He proposed the Atomic Theory in 1803, which stated that

der chemischen Nomenklatur für das antiphlogistische System, Wien 1793, and in shortened form by Christoph Girtanner (1792) Anfangsgründe der antiphlogistischen Chemie, Unger, Berlin, 494 pp.

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1 Introduction

nitrogen (N) carbon (C ) sulfur (S) hydrogen (H) oxygen (O) water (H2O) ammonia (NH3) carbonic oxid (CO) carbonic acid (CO2) sulphuric acid (SO3)

1. 2. 3.

Fig. 1.4: The chemical symbols introduced by John Dalton in 1808 (he named 36 elements).

all matter was composed of small indivisible particles termed atoms, atoms of a given element possess unique characteristics and weight, and three types of atoms exist: simple (elements), compound (simple molecules), and complex (complex molecules).

Dalton’s theory was presented in New System of Chemical Philosophy45 since the old alchemical symbols were not fit to use in his theory, he proposed a new set of standard symbols for the chemical elements in the first volume of his New System (Fig. 2.2). The Swedish chemist Jöns Jacob Berzelius (1779–1848) was one of the first European scientists to accept John Dalton’s atomic theory and to recognize the need for a new system of chemical symbols. He suggested just using letters, arguing those are easier to write and print (Berzelius 1814); he already named 47 elements: The chemical signs ought to be letters, for the greater facility of writing, and not to disfigure a printed book. Though this last circumstance may not appear of any great importance, it ought to be avoided whenever it can be done. I shall take, therefore, for the chemical sign, the initial letter of the Latin name of each elementary substance: but as several have the same initial letter, I shall distinguish them in the following manner: 1. In the class which I call metalloids, I shall employ the initial letter only, even when this letter is common to the metalloid and some metal. 2. In the class of metals, I shall distinguish those that have the same initials with another metal, or a metalloid, by writing the first two letters of the word.

45 Manchester, S. Russell for R. Bickerstaff, in three volumes (1808–1827), 560 pp.

1.2 Chemistry: a historic view

3.

31

If the first two letters be common to two metals, I shall, in that case, add to the initial letter the first consonant which they have not in common.

When writing the formula of a compound, Berzelius used small numbers for the number of atoms, but he placed them above the symbol, for example, sulfur dioxide, SO2. Apart from errors due to faulty analysis, there were several weaknesses in Berzelius’s system. Edward Turner (1798–1837), who used the symbols of Berzelius still in his fourth edition of Elements of Chemistry (1834) but most notably James Finlay Weir Johnston (1796–1855) and Liebig, brings us closer to the symbolism of today by writing the number of atoms as a subscript instead of as an index (Chemical Tables, Part 1, Edinburgh, 1836, donation to the Proceedings of the Royal Society of Edinburgh 10, 147). 1.2.4.2 On the origin and meaning of the words air, fog, and smoke Alexander von Humboldt, the founder of modern geography and in particular physical geography, writes (Humboldt 1850, p. 302): The two envelopes of the solid surface of our planet – the liquid and the aëriform – exhibit, owing to the mobility of their particles, their currents, and their atmospheric relations, many analogies combined with the contrasts which arise from the great difference in the condition of their aggregation and elasticity.

He further notes: “The Aërial Ocean rests partly on the solid earth . . ., we find that the strata of air and water are subject to determinate laws of decrease of temperature.” Air, water, and soil46 (or in modern terms the atmosphere, hydrosphere, and pedosphere) were not only the ancient “elements” forming the Earth with all its forms and phenomena but also characterize the states of matter (gas, liquid, and solid). “The relative quantities of the substances composing the strata of air accessible to us have, since the beginning of the nineteenth century, become the object of investigations, in which Gay-Lussac and myself have taken an active part . . . ” (Humboldt 1850, p. 311). Humboldt cites accurately the concentration of oxygen (20.8%) and nitrogen (79.2)47 and named as minor species “carbonic acid gas,”48 “carbureted hydrogen gas” (CH4), “sulfuretted hydrogen gas” (H2S), and “traces of ammoniacial vapors” (NH3). Humboldt also clearly states (Humboldt 1850, pp. 312–313):

46 Today, “soil” means the upper part (pedosphere) of the solid earth, whereas the rocky part (lithosphere) is situated below. In ancient times, “soil” was the synonym for the solid earth. 47 Only at the end of the nineteenth century was known that about 1% of this value is due to novel gases. 48 Citing Boussingault and Lewy, Humboldt (footnote on p. 311) mentioned that “the proportion of carbonic acid in the atmosphere . . . varied only between 0.00028 and 0.00031 in volume” – a very modern view.

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1 Introduction

Besides these substances, which we have considered as appertaining to the atmosphere . . . there are others accidentally mixed with them . . . Fogs, which have a peculiar smell at some seasons of the year . . . dust which darkens the air for an extended area . . .

Within these few phrases, Humboldt used six different terms (aëriform, aërial, atmosphere, air, vapors, and gas) for a phenomenon that we describe today simply by air. Old literature (before the middle of the nineteenth century) has used terms, which are today accurately defined in atmospheric sciences, synonymously but also with a different sense. Moreover, it is difficult when reading old literature because the same phenomenon might be described by many different terms. Before the middle of the seventeenth century, almost all scientific books were written in Latin but Latin terms for phenomena mostly originate from Old Greek. Only since the seventeenth century with an increasing number of scientific books in modern languages (German, French, and English), Latin terms were rendered differently, through existing words from the colloquial language, by different authors explaining the variety of terms (Table 1.3). However, the decrease in the number of terms (i.e., exactly one term for one phenomenon) together with its accurate scientific definition did not begin stepwise before the middle of the nineteenth century. The British chemist Thomas Thomson (1773–1852) writes (Thomson 1820, p. 162): The word AIR seems to have been used at first to denote the atmosphere in general; but philosophers afterwards restricted it to the elastic fluid, which constitutes the greatest and the important part of the atmosphere, excluding the water and the foreign bodies which are occasionally found mixed with it.

The English and French word for “air ” is derived directly from the Latin aer, which comes from the Greek άήρ. However, the German word “Luft” is a common ProtoGermanic word; in Old English lyft. The word “Luft” is associated with brightness; the German “Licht” (light), an air (in atmospheric sense) without fog or clouds. Air and water were originally “elements” in ancient Greek and were transmutable; they represented two kinds of the “layer of mist” (atmosphere). Dark or thick air was mist or cloud, hiding the Gods (who lived in the upper air or sky, the Aether). Different terms are presented, which describe fog and clouds in connection with the history of the process of understanding. Finally, the word “Luft” (air) as a term for gaseous chemical compounds (“kinds of airs”) was used by alchemists (Möller 2014a). The world Luft (also Old Saxon, Middle High German, Danish, Swedish, and Norwegian)49 finds its primordial roots from medieval texts as the “sphere between earth and heaven”.50 Relations of this Proto-Germanic world (Luft) with cognate

49 Old Greek άήρ, also gr. άέριος = up in air, misty; in Modern Greek: αέρας, Engl. air, Lat. aer, Ital. aria, Portu. ar, Roman. aer, Span. aise. 50 Deutsches Wörterbuch by Jacob and Wilhelm Grimm, Vol. 12, Column 1237–1249.

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Tab. 1.3: Historic terms for atmospheric waters (fog, vapors, drops, etc.), fume, and exhalation in German, British English, French, and Latin. German

English

French

Latin

Wolke Nebel (light) e Nebel (dense) e Dunst Dampf Wasserdampf Schwaden Brodem Dampfluft Feuchtigkeit tropfbares Wasser Dunstkörperchen Wassertröpfchen Bläschen, Bläsgen Tropfen Tröpfchen Rauchd Ausdünstung verdampfen

cloud mist, myst, fog, brume haze, brume, damp damp [vapour] steam damp, vapour vapour vapoury aira moisture drop-able water [haze particles]f [water droplets]f vesicles, spherules globules, drops droplet smoke, smoak, fume exhalation, effluvia evaporation

nues bruillas, bruillasse brouillard, brume fumeés vapeur la vapeur d´eau nuée buée vapeur d´eau invisible humidité gouttes d´eau petit corps opaques spères (d´eau) vésicles, spérules gouttes (d´eau) gouttelettes fumeé exhalaison, effluenceb evaporation

nubes nebula nebula nebula, vapor vapor vapor aquae vapor vapor vapor caeli humidus guttulis aquae – stillæ vesicula, bullulae guttae guttula fumus exhalatio, effluvium exhalo

The British English terms in brackets have not been used in historic British literature a Also invisible vapour. b Also: émanation. c Also: vaporization; volatilization. d Also: Qualm. e No separation in German. f Not used in historic literature.

languages have not been found because the most frequent meaning of Luft in the old language is a draught of air; Old High German: luft, aër, lufft, luht; Gothic: luftus; Old North German: lopt51; Anglo-Saxon: lyft; Old English (now antiquated): lift; Dutch: lucht. It is likely that the stem of “Luft” derives from “Licht” (light, German stem: luk),52 which has been recognized from celestial bodies and its radiation as an atmospheric phenomenon (Latin: lucis, luminis, lumen; Greek: λυχνος). The

51 The Old North German “lopt” also means the upper floor and the loft in a house (Low German: lucht), a meaning that is continuous in Swedish and Danish loft. 52 Old terms: liecht, lioht (Old High German), liehte (Middle High German), lecht (Middle Dutch and Middle Low German); the similarity with English light is evident (means also “easy,” in German “leicht”; see the difference to “thick air” below). Similar to Norwegian and Danish lys, Swedish ljus and like French lumière, Romanian lumina, Italian lume (and luce), Spanish and Portuguese luz, all derive from Latin lumen and lux.

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Proto-Germanic word Luft shows many variations, which even includes a similar sounding of Old-English word lyft (after Kluge 1999, Duden 1963, Pokorny 1959). The linguistic affiliation between Luft (air) and Licht (light) is expressed in old phrases, particularly in relation to the transparency and clearness of air (or atmosphere); cited from Grimm, Vol. 12, 1889): der claar und heiter luft, aether apertus (Megenberg)53; feiner heiterer luft, liquidae aureae; der schön luft54 oder heiter himmel, liber nubibus aether (Maaler).55 [Clean and bright air; fine bright air; fine air or bright sky], see Figure 1.5.

The relation between light (and sun) and air also follows from the association with growth and life: . . .sie hindern licht und luft, und stehn dem wachsthum vor (Günther)56; noch beraubt dich gott nit der sunnen noch des mons, des lufts und der brunnen (Kaysersberg)57 [. . .they hinder light and air and prevent growth; still God robs you not of sun and moon, not of air and wells].

The early use of the word Luft for wind58 can be found from the poetry “Crist” (991) attributed to the Anglo-Saxon author Kynewulf who lived in the eighth century in Southern England (King of Wessex 757–786): hû þät gestûn and se storm and seó stronge lyft brecað brâde gesceaft.

Mohr (1854) drew attention to the fact that the German language contains words whose pronunciation gives an intrinsic sense (he mentioned “Atmen” – breathing); he writes (ibid., p. 627): Ein anderes höchst malerisches Wort ist “Hauch”. Es fängt mit h an und endigt damit. Man muss die Bewegung des Hauchens nachahmen, wenn man es ausspricht [Another deeply picturesque word is “Hauch” (breeze breath). It starts with “h” and end with it. One must imitate the movement of a breeze when pronouncing it].

53 Konrad von Megenberg (1309–1374) Buch der Natur. 54 Interestingly that schone Lucht (Dutch) = clean air. 55 Josua Maaler (1529–1599) Die Teütsch Spraach, Zürich (1561); first large German dictionary. 56 Johann Christian Günther (1695-1723) Sammlung von bis anhero edirten deutschen und lateinischen Gedichten, Breslau and Leipzig 1735. 57 Johann Geiler von Kaysersberg (1445–1510) Das “Narrenschiff” (Nauicula siue speculu[m] fatuor [um] Presta[n]tissimi sacrar[um] literaru[m] doctoris Joannis Geyler Keysersbergij: concionatoris Arge[n]tinen[sis], Strassburg, 1511). 58 We also might assume that the word Luft comes from the imagination of tangibleness and vehemence; affiliation to Sanskrit rabh-as = stormy, force, and Greek λαβρος = severe, wild. In Corinthian lüftig = rapid, fast.

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Fig. 1.5: Page with the beginning chapter “Von dem Luffte” [on the air] from volume II (On the seven planets and four elements including different meteorological and atmospheric phenomena) by Megenberg (University library Heidelberg), digital full text representation: http://digi.ub.uniheidelberg.de/cpg300).

Pronouncing “Luft” produces a sibilation like a wind and a blow. The poet Georg Rodolf Weckherlin (1584–1653) underlines the “meteorological” elements: der luft schiesz dunder, strahl und plitz [the air shoots thunder, beam and lightning].

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Konrad von Megenberg, principal of the Vienna Cathedral School and canon in Regensburg, created the first German encyclopedia of nature, called “Buch der Natur” (authentic “Buch über die natürlichen Dinge”). It was primarily a translation from a Latin source; a shortened and changed version of the “Liber de natura rerum” by Thomas von Cantimpré (about 1200–1270), called “Thomas-IIIa.” Therein, we find the ancient description of air as an element (after Grimm): der luft ist daz næhst element nâch dem feur, wann dâ des feurs huot ain end hât, dâ hebt sich des luftes huot an und gêt umb und umb daz mer und umb die erden, . . . [Air is the next element to fire and when keeping of fire ends then the air rises and goes around the sea and the earth,. . .].

Note the masculine gender of “der Luft” (in the course of time all genders have been used). In Vol. 12 (1889) of Grimm’s Deutsches Wörterbuch, the citation of Megenberg is given as an indication of the identical use of terms for air, Aerial Ocean, and atmosphere: luft, der luftkreis selbst, ohne daß mehr die bewegung betont wird, die atmosphäre, nach der alten lehre von den elementen die erde umgebend [Air, Aerial Ocean itself, without pronouncing the motion, the atmosphere, according to the old doctrine of elements surrounding the earth].

In Gehler (1787), one can find the synonymous terms: Luftkreis, Dunstkreis, Dunstkugel, Atmosphäre der Erde, Atmosphaera terrestris, Atmosphère de la terre.

The term “atmosphere”, derived from Greek (άτμόσ = vapor, άτμις = vapor, damp, mist, σφαίρα = sphere, ball),59 was unlikely to have been used before the middle of the eighteenth century. The Dutch astronomer and mathematician Willebrord van Roijen Snell (1580–1626) translated the Old Dutch word “damphooghde” (in Latin altitudine vaporum, in German “Dunsthöhe”)60 into a new Latin term “atmosphæra” in 1608,61 which at first merely described the altitude between the surface of the earth and the bottom of the clouds. The term “atmosphaera” was first named in England by astronomers in the context of moon observations62 (Weekley 1967). Gottfried Wilhelm Leibniz (1646–1716) used the term “atmosphaera” manifold in his letters.63 Robert Boyle (1627–1691) often used the term “Atmosphere” (Boyle 1662, p. 18), partly

59 In old German books, instead of atmosphere (“Atmosphäre”), the term Dunstkreis and the words Luftmeer und Luftozean (ocean of air) are often used (Reimann 1857; Umlauft 1891). 60 Dunstglocke in Dutch mistigheid (see the discussion with the term mist below). 61 Snell translated “Wisconstighe Ghedachtenissen” (printers Ian Bouwensz in Leyden) by Simon Steven van Brugghe (1548–1620) into Latin Hypomnemata mathematica (Leyden 1605–1608). 62 For example, Boskovic, R. J. (1753) De laune atmosphera dissertation. Romae, Publ. G. Salomoni. 63 Sämtliche Schriften und Briefe (1662-1676): Reihe III. 2, S. 219, 220, 794, Ed. by BerlinBrandenburgische Akademie der Wissenschaften und der Akademie der Wissenschaften in Göttingen. Mathematischer, naturwissenschaftlicher und technischer Briefwechsel: Reihe VI, 1, S. 56-58, VI, 2,

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synonymous with “Air” ( . . . the Air or Atmosphere . . . ; ibid., p. 64).64 In most cases, Boyle used the world Air in terms of a substance: Since in that part of the Atmosphere we live in, that which we call the free Air (and presume to be so uncompressed) is crouded into so very small a part of that space, which if it were not hindred it would possess. (ibid., p. 33–34) . . . the Air may consist of any terrene or aqueous Corpuscle, provided they be kept swimming in the interfluent Celestial Matter; it is obvious that Air may be as often generated, as Terrestrial Particles; minute enough to be carried up and down, by the Celestial Matter, ascend into the Atmosphere. (ibid., p. 91–92)

Boyle also used the terms Corpuscles of Air (ibid., p. 19), Ambient Air (ibid., p. 24), Aërial Particles (ibid., p. 28), and Aërial Corpuscles (ibid., p. 70); the last one provided with the characteristics of “ . . . gravitating themselves . . ., ” apparently aerosol particles in today’s understanding as hydrometeors and dust particles. In German (until the middle of the nineteenth century), in place of “Atmosphäre,” the words Luftkreis (“aërial sphere” – air surrounding the earth or a part of it) and Luftmeer (aërial ocean) have been used, right up until the twentieth century.65 The ancient idea of transmutation (air ↔ water) survived until the end of the eighteenth century, when it was finally rejected by Lavoisier; however, Boyle (1662) already doubted it from his experiences of “New Experiments Physico-Mechanical Touching the Air” (ibid., p. 91): “ . . . thought not that Air may be generated out of the water, yet that in general Air may be generated anew.” For the first time, Boyle used the term Æoliphile (ibid., p. 85) as an “air-loving” substance,66 in particular for water; “ . . . that water may be rarefied into true Air.” While fog is always equated with “thick air” and darkness, the terms ὁμίχλη (mist), ἀχλυς67 (gloom), αϋρα (breeze of air – aura), νεφέλη, or νέφος (Nephele – cloud Nymph in Greek mythology) were in use. From nephos, the Latin terms nūbēs, nūbilus and nebula are derived (expressing its gloom and darkness); Old High German: nebul, Old Slavic: nebo (in modern Russian: sky), Sanskrit; nabhas (fog, vapor, clouds, air, heaven). Grimm´s Wörterbuch defines “Dunst”68:

S. 190, 233, 249f, 255, 271; VI, 3, S. 58, 229, 525, Ed. by Leibniz-Archiv der Niedersächsischen Landesbibliothek Hannover. 64 In contrast to terrestrial Globe (p. 19) as the total solid earth. 65 Möller (2003) defined air as the chemical mixture (consisting from gases, hydrometeors and dust particles) that fills the atmosphere. 66 Lampadius (1806) used in German for the first time the term Atmospärilien in the sense of all constituents of air with the exception of gases. 67 Acherōn is a mythological river in the underworld, identified by poets with the underworld (= darkness). 68 In English, there exist many terms for Dunst: mist, haze, damp, vapor, brume, fume, aura. According to Deutsches Wörterbuch (Vol. 2, Col. 1559, shortened) also: “für dünne, nasse oder

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Im eigentlichen Sinne: eine Menge von Wasserdämpfen, die in tropfbar-flüssigem Zustande unmittelbar an oder über der Erdoberfläche schweben und die Luft mehr oder weniger undurchsichtig machen [In a proper sense: a lot of water vapors that float in droplet liquid state near to or at the earth surface and making the air more or less non-transparent].

The English “fog” is defined as (OED) “thick, obscuring mist.” The origin of this term is dated to around 1540 and it is linguistically similar to the Old Norwegian fok, the Dutch vocht and the German feucht (moist). The Old English terms nebule and nifol (dark, gloomy) have been taken directly from Latin. The differences between haze, mist, and fog are not reflected in German69 where one term (Nebel) characterizes these words, which is likely to be an effect of the moist “English climate” on language (OED). Nevertheless, in Japanese, there exist more than 100 terms (rain = 雨) for different types of atmospheric moisture and also in French (after Sachs 1911) there are several totally different terms in use. However, in German, principally there exists a descriptive combination with the word Regen: feiner Regen (fine rain), Starkregen (heavy rain), Nieselregen (drizzle), Sprühregen (mist, spit, sprinkling of rain), Eisregen (freezing rain), and so on: embrun (mist and overcast sky), bruine (sprinkling of rain and fine cold dust rain), and crachin (drizzle). The closeness of the first two terms to brume is remarkable. Obviously, the English term mist derives from όμίχλη70; as does the Swedish and Norwegian: mist. In German, mistig means (in colloquial language) dirty.71 Today, mist is separated from fog mostly by droplet size: mist consists from larger

trockene Flüssigkeit die in die Luft steigt, meist sichtbar ist, doch auch nur durch den Geruch empfunden wird; vergl. dampf, duft, brodem, qualm, schwadem” [for thin, wet or dry liquid, rising into air, usually visible but also only conceived by smell; compare vapor (dampf, brodem – last term not longer used in German), flavor (duft), plume (qualm), billow (schwaden)]. Old High German tunst; Middle High German, Swedish, and Danish dunst. In Gothic, Old-Saxon, Old Friesian, Low German, and Dutch dunst does not exist; it is related to the Gothic þinsan and the lost þinan (strech); Old North German, Anglo-Saxon, and English dust (Staub). Nowadays, we translate atmospheric Dunst with haze. 69 The chapter “Of Mists and Fogs” in Prout (1834 p. 312) is reduced in the German edition (Prout 1836, p. 214) to “Vom Nebel” [Of fog]. The opening sentence of this chapter in Prout (1834) “When mists, from other causes, are general and extend to considerable heights above the earth surface, they acquire the name of fogs” was completely declined in the German edition, because mist = fog = Nebel. Scotch mist means very thin rain (Lloyd and Noehden 1836). In many British publications of the nineteenth century, the term mist has been used instead of fog. Giberne (1890) wrote: “A mist is commonly distinguished from a fog as being made of rather larger drops, therefore feeling more wet.” 70 In Lat. mingō and mejo (from that also derived the English “mist”; in its primordial meaning also urinate but in Sanskrit mih, megha (cloud, mist). The English “misty” (foggy) was in Old English “mistig” (see also footnotes 70 and 71). 71 On the other hand, the German word Mist means dung but in a colloquial sense also “brass farthing” – again, evidence of “gloom” and “evil” in mist (fog).

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drops that have a larger tendency to precipitate (more exactly: to sediment).72 In Old English, instead of mist, the term brume, derived from the Latin bruma (winter) has been used. In French, brume is the meteorological term for fog with visibility more than 1 km (which in German is called Dunst)73 and brouillard for fog with visibility less than 1 km (in German Nebel). From that stem brumaille and brouillasie (fine thin fog and fog shower). Seerauch (Meerrauch, Flussrauch) is evaporating fog above water (sea smoke, sea mist, water smoke, steam mist), which in French is fumée de mer. The Proto-German word Rauch (smoke, fume; Latin: fumus), which was always linked with house, fire, and some burning material – in a chemical sense, a mixture from soot, gaseous (including water vapor), and other solid combustion products – has been and still is in synonymous use with “Dampf” (vapor). Grimm defines Dampf as (Deutsches Wörterbuch, Vol. 2, Col. 714, shortened): ein dichter, sichtbarer, feuchter Rauch oder Dunst, schwerer als Duft, leichter als Qualm und Schwaden, Fumus, Vapor, Exhalatio [. . .dense, visible, moist smoke or haze, heavier than flavour, lighter than fume and billow].

Interestingly, the adjectives feucht [moist] (or wässrig, nass – aqueous, wet) and trocken [dry] have been used for the same term in the past to differentiate the state of matter of a general atmospheric phenomenon,74 that is, the “visible air” [sichtbare Luft]; the nongaseous components for which all terms, such as Nebel, Dunst, Dampf, and Rauch, were used. However, it should be noted that Nebel [broullaird], Dunst [brume], Schwaden [nuée], and Brodem [buée] have been used exclusively for water. In English, steam is used only for water vapor, whereas damp,75 vapor(s), smoke, vapeur(s), fumée(s) are also used for other (evaporating, escaping) substances. Incidentally, Luft/Lüfte (air/airs) was used for all gases, in addition to atmospheric

72 Such weather in colloquial German is called Mistwetter: dark, cold, and wet. Ehrenberg (1849, p. 122) cites the weather record of the British vessel Roxburgh on 4.2.1839 at Capeverdean: “Der Himmel war überzogen, das Wetter mistig [obviously the English ‘misty’ was used in the record] . . . ” [Sky was overcast, weather misty]. The term mistig (neblig – foggy) is unusual in German; the adjective means: full of “Mist,” dirty. 73 After Sachs (1911) brume means “thick fog,” that is, fog with visibility less than 1 km – also exactly reverse in modern meaning. Bruine is translated after Sachs (1911) as Staubregen [dust rain]; an unknown word in modern German. Nowadays, bruine = Sprühregen = drizzle (identical with crachin); brume = sèche = haze = Dunst after METAR (meteorological aerodrome report). 74 Today the adjectives trocken (dry, sec) and nass (wet, humide) are used in atmospheric science only for the process of deposition to distinguish between dry and wet deposition. In German, there is still a distinction between feuchter Dunst (moist haze, i.e., fog with visibility between 1 and 5 km) and trockener Dunst (dry haze, greater visibilities but still with a discernible opacity of the atmosphere). The latter represents cloud condensation nuclei in larger numbers, activated and exceeding the deliquescence point (almost 60–70 r.H.). 75 The similarity with German Dampf is significant (Old High German: damph).

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air,76 for a long time after van Helmont introduced the term Gas (gas, gaz). In the nineteenth century, “Gas” became the synonym for town gas, see Section 2.1.3.3. The German term “Ausdünstung” (in modern usage, evaporation of water, exhalation, and more generally, emission for all other substances) denotes the process (evaporation) as well as the product (vapor, gas); French: émanation, exhalaision, effluence, evaporation, vaporisation, volatilisation; English: evaporation, effluvium. The German word “Dunst” is defined by Johann Georg Krünitz (1728–1796) in the “Oeconomische Encyclopädie” (Vol. 9, 1785) in the sense of fog, fume, and vapors (in modern terms, “trace gases”). Similarly in Grimm77: “LUTHER gebraucht in der Bibel das Wort nicht, nur Dampf” [LUTHER did not use this word in the Bible, only vapor]. Goethe (Faust I, Walpurgisnacht) writes: “Da steigt ein Dampf, dort ziehen Schwaden, hier leuchtet Gluth aus Dunst und Flor” [There rises a vapor, there flow billows and here lights glow from haze and bloom].

76 Atmospheric air (as gas mixture) has also been characterized with the following terms (Krünitz 1779): atmosphärisches Gas, gemeine Luft; lat. Gas atmosphaericum, Aër atmosphaericus vulgaris, communis, Gas ventosum; frz. Gas atmosphérique, Air commun, Air de l’atmosphère. 77 Grimm sets a linguistic relation between Dunst and the English (Old North German and AngloSaxon) “dust” = Staub.

2 History of investigation and understanding the climate system This chapter is dedicated to Albert Lévy (1844–1907) who wrote the first Histoire de l’air (1879, G. Baillière, Paris, 184 pp.)

The history of science is the study of the historical development of science and scientific knowledge. This history is written by a chemist, who spends 40 years in studying atmospheric chemistry and air pollution. I’m not a historian who is able to present the past from a true perspective of their time – this also would not be my aim. In contrast, I also will not “study the past with reference to the present”, what the British historian Herbert Butterfield (1900–1979) called the “Whig history”, and criticized the “study of the past for the sake of the present” (Butterfield 1931); history, he stated, cannot be used to justify certain contents in the present. However, I try to interpret the past – almost limited to experimental findings in the nineteenth century – through current values, without dismissal of the problems and ideas of earlier scientists. In this way it is possible to draw some ideas on the historical air chemical status. Imre Lakatos (1922–1974)78 wrote (Lakatos 1981): “Philosophy of science without history is empty; history of science without philosophy is blind”. There is no book on the history of atmospheric chemistry; however, several books on history of air pollution exist: Thorsheim (2006), Jacobson (2002), Brüggemeier (1996), Spelsberg (1988), Brimblecombe (1987), Spiegelberg (1984). There is an excellent book on history of theories of rain by Middleton (1966) and there are many books on history of meteorology: Shaw79 (1942), Khrgian (1970), Frisinger (1977), Brush and Landsberg (1985), Fleming (1990, 2016),80 Harper (2008), Henson (2010), and in German: Hellmann (1883, 1904, 1908, 1914, 1917,

78 Birth name: Lipschitz, Hungarian mathematician, physicist and philosopher at the University of Debrecen, Hungary. In 1953 he fled to Vienna and finally to London to study at the University of Cambridge for a doctorate in philosophy. In 1960 Lakatos was appointed to the London School of Economics. Many works appeared after his death in editions. 79 Sir William Napier Shaw (1884–1945) English meteorologist; Shaw also studied air pollution, publishing his book The Smoke Problem of Great Cities in 1925. 80 James Rodger Fleming is the editor-in-chief of History of Meteorology, a peer-reviewed annual journal produced by the International Commission on History of Meteorology (ICHM); Vol. 1 in 2004. Fleming provides a “Guide to Historical Resources in Atmospheric Sciences. Archives, Manuscripts, and Special Collections in the Washinton D.C. Area (1997): http://www.colby.edu/sts/ 97guide/. There is another Journal on history: Earth Sciences History: Journal of the History of the Earth Sciences Society. USA, Vol. 1 (1982). https://doi.org/10.1515/9783110561340-002

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1921, 1922a, b, 1924, 1927), Schneider-Carius81 (1955), Körber (1987). The German meteorologist Johann Georg Gustav Hellmann (1854–1939) was the first who wrote many essays on history of meteorology; he worked at the Preußische Meteorologische Institut (Prussian Meteorological Institute) in Berlin (1882–1922), was the principal 1907–1922, and edited together with Julius von Hann the “Meteorologische Zeitschrift”.82 Interestingly, the books on history of hydrology83 – the science of the water cycle – cover rivers, aquifers, soil water, floods but not atmospheric water; only evaporation and precipitation (in terms of fluxes in time and space) at the earthatmosphere interface is of interest to hydrologists. However, hydrology84 has a long tradition: the ancient philosophers tried to resolve the mystery of the hydrological cycle (see Section 2.1.2). The invention of the barometer (1643)85 and thermometer (1714)86 marks the dawn of the real study of the physics of the atmosphere, the quantitative study by which alone we are enabled to form any true conceptions of its truth (Shaw 1942, p. 115). Aristotle’s Meteorologica is described in all books on history of meteorology but traditionally the history of meteorological elements (wind, pressure, temperature, humidity, rainfall, and evaporation) and its observation including weather forecast is in the center of interest (Aristoteles 1829). Only Schneider-Carius (1955) goes on form of clouds (pp. 130–143), dew (pp. 206–209), and physics of clouds and precipitation (pp. 274–285). Excellent is the book “History of the theories of rain” (1965) by William Edgar Knowles Middleton87 (1903–1998), which deals with theories of the hydrometeors (clouds, rain, snow, hail, and dew) up to about 1914. But no book

81 Karl Schneider-Carius (1896–1959) German meteorologist, director of the Geophysical Institute (University Leipzig) 1956–1959. 82 Meteorologische Zeitschrift has a long and rich history; the predecessor journal, the Zeitschrift der österreichischen Gesellschaft für Meteorologie, first appeared in 1866. In 1884, one year after the foundation of the German Meteorological Society, the first volume of the Meteorologische Zeitschrift was published. Merged with the respective Austrian journal two years later it existed for a first period until 1944. Following several separate publications in the post-war period after 1945 Meteorologische Zeitschrift was re-founded in 1992 as a joint publication of the Austrian, the Swiss, and the German Meteorological Societies. German was a well-accepted scientific language in meteorology until about the 1920s, when English started to become the dominant language (Emeis 2008). 83 For example: Landa and Ince (1987), Biswas (1970). 84 The term hydrology as scientific discipline was used only after 1950. 85 Evangelista Torricelli invented in 1643 the first mercury barometer which is used to measure atmospheric pressure. 86 The first exact mercury thermometer by Daniel Gabriel Fahrenheit (in 1709 he introduced the alcohol thermometer); there were some predecessors: in 1593 Galileo Galilei invented a rudimentary water thermoscope and in 1612 Santorio Santorio put a numerical scale on his thermoscope. 87 Middleton, a Canadian meteorologist, wrote 15 books and many scientific papers related to the science of weather instruments and meteorological optics as well as their history. His major contribution was the book Meteorological Instruments, first published in 1941.

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on history of meteorology deals with air chemistry. And no book on history of chemistry deals with air chemistry; but with substances found in air.88 In discovering the atmosphere we may distinguish between the following epochs: – Antiquity (about 600–300 BC): air phenomenology and earth philosophy; – Middles Ages and Renaissance (fifteenth to seventeenth century): understanding the air being a body, first meteorological measurements; – Reconnaissance (eighteenth/nineteenth century): identification of air composition (including foreign bodies), basic relationships between plant, animal, and air, establishing scientific disciplines such as chemistry, meteorology, geography, agriculture economy; – Industrial era (since about 1850): measurement of trace species in air, understanding of air pollution, cycling of matter; – Modern era (after 1950): air pollution control (monitoring), understanding of atmospheric chemistry, biogeochemistry, global change. In writing a history on a scientific discipline, there appear some problems for a “modern man”, first the language, namely the old terms and formulas for chemical substances that are not consistent with what we presently understand behind it (see Section 1.2.4.1). In some cases it is impossible to identify a defined chemical compound and I leave it with the historical term. In the time before about 1850, obviously the number of scientists in the field were so limited that each of them were familiar with all others either personally or had access to all the books and journals; hence they did not cite any bibliography and only mentioned the surname; for those persons who are not so familiar I did try to find the given name and the living dates (not being successful in all cases) to express my respect to the ancestors. A full citation in books and journal papers begun only at the end of the nineteenth century. However, I found many wrong and missing citations in works over the last 100 years; therefore, I never cite here a work without seeing and reading it either printed or online or in its original form. Only in a few cases, where it was not possible to get access to the original work – and I find it worth and credible to include it here – I refer to the author who cited it. I also like to mention that the reader has to be careful in the use of historic values, especially concentrations of chemical substances in waters and air. In publications before about 1880, no or only rudimentary details on the sampling and analytical methods were given; obviously that the methods (cited by its name) were familiar to all authors and readers. It is a separate scientific work to evaluate historic values on its measurement trueness, but it remains uncertain, for example, Brimblecombe and Pitman (1980), Volz and Kley (1988), Bojkov (1986).

88 For example Kopp (1843) who wrote a chapter on “Gases; atmospheric air; oxygen; nitrogen” in Vol. 3 (pp. 175–218).

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2.1 Air and atmosphere before exploring air chemical composition 2.1.1 Ancient views: origin of the world First written ideas on natural phenomena are known from Homer, likely eighth century BC. The origins of human language will perhaps remain for ever obscure. Our ancestors were probably speaking a million years ago. By about 3000–3500 BC several Semitic peoples played a prominent part in the early civilization over a large tract of desert89 territory from southern Arabia to the north of Syria (Mesopotamia). Writing begins in Sumeria over 3000 years BC.90 Evidence for the first controlled use of fire by Homo erectus is dated to some 600,000 years ago. We can only speculate that latest with that time, humans recognized the world where they were living, particularly the phenomena affecting her life directly and making an early “model” of the world (Table 2.1). Tab. 2.1: The ancient world view: the origin of the “elements” air, water, earth, and fire. region

ruler

phenomena

ether heaven world

solar deities (sun god) empire of gods (hierarchic system covering all regions)

earth

empire of men (as well as animals and plants)

underworld

empire of demons (death deities)

the Sun (light and heat) weather (lightning, thunderstorm, windstorm, clouds, precipitation, and more) habitable zone: interfacing and buffering phenomena from below and above earthquakes and volcanism (eruptions, gaseous emanations, fiery matter)

But likely with the first settlement about 50,000 years ago, humans “created” divine families to explain such phenomena (evidenced by cave paintings). Enlil (later known as Elil) was the Mesopotamian god of the atmosphere and a member of the triad of gods completed by Anu (Sumerian: An; heaven) and Ea (Enki; earth), thus, making the world habitable for humans. Enlil meant Lord Wind: both the hurricane

89 There are theories that suggest that this area was originally to a large extent forested but by producing metals by smelting all wood have been consumed over the Bronze Age (3000–1200 BC). 90 It is said that independently writing developed in Egypt (ca. 3150 BC), China (ca. 1200 BC) and Mesoamerica (ca. 300 BC) but other ideas claim that this was due to cultural diffusion. An earliest Greek alphabet is dated back to 800 BC. Greek and Hebrew peoble developed after fall of Mesopotamia with ending the Bronze Age.

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and the gentle winds; was sometimes called Lord of the Air (Encyclopedia Britannica). Together with other gods, they governed the heavens, earth, and underworld or, alternately, the universe, sky and atmosphere, and earth.91 There are two fundamental models of conceiving the origin of the world, an intransitive and a transitive one. The intransitive model views the origin of the world as a spontaneous growth, developing all of itself out of a primordial chaos or matter, mostly water. The transitive model takes the world to be the object of a constructive activity of a creator. In ancient Egypt, the two models combine and interact in a rather complex manner (Assmann 2007). However, the question, where does our world come from is tried to answer long time before. The oldest ideas down in written form come from Egypt in the early second millennium BC. It can be assumed that such views are old as human kind itself. In ancient Egypt (Assmann 2001) the concept of time (neheh) and eternity (djet) has been considered as unity, pointing out the immortality. Immanuel Kant (1724–1804) wrote in his comments (§ 49) to Kritik der Urteilskraft [the critique of judgment] that perhaps nothing loftier has been said, or a thought has been expressed more sublime than the (allegedly) inscription on a temple in Sais, built to honor the goddess Isis (around 690 BC). I, Isis, am all that has been, that is or shall be; no mortal Man hath ever me unveiled.92 Isis is the fourth generation after the Creator-God Atum, the ur-one, personifying the preexistence (universe arose not from nothing but from One). During his first transfer from preexistence (“non-being”) to existence (“being”), Atum transmuted into the sun whose radiation myth describes as scorching breath from fire and air. Atum has the son Shu (God of air) and the daughter Tefnut (Goddess of fire) who

91 Already in ancient time smoking caves (in German Dunsthöhle) were known to be killing due to gases (CO2, H2S, SO2); Plinius said Mortiferum Spiritum exhalantia (Landener 1856). There were the believe that these caves were the entrance to the underworld with his evil spirits and demons. 92 From the essay “Die Sendung Moses” [the mission Moses] by Friedrich Schiller (1790), Beethoven wrote off three phrases and framed it under glass and put on his desk (Assmann 1999): Ich bin, was da ist. Ich bin alles, was ist, was war, und was seyn wird, kein sterblicher Mensch hat meinen Schleyer aufgehoben. Er ist einzig von ihm selbst und diesem Einzigen sind alle Dinge ihr Daseyn schuldig. It is unclear were this phrase is originated. It is very improbable that in ancient Egypt there ever was such thing as a veiled statue because cult images were hidden in wooden shrines, allowed to be seen only by the priest (Assmann 1999). It is very possible that a statue in a hall that was open to visitors bore a hieroglyphic inscription in this way (there is nobody except me). Plutarch (45–127) tells the story of a veiled image in Sais in his “On Isis and Osiris” and wrote: “The seated statue of Athena, whom they consider to be Isis also bore the following inscription: I am all that has been and is and shall be; and no mortal has ever lifted my mantle.” Proctus (412–485) quotes the same inscription in different words (Commentary on Timaeus). Then the inscription migrated to Voltaire’s (Des Rites Ègyptiens, 1784, p. 100: Je suis ce qui est; & cette antre: Je suis tout ce qui a été & qui sera; nut mortal ne pourra lever mon voile) and to an article published in 1788 by Karl Leonhard Reinhold (1757–1823) (Reinhold 1788) and finally from there to Kant and Schiller.

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beget Geb (God of Earth) and Nut (Goddess of heaven). Finally, with the next (and last) generation of gods, Osiris, Isis, Seth, and Nephthys, time and history arose (cultural institutions). Pharaoh is the earthy embodiment of Horus, child of Osiris and Isis (who is also considered as child of Geb and Nut). This is the famous cosmogony of Heliopolis; all other cosmogonies and creation accounts (of which there are a great many) being just variations of and commentaries on this basic conception (Assmann 2007). This monistic view (the unity of the universe) was a fundament of alchemists: the unity is the universe and through her that universe and in her that universe and if it does not contain the universe it is nothing (Assmann 2012, p. 59).

2.1.2 Ancient views: air and water Humans have always dealt with and been fascinated by the properties of our atmosphere. In ancient times, the motivation to observe the atmosphere was clearly the driving force which increased the understanding of nature. Our ancient views on air and water are based on the ideas of Greek philosophers, beginning around 600 years BC. One of the most fascinating ideas was the cycling among the “four elements”, earth, water, air, and fire. 2.1.2.1 Greek philosophers The close connection between air and water is founded on the ancient Greek. Aristotle recognized that water evaporates from waters and the earth soil (άτμίς) and condenses in air (“solidifies” πύχνωσίς but also named “dense” δασύς by the ancients, from which the Latin dēnso and dēnsus are derived); in Modern Greek “to condense” means συμπύκνωσν (verbatim “contraction”). The Greek prefix συμ corresponds to the Latin con; hence, we see the origin of the modern condensare. In ancient Greek, άτμις (atmis: water vapor) denotes the transfer of water (by evaporation) from the telluric form (hydrosphere) into άηρ (aer), the water vapor of the atmosphere and its return as precipitation to the earth, (with water) one of the two lower elements. We know from Herodotus that in the fifth century BC this theory was known and accepted and described by Hippocrates. While the lower layer of the atmosphere (the celestial hemisphere from the ancient view) has been characterized as άήρ, the upper layer has been named αίϑήρ; both have been regarded not only as different areas but also as different matters (since Homer). However, only air (άήρ) was seen as transmutable. Hence, άήρ exists as βαϑύς (thick air) and appears to the eye as fog or cloud (Gilbert 1907, p. 18). Whereas αίϑήρ denotes the clean upper air or sky (the igneous sphere) and άήρ constitutes the lower layer of air, the “atmosphere” (in the German sense Dunstkreis, i.e., the misty sphere), filled with fog and clouds and being in darkness (. . . to mask the Gods).

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Initially, water (as precipitation) is celestial and feeds the terrestrial waters. Conversely, terrestrial water rising to heaven and there transforming into fog and clouds stands as a continuous process of becoming and metamorphosis of άήρ (Gilbert 1907, p. 25). While Homer understood air as a gloomy substance (atmosphere), characterized by fog and clouds, Anaximenes recognized air as being invisible, only recognizable through heat and cold, wetness, and motion (Gilbert 1907, p. 474). Insofar as the primordial term άήρ must be understood as fog (dimming), Anaximenes already understood πνεũμα as compression of άήρ, whereas Anaximander identified πνεũμα with the thinly dispersed substances of άήρ (what these might be remains beyond our imagination). Before the sixth century BC, air was identified as emptiness. Greek natural philosophers assigned air and water beside earth and fire to the four elements (in Latin, materia prima, primary matter). Thales of Miletus (624–546 BC) was the first person who is known to have tried to answer the question of how the universe could possibly be conceived as made not simply “by gods and daemons.” He defined water (the liquid fluid) as a primary matter and regarded the Earth as a disc within the endless sea. Pythagoras (about 540–500 BC) was probably the first to suggest that the Earth was a sphere, but without explanation (only based on esthetic considerations). Parmenides of Elea (about 540–480 BC), however, explained the spheroid earth due to his observations of ships floating on the sea; he was a scholar of Xenophanes from Kolophon (about 570–480 BC), the founder of Eleatic philosophy. Xenophanes in turn was a student of Anaximander from Miletus (about 611–546 BC). With Anaximander, a student of Thales, and Anaximenes (from Miletus, about 585–528 BC), the cycle of pre-Socratic philosophers is closed. Anaximenes assumed – in contrast to Thales – that air is a primary element (root or primordial matter) that can change its form according to density: diluted into fire, it may condense to wind and, by further condensation, into water and finally into soil and rocks. This was very likely the first “poetic” description of the idea that all material on Earth is subject to cycling, where “dilution” and “condensation” are the driving processes. Empedocles of Acragas (495–435 BC) introduced the four elements; earth, water, air, and fire. The list was then extended by Aristotle (384–322 BC) by a fifth one, the æther (explaining the heavenly, in Greek αιθέρας). Thus, the first to describe a number of weather phenomena and the water cycle was Aristotle in his Meteorologica (Aristoteles 1829, 1923). From his Meteorologica we know that Aristotle believed that weather phenomena were caused by mutual interaction of the four elements (fire, air, water, earth), and the four prime contraries: hot, cold, dry, and moist. In his book μετεωρολογιχά, Aristotle placed the transformation of four elements (soil, water, air, and fire) in focus. Each of these elements occupies its own region

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but with the understanding that the matter of άήρ (air – aër) and ϋδωρ (water – idor) cannot be treated separately. The changing states of elements are produced, according to the ancient philosophy, by two forces: heat and cold. Whereas older Greek philosophers treated water (Thales) or air (Anaximenes, Heraclitus) as elementary bodies, Aristotle (and his scholar Platon) did not consider the four elements as different basic materials but as carriers of different properties, belonging to a single primary matter (Meyer 1914). Aristotle attributed to each element paired properties (warm, cold, dry, and wet): water is wet and cold and air wet and warm. However, he deemed the four elements insufficient to explain nature and, therefore, introduced ούδία or αίϑήρ (Aether) as a fifth element, having an ethereal and more spiritual (the quinta essentia in the Middle Ages) property. Aristotle asked in his Meteorologica: “Since water is generated from air, and air from water, why are clouds not formed in the upper air?” He explained this as follows (Aristoteles 1923, Book I, 9, pp. 346–347): But when the heat which was raising it leaves it, in part dispersing to the higher region, in part quenched through rising so far into the upper air, then the vapor cools because its heat is gone and because the place is cold, and condenses again and turns from air into water. And after the water has formed it falls down again to the earth. The exhalation of water is vapor: air condensing into water is cloud. Mist is what is left over when a cloud condenses into water, and is therefore rather a sign of fine weather than of rain; for mist might be called a barren cloud. So we get a circular process that follows the course of the Sun. . . From the latter [clouds] there fall three bodies condensed by cold, namely rain, snow, hail. . . When the water falls in small drops it is called a drizzle; when the drops are larger it is rain. . . When this [vapor] cools and descends at night it is called dew and hoar-frost.

Aristotle further subdivided the lower layer of air. For an understanding of fog (and clouds), the area that immediately adjoins earth (nowadays called the boundary layer) is of great importance, through “reflected radiance of solar heat” and is characterized through “rising water vapor” (άτμίς). Aristotle denotes a cloud as πύχνωσις άέρος (thick air). Aristotle frequently argued against ideas which were actually closer to the truth than his own (Anthes et al. 1975). For example, he presented the views of Anaxagoras considering the cause of hail (Aristoteles 1923) as follows: some think that the cause and origin of hail is this: the cloud is thrust up into the upper atmosphere which is colder, because the reflection of the sun’s rays from the earth ceases there, and upon its arrival there the water freezes. They [Anaxagoras] think this explains why hailstorms are more common in summer and in warm countries. The Greek philosopher Anaxagoras of Klazomenai (500–428 BC) came to Athens as a young man, more than 100 years before Aristotle. Questioned on what he was born for, he answered: “To observe Sun, Moon and heaven” (Diogenes 1921). His philosophy is based on the Eleatics and Empedokles. With his doctrine that

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meteorological phenomena were caused by sun activities he was in contradiction to the generally prevailing opinion. Anaxagoras’ theory is amazingly correct but Aristotle wrote (Aristoteles 1923): . . . this is just opposite to what Anaxagoras says it is. He says that this happens when the cloud has risen into the cold air, whereas we say that this happens when the cloud has descended into the warm air . . . Aristotle, in contrast to this error, however, contributed many accurate explanations of atmospheric phenomena. The description of the water cycle (reasons for rain), as presented above, could have been taken from a modern textbook. 2.1.2.2 The time after Aristotle The Romans were not interested in the continuation of Greek doctrines; however, they preserved the Greek learning. Thus Plinius the Elder (23–79) assumed that clouds are formed through condensation of air. After the fall of the Roman Empire, around the fifth century, the occident forgot this ancient scientific heritage and replaced it with one single doctrine, that of the Bible. Archimedes of Syracuse in Sicily (287–212 BC) indirectly contributed with his buoyancy principle to the design of the hot-air balloon, an invention which added much to our knowledge of the vertical structure of the atmosphere in the nineteenth and the beginning twentieth century, and to the basis for theoretical investigation of the buoyant rise of cumulus clouds. Theophrastus (about 372–287 BC), the successor of Aristotle in the Peripatetic school and a native of Eresus in Lesbos, compiled a book on weather forecasting, called the “Book of Signs.” His work consisted of ways to predict the weather by observing various weather-related indicators, such as a halo around the moon, the appearance of which is often followed by rain. All “philosophies” of the middle Ages were based on ancient philosophers, new observations and conclusions were not added – in contrast, due to the predominance of nonscientific approaches (“alchemy”) there was no progress. In the Middle Ages religious belief prevailed, with the view that all “heavenly” things were governed by God (which, after all, was the belief of peoples all over the world and which led to the idea of the existence of special gods for many atmospheric phenomena). Medieval monks began to observe the weather and take records, out of personal interest. In the Middle Ages, any meteorological (i.e., weather) observation was linked to astrology. The idea that the motion of the stars and planets influenced all processes on Earth and in the atmosphere inhibited progress in the natural sciences. Although weather records had been taken at different locations as early as the fourteenth century, meteorology did not become a genuine natural science until the invention of weather instruments; after Hellmann this is called the second period in the history of meteorology. Aristotle’s theory survived 2,000 years: dew as a deposition from the air, despite the contradiction with his observation that “both dew and hoar-frost are found when the sky is clear and there is no wind”.

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In the orient, however, Aristotle’s doctrine remained vital, and from there it was reintroduced to Europe in the twelfth century, probably via Sicily, where famous alchemistic laboratories were established. It is very likely that the first physical treatment of rainwater was performed by the great Arab scientist Abd al-Rahman alKhazini who worked in Merv (formerly in Persia, now Turkmenistan) between 1115 and 1130 (unknown dates of birth and death). Al-Khazini is known for his book, Kitab Mizan al-Hikma (The book of the Balance of Wisdom), completed in 1121, which has remained a central piece of Muslim physics ever since. Al-Khazini was the first to propose the hypothesis that the gravity of bodies varies depending on their distance from the center of the Earth and he defined the specific weight of numerous substances including that of rainwater defining it to be exactly 1.0 g per cm–3 (Szabadváry 1966). Two other great scientists must be named; Abū ‘r-Raiḥān Muḥammad ibn Aḥmad al-Bīrūnī (973–1048), who first introduced the weighing of stones and liquids to determine their specific weight (Durant 1950, Hall 1973) and can be regarded as a founder of “medical pharmacy”. He was a contemporary of Abu Ali Al-Hussain ibn Abdallah ibn Sina (981–1017), known in the West by the name of Avicenna; his major contribution to medical science was his famous book al-Qanun, known as the “Canon” in the West. Ibn Sina did not believe in the possibility of chemical transmutation in metals; this view was radically opposed to those prevailing at his time. Aristotle’s meteorology was regarded as so absolute that it found general acceptance and distribution. Hellmann (1908) writes: “The system established by Aristotle remained for nearly 2,000 years the standard textbook of our science” (the meteorology). Water remained one of the four “elements”, i.e., indivisible bodies, and the idea prevailed that one element could be converted into another. All substances and materials in nature were considered different mixtures of these four elements. As a consequence of this belief, all substances were transmutable into all others and were contained in each of them. Each element had two qualities: earth: cold and dry; water: cold and wet; fire: hot and dry; air: hot and wet. This ancient view was continued by Paracelsus (1577) who also believed that water is transmuted into air by fire. In his posthumous “Ortus medicinae i. e. initia physicae inaudita” (1652) Johann Baptist (Jan) van Helmont (1577–1644), a scholar of Paracelsus,93 put forward the idea that all substances, except air, were derived from water. This view was also accepted by Robert Boyle and Newton. Newton, however, still believed that air and water are closely related. Still hundred years later, in 1786 Deluc expressed in his “Ideas sur la météorologie” that suddenly formation of clouds happens only through transformation of air into water vapor and vive versa.

93 Helmont did not believe that the philosopher’s stone was also the elixir of life, as Paracelsus assumed (Partington 1936).

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At this point, Albertus Magnus (about 1200–1280), the most prominent German philosopher and theologian of the Middle Ages, should be mentioned with his work “De Meteoris Libri”, which completely corresponds to the work of Aristotle but with his own supplements. In his work “De Passionibus Aëris” meteorology is briefly presented. Magnus had greatness and two scholars: Thomas von Aquinas (1224–1275) and Thomas de Cantimpré (1201–1272). From the latter, we cite two “typical” phrases on clouds and fog from his work “De Naturis rerum” (after Hellmann, 1904, pp. 123, 124): Nubes quasi nimborum naves dicuntur; ferunt enim pluvias de terra per vapores ad aera sublimatas. . . Nebula fit dum humidae exhalationes vaporaliter trahuntur in aera vel radiis solis repelluntur ad terram.

In the above mentioned book, “Buch der Natur” (from about 1350), Konrad von Megenberg adopted completely the chapter “Von dem nebel” (De nebula) by Cantimpré (Hellmann 1904). In the following, the opening sentences of chapters 10 “VON DEM LUFT”, 16 “VON DEM REGEN”, 17 “VON DEM TAWE,” and 26 “VON DEM NEBEL” are presented in (still understandable today) Middle High German (Pfeiffer 1861): Der luft ist von nâtûr warm und fäuht, aber diu wirm [Wärme] ist gaistleicher [geistig, spiritualis] an dem luft denne an dem feur. . .; Der regen kümpt von wässrigem dunst, dem der sunnen hitz auf hât gezogen in daz mitel reich des luftes. . .; Taw wirt auz gar behendem zartem wässrigem luft, der sô lind und sô zart ist, daz er die kelten der miteln reichs des luftes niht rleiden mag; Der nebel kümt von grobem wässrigem dunst, dâ vil swærs erdisches rauchs zuo gemischt ist, alsô daz in diu sunne niht aufgeheben mag hôch von den erden in die lüfte [The nature of air is warm and wet but the heat in air is spiritual unless in fire. . .; rain results from aqueous vapor, which rises aloft into the middle realm of air through solar heat. . .; dew consists of slight aqueous air, so balmy and gently that it cannot go to the cold middle realm of air; fog comes from coarse aqueous vapor, add much heavy telluric smoke so that it cannot rise from earth into airs when the Sun rises].

In “Heiligenleben”94 the climatic situation of England is wonderful expressed, declaring “fog as plague” (Wright 1861, p. 137): Of hawel, of deu, of reyn-forst, and of hor-forst that freoseth so lowe, Of clouden and of myst, for a lothing hit is, For alle hi cometh of water breth that the sonne draweth up i-wis.

In the “Anglo-Saxon Manual of Astronomy” (written in the tenth or eleventh century) one finds the definition of air (Wright 1861, p. 17)95:

94 “Fragment of Popular Science from the early English metrical Lives of Saints” 95 The meanings for cloud, rain, and hail are similar between Anglo-Saxon and German: wolcnu [Wolke], renas [Regen], hagol [Hagel].

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Aer is Lyft; ignis, fyr; terra, eorðe; aqua, wæter. Lyft is lichamlic ge-sceaft swyde þynne; seopfer-gæð ealne middan-eard,. . . [Air is atmosphere; ignis fire; terra, earth, aqua, water. Air is a very thin corporal element; it goes over the whole word,. . .].

2.1.3 The time after 1600 Atmospheric (weather) observations were closely associated with astronomy, and everything above the earth surface was named “heaven” or “ether.” Despite the weather phenomena – fog, mist and clouds, precipitation (rain, snow, and hail), and dew – have been described rather well since Antiquity, a phenomenological understanding of the physical (but not the chemical) processes associated with hydrometeors was complete only by the end of the nineteenth century. Today the physics and chemistry in the aerosol-cloud-precipitation chain are relatively well understood – also with relation to climate. However, it seems that because of the huge complexity a mathematical description of the processes (i.e., the parameterization of the chemistry and also for climate modeling) is still under construction. Moreover, it seems that clouds – because of its chaotic evolution – remain also in future a non-calculable phemomenon. Until the discovery of the chemical composition of air in the eighteenth century, air was regarded as a body, based on Aristotle’s definition of an “element” (together with water, soil, and fire). The idea of transmutation (air ↔ water) survived until the end of the eighteenth century, when it was finally rejected by Lavoisier. 2.1.3.1 Beginning measurements Between the Greek philosophers, who recognized the atmosphere only by visual observations and reflection, generalizing it in philosophical terms, and the first instrumental observations, there is a gap of almost 1,500 years. Agricultural development and the interest in understanding plant growth (i.e., the beginning of commercial interests) initiated chemical research in Europe in the seventeenth century. Chemistry, first established as a scientific discipline around 1650 by Robert Boyle, had been a nonscientific discipline (alchemy) until then (Boyle 1680). Alchemy never employed a systematic approach and because of its “secrets” no public communication existed which would have been essential for scientific progress. In contrast, physics, established as a scientific discipline even earlier, made progress, especially with regard to mechanics, thanks to the improved manufacturing of instruments in the sixteenth century. Astronomers, observing the object of their discipline through the atmosphere, also began to discover the earth atmosphere. There are two personalities to whom deep respect must be paid for initiating the scientific revolution in both the physical and chemical understanding of atmospheric water; Isaac Newton (1642–1726), who founded the principles of classical mechanics in his Philosophiæ Naturalis Principia Mathematica (1687), and, one hundred years later,

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Lavoisier, with his revolutionary treatment of chemistry (1789), which made it possible to develop tools to analyze matter; this is why he is called “the father of modern chemistry” (Lavoisier 1789).96 We should not forget that solely the estimation of volume and mass was the fundament of the basic understanding of chemical reactions and physical principles after Boyle. While instruments to determine mass (resp. weight) and volume had been known for thousands of years, the new instruments (thermometer, barometer) to supply scientists with the necessary data to test the physical laws were only available from the time of Galileo Galilei. Around the year 1600, Galileo established an apparatus to determine the weight of the air and invented a crude thermometer. Independently of Galilei, the thermometer was invented in Holland by Cornelius Jacobszoon Drebbel (1572–1633) and was first used in 1612 by the physician Santorio Santorio (1561–1632)97 (Hellmann 1920). The Italian mathematician and physicist Evangelista Torricelli (1608–1647), a student of Galilei, produced a vacuum for the first time and discovered the principle of the barometer in 1643; he was the first to state that air is something substantial. Torricelli also proposed an experiment to show that atmospheric pressure determines the level of a liquid (he used mercury). Torricelli’s student Vincenzo Viviani (1622–1703) finally conducted this experiment successfully and Blaise Pascal (1623–1662), a contemporary French scientist, carried out very careful measurements of the air pressure at Puy de Dôme near Clermont in France.98 He noticed the decrease of pressure with altitude and concluded that there must be a vacuum at high altitudes. In 1667 Robert Hook (1635–1703), an assistant of Boyle’s, invented an anemometer for measuring wind speed. In 1714, Fahrenheit, a German glassblower and physicist, born in Danzig (modern Gdansk in Poland) and later working in Holland, worked on the boiling and freezing of water, and from this work he developed a temperature scale. Horace-Bénédict de Saussure, a Swiss geologist and meteorologist, invented the hair hygrometer for measuring relative humidity in 1780. According to Umlauft (1891), Grand Duke Ferdinand II of Toscana (who reigned 1621–1670) invented the first hygrometer (Torricelli was his court mathematician). Benedetto Castelli (1578–1643), a friend of Galilei’s, used the first rain gauge in 1639 to measure rainfall.

96 Lavoisier wrote in 1789 the Traité élémentaire de Chimie (Elementary Treatise of Chemistry), the first modern textbook on chemistry, and presented a unified view of new theories of chemistry, containing a clear statement of the law of conservation of mass, and denied the existence of phlogiston. In addition, it contained a list of elements, or substances that could not be broken down further, which included oxygen, nitrogen, hydrogen, phosphorus, mercury, zinc, and sulfur. 97 Also called Sanctorius of Padu, Italian physiologist, physician in Padua where he performed experiments on temperature, respiration, and weight. 98 In 1648, Blaise Pascal orchestrated an experiment in which his brother-in-law, Florin Périer (1605–1672), who climbed the Puy-de-Dôme with the barometer to register the mercury level at different altitudes (Boschiero 2007).

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2.1.3.2 Theories on condensation and evaporation Air and Water are primigeniall or first-born Elements, and ever unchangeable, by cold, or heat, into each other. (Helmont 1662, p. 57) . . . we plainly perceive. . . that though Water may be rarefied into invisible Vapors, yet it is not really chang’d into Air, but onely devided by heat and scatter’d into very minute parts, which meeting together in the Alembick or Receiver, do presently return into such Water as they constituted before. And we also see, that even Spirit of Wine, and other subtle and fugitive Spirits, though they easily fly into the Air, and migle with it, do yet in the Glasses of Chymists easily lay aside the disguise of Air, and resume the divested form of Liquor. And so volatile Salts, as of Urine, Harts-horn etc. . .disperse themselves through the Air,. . .. (Boyle 1662, p. 83) The naturalist . . . recognizes that water is mass, in movement and as solvent, is one of the greatest agents of Nature and influences in a thousand ways its phenomena. (Fourcroy 1800, p. 8)

In ancient times, no further ideas on the form and constitution of vapors, fog, and clouds originated. The question, of what fog and clouds consist of, was first asked by the great French philosopher and scientist René Descartes (1596–1650) in his work “Les METEORES. Diʃcours Premier” (Descartes 1637). He describes atmospheric phenomena empirically but based on careful observations (of course, at that time without measurements). Descartes distinguishes exhalaisons (in terms of vapors) and vapeurs (in terms of haze and steam and the German Dunst), whereas solely vapeurs represent water particles. Vapeurs (he did use it only in plural; the best German equivalent is Dunst) he considers as being transparent. Only after condenʃant & reʃerrant (condensation and compression) are clouds (nuës) and fog (brouillas) formed. He writes (ibid., p. 122): . . .ʃi elles s’eʃtendent iuʃques a la ʃuperficie de la terre, on les nomme des brouillas; mais ʃi elles demeurent ʃuʃpenduës plus haut, on les nomme des nuës [. . .one named the vapors, dispersing at the earth surface, fog; when vapors, however, hang on high, they are called clouds].

Although the term vapeurs [Dünste] is used for water vapor as well as for water droplets, Descartes writes (ibid., p. 122): Et i leʃt à remarquer que ce qui les fait ainʃi deuenir moins tranʃparentes, que l’air pur, c’eʃt que lorʃque leur mouuement’s alentiʃt, & que leurs parties ʃont aʃʃés proches pour s’entretoucher, elles se ioignent & s’aʃʃemblent en diuers pétits tas, qui ʃont autant de gouttes d’eau, oubien de parcelles de glace [It is taken into account that what vapors make more nontransparent than clean air is only based on the fact that its motion slows and its particles come so close to each other that they contact each other and combine into small heaps, being either water drops or ice particles].

This corresponds to our present molecular-mechanistic view of condensation. His “petit parties des vapeurs” are nothing more than water molecules in air. Descartes describes the water particles as “ . . . longue, vnies, & gliʃʃantes, ainʃi que de petites anguilles” [long, interlinked and slippery as small eels]. Descartes also writes only

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on drops (gouttes, from Latin guttae = drop, Tropfen; guttula = droplets, Tröpfchen) but never from bulles [vesica, Blase] or vésicules [small vesica, Bläschen]; the water drops (in contrast to water particles, i.e., molecules) are “exactement rondes” [perfectly circular]. Only 20 years later, Otto von Guericke (1602–1686) carried out experiments (around 1660) linking air-filled and air-less flasks. Due to the expansion (without recognizing that the saturation arose due to cooling) he observed the formation of fog (nebula) or a cloud (nubes). In chapter 11 (Versuch, mittels dessen Wolken, Wind und Regenbogenfarben in Glasgefäßen erzeugt werden können)99 he writes (Guericke 1672): Quod tantò magis apparet, quantò magis vitrum interne humiditatibus refertum est; tunc enim plures ac copiosiores exurgunt bullulæ, ita ut (. . .) nebulam constituant; quæ per intromissionem aliquid aёris . . . tunc nebula illa in nubes dispergitur [This phenomenon becomes clearer the larger the humidity in the flask is; after that, more numerous and larger vesicles evolve so that a proper fog forms; but if there is free access to air, the clouds or fogs disappear. . .].

Shortly before that phrase, Guericke writes on guttulis minimis (small droplets) but later he uses the term bulla (in German Blase) definitely for a bubble in water. It is unclear whether later scientists stem the term “Bläschen” (vesicle, in Latin vesicula) from bullulæ (bulla = water blister). Generalized, a “vesicular” is a more or less globular envelope filled with water. However, the fog vesicle is a “reverse” bulla, an aqueous envelope filled with air. Guericke concludes from his experiments on cloud formation in the atmosphere,100 where his explanation of “compression” is nothing else than the “thick air” in antiquity. It seems that he adopted the knowledge of Descartes without changes. From his several experiment, Guericke did not believe that air is an element – on the contrary he found that due to fire, air losses some of its mass. Christian Gottlieb Kratzenstein (1723–1795) writes in his “Abhandlung von dem Aufsteigen der Dünste und Dämpfe” (Kratzenstein 1744)101: Dünste sind die kleinsten in der Luft schwimmenden Theilchen (wässerichten Materien) unterschieden den Dämpfen. . . Die Dünste bestehen aus kleinen Bläßgens. . . Die Dunstbläsgens, welche in der Luft schweben, sind inwendig mit Luft gefüllt . . . [Dünste are the smallest particles floating in air (aqueous matter), which differ from vapours. . . Dünste consist of small vesicles. . . The vesicles, floating in air, are internally filled with air. . .].

Charles Le Roy (1726–1779) uses the term “suspension de l’eau dans l’air” to describe fog and clouds (Le Roy 1751). The paraphrase “suspension of water in air” for fog (and thus, Le Roy’s understanding of naturally “drop-able water”) is already a 99 Experiment to produce clouds, wind, and rainbow-colours in glass vessels. 100 Although the Latinized term atmosphaera had already been introduced in 1608, Guericke uses the term aerea sphaera (aerial sphere, Lufthülle in German). 101 “Treatise on ascending vapors” (it is impossible to find a translation for Dünste und Dämpfe – both are “vapors” in English).

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modern scientific description of an aerosol102; suspendō (Lat.) = making or keeping floating. Horace Bénédict de Saussure (1740–1799)103 separates four types of “vapors”: vapeur élastique pure, vapeur élastique dissoute, both in the modern sense water vapor and then two “condensed types”: vapeur vésiculaire, vapeur concréte. He published his findings in “Essais sur l’hygrométrie” (1783). In a chapter of Magiae naturalis sive de miraculis rerum naturaliums (Naples, 1589), contained by Johann Baptista Porta (1535–1615) on the extraction of water from air, it is shown that if a large glass flask be filled with a mixture of ice and nitre, water condenses from the air to the outer walls of the vessel, and trickles down into a basin below as receiver (cited after Mellor 1922, p. 81). Newton (1704) said that potassium carbonate deliquesces in air because of an attraction between the salt and the particles of moisture in the atmosphere, and asked: Why does not common salt or nitre deliquesce in the same way except for want of such an attraction? In Saussure’s Essais sur l’hygrométrie there is an excellent study of the moisture which is normally present in atmospheric air. He exposed “equal quantities of salt of tartar, quicklime, wood, lime, etc., all dried as perfectly as possible,” to the same air, and found that they “imbibed water and increased in weight in unequal quantities”. The salt of tartar took more than the lime, and the lime more than the wood. Saussure said that “these differences can only proceed from the different degrees of the affinity of these bodies for water”, and he called this affinity, the hygroscopic affinity of the bodies for the vapor, so that the amount of vapor imbibed by different substances from the air “is proportional to their affinity for water vapor.” Saussure also showed that the thirst or the attractive force of the body for aqueous vapor diminishes from moment to moment “in proportion as it drinks the vapor”, otherwise expressed, the hygroscopic activity of the body diminishes in proportion as it approaches the point of saturation (cited after Mellor 1922, p. 81). The Encyclopædia Britannica (1771) defines fog as follows: “FOG, or Mist, a meteor, conʃiʃting of groʃs vapours, floating near the ʃurface or any part therof.” Gehler (1833) notes that fog comprises . . . aus wässerigen Dunstbläschen, oder aus Wasserdunste, . . . [ . . . from aqueous vapor vesicles or water vapor, . . . ].

102 The term aerosol was first introduced by Schmauß (1920). The terms sol, colloid, and colloidal state were introduced by Thomas Graham (1861). Wolfgang Ostwald (1909) – son of Wilhelm Ostwald – clearly saw that the system, which he characterized as heterogeneous or multiphase, must be studied and not only the colloid, i.e., the dispersed phase. Ostwald (1909) states fog as an example for the combination of gas-liquid and atmospheric dust for the combination of gas-solid. 103 Swiss aristocrat, physicist and Alpine traveller; he directed his attention to the geology and physics of that region; he made experiments with various forms of hygrometer in all climates and at all temperatures. The father of Théodore de Saussure.

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Dunst is already defined, writes Gehler (1826), under the keyword Dampf [vapor]. Diffusely, he tried to distinguish between gas and vapor, as well as to construct identities (by noncompliance of Mariotte’s law through vapors). However, today in physics, vapor is identical to gas but shows the feature that it is in contact with the liquid or solid phase (e.g., water); in colloquial language, water vapor is still equated with fog (correctly steam). Hence, Johann Samuel Traugott Gehler (1751–1795)104 equates the terms Dampf and Dunst but notes that in English one differentiates between vapour and steam. As discussed above, today we no longer define Dunst as Dampf (in the sense of a gas) but as small dry, as well as wet, particles but also as very small aqueous particles suspended in air (haze). In 1806, Wilhelm August Lampadius (1772–1842)105 writes: Das atmosphärische freye Feuer verbindet sich mit dem Wasser zu einem eigenen elastischen Fluidum, dem Wasserdampf; das Feuer ist fortleitendes Fluidum; das Wasser wägbare Substanz [Atmospheric free fire combines with water into its own elastic fluid, the water vapor; fire is the conducting fluid; water is the ponderable matter].

The ancient element “fire” was regarded in the sense of heat until the end of the eighteenth century (Deluc 1787). The ancient three elements Water – Fire – Air have been connected for an understanding of evaporation and condensation until establishing thermodynamic laws in the late nineteenth century. Since Aristotle it was known that dew only appears on calm and serene nights. Dew, fallen from the clear sky have been considered as matter from the Sun and even stars. Thus, alchemists treasured dew because they believed it to be sideric and were looking for the philosopher’s stone, see also Figure 2.10. Christian Ludwig Gersten (1701–1762), German professor for mathematics in Giessen, was the first who concluded (based on observations) that dew is not fallen from the heaven but is ascending from earth especially from plants.106 Charles François de Cisternay du Fay (1698–1739) a French chemist (known for finding of two kinds of electricity), published in 1736 a paper107 and wrote “glass and porcelain collected much dew, while polished metal surfaces collected almost none.” Also in 1736, Pieter van

104 German physicist, known for his Physicalisches Wörterbuch (Physical Dictionary) in five volumes (1787–1795), enlarged by Heinrich Wilhelm Brandes and others (Gmelin, Horner, Muncke, Pfaff) to 24 Vol. (1825–1845), the world largest lexicon on natural sciences and comprising the whole knowledge at that time. 105 Wilhelm August Eberhard Lampadius (1772–1842), German chemist and professor in Freiberg (Saxonia), founder of modern metallurgy; well-known with Humboldt and Goethe. 106 Tentamina systematis novi ad mutationes barometri ex natura elateris aerei demonstrandas, cui adjecta sub finem Dissertatio roris decidui errorem antiquum et vulgarem per observationes et experimenta nova executiens. Franciscum Varentrapp, Frankfurt (1733). 107 Mém. de Paris. (1736) p. 352 (cited after Gehler’s Physikalisches Wörterbuch, Leipzig 1839, p. 667).

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Musschenbroek (1692–1761) reported108 on dew observations at Utrecht, and confessed that “he did not understand why dew collects on some surfaces far more than on others”. He carried out many dew collections (and did store a sample 24 years in a flask without changes). Le Roy carried out dew experiments in 1751 in Paris, and the Polish naturalist Jan Michał Hube (1737–1807) considered dew in sense of the “dissolution theory” (Hube 1790). Deluc (1787) and later Lampadius109 were fighters against this “theory”. Lampadius was likely the first who said that the temperature difference between earth and the air layer above is important for dew formation (cited after Gehler’s). William Charles Wells (1757–1817), born in South Carolina (USA) as son of Scottish immigrants became a physician, philosopher, and printer, was the first to explain satisfactorily the phenomenon of dew (Wells 1814, Strachan 1866). After decisive experiments on dew, he published his book, “An Essay on Dew and several appearances connected with it”, in London in 1814. This was the first and now still accepted scientific description of dew formation, coming after a long debate. By using the most decisive experiments Wells showed, that, apparently, all these phenomena (including hoar frost and mist too) were owing to the effects of radiation of heat from the earth surface during the absence of Sun. Finally Aitken (1887) concluded form careful observations that dew never “falls” on the earth and that the great part of dew condensed on bodies is from vapor rising at night from the earth; further, that “dew-drops” formed on grass and other plants is not dew at all, but is formed of the exceeded sap of the plant (now called guttation). John Tyndall (1823–1893), an Irish physicist, known belong many other topics for his first explanation of atmospheric heat in terms of the capacities of various gases to absorb or transmit radiant heat, wrote the following very clear phrase110: Aqueous water is always diffused through the atmosphere. The clearest day is not exempt from it; indeed, in the Alps, the purest skies are often the most treacherous, the blue deepening with the amount of aqueous vapour in the air. Aqueous vapour is not visible; it is not fog; it is not cloud, it is not mist of any kind. These are formed of vapour which has been condensed to water; but the true vapour is an impalpable transparent gas. It is diffused everywhere throughout the atmosphere, though in very different proportion.

108 Peter van Musschenbroek; first published in Dutch: Beginselen der Natuurkunde, Leiden (1736) and translated into other languages: Essai de physique, 2 vols., Leyden, Chez S. Luchtmans (1739), Elements of natural philosophy. Translated from the Dutch by John Colson. 2 vols. London. (1744), Grundlehren der Naturwissenschaft, Ed. J. Chr. Gottsched, Leipzig (1747) 1242 pp. 109 Versuche und Beobachtungen über Elektrizität und Wärme der Atmosphäre angestellt im Jahre 1792 nach den Versuchen des Herrn de Lüc und einer Abhandlung über das Wasser. J. E. Hinrichs, Berlin and Stettin (1793) 200 pp. 110 Cited from Appendix (p. 123) written by R. Strachan in the edition of Wells “Essay . . . ” by Longmans, London, 1866.

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Lampadius (1806) writes: “Wenn der Thau sehr stark fällt, sieht man oft einen kleinen niedrigen Nebel schweben” [When the dew falls very hard, you see often floating a small low fog]. Although Lampadius correctly observes that dew only occurs at “ruhiger und heiterer Luft” [calme and serene air], he explains its formation wrong by a distillation process (evaporation – ascent – condensation – descent); hence its close relation to fog. The formation of fog Lampadius explains phenomenological correctly, but identifies fog partly with deep clouds because he means that “größern allgemeinen Nebel nehmen eine Höhe von 100 bis zu mehrern tausend Toisen von der Erdoberfläche an, ein” [the larger general fogs occupy a height from 100 up to several thousands Toise above earth surface]; 1 Toise equals to about 1.95 m. Consequently he defines “Wolken sind gar nichts anders als hohe Nebel . . .” [clouds are nothing else then high fog].111 Lampadius’s explanation on the formation of clouds and rain is cited here without further comment: Sie entstehen entweder bey dem Regen gewissermaßen als Abfall, oder sie geben Regen, oder es ist beydes zugleich. Beym Gewitter z.B. wird das Wasser aus der Luft erzeugt. Es fallen viele Wolken ab, da es electrische Materie in Menge giebt. Diese regnen selbst, wenn sich positive und negative vermengen. Viele dieser Wolken ziehen ab und verdunkeln eine andere Gegend. Zuweilen geht aber auch ein bloßer Nebel in Regen über [They either arise quasi as waste when it rains or they produce rain or it is both at the same time. During the thunderstorm water is produced from air.112 It will fall many clouds because there is a lot of electric matter. These are raining themselves when positive and negative mix. Many clouds pass away and darken other areas. But occasionally mere fog turns into rain].

The fog studies by Kratzenstein and Saussure have worked well into the nineteenth century as “textbook knowledge”. Ludwig Friedrich Kämtz (1801–1867), who is regarded as the founder of modern meteorology, wrote still in his book “Vorlesungen über Meteorologie” (Kämtz 1840; the first edition and volume is from 1831) two 111 This is a remarkable inversion of todays view. Pierre (1845, p. 492) write “a fog, as a celebrated naturalist said, is a cloud in which one is, and a cloud is a fog in which is not”. Some scientist say that fog is a cloud with contact to the earth surface. Of course we know today from physical point of view that actual fog = cloud, and insofar fog could be regarded as a special type of a cloud. Flammarion (1888, p. 615) writes in this sense: “Quoiqu’il n’y ait pas de différence essentielle entre les brouillards et les nuages, il y en a cependant une de fait: c’est qu’un brouillard es tun lieu dans lequel la vapeur d’eau passe de l’état invisible á l’état visible, tandis qu’un nuage es tun objet individuel, un groupement de vapeurs visible suivant une forme détermine [It exists no significant difference between fog and cloud, but it is fact that fog represents the transfer of water vapor from invisible to visible state whereas a cloud represents an aggregation of visible steam of a certain structure]. ” 112 This (wrong) speculation is likely based on the experiments by Cavendish (1784) and Priestley (1785), where nitric acid is produced in moist air under the influence of electric sparks, being wellknown in that time. Prout (1834) speculates (p. 569) “that a combination of water and oxygen is a frequent, if not a constant, ingredient in the atmosphere. This ingredient, which we suppose to be a vapour, and analogous to (we do not say identical with) the deutoxide of hydrogen [hydrogen peroxide] . . . .”

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pages on the vesicle form of fog. However, Krämtz was the first who used and carried out systematic weather records to find regularities. He gives, for example, the annual cycle of the diameter of fog bubbles, which is larger (original in Parisian inch) in winter (about 27 µm) than in summer (about 16 µm). Hellmann (1917) referred Kämtz’ textbook (Krämtz 1840) as to “the first great scientific textbook in meteorology”; it has been translated into French (1843), English (1845), Italian (1846), Polish, and Russian. Even the well-known climatologist Wladimir Peter Köppen (1846–1940) cites in his “Grundriss der Klimakunde” (1931 p. 89) Kämtz’ textbook, after which the vapor pressure does not follow Dalton’s law because . . .in den oberen Regionen der Atmosphäre vermöge der Temperaturabnahme nicht so viel Dampf in elastischer Gestalt vorhanden sein kann, als dieser Ausdruck angibt [in the upper regions of the atmosphere can not exist so much vapor as this law expresses because of the temperature decrease].

Similar to Saussure, Kämtz states that fog forms only in saturated air; Deluc meant that fog also forms in dry air (likely because on his imperfect hygrometer). Kämtz (1840, p. 138) writes that the circumstances under which fog forms are “very different form those of dew formation” [ . . . entschiedenen Gegensatz zu denen bei der Entstehung des Thaues]. Kämtz description of fog formation is completely right despite the assumption that fog particles are vesicles and not droplets (inside filled with air; before it was assumed that they are filled with “fire”) but heavier than air; he also explains the floating and climbing in the air because of airflows and permanent cycling between evaporation and condensation. Even Prout (1834, p. 313) still means that “ . . . mists and fogs . . . are . . . of minute hollow vesicles, having the quality of mutual repulsion . . . .” Since the experiments of Guericke it has been assumed that water vapor condenses when the dew point is fallen below. On the fundaments of the first kinetic gas theory by Daniel Bernoulli (1700–1782), Rudolf Julius Clausius (1822–1888) developed a kinetic model of evaporation and condensation as well the condition of a vapor-liquid equilibrium (Clausius 1864). The French pharmacist Paul-Jean Coulier (1824–1890) and the Scottish physicist John Aitken (1839–1919) carried out independently of each other first experiments with expansions chambers to study the process of water vapor condensation and found that “fine dust” must be present (Coulier 1875, Aitken 1881, 1883). Coulier, however, had some difficulties to explain the observations so that it is appropriate to name Aitken as discoverer of the condensation nucleus theory. Aitken cited Coulier only in his second paper (1883) and derived from Coulier’s and his own experimental results the theory. Aitken (1881) draw the conclusions: (1) that whenever water vapour condenses in the atmosphere it always does so on some solid nucleus; (2) that dust-particles in the air form the nuclei on which vapour condenses; (3) that is there was no dust there would be no fogs, no clouds, no mists, and probably no rain. . .; (4) every puff of steam as it escapes into the air, shows the impure and dusty condition of our atmosphere.

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However, a certain Dr. Berger113 from Frankfurt/M. already doubt the “droplet theory” before Aitken and Coulier and proposed condensation onto dust particles to explain fog formation (Berger 1863). He writes (ibid., p. 459): Zur Bildung eines . . . Nebels ist nothwendig, dass eine hinreichend gesättigte Luftmasse eine niedrigere Temperatur habe, als der Boden unter ihr [For the formation . . . of a fog it is essential that a sufficient saturated air mass has a lower temperature than the earth below].

Thus he confirms the observations made by Krämtz. Whereas the celebrated Clausius derived from theoretical thoughts on light reflexion114 (Clausius 1849a, b, 1863) that “diese Körperchen nicht massive Kügelchen seyn können” [these corpuscles can not be massive globules], Berger agrees with the opinion of Brücke (1853)115 who shows that . . . die Lichtstreuung mit der Teilchengröße rasch abnimmt, und dass es sich hiernach nur auf die Kleinheit und die gleichförmige Vertheilung der Dunstkörperchen, nicht aber auf ihre Beschaffenheit schließen lasse [. . .the light reflexion decreases rapidly with the particles size,

113 I only found that he was a teacher at the Selectenschule (Catholic senior citizen school and progymnasium). Dr. Berger published some papers in “Annalen der Physik” on Leidenfrost effect (1863 and 1872), freezing of water and hail (1865) and “forest and weather” (1863). 114 In that time nothing was known on scattering; today we know that UV radiation is scattered on air molecules (Rayleigh scattering) and giving the “blue sky” (the more clean and dry the more blue, as also recognized by Clausius), whereas the red light is scattered on dust particles (Mie scattering). Clausius (1849a, p. 188) assumed that reflexion does not take place on “undurchsichtigen, in der Atmosphäre schwebenden Körperchen” [non-transparent, in air floating corpuscles] but these color appearances can only be explained through “ . . . die reflectierenden Körper dünne Platten mit parallelen Grenzflächen sind. Dadurch werden wir fast mit Nothwendigkeit zu der Annahme von feinen Dampfbläschen geführt, die selbst bei klarem Wetter noch in der Luft schweben und die Reflexion verursachen” [ . . . the reflecting bodies are thin plates with parallel interfaces. This will be lead to the assumption of fine vapor vesicles that float even at calme weather in air and causes reflexion]. Deflection, reflexion, and scattering on small droplets is physically very difficult to describe. Johann Silberschlag (1721–1791) first described the “Brockengespenst” in 1780. This German word has been accepted as technical term in meteorology [English: Brocken spectre, Brocken bow, mountain spectre or glockenspectre; French Spectre de Brocken). It is a matter of an optical phenomenon where you see the very enlarged shadow of an observer against a fog- or cloudbank due to back scattering of sun light. Frequently the head of the shadow is sourrounded by colored circles (that is a glory, a system of fine concentric interference fringes). First reports on glory observations are given during a French geodesic expedition to Perud 1737–1739 by the French scientist Pierre Bouguer (1698–1758) and the Spain captain Antonio de Ulloa (1716–1795); Bouguer (1749). Hellmann (1904) points out that this remarkable optic phenomenon has been described already 600 years before by El-Kazwini or al Quazwini (1203–1283), quadi of Wasit (today in Iraq) in his book “Cosmography.” 115 In response, Clausius (1863) again repeats his argument from 1849 and emphasized the existence of haze spherules. However, it must be considered that these “haze spherules” would be very small (λ/4) to cause the blue sky according to Clausius, i.e., they can not be cloud nor fog droplets. Such size (around 0.1 µm) corresponds to condensation nuclei, which are not vesicles.

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and that’s hereafter one can conclude only on the smallness and uniform distribution of the fog corpuscles but not on their constitution].

Berger (1863, p. 466) writes further (it reads like a modern theory on nucleation): Der Wasserdampf schlägt sich an jedem Körper von genügend niedriger Temperatur nieder, mag dieser eine Fensterscheibe oder ein Stäubchen seyn. Warum sollte er sich nicht ebensogut und auf dieselbe Weise an erkalteten Lufttheilchen niederschlagen? Fallen erkaltete Lufttheilchen in einen gesättigten Raum herab, so wird dadurch also nicht eine Ausscheidung des Wasserdampfes bewirkt werden, sondern er wird sich an denselben condensieren [The water vapor condenses on each body of sufficient low temperature, either it is windowpane or a dust particle. Why it should not deposit in the same way on on air particles that are cooled down? Fall cooled down air particles116 into a saturated space, so it does not become a separation of the water vapor but it will condense onto them].

After Saussure, the Britisch physiologist Augustus Volney Waller (1816–1870) was the first who observed fog droplets with a microscope and who concluded based on optical reasons that they are drops and not vesicles (Waller 1847). Diness (1879) estimated in England by use of a microscope the diameter of droplets in dense fog in the range 16–127 µm. Adolph Richard Aßmann (1845–1918) carried out several studies on Mt. Brocken on microphysics of clouds and estimated the droplet diameter in the range 6–35 µm in 1884/1885. Aßmann finalized the dispute over the nineteenth century about the “vesicle theory” by careful microscopic examinations of single droplets (Aßmann 1885). However, the findings just before that vapor condenses in air only onto solid (hygroscopic) particles counteracted the believe that droplets are cavernous inside. Aßmann also did try to estimate the size of the residue (i.e., the condensation nucleus) after evaporation of a cloud droplet under the microscope – because of the limited resolution of the microscope he did not see any residual and concluded, therefore, that it must be smaller than 1 µm (its size is really in the range 0.1–0.5 µm). Because of the general urge to scientific education and the fascination, weather phenomena and exploring the atmosphere, exerted to many people in the nineteenth century, many books have been published to that issue (but nothing beyond the scientific knowledge already described by Kämtz): Anonym (1847), Houzeau (1851),117 Reimann (1857),118 Zimmermann (1865, 1880),119 Mangin

116 It remains unclear what Lufttheilchen [air particles] means; we can speculate that simple air (as an air parcel) is meant or even “particles in air” (dust). 117 Jean-Charles Houzeau (1820–1888), Belgium astronomer – not to confuse with the French chemist Jean Auguste Houzeau (1829–1911). 118 Ernst Julius Reimann (unknown biographic data) 119 W. F. A. Zimmermann - Pseudonym of Carl Gottfried Wilhelm Vollmer (1797–1864), German author.

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(1866),120 Reclus (1874),121 Flammarion (1874, 1888), Giberne (1890),122 Umlauft (1891), Marcuse (1896).123 The French astronomer and author of many popular scientific books, Camille Flammarion (1842–1925) not yet adopted in his book “l’atmosphère” (1888)124 the new insight that fog and clouds form only in presence of condensation nuclei and that they not consist from vesicles but from droplets (likely because the text from the first edition in 1874 have been not revised). The Austrian geographer and teacher Friedrich Umlauft (1844–1923) probably has first published the new views in his textbook (Umlauft 1891, p. 244): Die Wasserdämpfe scheiden sich in Form von ganz kleinen Wasserkügelchen aus, die in der Luft frei schweben. . . Zur Nebelbildung scheint die Anwesenheit von Staubtheilchen in der Luft notwendige Voraussetzung zu sein [Water vapors deposit in form of small water globules, which freely float in air. . . For fog formation the presence of dust particles in air seems to be essential].

The German chemist Hans Blücher (1867–1927) presents a modern definition in his book “Luft” (Blücher 1900, p. 62): . . .die Nebelbildung ist Kondensation von Wasserdampf aus der Atmosphäre an festen Körpern (Staubteilchen), die in der Atmosphäre selbst schweben [. . . formation of fog is condensation of water vapor from the atmosphere onto solid bodies (dust particles), which float in the atmosphere].

In contrast to temperature, air pressure, humidity, wind, and rain, which can only be estimated by using of measurement instruments, fog has been recorded (until end of the twentieth century) only by personal observation of the visibility at daily fixed term values. One can therefore assume that such “atmospheric state” already have been recorded with first weather observations (Hellmann 1883). With the establishing of meteorological networks in many countries125 in the second half of the nineteenth century, days on which fog appeared were noted. However, only few

120 Arthur Mangin (1824–1887), French author of popular scientific monographs. 121 Jacques Élisée Reclus (1830–1905), French geographer and anarchist. 122 Agnes Giberne (1845–1939), British author. 123 Adolf Marcuse (1860–1930), German astronomer. 124 First edition: Camille Flammarion: L’atmosphère. Description des grands phénomènes de la nature, Paris 1872; 1874 published in English translation and edited by the famous baloonist James Glaisier. 125 The first modern station of so-called 1th order have been established in Munich, Germany in 1846. The first series of observation (over 24 years) begun 1623 in Kassel by the Landgrave Hermann von Hessen-Rotenburg (1607–1658); Hellmann (1883). In 1664 begun the meteorological series of observation at the Parisian Observatory, which is the oldest and longest in operation in the world; unfortunately, the observation journals preserved only since 1785 (Hellmann 1927). A real meteorological network (65 stations) begun 1776 in France through the Société Royal de Médicine, but closed already in 1786.

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scientific articles have been published before 1900, namely on fogs in England and London, for example by Marcet (1889), Clayden (1891), Frederick (1892), Scott (1893, 1896) and Russell (1897). Scott (1893) writes: “It is impossible to obtain any information from our records as to the duration of fogs . . . for the three phenomena of ‘fog,’ ‘mist’ and ‘haze’ . . . there is, as yet, no clear distinction between them”. Scott (1896) notes that fog on the British islands occurs frequently together with strong wind and rain, lasting sometimes up to a month. First attempts to estimate the liquid water content (LWC) of fog have been made by using an aspirator, i.e., to suck air through sulfuric acid or calcium chloride where naturally also the humidity to a large extant have been collected.126 Such first examinations were carried out by the brothers Hermann and Adolph Schlagintweit (1854)127 on Monte Rosa (3,152 m) next to the actual goal, the estimation of the atmospheric carbon dioxide.128 They found 3 g m–3 in dense clouds; but Viktor Conrad (1876–1962), Austrian Geophysicist, comments that they used a wrong volumetric correction (on which Hann (1889) draw attention) so that the “true” value would be 0.4–2.0 g m–3 Conrad (1901). Diness (1879)129 found in London fog at low temperature with 0.7 g m–3. William Henry Dines (1855–1927) argued that one should not be quick to attribute increased mortality during the winter quarter to reduced temperatures, but rather to increased crowding and a heavily polluted atmosphere (Dines 1894). While the cold was a general event (affecting all cities and towns around London), the fogs and the spikes in mortality were not; they occurred only in London. Eberhard Fugger (1842–1919) found in Salzburg in fog 1.2–3.4 g m–3 (unpublished and cited by Conrad 1901). Conrad (1901), who first applied a method for exact LWC estimation (well described in Köhler 1926) on different mountains, such as Schneeberg (1,884 m), Schafberg (1,798 m), and Hohen Sonnblick (3,106 m), found LWC within the range 0.3–4.6 g m–3; Köhler (1926) corrected these values down. The nineteenth century ends with the knowledge on the essential presence of cloud condensation nuclei for water vapor condensation and the fact that fog and clouds consist from droplets. The role of dust particles in fog formation describes Gustave Léonard van der Mensbrugghe (1835–1911): “aqueous vapor condenses in the air only in the presence of solid particles around which the invisible vapor becomes a liquid’’ (Mensbrugghe 1892). It follows a summary.

126 The absolute humidity at 100% saturation is between 5 and 10 g m–3 for 0–10° C whereas the liquid water content does not depend from temperature and amounts around 0.3 g m–3 (Möller 2003). 127 Hermann (von) Schlagintweit (1826–1882) and Adolph Schlagintweit (1829–1857), German naturalists and travellers. 128 By using the same methode, they estimated CO2 in the range of 400 to 1,000 ppm – much to high. 129 George Diness (living data unknown) not to confuse with W. H. Dines.

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Clouds – together with fog and precipitation – are surely the most fascinating weather phenomena of our atmosphere being observed by humans since antique eras. A phenomenological understanding of the water cycle was first described by Aristotle. In ancient times, no further ideas on the form and constitution of vapors, fog, and clouds originated. The idea of transmutation (air ↔ water) survived until the end of the eighteenth century, when it was finally rejected by Lavoisier end of the eighteenth century. The milestones in stepwise approach to explain the formation of clouds and rain from the beginning seventeenth until ending nineteenth century are listed here: – statement that atmospheric water is not air by Descartes (1637), – first artificial cloud/fog formation, “bubble theory” (vesicles) by Guericke (1672), – cloud being a water suspension by Le Roy (1751), – first direct observation (walking in) of clouds by Saussure (1783), – first physical theory (no water dissolution in air) by Deluc (1787), – first cloud classification by Lamarck (1802)130 and Howard (1803),131 – first microscopic examination of fog droplet and conclusion that they are not vesicles by Waller (1847), – first collection of fog water for chemical analysis by Baussingault (1854), – the brothers Schlagintweit (1854) estimated first the liquid water content in fog/cloud, – water condenses only on particles by Aitken (1881), – final evidence that clouds consist from droplets and not vesicles by Aßmann (1885), – the London fog was first chemical examined by Cohen (1895). It should be noted that a scientific understanding of phase transfer processes (smelting, boiling, condensing, and freezing) was not before middle of nineteenth century (with development of thermodynamics). Already our ancients separated fog from clouds by the criterion of the altitude above earth surface. Microphysical, there is little difference between cloud and fog droplets; however, meteorologically the most important different parameter is the wind speed. Even today, there is no consensus in separation between mountain fog and clouds (Eugster 2008). Our view is that fog is a “fixed” (not moving) cloud such as an orographic cloud (cap cloud). In the twentieth century the following milestones can be listed in physical fog and cloud research (on chemical fog and cloud water research see Section 2.4.8):

130 Jean-Baptiste Pierre Antoine de Monet, Chevalier de Lamarck (1744–1829), French biologist. 131 Luke Howard (1772–1864) was a British manufacturing chemist.

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– Conrad (1901) developed the first exact method for LWC estimation, and Köhler (1926) carried out the first “exact” LWC measurements, – first patent for fog dissipation by Archenhold (1913),132 – Köhler (1923) first describes the nucleation process, – first fog classification by Willett (1928),133 – Veraart (1931)134 first carried out experiment in cloud seeding by using of dry ice; Schaefer (1946)135 provides the theoretical explanation, – Vonnegut (1947)136 studied nucleation of ice formation by silver iodide, – Findeisen (1932) measured size and number of fog droplets, – Köhler (1936) described the growth of condensation nuclei, – Findeisen (1938) presents a theory of precipitation formation, – Houghton and Radfort (1938a, b) first carried out extended chemical analysis of fog and estimated droplet sizes distribution, – A first sophisticated instrument (FSSP-100) for estimation of droplet size distribution and one (PVM-100) for LWC was introduced by Knollenberg (1981) and Gerber (1984), respectively.

2.1.3.3 Alchemy: airs and gases An accurate knowledge . . . of the Air, by which its actuating properties may be understood, is absolutely necessary for the Chemist, Physician, and natural Philosopher (Boerhaave 1735, p. 317).

Recall that air and water had been regarded as “elements” convertible into each other since Aristotle. The statement by René Descartes, the French philosopher, mathematician, scientist, and writer, that water vapor is not (atmospheric) air, is remarkable as this was 15 years before the introduction of the term “gas” by van Helmont. The gaseous substances that were observed in alchemical experiments were named fumes, vapors, and airs. Atmospheric air (called common air) was still regarded as a uniform chemical substance (Figure 2.1). Whereas the (qualitative) description of air quality using terms such as: clean [reine], foul [unreine], good [gute], bad [böse], stuffy [stickige], corrupted [verderbte], cold [kalte], cool [kühle], and warm [warme] have been used verbally since Biblical

132 Friedrich Simon Archenhold (1861–1946), German astronomer in Berlin. Likely one of the last recent patents in fog dissipation using dry ice (cold fog) and water ice (warm fog) blasting are by Möller et al. (1999b, 2001). 133 Hurd Curtis Willett (1903–1992), American meteorologist, known for developing techniques in weather forecasting. 134 August Willem Veraart (1881–1947) was a Dutch amateur meteorologist. 135 Vincent Joseph Schaefer (1903–1993), American meteorologist and chemist. 136 Bernard Vonnegut (1914–1997) was an US atmospheric scientist, 1967 professor at University Albany.

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Fig. 2.1: Alchemistic signs of “Air (as one of the 4 elements)”; after Geßmann 1922, Table XXXVIII.

times, different kinds of air [Luftarten or Luftgattungen] have been discovered first by alchemists. This was not yet a complete analysis of atmospheric air but the identification of the formation of different gases (called airs at that time) as a result of alchemistic experiments. The term gas was still unknown. Obviously there was a requirement to distinguish the vapors137 and airs found in chemical experiments from (atmospheric or common) air through a new term. It is notable that at that time, atmospheric air was still regarded as a consistent chemical body. The medieval physician and alchemist Theophrast von Hohenheim,138 who was known under the name Paracelsus, in that sense, called the “airspace,” chaos. Air and chaos were a synonym to him (Loewe 1936). The primordial Greek term χάος denotes139 an empty space and the beginning. However, emptiness cannot be identified with nothing. According to ancient cosmogony, after which the world was born from the chaos and, hence, chaos was creativity; having all opportunities (Genz 1994). From the primordial chaos (or mysterium magnum) arose through “separatio” the four

137 See also Section 1.2.4.2: Dämpfe, Dünste and Lüfte, also Fumus, Vapour, Exhalatio; Old High German: dampf; Middle High German: tampf; Danish, English, Dutch, and Low German: damp; Old North German: dampi; Polish: dim. It belongs to the strong verb dimpfen (reek, smoke). It is related with Old High German daum, Middle High German toum and Austrian Dam (Ausdünstung) and Swedish Dam (flushy cloudy dust). 138 Paracelsus, practically Philippus Aureolus Theophrastus Bombastus von Hohenheim (1493–1541). The sixteenth and seventeenth century is therefore considered as the iatrochemical era. 139 In ancient poetry also used for “airspace.”

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elements: water, fire, soil, and air. These elements caused further emergence and subsequent decomposition140: Dis mysterium magnum ist ein muter gewesen aller elementen und gleich in solchen auch ein grossmuter aller stern, beumen und der creaturen des fleischs . . . und ein element ist ein muter, deren seind vier, luft, feur, wasser, erden; aus den vier mutern werden alle ding geboren der ganzen welt. . . [This mysterium magnum was a mother of all elements and contemporary a grant mother of all stars, trees and creatures of bodies . . . and an element is a mother, of that are four, air, fire, water, soil; from these four mothers all things of the whole word were born. . .].141

The great achievement of Paracelcus was to use alchemy to search for medical substances. Perhaps he was the first who considered substance-forming properties to be more chemical then philosophical, creating a preconception of chemical elements (however, only introduced scientifically by Boyle). Vital processes, telluric and cosmic physics (for Paracelsus, the atmosphere acts as the special matter “chaos”) had already been connected through substantial relationships142 (Bugge 1929, p. 96). Van Helmont was the first who distinguished different airs or gases, being relates to atmospheric air (gas ventosum – common air) but recognized not identical due to different properties. He deals with gas in his treatise De flatibus in which he speaks of gas ventosum, gas pingue, gas siccum, gas fuliginosum sire endemicum, gas sylvester (sive incoercible, quod in corpus cogi non potest visibile),143 gas sulphureum, gas uva, gas vini, gas musti, gas flammeum, and more; some of which are really the same. He was the first clearly to realize the production of gas in various chemical processes (Helmont 1662, p. 106; Leicester and Klickstein 1952, p. 25): Suppose thou, of 62 pounds of Oaken coal, one pound of ashes is composed: Therefore the remaining 61 pounds, are the wild spirit, which also being fired, cannot depart, the Vessel being shut. I call this Spirit, unknown hitherto, by the new name of Gas, which can neither be constrained by Vessels, nor reduced into a visible body, unless the seed being first extinguished.

140 In the lifetime of Paracelsus only very few books have been published. Only since 1560 have (partly in alchemistic compilations) Paracelsus’s essays (several Hundreds) been published as “Liber Natura, sive Chaos veterum; generalem metallorum generationem, etc. demonstrans.” In: Liber vexacionen. John Stacy (1656) pp. 83–89 (Glasgow University, bibliography MS Ferguson 237). 141 Achter Theil der Bücher und Schriften / des Edlen / Hochgelehrten unnd Beiwehrten PHILOSOPHI unnd MEDICI, PHILIPPI THEOPHRASTI Bombast von Hohenheim / Paracelsi genannt: Jetzt auffs new auß den Originalien / und Theophrasti eygener Handschrift / so viel derselbigen zubekommen gewesen / auffs trewlichst und fleissigst an Tag geben: Durch Iohannem Huserum Brisgoium, Churfürstlichen Cöllnischen Rath und Medicum. In diesem Tomo (welcher als Erstes unter den Philosophischen) werden solche Bücher begriffen / darinnen fürnemlich die Philosophie de Generationibus & Fructibus quatuor Elementorum beschrieben wirde. Joh. Wechels Erben, Franckfort am Meyn (1603), 240 pp. 142 However, he also retains the three basic substances in alchemy: sulfur, mercurius, and sal, which corresponds to the physical phenomena of combustibility (oiliness), liquefaction (evaporation) and solidification (solidity). 143 Hoefer, J. C. F. (1843) Historie de la chemie. Tome 2, Chez L. Hachette, Paris, p. 145.

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Helmont observed also the Gas of Wines when grapes and other fruits are fermented and a gas from burning gun-powder (saltpeter, sulfur, and coal). Van Helmont says more than once that he was the “inventor” of gas (halitum illum Gas vocavi), which Paracelsus was ignorant of (ignoravit . . . quidditatem Gas, meum scil. inventum), and there is no doubt that Paracelsus had no such ideas on gases as he. Van Helmont definitely distinguishes gases from condensible vapors and from air, and from one another. He says that gas is composed of invisible atoms which can come together by intense cold and condense to minute liquid drops (atomi Gas, ob nimiam exiguitatem invisibiles . . . frigori excessum, in minimas rursus guttulas concidant), Partington (1936). As before mentioned, contemporaries such as Otto von Guericke and Robert Boyle did not believe that (common) air is an element. From observations on reducing the air volume while combustion, calcinations, and animal breathing it was right conclude that some part of air must be responsible for such processes. Moreover, from the weight increase during metal calcinations it was concluded that either from the fire or the air some material must be added. This was also observed by other scientists such as Jean Rey (ca. 1590–1645), Samuel Cottereau Du Clos (1598–1685)144 and Henri-Louis Duhamel du Monceau (1700–1782), all French chemists. The meaning of different terms in different languages (e.g., French, English, and German) has been changing over time; the words were used in slightly different senses by various scientists. There was obviously a need for a new word to name and distinguish the laboratory airs (i.e., gaseous substances) from atmospheric (common) air. The new word was proposed by van Helmont in his posthumously published book, Ortus medicinae, i.e., initia physicae inaudita (Amsterdam 1652, p. 86): hunk spiritum, incognitum hactenus, novo nomine Gas voco [I call this entity, unknown hitherto, by the new name of Gas], and ideo paradoxi licentia, in nominis egestate, halitum illum Gas vocavi, non longer a Chao veteran secretum; in following the full English text from Helmont (1662, p. 69): But because the water which is brought into vapour by cold, is another condition, than a vapour raised by heat. Therefore by the Licence of a Paradox, for want of a name, I have called that vapour, Gas, being not far severed from the Chaos of the Auntients. In the mean time, it is sufficient for me to know. That Gas, is a far more subtile or fine thing than a vapour, mist, or distilled Oylinesses, although as yet, it by many times thicker than Air.145

Johann Christoph Adelung (1732–1806) explains why this new term is necessary (Adelung 1796, p. 425): . . .dass unsere Naturkundige ein schicklicheres Wort, welches nicht so sehr das Gepräge der Alchymie an sich hätte, ausfündig machten [. . . that our natural scientists might find a seemlier word, not so much having the imprint of alchemy].

144 For Du Clos was chemistry the science of substances, the physics of qualities (Franckowiak 2011). 145 The following phrase is very alchemistic and fully unclear: But Gas it self, materially taken, is water as yet masked with the ferment of Composed Bodies.

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Adelung believed that Helmont had derived the word “gas” from the Dutch Geest (ghost). Carbon dioxide, hitherto called spiritus sylvestris (wild spirit), was renamed by Helmont as “gas sylvestre.” There are other ideas on the origin of the word gas, however. Paracelsus (1493–1541) denoted the “atmosphere” to be Chaos – air and chaos were synonymous for him. The Greek word χάος denotes both an empty sphere and the initiation. Emptiness is not synonymous with nothing because the Greek philosophers stated that the world is born from chaos or, in other words, the chaos is creative of life (Genz 1994). Today, there is also the belief that Helmont introduced the term gas from the term “chaos” (the essays by Paracelsus were well known to him), according to Dutch pronunciation; omitting the “o” and pronouncing “ch” like “g” (Egli 1947). The Flemish text has: Gas-maeckinge: uyt bet water eenen gas (dat is eenen griexschen water-chaos), Partington (1936). However, it is also possible that the term is derived from Geist146 (ghost or spirit, Lat. spiritus), which at that time was common for gases and airs in alchemy. Kopp (1847, Vol. 3. p. 178) writes: Woher das Wort zunächst gekommen ist, weisz man nicht; nach Juncker, den bekannten Schüler Stahl's, soll es aus Gäscht, dem bei der Gährung entstehenden, Schaume, abgeleitet sein [Where the word originally comes from, we do not know; according to Juncker, the well-known scholar of Stahl, it should stem from Gäscht, the foam forming during fermentation].

Lavoisier writes in his work “Opuscules physiques et chimiques” (2e éd., Paris, 1802, p. 5): Gas vient du mot hollandais Ghoast, qui signifie Esprit. Les Anglais expriment la même idée par le mot Ghost, et les Allemands par le mot Geist qui se prononce Gaistre. Ces mots ont trop de rapport avec celui de Gas, pour qu'on puisse douter qu'il ne leur doive son origine.

In Deutsches Wörterbuch, Vol. 4 (1897), the term gas is defined as follows: Gattungsname für Luftarten, oder luftförmige Flüssigkeiten wie die Wissenschaft den Begriff bestimmt, die sich von den Dämpfen unterscheiden durch die Unmöglichkeit oder Schwierigkeit sie in tropfbare Gestalt zu bringen; auch von der gewöhnlichen Luft sind sie verschieden und wurden im Gegensatz zu ihr zuerst erkannt, während dieselbe jetzt selber von der Wissenschaft als gasförmig, als ein Gasgemenge bezeichnet wird [Common noun for kinds of air or aerial liquids as science defines that term, distinguished from vapors through the

146 Dutch and Low North German: geest; Anglo-Saxon: gâst (also Old Friesian) gæst. The origin is seen in whiff [Hauch] and breath [Atem]. Luther writes (Hiob 4, 9): der himel ist durchs wort des herrn gemacht und all sein heer durch den geist seines munds [By the word of the LORD were the heavens made; and all the host of them by the spirit of his mouth]. Insofar as the synonymy between breath, spirit, vapour, wind, and kinds of air is given.

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impossibility or difficulty to bring them into a drop-able form; but also that they differ from common air and in contrast to it they have been at first perceived, while the same now is described by science gaseous, as gaseous mixture].

Helmont is said to have called (after Adelung 1796) common air [gemeine Luft] a gas, or more specifically, gas ventosum. After Gehler, the terms gas atmosphericum and Dunstkreisluft [aerial spherical air] have been used synonymously.147 In Krünitz (1779, Vol. 16, p. 404) it is written: Das Gas nennen Helmont und andere Chemiker die unsichtbaren flüchtigen Theile, welche von selbst aus gewissen Körpern ausdampfen . . . z. e. die Dämpfe der in eine spirituöse oder in eine faulige Gährung gerathenen Materien, tödtliche Dämpfe aus brennenden Kohlen, die Schwaden in Bergwerken, u.s.w., und selbst den spiritus rector gewisser Substanzen, z. e. des Bisams, denn es wurde zuerst unter die spiritus oder Geister der Dinge gezählt [As gas, Helmont and other chemists call the invisible volatile parts that escape spontaneously from certain bodies. . . e.g., vapors of a spirituous or in fermentation processing matter, deadly vapors from burning coals, damp in mining etc., and even spiritus rector of certain substances, e.g., that of musk because it was called first among the spirits and ghosts of things].

However, for the next hundred years after Helmont, the term gas was not used by others. Robert Boyle describes in his book “AN Experimental Discourse Of some UNHEEDED CAUSES OF THE Insalubrity and Salubrity OF THE AIR (1690) several properties of atmospheric substances (called effluvia, exhalations, damps, corpuscles, smoak) concerns air quality, diseases, and chemical operations. He writes (ibid., pp. 1–3): The insalubrity and salibrity of the Air depends, . . . from Effluvia. . . some are almost constantly or daily sent up into the Air, and those I call Ordinary Emissions; and others. . . Extraordinary Emissions;. . . at stated times, and so deserve the title of Periodicals, or else uncertainly, . . . irregular.

In a certain sense Boyle writes on air chemical actions (ibid., pp. 64–65) when different “subterraneal exhalations” in the air “fit to associate with them” making them more hurtful: This may be somewhat illustrated by considering, that the spirituous steams of Salt-peter are not wont sensibly to work on Gold, nor yet the spirituous Parts that the Fire raises from Sal-armoniac; and yet when these two sorts of Particles convene, there results from their Coalitions certain Corpuscles of a new nature, that compose the liquor Chymists call Aqua Regis.

147 Humboldt writes on kinds of air [Gasarten] in “Versuche über die chemische Zerlegung des Luftkreises” (Braunschweig, 1799): “Doch ist im Buche selber noch immer mehr von Luft als Gas die Rede” (Deutsches Wörterbuch) [Experiments on chemical decomposition of air . . . . However, in this book, self is more the term of air than of gas].

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This is not only a statement of “gas-to-particle conversion” in modern terms but also an expression of a synergistic effect (ibid., p. 65): By Analogy to this we may conceive, that sometimes the Subterraneal Effluvia may find the Air already impregnated with such Corpuscles, that by associating themselves therewith they may compose Corpuscles far more capable, than themselves were whilst apart, of having ill Effects. . .

A few pages later Boyle likely gives the first mention of vegetation damages in print (ibid., p. 67): On which occasion, I remember, that a great many Trees in some Land that belongs to me, having been suddenly much endamag’d. . . Leaves were some moiré, some less blasted:. . . that some Arsenical or other corrosive or poisonous Exhalations, being suddenly emitted from the Subterraneal parts into the Air. . .

Furthermore, Boyle writes on “self-cleaning” the air (ibid., p. 71): . . . Subterraneal Bodies, be sent up into the Air, store of Expirations of another kind, which meeting with those that formerly impregnated it, may either precipitate them, and so free the Air from them; or by other operations on them, and sometimes even by Coalitions with them, so alter their nature as to disable them from doing any farther mischief.

Boyle, however, had the wrong believe (that lasted still further 150 years, the theory of miasma) that diseases such as pestilence and fever are caused by “subterraneal effluvia”. In his book “General History of the Air” (1692)148 Boyle describes the formation and study of different kinds of air but he writes nothing on its realization; he separated between artificial and performed air (aër artificial vel factitius). Here are some phrases (Boyle 1692) from the chapter “TITLE XI. Of Salts in the Air”: Amongst the effluviating Substances of the Terraqueous Globe, there are, as I have declared in another Paper, huge quantities of common or Marine Salt, besides Nitrous, Aluminous, Vitriolate, and perhaps other kinds of Salts. (ibid., p. 40) . . . by those Vulcans, that have open Vents to discharge their Fumes into the Air; by those numerous Fires which burning in our Chimnies, produce much saline Smoak. . . I am prone to think, that the saline Particles of the Atmosphere are not all of one sort, but that there may be three or four differing kinds of Aerial Salts. (ibid., p. 41) . . .to the volatile Nitre of the Air; these Spirits being so far from being refreshing to the Nature of Animals, that they are exceeding corrosive. (ibid., p. 42)

148 This posthumously published work “The General History of the Air, Designed and Begun by the Honble. Robert Boyle Esq.” (Awnsham and John Churchill, London, 1692, 259 pp.) on the nature of gases, seen through the press by Boyle’s friend John Locke (1632–1704) and containing some of Locke’s own early meteorological observations.

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Besides the hitherto-mention'd kinds of Salts, it seems not improbable to me, that the Air (especially about great Towns, and some other particular Places) may be impregnated with volatile Salts, that are of a Nature contrary to Acids. (ibid., p. 44) . . . not only in the parts of Animals, but also in those of many Vegetables, that Putrefaction may either extricate or produce volatile Salts. (ibid., p. 45) [Boyle means “Spirit of Hartshorn,” i.e. ammonia] . . .differing kinds of Salts, as Nitrous, Salino-Sulphureous, &c. that we have shewn may be met with in the Air, some guesses may be made in a short time of this or that Salt. . .. (ibid., p. 52)

Ramsay (1907) believed that having carried out such experiments, the composition of air had been discovered hundred years before. However, already 100 years earlier, Fischer (1802)149 reviewed that Boyle (and other contemporaries) were still too much oriented on finding philosopher’s stone while carrying out skillful experiments and gaining valuable observations but did overlooking the real truth [ . . . die eigentliche Wahrheit, die oftmals so schön hervorleuchtete, übersahen] (Fischer 1802, p. 187). As already mentioned, the terms Luft [air] and Gas [gas] have been used in parallel later on but it was spoken also in the form of Luftarten, Luftgattungen [kinds of air] and luftförmigen Stoffen [aerial substances]. Until the end of the nineteenth century, known types of airs (gases) have been subdivided into two main classes, which support combustion and breathing (einatembare Luftarten – inhalable airs) and those which fade light and kill animals (mephistische Luftarten – mephitic airs). Among the former are included common air and dephlogistigated air (oxygen), which does not allow further subdivision. The second class (mephitic) is subdivided into inflammable and noninflammable categories and then subdivided again into those mixable with water (in other terms, water soluble) and those that cannot be mixed with water (Table 2.2).

2.2 Discovery of air chemical composition 2.2.1 A brief history of the discovery of gases Leopold Gmelin (1788–1853), German chemist in Heidelberg, who edited the first modern compilation of chemistry, wrote in his Handbuch der theoretischen Chemie (Gmelin 1827, Vol. 1, p. 134): Die Zahl der bis jetzt bekannten einfachen wägbaren Stoffe beträgt 48; hiervon sind 38 metallischer Natur; die übrigen 10 erscheinen ohne metallisches Ansehen, theils gasförmig, theils in fester Gestalt. Sie sind die wichtigsten, welche durch die Mannigfaltigkeit ihrer Verbindungen die Einförmigkeit der Metalle aufheben [The number of hitherto known simple ponderable

149 Johann Carl Fischer (1760–1833), mathematician and physicist in Jena and Greifswald, wrote the first “history of physics” in several volumes (1801–1809).

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substances amounts 48; thereof are 38 of metallic nature; the remaining 10 appear without metallic view, partly gaseous, partly in solid form. They are to most important, which suspend the uniformity of the metals through the great diversity of its compounds].

In 1817, these 10 nonmetallic elements included H, B, C, N, O, F, P, S, Cl, and I (only Br was not yet known); with the exception of the rare boron,150 all other elements have been treated in this “Chemistry of the Climate System” (Table 2.4).

Tab. 2.2: Historic terms of gases (airs, kinds of airs, vapors) in English, German, French, and Latin; note instead of air (Latin aer or āēr and aër) also gas (French gas) and instead of Luft also Gas is used (in early alchemistic times “spirit” [in German Geist] have been used as general term). The general terms in Latin are listed in table 2.3. After Macquer (1788), Gehler (1787), Strohmeyer (1808)a, and Coxe (1808)b. Note that the formulas (chemical composition of molecule) where almost unknown or uncertain before 1800. Note that in historical works only the spelling (de)phlogistigated occurs, whereas in moderns dictionaries (de)phlogisticated is used; in Latin, phlogisticum. Here, I only use the historic spelling, but phlogistic and anti-phlogistic. formula

term

O

oxygen gas, good air, pure air, vital air, fire air, dephlogistigated air, empyreal air, factius air Oxygengas, dephlogistisirtec Luft, dephlogistisirtes Gas, Lebensluft, gute Luft, reine Luft, einathembare Luft, entbrennbare Luft, brennstoffleere Luft, Feuerluft, Lebensluft, künstliche Luft, reine künstliche Luft, wahre künstliche Luft, Empyrealluft, säurezeugendes Gas, säurendes Gas, Sauerluft, Sauerstoffgas, respirable Luft, Mayows luftiger Salpetergeist gaz oxygène, air déphlogistiqué, air defeu de Scheele, air vital, air pur gas oxygenium, aër dephlogistigatus, gas dephlogistigatum, aër igneous, aër vitalis, aër purissimus, aër verus factitius, spiritus nitro- aëreous Mayowill

HS

sulphuretted hydrogen gas, hepatic air, heptic air, inflammable sulphureous air, sulphuretted inflammable air schwefelhaltiges Wasserstoffgas, schwefliges Wasserstoffgas, Schwefelgas, hepatische Luft, Leberluft, stinkende Schwefelluft, Schwefelleberluft, geschwefeltes Wasserstoffgas, gasförmiger sulphurisirter Wasserstoff, Hydrothiongas, hydrothionsaures Gas, Hydrothion gaz hydrogène sulfuré, gaz hepatique, air hepatique, air puant du soufre gas hydrogenium sulphuratum, gas hepaticum, aër hepaticus, mephitis hepatica

150 Boron is found to around 90% gaseous as H3BO3 and 10% particulate in the atmosphere; volcanic exhalation are likely in the form of BF3, which fast hydrolyse into borate. First Gast and Thompson (1959) proposed the sea as source, and after a long debate (Nishimura and Tanaka 1972), Fogg and Duce (1985) confirmed the sea as a main B source (about 80%), other sources are anthropogenic (coal combustion) and volcanic. In rainwater, B is within the range 0.3–15 µg L–1 (Fogg and Duce 1985, Demuth and Heumann 1999).

2.2 Discovery of air chemical composition

75

Tab. 2.2 (continued ) formula

term

NH

ammonia gas, ammoniacal air, alkaline air, volatile air, spirit of hartshorn Ammoniacgas, gasförmiges Ammoniac, ammoniacalisches Gas, flüchtige alkalische Luft, laugenartige Luft, alkalische Luft, urinöse Luft, laugensalzige Luft, flüchtig-alkalische Luft gaz ammoniaque, gaz ammoniacal, gaz alcali-volatil, gas alcalin, esprit alcalinum volatile gas ammonium, gas ammoniacale, aër alcalinus, mephitis urinosa, gas alkalin volatil

PH

phosphuterred hydrogen gas, phosphorated hydrogen gas, phosphorized hydrogen gas, phosphoric inflammable air, phosphoric gas Phosphorwasserstoffgas, Phosphorluft, phosphorische Luft, gephosphortes Wasserstoffgas, phosphorisirtes Wasserstoffgas, phosphorhaltiges Wasserstoffgas, gasförmiges phosphorisirter Wasserstoff, entzündliches Phosphorgas, phosphorischhepatische Luft, Phosphorleberluft air phosphorique, gaz hydrogène phosphorisé gas phosphoricum, mephitis phosphorica, gas hydrogenium phosphorisatum

HFd

fluoric acid gas, gaseous fluoric acid, fluoracid gas, acid of spar, acid of sparry, sparry acid gas fluʃssaures Gas, gasförmige Fluʃssäure, spathsaure Luft, spathsaures Gas, spathgesäuertes Gas, fluʃsspathsaure Luft, Fluʃsspathgas, luftige Fluʃsspathsäure gaz acide fluorique, air acide spathique gas acidum fluoricum, acidum fluoricum gas fluoris mineralis, gas acidum spathosum, aer acidus spathosus, mephitis fluoris mineralis

Hr

hydrogen gas, air inflammable, inflammable air, phlogiston of Kirwane Wasserstoffgas, wassererzeugendes Gas, wasserbildendes Gas, inflammable Luft, brennbare Luft, entzündbare Luft, entzündliche Luft, brennende Luft, Brennluft, gemeine brennende Luft, brennbares mephitisches Gas, Kirwans Phlogiston gaz hydrogène, gaz inflammabile, phlogistique de Kirwan aer inflammabilis, mephitis inflammabilis, cas carbonum, gas pingue (Helmont), gas inflammable, aer inflammabilis.

CH

marsh gas, swamp gas, carburetted hydrogen Sumpfluft, schlechte Luft gaz palustre, gaz inflammable des marais gas pastu paludis virecta

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Tab. 2.2 (continued ) formula

term

VOCf

carburetted carbon gas, carbonaceous inflammable gas, hydro-carbonate gas Kohlenstoffwasserstoffgas, kohliges Wasserstoffgas, kohlehaltige endzündbare Luft, schwere brennbare Luft, ölbildendes Gas gaz hydrogèn carburé, gaz inflammable charbonneux, gaz olefiant, gaz inflammable mephitisé gas hydrogenium carbonium

CO

carbonic acid gas, fixed air, mephitic air, acid air, acid of aerial, calcareous gas, acid of chalk, acid of charcoal, gas sylvestre, air fixe, factious air, air of Hales kohlenstoffsaures Gas, gasförmige Kohlenstoffsäure, kohlengesäuertes Gas, Kohlensäure, fixe Luft, Luftsäure, luftsaures Gas, Sauerluft, Kalkgasg, Kreidensäure, kreidensaures Gas, wildes Gas, wilder Geist, Gährungsluft, Weingas, weinigtes Gas, weinigter Schwaden, Mostgas, mineralischer Brunnengeist, elastisches Mineralgas, künstliche Luft, feste Luft, Kalksäure, Kalkspathsäure, mephitisches Gas gaz acide carbonique, acide méphitique, gaz méphitique, gaz acide crayeux, air factice, air solide de Hales gas acidum carbonicum, aër fixus, aër fixatus, aer factitius, gas äereum, aër mephiticum, gas calcareum, gas silvestre, spiritus sylvestris, gas vinosum, mephitis vinosa, gas calcareum, gas musti, aër fermentationis, acidula, acidum mephiticum, acidum aëreum, acidum atmosphaericum, acidum cretae

CO

reduced fixed air reduzierte fixe Luft h h

HClk

marine acid gas, gaseous muriatic air, marine acid air, spirit of salt salzsaures Gas, gasförmige Salzsäure, seesaure Luft, kochsalzsaure Luft, luftige Salzsäure, gemeines salzsaures Gas, Salzgas gaz acide muriatique, gaz acide marin, air acid marin gas acidum muriaticum, mephitis muriatica, gas muriaticum, aër muriaticus, aër acidus salinus, gas muriatosum Greniig

Clk

dephlogistigated marine acid (air), oxymuriatic air dephlogistisirte Salzsäure h h

2.2 Discovery of air chemical composition

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Tab. 2.2 (continued ) formula

term

CHCOOH acetic acid gas, acetous air, vegetable acid air essigsaure Luft, gasförmige Essigsäure, Essigluft, vegetabilisch-saure Luft gaz acide acétique, gaz acide acéteux gas acidum aceticum, acetosum, aër acidus vegetabilis, mephitis acetosa SOm

sulphureous acid gas, gaseous sulphureous acid, (volatile) vitriolic acid air, phlogistigated acid of vitriol schweflichtsaures Gas, schwefelsäurichtes Gas, flüchtiges schwefelsaures Gas, schwefelsaures Gas, Schwefelluft, vitriolische Luft, vitriolsaures Gas, luftförmige phlogistisirte Vitriolsäure, unvollkommene Schwefelsäure in Dampfgestalt, luftförmige Schwefelsäure gaz acide sulfureux, gaz acide vitriolique, acide de soufre aëriforme gas acidum sulphurosum, gas acidum vitriolicum, gas acidum sulphureum volatile, aer acidus vitriolicus, acidum vitrioli phlogisticatum aëriforme, mephitis acida sulphuris, gas acido sulfureo

SOm

vitriolic acid air, acid of vitriol, spirit of vitriol (vitriol = sulfate), vitriolsaure Luft, vitriolsaures Gas, flüchtiges schwefelsaures Gas, luftförmige Schwefelsäure, luftförmige phlogistisirte Vitriolsäure, Schwefelluft air acide vitriolique spiritus vitrioli

HNOn

spirit of nitre, acid of nitre, dephlogistigated nitrous air, nitric acid air, acid of saltpetre, septic (nitric) acids Salpetergeist, Salpeterluft, Salpetersäure, Luftsäure, gemeine Salpeterluft, salpetersaure Luft, phlogistisirte Salpetersäure, Salpeterdämpfe acide nitrique, gaz acide-nitreux gas acidum nitrosum, acidum nitri phlogisticum, mephitis acida nitri, spiritus nitri (nitre = KNO and/or NaNO, and nitres = nitrates).

HNOp

acid of nitre, phlogistigated nitrous air, septous (nitrous) acids, septic acid gass salpetersaures Gas, unvollkommene Salpetersäure in Dampfgestalt, dephlogistisirte Salpeterluft, dephlogistisirte Salpetersäure gaz nitreux oxygèné, gaz nitrique, oxide gaseux d’azote h

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Tab. 2.2 (continued ) formula

term

NOn

nitrous oxide, gaseous oxide of nitrogen, gaseous oxide of azote, gaseous oxide of septon, septic gas, nitrous gas, dephlogistigated nitrous gas salpeterartige Luft, salpeterhalbsaures Gas, nitröse Luft, oxydirter Salpeterstoff, salpetrige Luft gaz nitreux oxygèné, gaz nitrique, oxide gaseux d’ azote gas acidum nitrosum, gas acido nitroso, mephitis acida nitri, acidum nitrosum, nitri phlogisticatum

NOn

gaseous nitric oxide, nitrous gas, nitric air, septous (nitric) gas oxydiertes Salpeterstoffgas, gasförmiger oxydulierter Salpeterstoff, gasförmiges Salpeterstoffoxydule, oxydirtes Stickstoffgas,oxydirtes Stickgas, dephlogistisirte Salpeterluft, gasförmige azotische Halbsäure, sauerstoffhaltiges Stickgas, salpetersaure Luft gaz nitreux, air acide-nitreux gas oxydum nitrogenii, gas nitrosum, aër nitrous, mephitis nitri phlogistica

NO

phlogistigated nitrous air phlogistirte salpetrige Luft air nitreux complex h

N

mephitic air, impure air, vitiated air, phlogistigated air, inflammable air, septon, azotic gas phlogistisirte (or phlogistische) Luft, verdorbene Luft, unreine Luft, Stickluft, Stickgas, Salpeterstoff, Salpeterstoffgas, azotisches Gas, Stickstoff, tödtliches Gas gaz ou air phlogistiqué, gaz azotique, azote aër phlogislicatus, aër vitiatus, mephitis aëris phlogistica, gas phlogislicatum, gas azoticum, azoticum

a

Friedrich Stromeyer (1776–1835), German chemist in Göttingen. John Redman Coxe (1773–1864), Scholar, collector, writer, and teacher of materia medica in Philadelphia, USA. c Both spellings have been used: (de)phlogistirt and (de)phlogistisirt. In modern German it is (false) written as (de)phlogistisiert. d Discovered by Scheele in 1773; Priestly observed that fluoric acid gas (HF) corrodes and penetrates common glass. e Richard Kirwan (1733–1812) was an Irish chemist, adherent of phlogiston theory, as described in his 1787 Essay on Phlogiston and the Constitution of Acids, wherein he identified phlogiston with hydrogen; by 1791, however, he seems to have abandoned phlogiston theory in favor of Antoine Lavoisier’s caloric theory. b

2.2 Discovery of air chemical composition

79

Tab. 2.2 (continued) f

Under this substance hydrocarbons (generally organic substances) in modern terms are meant. German spelling of Kalk before 1800: Kalch, e.g., Kalcherde = quicklime (CaO). h Unknown in time when Latin was used for scientific publications. k Hydrochloric acid (HCl) was discovered by the alchemist Jābir ibn Hayyān around the year 800 AD. Scheele discovered in 1774 dephlogistigated muriatic acid (chlorine, later renamed into oxygenated muriatic acid and simply oxymuriatic acid by Kirwan). Humphry Davy (1778–1829) recognized oxymuriatic acid to be an element and gave the name chlorine, derived from the Greek χλωρος (chlōros), meaning green-yellow. HOCl was discovered by the French chemist Antoine Jérôme Balard (1802–1876) in 1834 who gave it the name hypochlorous acid; however, the bleaching properties of solutions of oxymuriatic acid in water were recognized already in the late eighteenth century by Bertollet and others. m SO2 (H2SO3) and SO3 (H2SO4) have not been separated before 1800 (the gas obtained by burning of sulfur and that from concentrated sulfuric acid – oleum). Fourcroy (1790, p. 380) writes “Sulphuric acid, when heated in a retort, soon loses part of its water, a very odorous and penetrating gas is disengaged .. the sulphureous acid gas.” From oleum SO3 escapes (forming again H2SO4 in air) but sulfurous acid gas is that gained from burning sulfur (SO2). n HNO3, NO, and NO2 often confused (the constitution of NO2 was known already around 1790). Bergmann distinguishes between two states of the acid of nitre: dephlogistigated (nitric acid) and phlogistigated (nitrous acid). p It remains unclear whether HNO2 was separated from HNO3 before 1800. r Often confused with CH4 as inflammable air. s Nomenclature introduced by Samual Latham Mitchill: septon = nitrogen, septic acid = nitric acid, septous acid = nitrous acid, septate = nitrate, septite = nitrite, septic gas = nitrous gas, not defined to be NO and/or NOx, septous gas = azotic gas, i.e., nitrogen, gaseous oxide of seption = dephlogistigated nitrous air, i.e., HNO3). Mitchill advocated the new French nomenclature in chemistry (see also Section 1.2.4.1) in America in 1792 (Nomenclature of the new chemistry, New York, 1794); most remarkable is his emphasis the teaching of an anti-phlogistic chemistry. g

Tab. 2.3: Historic general terms of gases in Latin. term

formula

gas acidum acetosum gas acidum fluoricum gas acidum muriaticum gas acidum nitrosum gas acidum regale gas acidum spathosum gas acidum sulfureum gas acidum vitriolicum gas ammoniacale gas hydrogenium sulphuratum gas inflammable gas mephiticum gas nitrosum gas oxygenium

CHCOOH HF HCl NOy (NO, NO, HNO, HNO) HNO + HCl (volatilized aqua regia) HF SO SO NH HS all inflammable gases CO NOx O

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Tab. 2.3 (continued ) term

formula

gas palustre gas phlogisticum gas phosphoricum gas pingue gas siccum gas silvestre gas ventosum gas vinosum

CH N PH H inflammable gas CO common air CO

Tab. 2.4: Discovery of atmospheric relevant trace substances (gases). year

gas

explorer

in air

 / /    /  /  /   

CO H O N Cl SOa NH HCl HSa O HO Ar Ra Kr, Ne, Xe

Helmont and Black Cavendish/Gautier Scheele/Priestley Rutherford Scheele Priestley Priestley /Scheele Priestley Scheele/Berthollet Schönbein Meißner/Schöne Rayleigh Rayleigh and Ramsey Ramsey and Travers

yes no/yes yes yes no no no/yes no no yes yes yes yes yes

a

This gas was already known in the Middle ages.

In the eighteenth century the interest in natural processes generally expanded. Travelers and biologists were interested in describing the climate and its relation to culture and biota, and in the late 1700s chemists began to understand the transformation between solid, liquid and gaseous matter. A fundamental interest in biological processes, such as plant growth, nutrition and respiration among others, stimulated the study of the water cycle and the gas exchange between plants and air (Table 2.5). Nitrogen (N2), oxygen (O2), water vapor (H2O), carbon dioxide (CO2) and rare gases are the permanent main gases in air. With the exception of rare gases, the main composition of air has been discovered in the eighteenth century (Table 2.4). However, the role of water in its changing phases (condensation and evaporation) has been fully understood only in the nineteenth century. Already in the first half of the nineteenth century other gaseous substances had been supposed and later

2.2 Discovery of air chemical composition

81

Tab. 2.5: Milestones in investigation the atmosphere air and discovery of gases. air as an “element”

Anaximenes ( around  BC)

first “bioclimatology”

Hippokrates (ca.  – ca.  BC)

first phenomenology of air

Aristotle (– BC)

air as body

Heron (–)

air as “chaos” and “kinds of air”

Paracelsus (–)

weight of air

Galileo (–)

term “gas”

Helmont (–)

air pressure: vacuum and barometer

Torricelli (–)

pressure decline with altitude

Pascal (–)

combining pressure, volume, and temperature

Boyle (–)

discovery of CO in link with plant growth and combustion

Mayow (–), Hales (–), Black (–), Senebier (–)

discovery of N in air

Rutherford (–)

discovery of O in air

Scheele (–), Priestley (–)

first air analysis (N and O)

Lavoisier (–), Cavendish (–), Gay-Lussac (–), Humboldt (–)

discovery of O in air

Schönbein (–), Houzeau (–), Andrews (–)

“nutrient” from air

Liebig (–)

plant injuries from SO

Stöckhardt (–)

chemical climatology: three zones of air pollution; fields and open country with carbonate and ammonia, ammonium sulfate in suburbs, and acid sulfate and sulfuric acid in town

Smith (–)

sprouts in air

Pasteur (–)

discovery of rare gases in air

Ramsay (–), Rayleigh (–)

first observation of ultrafine particles in air

Aitken (–)

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detected in air. Due to the fact that the concentration of almost all trace gases are orders of magnitude smaller than those of the main gases, only with the development of analytical techniques in the late nineteenth century they were proved to be present in air. Nevertheless, from chemical analysis of rain water constituents it was already in the eighteenth century concluded on “foreign substances” in air. It is important to note that all trace species mentioned and discovered or assumed to be in air were believed to be natural or, in other words, substances with a (at that time still unknown) special function in nature. The assimilation of gases and the uptake of nitrogen compounds dissolved in water by plants and the decomposition of dead biomass as source of gases led to a first understanding of matter cycles by early agricultural chemists (e.g., Knop 1868). In the second half of the eighteenth century, air was found to consist of two different constituents, maintaining respiration and combustion (O2) and not maintaining it (N2). The discovery of nitrogen is generally credited to Rutherford whose Dissertatio Inauguralis de Aero Fixo Dicto, aut Mephitico (On Air said to be Fixed or Mephitic) was published in Edinburgh in 1772. Seventeen years after Black’s dissertation on “fixed air” (CO2), just before Priestley’s (and Scheele’s) discovery of “good air” (O2), Rutherford conducted experiments where he removed oxygen from air through burning substances (i.e., charcoal) and afterwards carbon dioxide by absorption with lime; the rest (nitrogen) he denoted as “phlogistigated air,” despite the fact that it was not flammable. Priestley wrote in 1771 about the goodness of air (air quality in modern terms) and noted that injured or depleted air can be restored by green plants. In 1772 Priestley started his studies on air using mercury for locking gases. After a break in 1776 he systematically began to investigate different “kinds of air”: nitrous (salpetric) air (NOx), acid (muriatic) air (HCl), and alkaline air (NH3). He stated that these “kinds of air” are not simple modifications of ordinary (atmospheric) air. He published his observations in a paper titled Observations on Different Kinds of Air Priestley (1772, 1775). By heating red mercury oxide, he produced dephlostigated air (O2) in 1774. When reading these old papers with our present scientific knowledge it is often difficult, if not impossible, to understand what the scientists meant by different terms151; confusion also results from attributing the same term to different substances (we may only conclude that in those days such distinctions were not always possible): phlogistigated air for both N2 and H2, acid air for both CO2 and O2. Kopp (1869) accepted that phlogiston was actually hydrogen.

151 Phlogiston = fire element, from Ancient Greek φλογιστόν (phlogistón), neuter of φλογιστός (phlogistós, “burnt up, inflammable”), from φλογίζω (phlogízō, “to set fire to”), from φλόξ (phlóx, “flame”); Phlogiston, phlogistigated air = nitrogen gas (Priestley); Phlogiston = Feuerluft (O2) – fixe Luft (CO2) (Scheele); Phlogiston = hydrogen (Cavendish, Kopp); water = phlogiston + dephlogistigated air (Cavendish); dephlogiston, dephlogistigated air = oxygen gas (as originally thought to be air deprived of phlogiston; Priestley). Dephlostication (dephlostisation) = to remove the inflammable part from a body/substance (in German: dephlosticiren, in Latin: dephlosticatio).

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Another remarkable scientist was Cavendish who did not publish his results on air studies until 1783 (Cavendish remained a supporter of the phlogiston theory until his death). Already in 1772 he privately told Priestley about his experiments with “mephitic air” (nitrogen); thus it seems likely that Cavendish already knew before Rutherford about “inflammable air” (N2). In 1766 Cavendish separated hydrogen from other gases and showed that it burned to water. In 1781 he realized that water is produced in a reaction of hydrogen (“flammable air”) with oxygen (“vital air”) and soon he noted that there are also acidic substances not containing any oxygen. In 1781 he sampled atmospheric air at different sites and analyzed it gravimetrically after sorption of water-soluble gases (CO2, NH3 and water vapor). Cavendish had already tested to find whether airy nitrogen is a uniform matter and found that there is a small residue (noble gases). He did not conclude, however, that these remains are an element (argon). In connection with Lavoisier’s discovery of the role of airy oxygen (1777) it became clear that water is a chemical compound. Armand Émile Justin Gautier (1837–1920), Professor for Chemistry at the university in Paris, was the first in 1900 to proclaim the presence of hydrogen in atmospheric air. This was verified in 1902 by Rayleigh’s spectroscopic studies in air. Sir William Ramsay wrote an excellent history of the study of our atmosphere (Ramsay 1895, 1907). Ramsay wrote that to present a historic overview on the theories which did try to explain the nature of atmospheric air, would almost mean to write a history on chemistry and physics.

2.2.2 Carbon dioxide Carbon dioxide was the first gas to be distinguished from common air, perhaps because it is so intimately connected with the cycles of plant and animal life. The discovery of carbon dioxide must be attributed to several scientists, Jan van Helmont, John Mayow (1643–1679), Stephen Hales (1677–1761) and Joseph Black (1728–1799). As mentioned before, Helmont already found about 1630 that the gas bubbling in a brewery during fermentation is the same as that obtained by burning charcoal, as both gases turned limewater milky – a test which is used even today to identify carbon dioxide; he called it spiritus sylvestre (wild gas). Hence he is credited with its discovery. John Mayow, an Scottish chemist and physiologist, proved that carbon dioxide, which he called fixed air, is present in the atmosphere. He showed that air contains a gas which is a special agent for combustion and respiration and is fixed from calcified metals (i.e., metal oxides). He also showed that the new gas extinguished a flame, that it could not support life, and that it was present in gas exhaled from the lung. Furthermore he concluded (Mayow 1674) from his experiments on respiration of animals that there is a constituent of the air that is absolutely necessary for life

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(oxygen), which he called spiritus nitroaereus and another not supporting life (nitrogen); however, he was still unable to characterize these gases. Stephen Hales, who early in the eighteenth century began his important studies of the elasticity of air, pointed out that various gases, or “airs” as he called them, were contained in many solid substances. His many careful measurements (published in Vegetable Statics, or an account of some statical experiments on the sap in vegetables, London 1727) of the absorption of water and its transpiration to the atmosphere were the basis for the understanding that air and light are necessary for the nutrition of green plants. The careful studies of Hales were continued by his younger colleague, Joseph Black, a Scottish chemist, whose experiments concerning the weights of gases and other chemicals were the first steps in quantitative chemistry. Black was the first who found it in the air of Edinburgh, probably between the dates 1752 and 1754 (Black 1754). He writes (Black 1803, p. 74): . . . From this it was evident that the sort of air with which the lime is disposed to unite in a particular species which is in a small quantity only with the air of the atmosphere. To this particular species I gave the name of fixed air.

Black also identified carbon dioxide in exhaled breath, determined that the gas is heavier than air, and characterized its chemical behavior as that of a weak acid. Fixed air was renamed into carbonic acid [acide crayeux aériforme] by Lavoisier in 1781. The English chemist John Dalton guessed in 1803 that the molecule contains one carbon atom and two oxygen atoms (CO2); this was later proved correct. In 1787, Horace Bénédict de Saussure (Sausure the elder) employed lime water as a test for CO2 in the air when he was at the summit of Mont Blanc (Saussure 1796). First quantitative attempts to determine CO2 in atmospheric air were made at the end of the eighteenth century by Alexander von Humboldt and John Dalton; however, only showing that its level is less than 0.1% (see for more details Section 2.2.7.3).

2.2.3 Nitrogen Mayow (1674) found that from common air after combustion in a closed volume the remaining “air” (almost N2) does not support life and further combustion. This observation was also made in 1710 by Francis Hawksbee the Elder (1660–1713), a scholar of Boyle. It was Scheele who likely isolated nitrogen from air first around 1770 (but published only in 1777); independent from Scheele and Rutherford, Cavendish isolated nitrogen from air (Weeks 1956). Daniel Rutherford (1749–1819) a pupil of Black, isolated nitrogen from an air volume by consumption of oxygen through combustion and

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removal of carbon dioxide by alkali (Rutherford 1772).152 It was Black who gave Rutherford the problem of studying the properties of this residual “air”. Since the residual gas did not support life, he called it “noxious” or “injured” air. He did not recognize that this gas is the constituent of the atmosphere after removal of oxygen and carbon dioxide. He though that “noxious air” was atmospheric air that had taken up phlogiston from the substance that had been burned (Weeks 1957, p. 221). This gas was termed by Priestley in 1775 as phlogistigated air and by Scheele in 1777 as “verdorbene Luft” [spoiled air]. Jean-Antoine Chaptal (1656–1831) called it “nitrogène” after finding its relation to nitric acid.153 Lavoisier called it “azote from the Greek privative particle ά and ζή, vita; hence the name of the noxious part of atmospheric air is azotic gas . . . it is proved to compose a part of the nitric acid, which gives as good reason to have called it nitrigin” (Lavoisier 1789, p. 52–53).154 Over the next decades was lot confusion concerning the chemical nature of nitrogen. Bergmann and Scheele were the view that nitrogen is nitric acid, being gaseous through uptake of phlogiston. Lavoisier assigned nitrogen to the elements in his antiphlogistic nomenclature (1787). Girtanner (1792) describes nitrogen gas to nitrogen with caloric (Salpeterstoffgas = Salpeterstoff + Wärmestoff). Without knowing at that time that nitrogen exists free only as molecule (N2), this “definition” expresses that the atmospheric nitrogen (N2) was not identified with the “element” nitrogen (N). Hence Berzelius termed it in 1820 nitric radical. He separated between azote (Az) and nitric (N), Berzelius (1813a). Berzelius (1814), starting from N (nitricum), denoted related compounds as follows (Crosland 1962, p. 274); oxygen was represented by a dot to other electronegative elements: ·

Nitrogenium N (= NO) ·· Oxidum nitrosum N· (= NO2) Ammoniacum N H6 (= NOH6)

(modern notation N) (modern notation NO) (modern notation NH)

The elementary nature of nitrogen was long disputed by some chemists despite Lavoisier (1789, p. 196–197) already clearly describes the formation of nitrogen from ammonia: The hydrogen of the ammonia combines with the oxygen of the oxide,155 and forms water, whilst the azote being left free escapes in form of gas. . . Mr Cavendish first observed it in

152 It is certain that Cavendish carried out experiments with air and found nitrogen before Rutherford but he told private on these finding in 1972 to Priestley. He published first results from his experiment on air in 1883 (Ramsay 1896). 153 Nitrogène, nitrigen, and nitrogen are derived from the archaic name for potassium nitrate (KNO3). Nitrium (Latin) and nitrèn (French) but saltpetre (English) and Salpeter (German). 154 It must be noted that Lavoisier (and other chemists as well as naming in other languages) called the “noxious part of atmosphere air . . . azotic gas.” 155 In experiments when ammonia is heated together with metal oxides.

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nitrous gas and acid, and Mr Berthollet in ammoniac and the prussic acid. As no evidence if its decomposition has hitherto appeared, we are fully entitled to consider azote as a simple elementary substance.

Cavendish begun in 1777 first experiments with common air under the influence of electric discharges – his observation of products from the reaction between nitrogen and oxygen must be honored to be the first laboratory study in atmospheric chemistry. The following nineteenth century was full of quantitative measurements of some atmospheric trace species having low quality and speculations based on limited observations. David Low (1786–1859), a Scottish agriculturalist, believed that nitrogen must consist from carbon and oxygen (Low 1848) because of its close relation to the organic matter. Later (Low 1856, p. 204) he wrote that “nitrogen has been seen to be a simple combination of hydrogen and carbon, namely HC that is to be a common element”. The formula N2 finally was derived from the gas density156; Lavoisier already estimated the density of nitrogen to be 0.4444 grain per cubic inch (1.450 kg/m3), not very much different from today’s estimate (1.250 kg/m3); note that all density measurements before Rayleigh’s discovery of argon included nitrogen plus argon (1.2572 kg/m3).

2.2.4 Oxygen The facts on the air chemical composition were expressed most clearly by Scheele in his booklet Abhandlung von der Luft und dem Feuer (Treatise on Air and Fire), which was published in 1777 (Scheele 1777). From laboratory scripts it is now known that Scheele discovered oxygen – dephlogistigated air – before Priestley and by similar methods: heating silver carbonate, red mercury oxide, saltpeter and magnesium nitrate (Priestley 1775).157 Scheele named the ingredients of air as “Feuerluft” (oxygen) and “verdorbene Luft” (nitrogen). Scheele found evidence that one unit of oxygen produces one volume of carbon dioxide and defined that Feuerluft ðoxygenÞ = Phlogiston + fixe Luft ðcarbon dioxideÞ

156 See Eq. (4.23) in Volume 1: M = (ρ/p)RT. 157 It is not generally accepted that the priority in discovering oxygen must be attributed to Scheele, because Priestley published (direct) his results before Scheele. However, there is strong evidence in support of Scheele from the so-called “Braunbuch” (brown book), a bound collection of Scheele’s laboratory scripts, prepared by Berzelius in 1829, 40 years after the early death of Scheele. There is also a letter from Scheele written to Lavoisier in 1774, explaining the experiment for isolating oxygen, as well as (and this is the most important evidence for the priority) the published correspondence of Torbern Bergmann (to whom the much younger Scheele reported on his experiments) between 1765 and 1775. In his Abhandlungen von der Luft und dem Feuer, Scheele describes no less than 10 different methods for preparing oxygen (Feuerluft).

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This is incorrect, it should be written (in the old terms): carbon = fixe Luft (fixed air) + phlogiston, i.e., when carbon is burning, it is transformed into carbonic acid (CO2) while releasing “phlogiston.” These days it is difficult to understand what “phlogiston” meant to eighteenthcentury scientists. The phlogiston theory, founded by Johann Joachim Becher (1635–1682)158 and developed further by Georg Ernst Stahl (1659–1734) – both of them German chemists – was to some extent derived from the old belief that there was a fire element and that all combustible bodies contained a common principle (element), phlogiston (which in Greek means “flammable” or “inflammable”), which is released in the process of combustion. Substances rich in phlogiston, such as wood, burn almost completely; metals, which are low in phlogiston, burn less well. The phlogiston theory created great confusion and essentially embedded the understanding of the chemistry of phase-transfer processes and solid-gas reactions. Chemists spent much of the eighteenth century evaluating Stahl’s theory before it was finally proved to be false by Lavoisier. Lavoisier founded his theory on combustion on the discovery of the chemical composition of air. Priestley reported in Paris in 1774 of his discovery (oxygen) and said that he had no name for this gas. Lavoisier repeated the experiments of Priestley and dealt especially with the question of calcinations caustic substances (metal oxides) as well as their reduction by charcoal. In Reflexions sur le Phlogistique (1783), Lavoisier showed the phlogiston theory to be inconsistent with observation. He believed that this element (oxygen, denoted as dephlogiston) is an immanent part of acids159 and this gave him the name oxygéne (from Greek οξνς – acid). He also named the other element, called by Scheele “verdorbene Luft” (bad air, and by Priestley “phlogistigated air”) “azote” (this was nitrogen).160

2.2.5 Water The observation that remote water (materia prima) only comes from the atmosphere (atmospheric water) certainly promoted experiments to derive the philosopher’s

158 German physician, alchemist, precursor of chemistry, scholar, and adventurer, mainly in Mainz and Vienna; best known for his development of the phlogiston theory. 159 This wrong statement created for long time confusion in understanding the nature of muriatic acid (HCl), not containing oxygen. 160 Interestingly that in all languages the word for oxygen (if not directly transferred such as to French, English, Greek, Spanish, Italian, Danish, Norwegian, Hungarian, Turkish, Albanian, Azerbaijani, etc. using prefixies such as oxy, oxi, oksi) is constructed as “acid matter” using the word for acid (prefix kis in Slavic languages, sauer in German, zuur in Dutch, syre in Swedish).

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stone from it (see also Section 2.4.1). Despite much progress in science at the beginning of the seventeenth century, the belief of convertibility between air and water, and water and soil (and vice versa) was widely accepted until the chemical composition of the air and the structure of water was discovered by Scheele, Priestley, Cavendish, Watt, Lavoisier and others161 after 1770. The debate about who actually discovered the chemical composition of water (H2O) was called the “water controversy” in the nineteenth century. With respect to the discovery of the chemical composition of water, three scientists must be regarded as candidates (Kopp 1869): Cavendish, who was probably the first (in 1781) to carry out experiments to form water by combining phlogiston (H2) and dephlogistigated air (O2).162 Cavendish mixed in a globe inflammable (hydrogen) with dephlogistigated (oxygen) air which then was “fired by electricity”. In several experiments the mixture were more or less phlogistigated (nitrogen) and dephlogistigated, resp., i.e., with changing ratios between nitrogen and oxygen. Consequently he obtained “liquor” being not acid (water) and with different degree of acidity (nitrous acid), Cavendish (1784). He concludes that dephlogistigated air (oxygen) is “dephlogistigated water, or water deprived of its phlogiston; or, in other words that water consists of dephlogistigated air united to phlogiston; and that inflammable air [hydrogen] is either pure phlogiston”.163 Cavendish only announced his results to the Royal Society of London in January, 1784. However, when Priestley learned of Cavendish’s experiments in early 1783,164 he repeated them (Priestley 1783, 1785), and quickly communicated his findings to his friend James Watt (1736–1819). Watt then wrote to Jean Andre Deluc and Joseph Black, suggesting that “water is composed of dephlogistigated air and phlogiston deprived of part of their latent or elementary heat . . . My assertion was simply that air was water deprived of its phlogiston and united to heat.”165 Thus, Watt formulated the composition of water in 1783 in a similar way

161 It must be mentioned Gaspard Monge (1746–1818) who independingly from Lavoisier carried out in 1783 similar experiments to gain water. 162 Ramsay (1896, p. 123) writes “ . . . his experiments were in many cases not published until long after they had been made. He appears to have carried on his work for his own information, and to have been indifferent to the impression which his labours made on his fellow-man”. Cavendish was very rich due to heritages and consumed only a small percentage of it. 163 Two reaction chains occur parallel, H2 + O2 (= H2O) and N2 + O2 (= NO + NO2 + HNO2 + HNO3). The problem in understanding Cavendish’s (and others) papers result from different meaning of phlogiston; sometimes phlogiston is equal to hydrogen and othertimes to any unknown principle or matter (fire?). 164 Priestley writes that the experiments of sparkling inflammable air and dephlogistigated air to get water were originally performed by Cavendish (Schofield 1964). 165 This phrase is rather confusing; Watt and Cavendish remained until her dead proponents of the phlogiston theory.

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as Cavendish (Watt 1784)166; and finally Lavoisier, who, in 1783, made the first public announcement that water consisted of inflammable air (H2) and dephlogistigated air (O2), Lavoisier (1783): L’eau n’est pas une substance simple . . . Elle est susceptible de décomposition et de recomposition.

Watt claimed the priority only after Lavoisier’s announcement of “his” experiments (he was “forced” by Deluc). In June 1783 Charles Blagden (1748–1820)167 visited Paris and told Lavoisier of Cavendish’s experiments. Lavoisier had been searching for the acid which he thought must be formed by the union of hydrogen with oxygen, the “principle of acidity”. On 24th June, both repeated Cavendish’s experiments and next day Lavoisier send a memoir to the French Academy of Science, claiming the discovery of the composition of water. Lavoisier states “that we may conclude that water is not a simple substance, and that it is composed, weight for weight, of inflammable air and vital air” (Partington 1928). Lavoisier is definitively not the discoverer of the composition of water but he was the first to give the correct explanation of them (1783). Priestley had burned inflammable air with dephlogistigated air before 1775 and while Alessandro Volta (1745–1822) had exploded such mixtures with the electric spark before 1776, Pierre-Joseph Macquer (1718–1784) in 1777 was probably the first to note that water was the result of burning these two gases (Edelstein 1948).168 In winter 1782 Priestley began experiments in an attempt to convert water into a permanent gas (Priestley 1783, 1785, 1788); the results were communicated from time to time to Watt, with whom Priestley had been friendly. Watt did not carry out many experiments with gases. Although Priestley observed the appearance of moisture several times, he neither realized that this water was the product of the union of the two gases.169

166 In this paper, Watt summarized the experiments made by Priestley and Cavendish as well being repeated later in Paris. There is no evidence that Watt made own experiments; he notes that before he was believing that air was a modification of water (despite Boyle already stated more then 100 years ago that water is not air). It is worth to note that Watt noted in this paper “that Mr Cavendish was the first who discovered that the combustion of dephlogistigated and inflammable air produces moisture”. 167 He was an assistant of Cavendish and became in May 1784 one of the two Secretary’s of the Royal Society in London. 168 Citing George Wilson “The Life of the Honorable Henry Cavendish”, London, 1851, p. 23. 169 The formation of “phlogiston” (hydrogen) from common air passing burning charcoal, was almost carbon monoxide and not hydrogen (Priestley observed black soot beside moisture); hence he produced carbon dioxide (Schofield 1964). In a letter to Deluc from December 27, 1783, Priestley writes that “no facts of my discovery proves that water consist of pure air and phlogiston . . . and it was Mr Cavendish who first found water on decomposing dephlogistigated and inflammable air. In

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Cavendish and Watt remained on friendly terms. Instead, the dominant question is why this discovery remained a subject of controversy among prominent figures in Victorian science, some 50–70 years after Cavendish’s experiments (Miller 2004). According to Christoph Girtanner (1760–1800), Swiss chemist, who wrote the first German anti-phlogistic textbook in chemistry (Girtanner 1792), water consist from 0.06 hydrogen and 0.88 oxygen (0.11 and 0.88 is correct). The weight of oxygen could be calculated because of earlier works by Humboldt and Gay-Lussac, who found 1805 that water consisted of only two elements, hydrogen and oxygen (2 volumes of hydrogen combine with 1 of oxygen to form water), Humboldt and GayLussac (1893).170 Lacking any knowledge about how many atoms of hydrogen and oxygen combine in a molecule of water, Jean-Baptiste André Dumas (1800–1884) again had to make some assumptions in 1842. He assumed that nature is basically very simple and, therefore, one atom of hydrogen combines with only one atom of oxygen. Using this hypothesis and the fact that hydrogen was assigned a weight of one unit, it follows that oxygen, which is eight times heavier than hydrogen (from H2O. i.e., 2/16), would have a weight of eight units. In 1842 Dumas determined the composition of water by weight and found that two parts (by weight) of hydrogen combined with 15.96 parts of oxygen. Later experiments changed the ratio to 2 to 15.88. However, the Proceedings of the Royal Society in London accepted still in 1843 a paper where “the author is of opinion that the evidence on which the modern theory of the composition of water is founded, is fallacious; and believing water to be a simple body, he conceives that it forms hydrogen by combining with the electric fluid” (Stevenson 1843). In 1895 the American chemist Edward Williams Morley (1838–1923) introduced a new value for the atomic weight ratio of oxygen to hydrogen, providing the most precise determination of the atomic weight of oxygen at the time (Morley 1895). His work on the atomic weight of oxygen covered a period of eleven years. Much time was spent in the calibration of instruments and improving the measurement accuracy. The final result was for the density of oxygen 1.42900 ± 0.000034 g L–1 and for hydrogen 0.089873 ± 0.0000027 g L–1. The ratio of the volumes of hydrogen and oxygen combining he found to be 2.00269 and thus it follows for the atomic weight of oxygen 15.877 (currently accepted 15.874). The Scottish chemist Alexander Scott (1853–1947) carried out between 1887 and 1893 studies on the composition of water and found that 1 volume of oxygen

my opinion Mr Watt first entertained the idea [on the composition of water] . . . and the experiments of Mr Cavendish proved the justness of it, tho Mr Cavendish had not that idea itself”. 170 The original paper appears in French: Gay-Lussac, J. L. (1809) Mémoires sur la combinatiion des substancces gazeuse, les unes avec les autres. Mémoires de Physique et de Chimie de la Societé d`Arcueil 2 (1808) 207–234 and 252–153; and in German: Gay-Lussac, J. L. (1810) Ueber die Verbindung gasförmiger Körper eines mit dem andern. Annalen der Physik 36, 6–36.

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combines with 2.00285 volumes of hydrogen (Scott 1893), whereas Burt and Edgar (1916) found it to be 2.00288 from which they concluded on the atomic weight of hydrogen to be 1.00772 (today’s estimate is 1.00794). Sidney Edelstein (1912–1994), American research chemist, makes a persuasive case for Watt’s priority (Edelstein 1948) whereas the US historian Robert Schofield (1923–2011) and the British chemist and historian James Riddick Partington (1886–1965) argues that to Cavendish the first claim must be given (Partington 1928, Schofield 1964); myself (DM) come round to the latter opinion.

2.2.6 Argon and the other novel gases In a certain sense the discovery of argon must be attributed also to Cavendish. Cavendish’s investigations of phlogistigated air (nitrogen) did show that a small part of this “air” could not be oxidized into nitric air (by oxygen and electric sparks) and after removal of excess oxygen and water he stated that 1/120 part of the total air remains (Bauer 1895, Rayleigh and Ramsay 1896). This was 100 years before Rayleigh identified it to be argon.171 Lord Rayleigh was the first who observed (between 1882 and 1892) that oxygen and other gases produced from different sources always showed the same density but not airy nitrogen (Rayleigh and Ramsay 1896). It has been shown that nitrogen extracted from chemical compounds is about onehalf per cent lighter than “atmospheric nitrogen” (Rayleigh and Ramsay 1896, p. 1). The difference of about 11 mg was already far away from measurement errors. In his address on the occasion of receiving the Nobel Prize (1904) Rayleigh explained how he made his discovery, showing the (from today’s point of view) simple but accurate experiments and conclusions: The subject of the densities of gases has engaged a large part of my attention for over 20 years. . .. Turning my attention to nitrogen, I made a series of determinations . . . Air bubbled through liquid ammonia is passed through a tube containing copper at a red heat where the oxygen of the air is consumed by the hydrogen of the ammonia, the excess of the ammonia being subsequently removed with sulfuric acid. . .. Having obtained a series of concordant observations on gas thus prepared I was at first disposed to consider the work on nitrogen as finished. . .. Afterwards, however . . . I fell back upon the more orthodox procedure according to which, ammonia being dispensed with, air passes directly over red hot copper. Again a good agreement with itself resulted, but to my surprise and disgust the densities of the two methods differed by a thousandth part - a difference small in itself but entirely beyond experimental errors. . .. It is a good rule in experimental work to seek to magnify a discrepancy when it first appears rather than to follow the natural instinct to trying to get quit of it. What was the

171 “Although Cavendish was satisfied with his result, and does not describe whether the small residue was genuine, our experiments about to be related render it not improbable that his residue was really of a different kind from the main bulk of the “phlogistigated air,” and contained the gas now called argon” (Rayleigh and Ramsay 1896, pp. 8–9).

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difference between the two kinds of nitrogen? The one was wholly derived from air; the other partially, to the extent of about one-fifth part, from ammonia. The most promising course for magnifying the discrepancy appeared to be the substitution of oxygen for air in the ammonia method so that all the nitrogen should in that case be derived from ammonia. Success was at once attained, the nitrogen from the ammonia being now 1/200 part lighter than that from air. . .. Among the explanations which suggested themselves is the presence of a gas heavier than nitrogen in air. . ..

This new gas was identified by Ramsay in 1894 who made spectroscopic studies, as an element and named argon (Ar), derived from Greek αργόν = slack (Ramsay was awarded the Nobel Prize together with Rayleigh in 1904). While investigating for the presence of argon in a uranium-bearing mineral, he instead discovered helium, which since 1868 had been known to exist, but only in the Sun. This second discovery led him to suggest the existence of a new group of elements in the periodic table. Ramsay and his co-workers quickly (1898) isolated neon (Ne), krypton (Kr), and xenon (Xe) from the earth atmosphere (Rayleigh and Lord 1901, Ramsay 1907).

2.2.7 Air analysis 2.2.7.1 Determination the goodness of air: eudiometry For centuries doctors speculated that contaminated air (“bad” air) brought diseases (see also end of Section 4.5.3). Even in the nineteenth century one of the proponents of the great Victorian sanitary works, Edwin Chadwick (1800–1890), wrote “all smell is disease” (Finer 1952). For chemists of the nineteenth century and earlier, there were three “sensors” in determination chemical substances: smell, look, and taste.172 From historic reports we know that it stunk often in cities before installation of sewerage. Moreover, factories were close to residential areas and waste of all kind were exhausted into air or passed into rivers. Thus smell was omnipresent. The percentage of nitrogen and oxygen in air have been only roughly estimated and there was the believe that the concentration of oxygen varies and is lower in polluted air and higher in remote air. Even carbon dioxide have been regarded in a range of a few percent and first removed (by alkalines) in all analysis of atmospheric air. The accuracy of first air analysis was very low, resulting in oxygen values between 18% and 27%. The remaining gas was attributed to nitrogen and noxious gases.173

172 This was still valid for (very experimentally working) chemists in the twentieth century. Many compounds have a characteristic smell, color or crystalline structure (see also Section 2.4.4 and namely Figure 2.15) that helps for their identification. 173 Today we know that the oxygen concentration only in flue and process gas can be significantly lower (typically 5% in flue gas).

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The first “air analyzer” was constructed by Marsilio Landriano (1751–1815), an Italian chemist, physicist, and meteorologist, who was intrigued by a remarkable observation made Joseph Priestley: when nitrous air174 mixed with ordinary air in the presence of water, there was a startling one-fifth contraction in the volume. Priestley believed he had found a way to measure the “goodness” of the air by keeping careful track of the volumes of gas he was mixing (Priestley 1799). Landriano believed that measuring the goodness of air might explain the origin of disease; he repeated Priestley’s experiment and designed a compact system175 and called it eudiometer.176 At the same time, the physicist Abbé Felice Fontana (1730–1805)177 in Pisa had built a very similar device. An eudiometer is a graduated glass tube (burette) used in the study and volumetric analysis of gas reactions (Figure 2.2). Landriano’s and Fontana’s “eudiometer of nitrous gas” is based on the gas reaction observed by Priestley, giving largely uncertain values because of the uncontrolled stoichiometry of a) the formation “nitrous gases” and b) the reaction of nitrous gases with oxygen. The procedure is in short, that nitrous gas, produced from copper wires and nitric acid, is mixed in a well-known volume with common air resulting in a gas volume that is smaller than the original volumes of nitrous air (NOx) and common air because of the reaction between NOx and oxygen. The volume difference (measured in millimeters of 100 or ratios) is a measure for oxygen and hence the “goodness” of air. Scheele developed an “eudiometer of sulphurets”, where a mixture of iron filings and sulfur, formed into a paste with water have been used to absorb oxygen, which was significantly improved by Antonio de Marti Franquès (1750–1832), a Catalonian chemist and naturalist, who measured the oxygen content in air to be 21–23%. Landriani’s friend Alessandro Volta (1745–1827) went one step further, based on Cavendish’s experiments. He equipped an eudiometer with spark wires to study the hydrogen-oxygen reaction; hydrogen was produced from zinc and hydrochloric acid. The accuracy if this device was already 0.1% in oxygen. It is worth to cite (Thomson 1807, p. 62) the process of examination: When 100 measures of hydrogen are mixed with 200, or any greater bulk of oxygen, the diminution of the bulk after detonation is always 146 measures. . .. Hence the method of using this eudiometer is very simple: mix together equal bulks of the air to be examinated, and of

174 It remains unclear, what “nitrous air” denotes (Table 2.2): NO, NO2 and/or HNO3 (and HNO2 because NO + NO2 = N2O3 which reacts with water to HNO2). Ingenhousz (and also described by Scherer) denotes it “Salpersäureluft.” 175 Andrea Sella (University College London, UK): https://www.chemistryworld.com/opinion/land rianis-eudiometer/8200.article 176 The name comes from the Greek εύδία meaning clear sky. 177 An Italian physicist who discovered the water gas shift reaction in 1780. This eudiometer is described in Ingenhousz (1779).

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Fig. 2.2: Eudiometer. Left the glass “Eudiometro di Landriani” (Inv. 1371, 1776, dimension 700 × 75 mm) and right “Eudiometro di Volta per la detonazione dei gas” (Inv. 1627, ca. 1790, dimension 490 × 20 mm), Museo Galileo. Florence https://catalogo.museogalileo.it/multimedia/ Eudiometria.html. hydrogen gas, ascertain the diminution of bulk after combustion, divide it by three, the quotient represents the number of measures of oxygen in the air. . . 200 measures of air and much of hydrogen amounting in 126 measures of bulk diminution. Hence 126/3 = 42, the quantity of oxygen in 200 measures, hence 100 parts of air contain 21 of oxygen.

A “eudiometer of phosphorus” was first proposed by Franz Carl Achard (1753–1821) in 1784 and soon later considerably improved by Henri Paul Irénée Reboul (1763–1839). Reboul carried out 800 examination and found oxygen to be 18–20% in air.178 Scheele determined the oxygen content of air in Stockholm in 1779 to be between 9/33 and 10/33 (27–30%) and Lavoisier found in Paris 1/4 (25%) in 1780.

178 Annales de Chimie (1793) 13, 633.

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Soon later other researchers (Ingenhousz, Lavoisier, Magellan,179 Saussure (Jr.), Scheele, Senebier, Cavallo180 and others) used such eudiometers, which has been further improved, to estimate the “goodness of air” in many European towns, mountains, and on sea as described in 1785 by Johann Baptist Andreas Ritter von Scherer (1755–1844) in his book “Geschichte der Luftgüteprüfungslehre für Aerzte und Naturfreunde” [History of air quality testing teaching for doctors and nature lover].181 Scherer (1785, p. 27), in comparing different eudiometers, writes very clear the sources of errors to be – imperfection of the air meter (eudiometer), – the lack of experience with the device and – random causes. Furthermore (ibid., pp. 101–102) he describes results, which are correct but cannot be derived from the use of eudiometers, because a) the differences of the oxygen values measured did not reflect the reality and b) even in case of correct oxygen estimation the “bad” air was on concentration orders of magnitude smaller than the oxygen content: – sea air is cleaner, – country air is cleaner than city air, – air in winter at cold weather is most clean, – in summer, when a lot of rain is, the air is not so clean, – marsh and morass areas are in winter not so harmful like in summer. These conclusions are obviously based on smell and observation that higher temperature result in more putrefaction and rain washes air. On the other hand, Scherer (1785, p. 98) writes curiously, that “Die Luft in Oesterreich, Baiern and Schwaben war weniger dick als in der Schweiz . . . die Luft wäre in Italien noch dicker” [The air in Austria, Bavaria and in Swabia was less fat than in Switzerland . . . air in Italy would be even thicker]. Scherer (ibid., p. 73) recommended a daily examination of “die Reinheit des Luftmeeres” [the goodness of the ocean of air] and to log “eudiometric tables” together with the values of temperature and pressure.182 2.2.7.2 Analysis of oxygen First Cavendish analyzed in 1783 the composition of air using a “eudiometer of nitrous gas” for the first time very close to the correct values (Table 2.6). Joseph Louis

179 Jean Hyacinthe de Magellan (1723–1790) was a Portuguese natural philosopher. 180 Tiberius Cavallo (1749–1809) was of Italian birth but lived in London. 181 Wien 1885 in two Volumes (214 and 218 pp.). 182 This is surely the first idea of registration a “chemical weather” (see Volume 1, p. 48).

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Tab. 2.6: Historic data on air composition (in Vol-%). Substance

Cavendishe ()

Gay-Lussac and Humboldt (–)f

Benedict ()

Krogh ()b

Cadle and Johnstone ()

presentd ()

N O CO

.a . –

. . –

.a . .b

.a . .

. . .

.a,c .g .

a

Within these figures novel gases are (Ar at present 0.934). Benedict himself gives the average of CO2 as 0.031%; corrected to 0.30 by Krogh due to 0.002% CO formation while oxygen absorbing by potassium pyrogallate. August Krogh (1874–1949) Danish physiologist (Nobel price 1920). c Ar amounts 0.9340%. d Earth Fact Sheet reference (https://nssdc.gsfc.nasa.gov/planetary/factsheet/earthfact.html). e After Humboldt (1799), Ramsay (1896, p. 125), carried out 1781 in London and Kensington, f Both scientists collected air samples from different place, including balloon ascends and mountain tops; this average is taken from Humboldt (1850, p. 311). g 20.9392 (Tohjima et al. 2005), continously decreasing. b

Gay-Lussac (1878–1850) collaborated with Humboldt in using different eudiometers to examine the air; with the Volta eudiometer, they confirmed the values found by Cavendish, Table 2.6 (Gay-Lusssac 1805, Humboldt and Gay-Lussac 1805). On September 16, 1804, Gay-Lussac went up alone with a hydrogen-filled balloon up to 7,016 m above Paris. Beside measurements of magnetism, pressure, temperature, and humidity he collected two samples of air at altitudes of 6,561 and 6,636 m. He writes (Gay-Lussac 1804), Figure 2.3:

Fig. 2.3: Table of Gay-Lussac’s results from air analysis in The Philosophical Magazine (1805) Vol. 21, p. 255.

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When I arrived at Paris, my first care was to analyse the air I had brought back. All the experiments were made at the polytechnic School, and the inspection of Messr. Thenard and Gresset and found it precisely the same as the air at the earth surface to be 0.2149 of oxygen.

Many well-known chemists analyzed the oxygen content of air (the difference was attributed to nitrogen) in the early 1800s such as de Saussure, Berthollet, Dumas, Baussingault, Regnault, Thomson, Davy, Vogel, Dalton, Helmstädt, and other between 20.5% and 21.6% (Table 2.6). Measurements in the second half of the nineteenth century became more accurate with values between 20.91% and 20.96% (cited by Krogh 1919).183 Because Gay-Lussac’s summary and conclusions concerns oxygen measurements in the early nineteenth century are so clear, I will cite them here (Gay-Lussac 1805): Saussure Jr., found184 also that air collected on the Col-du-Geant contained, within an hundredths of part, as much oxygen as that of the plain, and his father confirmed the presence of carbonic acid on the summit of Mont Blanc. Besides, the experiments of Messrs. Cavendish, Macartney, Berthollet, and Davy, have confirmed the identity of the composition of the atmosphere over all surfaces of the earth to greatest heights to which it is posible to attain. . .I think, also, I have proved that the prosporous of oxygen and azote, which constitute the atmosphere, do not sensible vary in very extensive limits. There still remain a great many things to be cleared up in regard to the atmosphere.

Robert Bunsen (1811–1899) showed in 1846 that the oxygen content in air varies slightly between 20.84 and 20.95% (measurement error was 0.03%), Bunsen (1857). Smith (1872) carried out in the 1860s many air analyses in England and found on average 20.94% and no differences between remote, polluted, laboratory, and mountain air. He writes (Smith 1872, p. 33): “We are exposed to currents of good air in the worst, and of bad air in best atmosphere in towns like Manchester.” Benedict (1912) found that atmospheric O2 concentration was constant, a conclusion that was reinforced by Machta and Hughes (1970) many years later, although both studies were limited by the precision of the analytical techniques employed. Sophisticated air and gas analysis (Haldane 1918, Hempel 1913) have been developed by John Scott Haldane (1860–1936), British physiologist and the German

183 The amount of publications with the title “on the composition of air” (in English, French and German) is vast. Here are only citations from German journals (year, volume, pages): Archiv der Pharmacie (1823) 4, 215–229, (1835) 52, 132, (1853) 126, 149–156, (1862) 160, (1867) 180, 107–108; Journal für Praktische Chemie (1841) 23, 237–243, 24, 66–91, (1842) 26, 294–297, 297–298, (1842) 27, 215–227, (1843) 30, 207–227, (1844) 32, 444–448 (1851) 52, 278–279; Annalen der Physik und Chemie (1834) 107, 148–158, (1835) 112, 436–456, 456–458, (1841) 129, 392–408, (1879) 242, 520–544; Annalen der Chemie und Pharmacie (1848) 68, 221–223, (1851) 78, 123–124, 80, 227–229, (1852) 84, 207–209; Archiv der Pharmacie (1823) 4, 215–229, (1835) 51, 132, (1853) 126, 141–156, (1862) 160, 65–66, (1867) 180, 107–108; Berichte der Bunsengesellschaft (1879) 11, 1696–1698, (1885) 18, 267–282, (1887) 20, 991–999, 1864–1873. 184 With a “nitrous gas eudiometer” (Saussure 1804).

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chemist Walter Matthias Hempel (1851–1916).185 Beside nitrogen and oxygen, at the end of the nineteenth century, the concentrations of carbon dioxide (0.003%), argon (0.93%) and that of hydrogen ( )

 ppm (Saussure )  ppm  ppm  ppm ( observers)  ppm ( observers)

Tab. 2.7: Simultaneous measurements of oxygen and carbon dioxide (given in % of dry air) in Dresden, November 8–18, 1884 (made by Felix Oettel); data from Benedict (1912). substance

standard variation mean

O

CO

sum

. . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . .

. .

. .

. .

189 Georg Rudolf Reinhart Blochmann (1848–1920), German chemist at Königsberg, student of Bunsen.

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Richard Felix Marchand (1813–1850), professor for chemistry in Halle, was the first who estimated a mean from 150 observations (around 1845) in Halle significant less than the “4” figure to be 310 ppm. His finding is only cited by very few following scientists. Petermann and Graftiau (1891, pp. 29–30) write: . . . acide carbonique de l’atmospère est en general d’une grade constance. . . se rapproche trés sensiblement de 3 litres par 10,000 litres d’air à 0° et 760 millimétres de pression.

Albert Edmund Letts (1852–1918), professor of chemistry in Queen’s College, Belfast, and Robert Frederick Blake (1867–1944) published together two remarkable papers (Letts and Blake 1900, 1901), giving a new accurate CO2 determining method and the most extensive critical overview on CO2 observations in the nineteenth century, citing 198 authors. They write (Letts and Blake 1900, p. 172): From the time of De Saussure whose researches extended over the period 1809–1830, and who made some hundreds of observations . . . until about the year 1870, the normal amount of atmospheric carbonic anhydride appears to have been taken as 4 in 10,000 vols. . . . but it is interesting to notice, as Blochmann has pointed out, that his figures almost steadily decreased as his work progressed.

It is remarkable that many authors agreed with 0.03% (according to 300 ppm) as “natural reference value” (Schloesing 1880, Blochmann 1886, Renk 1886, Letts and Blake 1900, Brown and Escombe 1905a, Friedheim 1907, Lode 1911, Benedict 1912, Krogh 1919, Loewy 1924, Quinn and Jones 1936, Mellor 1940, D`Ans und Lax 1943, Remy 1965). Humboldt writes (Humboldt 1850, p. 311): The relative quantities of the substances composing the strata of air accessible to us have, since the beginning of the nineteenth century, become the object of investigations, in which Gay-Lussac and myself have taken an active part. . .

He cites accurately the concentration of oxygen (20.8%) and nitrogen (79.2)190 and named as minor species “carbonic acid gas” citing Boussingault and Lewy, Humboldt mentioned in a footnote on p. 311 (Humboldt 1850) that “the proportion of carbonic acid in the atmosphere . . . varied only between 0.00028 and 0.00031 in volume” [ 280–310 ppm]. What is the “error” of such analytical figures? It is known from chemical practice that a precision (it is the standard deviation from several measurements of a sample with the same concentration) to be ± 3% is excellent. However, a high precision does not mean automatically that the value is “true”; the trueness is the degree of match with the “true value.” A high precise measurement can be far away from the true value, as found in inter-comparisons for rain water analysis; today’s wet chemical analysis of ions have a precision of 0.02 mg Ca L-1 and an inter-network bias of 15% for

190 Only end of the nineteenth century it was known that about 1% of this figure is due to novel gases.

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calcium.191 However, when the analysis has a good accuracy, the mean from many measurements can fit the “true” value. Letts and Blake (1901, p. 139) write: These variations, if actually small, are relatively large, and correspond with fluctuations of at least 10 per cent of the total quantity, and according to some observers to a much higher proportion . . . . . . and that very few of these have been tested as regards their degree of absolute accuracy; and also that the observers have collected their samples at different heights above the ground. . . Müntz and Aubin are an exception to this rule (ibid., p. 436).

CO2 has been analyzed wet-chemically by absorbing from air always in alkaline solutions (almost baryt water, i.e., Ba(OH)2); after precipitating of BaCO3 after 1–2 h, an extracted part of the clear solution is titrated (mostly by oxalic acid). Many modifications have been made (apparatus such as bottles or tubes with an aspirator, instead of titration gravimetric estimation, other titrating acids such as HCl solution, different indicators for the neutralization point, and more). Blochmann (1886), Walker (1900) and Letts and Blake (1900, 1901) found that the ordinary process by Max Joseph von Pettenkofer (1818–1901),192 the “Flaschenmethode” and the “aspiration method” (Pettenkofer 1862) gives systematically too high values due to additional absorption of CO2 by the baryt water (e.g., when handling solutions in laboratory air). Letts and Blake (1901) made careful simultaneous sampling and analysis by the Pettenkofer’s and its own new process, showing that the Pettenkofer ordinary process results in 25–35% to high values and such explaining the difference between “4” and “3” parts of 10,000. It is clear to any chemist that many sources of errors can appear in the procedure and a long experience or practice by the operating person is necessary to get a high accuracy. Fresenius (1875) states that for air analysis a precision of ±0.002% absolute CO2 level (according to ±20 ppm) is excellent and Haldane (1918) gives ±10 ppm as precision (3–7% relatively). Hempel (1913) first cites results from inter-comparisons; the accuracy is not better than ±100 ppm for three different methods (50–100 ppm for ambient air analysis and 100–200 ppm for indoor CO2 analysis) and ±(30–50) ppm by comparing Petterssons and Pettenkofers method.193 Today it is self-evident that measurements are corrected to standard conditions and related to dry air. In many older papers (before 1870s) this is not clear expressed and we have to consider another source of “variation”. When discussing historical values, we have to take into account that CO2 in laboratories’ air can go up to 0.2% (Hempel 1913) and therefore any analytical operation not undertaken carefully might lead to higher analytical figures. The next fact 191 Assuming this being similar also for barium; however, later we discuss that not the (excellent) precision of chemical analysis (already likely provided in nineteenth century) is important but the errors while CO2 sampling/absorbing (incompleteness) and alkaline titration (additional CO2 absorption) are essential. Such precision (0.02 mg Ba L–1) would result only in 1% relative error when sampling CO2 from 6 L air. 192 Bavarian chemist and hygienist; in 1865 he became also professor of hygiene in Munich. 193 Sven Otto Peterssson (1848–1941), Swedish chemist in Gothenburg.

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which must be taken into account when comparing different historical CO2 values is the town influence, which was estimated between 30 and 200 ppm higher than in the rural surroundings (Renk 1886, Lode 1911) very close with today’s values of city dome CO2 (see Section 4.4.3.4). Only very few of the historical measurement series where able to reflect a seasonal cycle; accuracy with 10–20 ppm and a too small number of measurements mask this natural variation. However, the seasons influence on CO2 already was stated by Saussure, who found it in summer higher than in winter, supported by Fittbogen and Hässelbarth (1879) who found a minimum in December and Petermann and Graftiau (1891) with very small variation of only a few ppm. Edme Hippolyte Marié-Davy (1820–1893), meteorologist at the Montsouris Observatory at Paris, found a CO2 maximum in December (Marié-Davy 1880). Whereas seasons and town influences on the CO2 level may be excluded or to be assessed of minor importance in evaluation of historic background levels, there remain two significant factors, responsible for large variations among the observers, the sampling height above ground and the time of sampling. The most serious effect of CO2 variation is the diurnal cycle, which amounts 30–80 ppm (as maximum-minimum, and often more; there are many measurements in literature, not cited here) and appears as sinusoidal curve. Hence, the difference between continental daytime-means and nocturnal means could range 10–30 ppm.194 In past, often only one value (and almost daytime) per day or only few values per month have been produced. According to the time of day, such figure cannot reflects a daily mean; only a large number of measurements made at different time, can reflect a mean daytime value. The majority of CO2 measurements have been carried out at business times; hence, a “corrected” daily mean must be around or higher than 10 ppm. The diurnal amplitude depends strongly from the local situation. Principally this was known at the end of the nineteenth century by a few more intense studies; but extensive sampling over longer periods was impossible due to the long time for sampling and single analysis (several hours) and hence large man-power needed. Letts and Blake (1900) write . . .and also that the observers have collected their air samples at different heights above the ground.

More CO2 is found in the ground air from lower than from higher levels; the gradient has a definite connection with the season and rainfall has a marked influence, Letts and Blake (1900, p. 216) summarize, citing Jozef von Fodor (1843–1902), professor for hygiene at the University Budapest: . . .the fluctuations in the amount of atmospheric carbonic anhydride are mainly due to the absorbing action of soil on the one hand, and the evolution of ground air on the other.”

194 Today, CO2 is measured continuously, “automatically” giving a mean daily value, resulting in representative monthly means and subsequent annual mean figures (when the time gaps of measurements are not too large).

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Fodor (1879) found soil CO2 emission to be 0.175 L m–2 d–1. In summary of the discussed facts, affecting the CO2 measurement, it is no longer surprising that historically published values after 1870 between 270 and 360 can be seen as no principally erroneously but not representing a “true” mean (climatological) CO2 figure. As found from the few inter-comparisons, the scattering of only single or a few CO2 measurements can be ±(50–100) ppm due to different reasons: methodical errors by different authors and/or methods, timely influences (almost diurnal cycle), and different local influences (but these are likely of minor influence). Consequently, it makes no sense to list and to interpret published historical CO2 data based on only few measurements. Therefore, only results from “long-term” observations and/or more than 50 single measurements will be regarded here. Also some of the longer times series show large timely (but not periodically as we know it today) variations of the single measurements which can be interpreted as the scattering of the analytical figure by errors and likely predominant by the different time of the single measurements and the subsequent average. This is best illustrated by the well-known Montsouris Observatory monitoring (1876–1910), Figure 2.4. First, the inter-annual (5–15 ppm) and monthly variations (>10 ppm) cannot be explained by natural physical reasons (Waterman 1983) and secondly, the marked rise in 1890 (by 27 ppm) suggests a change in the sampling and/or analytical procedure. Here are the characteristics of two periods (period average based on mean annual values, standard variation, min-max):

– (n = ) – (n = )

 ±  (–)  ±  (–)

CO2 mixing ratio (in ppm)

330 320 310 300 290 Montsouris Paris Law Dome Antarctica

280 270 260 1875

1880

1885

1890

1895

1900

1905

1910

year Fig. 2.4: Historical records of CO2 measurements at Montsouris Observatory near Paris (data from Stanhill 1982), compared with CO2 data from Law Dome in Antarctica (see Fig. 4.49 for data source).

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The obvious problems with the Montsouris analysis (mentioned already by Reiset (1880)) is illustrated by the data published by Marié-Davy (1880) despite his explanation of different air mass influences (without doubt, the Montsouris station north of Paris in a park – today within Paris – is much less suitable then the Dieppe station for background estimates). Table 2.8 shows the monthly means from April 1876 until December 1879; the standard variation of total monthly means ranges 35–56 ppm and that for annual means ranges 12–41 (monthly minimummaximum 244–359 ppm). These data illustrate the above discussed uncertainties. Tab. 2.8: Monthly means at Mountsouris station (unknown number of single measurements) after Marié-Davy (1880), in ppm. Mean from all monthly data: 312 ± 39 ppm and from all annual averages: 319 ± 25 ppm.

   

























–   

–   

–   

   

   

   

   

–   

–   

   

   

   

Lévy and Miquel (1891) give a mean from the Mountsouris series (1881–1890) to be 287 ± 8 ppm (277–302) based on annual means whereas the mean from all monthly means amounts 293 ± 2.5 ppm (289–297) showing very small variations only. Despite the large general uncertainties of Montsouris data, the last figure is close to the following cited mean values (and the “selected pre-industrial value” by From and Keeling (1986)). In Gembloux, a rural site in Belgium, Petermann and Graftiau (1893) found for the period 1889–1891 a mean of 294 ± 18 ppm from 525 daytime measurements. Similar values have been found by Schulze (1871) who carried out over 4 years (1868–1871) daily CO2 measurements in Rostock:

– (n = )

 ±  (–) ppm

Remarkable that Franz Ferdinand Schulze (1815–1873), professor for chemistry, physics, and pharmacy since 1850 at the University Rostock, doubt by himself his earlier measurements:

– (n = )

 ±  (–) ppm

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As examples of other (unbelievable) high values owing to systematic errors, the following figures are given, by Gilm (1857)195 from Innsbruck (November 1856 – March 1857, n = 18) to be 415 ± 23 (381–458) ppm and by Farsky (1877)196 from Tabor, Bohemia (1874–1875, n = 27) to be 342 ± 8 (328–362) ppm. Farsky (1877) denotes himself as newcomer (“Als Neuling dieser Art von Untersuchungen . . . ”), giving to us as an example that handling and long-term experiences is needed for “correct” CO2 atmospheric air analysis as Blochmann (1886) emphasizes. On the other hand, there are a few historic measurements with averages significant less than 290 ppm. Remarkable measurements have been done in Dorpat (today Tartu, Estonia) belong the Medical Faculty in two doctor thesis (Heimann 1888, Frey 1889). Frey (1889) found a mean of 262 ppm (n = 556) with 189 (min) and 336 (max) whereas Heimann (1888) found 269 (n = 601) with 182 (min) and 375 (max); variation among monthly means are 250–283 ppm. When reading both works, the reader gets a strong feeling on its seriousness and that the measurements are accurate done. The interesting finding by Heimann (1888) is the day-night difference to be on average 28 ppm: day-time average 258 ppm (n = 379) and night-time average 286 ppm (n = 222). I fully agree with the statement by From and Keeling (1986) that analysis by French chemist Jules Reiset (1818–1896) show the highest level in analytical science for that time and seems to be most reliable. Reiset (1879) carried out a first series at a rural station 8 km from Dieppe (September 1872 until August 1873) with analysis at day- and night-time (n = 92) giving a mean of 294 ppm; additional parallel measurements above different crops and under free field conditions show differences up to 10 ppm less above vegetation and near a herd of sheeps (300 head) the CO2 increases to 318 ppm. In a later measurement campaign from June until November 1879, using improved sampling, described in very details, Reiset (1880) estimates a mean of 298 ppm (n = 91), including daytime (mean 289 ppm) and nighttime measurement (mean 308 ppm), unfortunately not mention the number of analysis. While fog, a mean of 317 ppm (up to a maximum of 342 ppm in intense fog) he found. All data have been related by Reiset to standard conditions (dry air, 0℃ and 760 torr). Besides Reiset, Müntz and Aubin (1882b) made very careful measurements at different sites; unfortunately only for relatively short time. In Vincennes, suburb of Paris, they found (n = 37) 284 ± 13 (270–317) ppm in April and May 1881, in Paris (December 1881 – February 1882, n = 20) 319 ± 26 (301–422) ppm and in April/June 1882 (n = 8) 293 ± 6 (288–306) ppm, at a rural site in 1881 (agricultural institute, n = 8) 300 ± 15 (273–329) ppm, and at

195 Hugo von Gilm (1831–1906), Austrian chemist. 196 Franz (František) Farsky (1846–1927), Czech chemist.

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Pic du Midi (2887 m a.s.l) in August 1881 as mean 286 ± 9 (269–301) ppm (n = 14). The number of single measurements is too low to get robust figures; the standard variations are therefore larger than expected from natural variations. Petermann and Graftiau (1891) compare his result with other measurements:

Rostock (Schulze),  Dieppe (Reiset), – Plaine de Vincennes (Müntz and Aubin), – Montsouris (Marié-Davy and Lévy), ca.  Gembloux (Petermann and Graftiau), –

    

More findings around “3” can be added: Halle, Germany (Marchand),  Atlantic Ocean (Thorpe),  Leeds, UK (Armstrong),  Belfast, Ireland (Letts and Blake),  Kew, UK (Brown and Escombe), – Boston, USA (Benedict), – Stockholm (Selander), – Copenhagen (Krogh),  Sweden, costal site (Lundegårdh), –

        

From the cited data 274we can assess the mean town contribution to background CO2 (remarkable only in winter) to be 40 ± 20 ppm and the day-night difference of 20–30 ppm. Assuming that 285–295 ppm is the range for a “best” daytime average, it follows a daily mean in the range of 295–30 ppm with the most probable mean between 300 and 310 ppm for continental background. Jean-Baptiste Dumas (1882) states as “la grande moyennes” 24–310 ppm CO2 as “normal value” (background in today’s sense). Baumann (1893) states in an excellent overview that the (mean) CO2 content of the atmosphere varies only small. However, according to Baumann (1893), the absolute minimum and maximum from all these measurements was 260 ppm and 354 ppm, respectively. This is much more than it can be explained by natural timely variations from such relatively remote sites. Brown and Escombe (1905b) estimated in Kew (UK) from 1898–1901 (n = 94) also a mean of 294 ppm CO2 (243–360, where only 9 values where larger than 320 ppm); they give an error of only ±1% (±3 ppm) which is unlikely low. The measurement series

197 Henrik Gunnar Lundegårdh (1888–1969) was a Swedish botanist.

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carried out in Boston by Francis Gano Benedict (1780–1957)198 between April 1909 and January 1912 is probably the longest and most precise of that time. Benedict (1912) tried carefully to avoid town influences, and by separating the values shown in Table 2.9 it is possible to derive a seasonal amplitude of about 9 ppm and a town contribution (adding to the rural background) of about 45 ppm; the most likely background mean is 307 ppm. Krogh (1919) states from Benedict’s analysis the background averages for CO2 of 0.030% (0.001% accuracy) identical with his own measurements (adding 10–70 ppm by town influence from Copenhagen). To give an example, how different values become when averaging, Callendar (1958) cites Benedict’s analysis as mean of 317.5 ppm (n = 645), much higher than shown in Table 2.9 for all cases but correct Krogh’s analysis to be 300 (n = 40). Callendar (1938) states a CO2 mean for the USA to be 310 ppm for the 1930’s (Table 2.10).

Tab. 2.9: Statistics of the CO2 measurements by Benedict (1912) carried out in Boston at the Nutrition Institute from April 1909 to January 1912 (assessed imprecision larger than 10 ppm).

mean (ppm) standard deviation min max n

all data

summera

winterb

all <  ppm

all >  ppm

    

    

    

    

    

a

April-September October-March

b

2.2.8 Trace gases Beside the major atmospheric gases, N2, O2 and CO2, atmospheric trace gases were known from the experiments by Priestley around 1774 (HCl, NOx, HNO3, SO2) but not yet identified in air. From alchemistic experiments (Section 2.1.3.3) many gases have been known (without its constitution but some main features) under archaic names. Hydrochloric acid (HCl), namely from “decomposing” sea salt seems to be known since ancient time: Nec decolour species æris, argentive . . . Argentum medicates aquis inficitur, atque etiam afflatus salso, sicut in mediterraneis Hispania (Plinius XXXI, 6)

198 American nutritionist (director of the nutrition institute in Boston), who developed a calorimeter and a spirometer, used to determine oxygen consumption and measure metabolic rate; known for his precise CO2 and O2 measurements.

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Tab. 2.10: Historic CO2 measurements (concentration in ppm); n number of samples or measurements. site or station Halle, Germany Innsbruck Rostock Atlantic Ocean Dieppea Taborb Leeds, UK Mountsouris Vincennesc Paris France, rural site Pic du Midi Stockholm Gembloux Dorpatd Belfast Kew, UK Boston, USA Copenhagen USAe

year

concentration

n

 – – –  –  –  –

  ±  (–)  ±  (–)f  ±  (–)   g  ±  (–)   ±  (–)h  ± . (–)i  ±  (–)  ±  (–)  ±  (–)  ±  (–)  ±  (–)   ±   (–)  (–)j   (–)   

   

 /    – –    – –  ’s

  

          

reference Marchand () Gilm () Schulze () Thorpe ()k Reiset () Reiset () Farsky () Armstrong ()l Lévy and Miquel () Müntz and Aubin (b) Müntz and Aubin (b) Müntz and Aubin (b) Müntz and Aubin (b) Müntz and Aubin (b) Selander () Petermann and Graftiau () Frey () Heimann () Letts and Blake (, ) Brown and Escombe (b) Benedict () Krogh () Callendar ()

a

All data have been related to standard conditions (dry air, 0 °C and 760 torr). Bohemia. c Suburb of Paris. d Today Tartu, Estonia. e Site rural mean. f Doubt by the author himself. g Daytime mean 289 ppm and nighttime mean 308 ppm. h Based on annual means. i Mean from all monthly means. j Variation among monthly means are 250–283 ppm; day-night difference to be on average 28 ppm: day-time average 258 ppm (n = 379) and night-time average 286 ppm (n = 222). k Sir Thomas Edward Thorpe (1845–1925), Bristish chemist. l George Frederick Armstrong (1842–1900), English sanitary engineer. b

[Or discolouring air constituents . . . Silver, on mixing with mephitic water, and even through salt emanations, particularly in the Mediterranean Spain]; cited after Lersch (1863, p. 64) who notes that the latter is related to free hydrochloric acid, occurring in the sea air. The first phrase is surely related to hydrogen sulfide, making silver black.

2.2 Discovery of air chemical composition

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Sulfur, or more precisely sulfur dioxide (SO2), is the oldest known pollutant (cited in the bible but known long before) because it was found residing close to volcanoes and the people quickly recognized its specific properties such as burning with a penetrative odor. Burning sulfur was used as fumigant, bleach or incense in the classical world. In Homer’s Odyssey, Ulysses said . . . “Bring my sulfur, which cleanses all pollution, and fetch fire also that I might burn it, and purify the cloisters” (Odyssey Book 22, translated by S. Butcher, Orange Street Press, 1998, p. 278). Without knowing the chemical species, its influence on air quality was described several hundred years ago in European cities where it was prevalent because of coal burning (e.g., Evelyn 1661). About 170 years ago, SO2 was first identified as the cause of forest damage in the German Erzgebirge. However, despite sulfur being the main chemical (among mercury) of the alchemists, it was regarded until 1809 (by Humphrey Davy (1778–1829)) as a composite body even though Lavoisier in 1777 had already recognized it as an element (simple body). Gay-Lussac and Louis Jacques Thénard (1777–1857) confuted still in 1809 this mistake (Kopp 1931, pp. 310–311) and from this time, sulfur has been seen as an element. Cavendish (1784) and Priestley (1789) described the HNO3 formation in moisture air under the influence of electric discharges. However, it seems that nitrous gases (NOx) and nitric acid (HNO3) as well as sulfur dioxide (SO2) have been supposed earlier, as described by Boyle (1692, p. 49): We may also hang up in such an Air, Clothes or Silks died with such Colours, that Nitrous (for Instance) or Salino-Sulphureous Spirits (as some Chymists call them) have been found peculiarly apt to make to fade, or to discolour them.

Boyle writes (likely observations already long known) on decolourization of linen at remote sites,199 obviously due to air chemical operations (ibid., p. 50): In some Places also, which are judged likely to afford subterraneal Steams, guesses may be made, whether this or that kind of Salt ascends into the Air, by spreading upon the Ground, in Places free from Dirt and Dusts, large Pieces of clean and white Linen Cloth, that has no Relish of Sope or Lees; and observing, after they have lain a competent while, whether, and how they are discoloured, and what kind of Saltness, if any, is to be found in the Moisture imbibed by them, from the ascending Steams and falling Dew.

Half a century later, from the same observation but including investigation of the dew by Boerhaave (1735, p. 460) it seems to me a first evidence for atmospheric hydrogen peroxide (H2O2)200: 199 The bleaching properties of dew have been known for centuries and dew has been used for the cleansing of clothes. Textiles have long been whitened by grass bleaching (spreading the cloth upon the grass for several months), a method virtually monopolized by the Dutch from the time of the Crusades to the eighteenth century. 200 Metallic copper causes the explosive decomposition of hydrogen peroxide when the solution has a concentration of 30 percent or greater. John Papiewski https://sciencing.com/copper-explode -16298.html.

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So again, perfectly pure water, thrown upon wax, or fprinkled upon linnen to be whitened, gives them a perfect whitenefs; but if the Water be impure, it leaves them lefs white: it grows hot and cold fooner than other water, and is never improved by boiling. Pure gold and filver, being melted feparately or conjointly, and poured into this pure water whilft cold, pals quietly thro' it, and are found granulated at the bottom: but iron, tin and lead, melted and poured into water, enter it with a violent explofive motion, and immediately fly from it like (hot, in a dangerous manner: and copper, treated in this way, explodes with the violence of gun-powder; of which there are terrible examples). This wonderful property of water feems to me unexplicable upon any known principle. Pure, fimple rain-water may, in a proper fenfe, be efteemed the mercury of animals and vegetables; as being not unlike quickfilver in fimplicity, and, according to Helmorit, the firft principle from whence all things proceed, and into which they are ultimately refolvable.

Finally, William Prout (1785–1850), British physician and chemist, who was the first to propose the existence of H2O2 in air, draw from such observations the following clear conclusion (Prout 1834, p. 570)201: . . . the bleaching qualities of dew, and of the air itself; as to the large proportion of oxygen sometimes contained in snow water and in rain water . . .

Ammonia202 (Scheele identified nitrogen in “alkaline air” (NH3); the formula was established in 1785 by Berthollet) was found in air by Scheele in 1786 by observing that a precipitate originated on the cork a bottle containing hydrochloric acid, identified as salt ammonia (NH4Cl) and it was later confirmed by Théodore de Saussure in the early 1800s. Still in 1900, it was stated that ammonia never exists freely (i.e., in gaseous form) in air but only in compounds with carbonate and others (Blücher 1900). A paper entitled Composition de l’atmospère by Jean-Baptiste-Alphonse Chevallier (1793–1879), a French pharmacist and student of Vaquelin, the finest analytical chemist of his days in France, is likely the first written document (without any details on sampling and analysis) concerns trace gases in the air (Chevallier 1834): – in general, the air in Paris and many other site contains ammonia and organic matter, – dew contains ammonia and organic matter, – the composition of the air varies not much because of then overall combustion and decomposition of vegetable and animal matter, and more, – the air of London contains sulfuric acid, – the air of sewage in Paris contains ammonium acetate and hydrogensulfate, – the air in the valley of Montsaucon (north of Paris) contains ammonium hydrogensulfate. 201 From our current knowledge on photosensitized formation of oxygen radicals in surface wetness this is a clear evidence for H2O2 formation (see Section 5.2.5 in Vol. 1). 202 Ammon was worshipped under several names with different attributes. As Ammon-Ra, he was the sun god, with his chief temple at Thebes; as Khem or Min, he was the god of reproduction; as Khnum, he was the creator of all things, “the maker of gods and men.” The chief temple of Khnum was in the oasis of Ammon (now Siwah). The Greeks and Romans identified Ammon with Zeus or Jupiter (see for more details Sutton et al. 2008).

2.2 Discovery of air chemical composition

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Hayes (1851, p. 208) writes: Considerable quantities of ammonia have been found by several observers at different times; but the most trustworthy results are those of Fresenius, in a series of experiments on the air over a dwelling in Giessen.

In the nineteenth century, two methods for sampling and determination of soluble and insoluble atmospheric bodies have been used; first so-called air-washing, that is, water or a specific solution is shaken in a bottle together with the air to be examined (until hundreds of times), and second, passing the air through water or absorbing solution (aspiration method). First quantitative determination of ammonia in air (according to the sampling technique it refers to the sum of gaseous ammonia and particulate ammonium) were carried out by Kenneth Treasure Kemp (1805–1842), chemist in Edinburgh, by A. Gräger, German pharmacist in Mühlhausen (Thuringia) in 1845, who also translated Boussingault’s Écomonie rurale into German, and Fresenius in 1848: . . .

(ppmm), before ,  feet above the Irish Sea (Kemp) (ppmm),  days in May  in Mühlhausen (Gräger ) (ppmm),  days Aug. – Sept.  suburb of Wiesbaden (Fresenius )

203 Mass ratio, i.e., gram per million gram of air. To recalculate in mg m–3, this value must by multiplicated by factor 1.293 (1 kg air corresponds to 1,293 kg). 204 Kemp likely never published a paper; he is first cited by Fresenius (1849) without any source of communication. D. F. Gregory writes (The London and Edinburgh Philosophical Magazine and Journal of Science 13 (1838) 434) on Kemp: “I do not know wether or not Mr. Kemp communicated a paper . . . to any of the journals, but I know that he communicated them freely to other chemists”. Kemp’s first appointment was that of a lecturer on practical chemistry in Surgeon’s Square. He proceeded thence to a similar position at the University, which he held until his early death. He seems to have possessed great experimental skill. Among other subjects he investigated the laws of combustion and the liquefaction of gases. He was the first chemist in this country who succeeded in solidifying carbonic acid gas, which he appears to have hoped for equal success in relation to every other gas. He told his students that they might one day see him carrying a stick of solid hydrogen (source: www.kempfamilyhistory). 205 Gräger writes 0.6149 parts ammonium carbonate [kohlensaures Ammoniak] in 1,000,000 of air (ppmm). Gmelin (1852, p. 837) cites wrongly 0.938 (ppm) kohlensaures Ammoniak or 0.508 (ppmm) Ammoniumoxyd or 0.333 (ppmm) ammonia; the latter value is cited by all later scientists. However, there are several “problems” in recalculation; Gräger estimated after absorption of 36 cubic feet air into hydrochloric solution and precipitation with platinum chloride the weight of Platinsalmiak to be 0.006 g = 0.0008466 g kohlensaures Ammoniak. Fresenius (1849) recalculates Gräger’s 0.006 g Platinsalmiak in 0.0007 g Ammon (NH4O), which gives 0.508 ppmm Ammon = 0.323 ppmm NH3 = 0.938 ppmm NH4OCO3 (thus, the values in Gmelin are taken from Fresenius). The latter value, however, is only correct (0.938/0.323) when the formula (NH4)2CO3 for kohlensaures Ammoniak is used. Assuming Platinsalmiak to be platinum hexachloroplatinate (NH4)2PtCl6 it follows never 0.008466 g for kohlensaures Ammoniak as given by Gräger (1845) but either 0.0013 g (NH4)2CO3 or 0.002 g NH4OCO2. The ratios between Fresenius’ Ammon and Gräger’s kohlensaures Ammoniak remain obscure too. 206 Daytime 0.098 ppm and nocturnal 0.257 ppm. Fresenius writes that Gräger not proved the chemicals to be free of ammonia; the value by Kemp he doubt to be to high.

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. .–. .–. . . . (.–.) .–. . . . .–. .–. . .–.

(ppmm), n = , Boston  (Horsford ) (ppmm), –, Paris (Ville ) (mg m–), Caen, winter – (Pierre ) (mg m–), Caen, one year observation – (Pierre , p. ) (mg m–), Pic du Midi (Müntz and Aubin a) (mg m–), Lyon (Bineau ) (mg m–),  Prince’s road in Manchester (Smith ) (mg m–), n =  (.–.) London  (Smith , p. ) (mg m–), n =  (.–.), Glascow  (Smith , p. ) (mg m–), London (Smith ) (mg m–), annual means Montsouris (Paris) –, Lévy () (mg m–), Budapest (Fodor ) (mg m–), Buenos Aires  (Anonym )

It seems that Georges Ville (1825–1897), French agricultural chemist and agronomist at Paris, conducted the first reliable and long-term measurements of ammonia in air, showing only small variations, corresponding to 22–38 µg m–3. His valued are close to that gained 25 years later by Lévy. Alfred Daniel Hall (1864–1942), director of the Rothamsted Experimental Station (1902–1915), studied together with N. H. J. Miller the absorption of ammonia from the atmosphere, hence, it was one of the first studies on dry deposition (Hall and Miller 1911); likely Miller was the principal investigator, who studied for many years the rainwater chemical composition (see Section 2.4.6.2). However, Smith (1878, pp. 269–270) already clearly expressed that “ammonia was everywhere”, “and in the air it is always found”, and being very soluble in water “it touches all substances and can be found on many”. Smith hung clean and empty flaks in various parts of his laboratory and “ammonia could be observed after an hour and a half’s exposure at any rate”; he presents several Tables concerns “absorption of ammoniacial substances from air near the ground and other places by pure water placed in a basin under a bell jar” in Manchester 1875. From Smith’s data a mean dry deposition value of 27·10–5 mg m–2s–1 results; from “typical” today’s values (NH3 concentration 5 µg m–3 and dry deposition velocity 0.8 cm s–1) a deposition of 4·10–5 mg m–2 s–1 results, about 7-fold less – but Smith found NH3 in air to be 86 µg m–3, thus the historical values are reliable. Carl Alexander Müller (s. p. 186) from Stockholm reports in a very short communication (Müller 1865) on a long-term experiment210 on absorption of ammonia onto shallow

207 Eben Norton Horsford (1818–1892), US American chemist, student at Liebig. He stated that his value are several time higher than those of Fresenius (Horsford 1849). 208 Smith found in his office 0.167 mg m–3 ammonia, more than outside. 209 Small variations from year to year (1875–1879) and in 1879 from month to month (0. 017–0.024) and between 4 sites (0.015–0.019) in Paris. 210 He announced an extended communication for the next year (1867), however, I have not found any later paper by Müller on this issue.

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glass bowls (cuvette), filled with distilled sulfuric acid and protected with a roof to avoid rainwater deposition, over four month and found a deposition of 0.028 g per square foot or equivalent to about 4 kg ha–1 (mentioned that 23 kg is the minimum for fertilizing, thus atmospheric deposition cannot replace nitrogen fertilizing, he concluded). Sulfur dioxide (called sulfurous acid in the nineteenth century, and not always clearly separated from sulfuric acid or SO3) became in the interest of research first in England due to coal combustion (Smith 1845) and in Germany, namely Saxonia due to observation of forest damages in relation with mining and ore smelting (Stöckhardt 1850). Chevallier’s remark (see above) is likely the first written source on sulfuric acid in the air (of London). The gas (SO2), observed while burning of sulfur, was first particularly investigated by Stahl (who called it phlogistigated vitriolic acid), 1771 by Scheele and 1774 by Priestley, 1782 and 1789 by Berthollet, and 1797 by Fourcroy and Vauquelin (Gmelin 1852, p. 602). Lavoisier showed that sulfurous acid was an intermediate oxidation compound between sulfur and sulfuric acid. The French chemist Jean Pierre Joseph d’Arcet (1777–1844),211 traveling in 1831 to London, was the first who detected in fresh rainfall (collected with porcelain bowls) sulfurous and sulfuric acid; blue litmus paper turns red (D’Arcet 1834). Robert Angus Smith is the first who systematic measured SO2 and HCl in the air of Manchester and London, published in the “Annual Report by the Inspector of the Alkali Act” (first report for the year 1863 published in 1864, London) from 1868 onwards (see also Smith 1872, pp. 427–428); in µg m–3: SO SO HCl HCl

 (–), n =  (Manchester )  (–), n =  (London )  (–), n =  (Manchester )  (–), n =  (London )

Albert Ladureau (no living data known), director of the agricultural experimental station at Lille estimated the atmospheric SO2 concentration to be 1.8 ppm(v) and found in rainwater 22 µg L–1 sulfuric acid (Ladureau 1883). Julius Stoklasa measured SO2 in Prague (Stoklasa 1923), in mg m–3: .–. .–. .–.

  , industrial area

Smith (1859a) determined the relative amount of organic matter (including other oxidizable substances) by air-washing:

211 Not to confuse with his father Jean D’Arcet (1724–1801); to him were Leblanc and Pelletier as students.

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. . . . . .

2 History of investigation and understanding the climate system

Manchester (n = ) London (n = ) London, after a thunder-storm open sea (German Sea,  miles from Yarmouth) forest at Chamonix Lake Lucerne

It cannot be stressed enough how far-sighted Robert Angus Smith the idea of a Chemical Climatology emphasized; he wrote (already 1869) (Smith 1877): For a satisfactory investigation of the subject, one must look to the multiplication of these experiments, and perhaps to the establishment of a department at some Observatories for Chemical Climatology and Meteorology. . . The importance of having a chemical department to out observatories cannot be long overlooked.

Smith, obviously disappointed, writes further: I should have been glad had may work caused in this country a beginning such as has been lately at the observatory Montsouris, at Paris, or at least resembling it: and I blame myself for not pushing forward the idea, although my numerous engagements may well form kind of apology.

Clarke (1920, p. 46) expresses the knowledge on SO2 at the turn of the century in following words: It undergoes rapid oxidation in presence of moisture, being converted into sulphuric acid, and that compound, either free or represented by ammonium sulphate, is brought back to the surface of the earth by rain.

Remarkable is the attempt by Hugo Reinsch (1809–1884)212 who first unsuccessful collected air using woulff’s bottles (aspirator method) and afterwards constructed “air absorbing” large linen roofs (26 square feet), monted on 4 stakes, permanent wetted and sprinkled by aqueous solutions over 12 h per day for a 14 day experiment. A first absorber was sprinkled with diluted hydrochloric acid, a second with sodium hydroxide solution and a third with distilled water, where the linen was impregnated with gypsum (Reinsch 1865); later he suggested to install the linen vertically instead of horizontally.213 In the solution from the first (acid) absorber roof he found Al, Na, K, Ca, Mg, H2SO4, Pb, Zn, Cu, Fe, Mn, and SiO2. In the solution from

212 Edgar Hugo Emil Reinsch (but in literature only as H. Reinsch), German pharmacist and later technical chemist, teacher and Rector at Zweibrücken and Erlangen; wrote the book “Grundriss der Chemie für technische Lehranstalten” [fundamentals of chemistry for technical schools], Bassermann & Malty, Mannheim, 1854, 316 pp. 213 To my knowledge, no further such experiments have been carried out to collect atmospheric trace species; however, this principle (using large pieces of vertical canvas) has been used in the twentieth century for fog water collection (Schemenauer and Cereceda 1994).

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the second (alkaline) absorber roof he found H2CO3, H2SO4, H3PO4, HCl, FeO, MnO, and SiO2 and from the third roof mainly ammonium sulfate. A few years later (Reinsch 1869) he collected large amounts of air over 4 weeks by using four bubblers in line (water + ammonia, water, water + HCl, and water) and concluded on the permanent presence of H2SO4, H3PO4, HNO3, and HCl in the air. Henry Henriet, together with Albert Lévy (Henriet 1904) determined formaldehyde (HCHO) in the air at Montsouris in 1903 to be in the range 20–60 mg m–3 and mentioned its extreme amount in comparison to that of ozone (10–30 µg m–3); however, the value for HCHO is orders of magnitude too high. It is amazing, what was known in the middle of the nineteenth century on the impact of SO2 onto vegetation and the emission as well as technical problems from different technological processes such as brick fabrics, sulfuric acid manufacture, soda factory, copper smelter, and more; the emission of SO2 for the year 1872 in Germany is given to be 1 Mt from combustion of 33.7 Mt hard coal (Schubert 1857, Anonym 1876). Only around 1900 were all these gases (NH3, HNO3, and HNO2) directly identified in the atmosphere. In the nineteenth century, the terms ammonia, nitric acid, nitrous acid, sulfurous acid, sulfuric acid, and so on, were used in the same sense for dissolved species (ammonium, nitrate, nitrite, sulfite, and sulfate) as well as anhydrites (e.g., SO2). Ammonia (NH3) was known as a result of putrefaction of vegetable and animal matter. Nitric acid (HNO3) was “known” as a result of thunderstorms and was believed from oxidation of atmospheric ammonia. The various oxides of nitrogen had created some confusion in the early nineteenth century. In 1816, Gay-Lussac had succeeded in distinguishing five oxides of nitrogen and had given their correct chemical composition. Atmospheric H2S was known from mineral springs and rotting organic material. “Hydrocarbon” (not yet specified as methane, CH4) was known from marshes and swamps (called swamp gas) and many natural gas sources (from which it was already sometimes used as fuel). This gas was feared by coal miners, who called it “firedamp” because it caused dangerous explosions. Natural sources of phosphurated hydrogen (phosphine PH3) have been identified as sewage sludge, swamps, and human flatus. In the early nineteenth century phosphine (which is spontaneously inflammable) was also known from cemeteries where it sometimes burned with blue flames. Nothing was known in the nineteenth century on the origin of ozone and hydrogen peroxide – they have been considered as natural constituents of the atmosphere. Atmospheric chemistry was still reduced on “electric” activities in the atmosphere, mainly lightning. Photochemistry have been considered with the beginning 1920s, but only the O3 formation from O2 photolysis have been described. Radicals have been detected in combustion gases in the 1930s, assumed to be in the atmosphere in the 1950s but detected only after 1970 (Table 2.11). What is follows is only the history of ozone and hydrogen peroxide; it is my aim to write an extended History of Air Chemistry that will be printed in 2022 on the 250th anniversary of the discovery of oxygen.

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Tab. 2.11: Discovery of chemical species in air (metals and metalloids are not listed); note that discovery of some elements and compounds in mineral, vegetable, and animal matter was earlier.

O N C S Cl Br I H P

eighteenth century

nineteenth century

twentieth century

O N CO

O, HO HNO, NH, NO/NO (NOx) a, ONb carbonate, CH, OMc, CO SO (sulfite), SO (sulfate), HS HCl (chloride) bromide iodide H phosphate, PH

O, OH, HO NO, HNO, NO, NO, org. N NMVOCe, POPf, organic radicals CS, COS, org. S Cl, Cl, HOCl, ClOd, org. Cl HBr, BrOd, org. Br HI, IOd, org. I H, H+, HO– other phosphanes, org. P

HO

a

Including nitrate, ammonium and nitrite. Organic nitrogen (“albuminoid”). c Organic matter (unspecified). d Many more oxides and oxo acids. e Non-methane volatile organic compounds. f Persistent organic compounds. b

2.2.8.1 Ozone To the philosophers, the physician, the meteorologist, and the chemist, there is perhaps no subject more attractive than that of ozone (Cornelius Benjamin Fox (1839–1922), US American chemist). (Fox 1873, p. 1) Ozons, jenes oxydierenden Stoff, über dessen Nature man ungeachtet der schönen Arbeiten der HH Schönbein, Marignac und De la Rive, Frémy und E. Becquerel so wenig übereinstimmt [Ozone, this oxidizing matter, on that nature despite the fine works of Messrs Schönbein, Marignac and De la Rive, Frémy and E. Becquerel, one agrees so little] (Jean Auguste Houzeau (1829–1911), French agriculture chemist in Rouen). (Houzeau 1855) Es giebt wohl keine Körper, welche in der Literatur der Chemie in den letzten Jahrzehnten so häufig auftreten, als das Ozon und das Wasserstoffperoxyd [There are probably none bodies, which occur so often in the chenical literature of the last decades such as the ozone and the hydrogen peroxide] (Carl Weltzien (1813–1870) professor for chemistry in Karlsruhe). (Weltzien 1866) Der electrische Sauerstoff, welcher Stoff und Kraft zugleich ist, zeigt die Einfachheit des irdischen Haushalts, weil er in der grossen Natur grosse Aufgaben zu lösen hat [The electricized oxygen, which is together matter and power, shows the simplicity of the earth’s economy, because he has to solve great tasks within the great nature] (Carl Friedrich Constantin Lender (1828–1888) German physician). (Lender 1873a) Though it has been known for more than a century that air and oxygen acquire a peculiar odour when exposed to the action of electric sparks, and though Schönbein ascertained nearly half a century ago that this odour is due to a distinct form of matter, now called ozone, which is produced by the electrolysis of dilute sulphuric acid, by the action of electric discharge in air, and as a product of the slow oxidation of phosphorus, chemists are still trying to learn the

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exact conditions of the formation of this substance, and still investigating some of its simplest reactions; whilst inventors are but beginning the work of making it useful to man. [Anonym (1898) The production and uses of ozone. Nature 58, 416–418]

These historical phrases illustrate the diverse interest of chemists in understanding the role of ozone in the atmosphere – as intrinsic component of air and not foreign body – and thus in the balance of nature. It was recognized to be a substance of unusual properties which has never been isolated in the pure state. The given names (before accepting ozone) show the relation to oxygen: electricized oxygen, allotropic oxygen, nascent oxygen, active oxygen, excited oxygen (from the German erregter Sauerstoff]. Today we know that ozone is produced under natural conditions only in the atmosphere under the influence of lightning and / or UV radiation from oxygen214; no biological and other geochemical process can produce ozone (in contrast to hydrogen peroxide).215 Ozone was discovered by German chemist Christian Friedrich Schönbein (1799–1868) in Basel while conducting electrolysis experiments with water; he reported on March 13, 1839, to the local Naturforschende Gesellschaft in Basel (founded in 1817) on an odor at the positive electrode which was the same as the odor produced by an arc between electrode: Herr Schönbein macht die Gesellschaft auf die merkwürdige und bisher noch nicht beobachtete Thatsache aufmerksam, dass bei der Electrolyse von Wasser an der positiven Electrode ein Geruch entwickelt wird, auffallend ähnlich demjenigen, den man beim Ausströmen gewöhnlicher Electricität aus Spitzen wahrnimmt [Mr. Schönbein calls the Society’s attention to the noteworthy new observation that a smell develops at the positive electrode during electrolysis of water which is strikingly similar to that obtained by the flow of electricity across electrode], cited after Rubin (2001).

Dutch chemist Martinus van Marum (1750–1837), subjecting oxygen to electrical discharges in 1785, noted “the odor of electrical matter” and the accelerated oxidation of mercury. Thus, van Marum reported the odor of ozone but he failed to identify it as a unique form of oxygen. The Scottish chemist William Cruickshank (1745–1800) also mentioned in his last life year during electrolysis of sulfuric acid a “chlorine-line“ odor (Gilb. Ann. 7 (1801) 88–113).216 Schönbein names this gas “ozone” after the Greek word όζειν (to smell). His friend Friedrich Mohr (1806–1879), pharmacist in Coblenz,

214 The only other way is via photolysis of NO2 into NO + O, where the latter reacts with O2. 215 There are two processes of O3 formation under human operation, already discovered by Schönbein. In electrolysis of acids and salts, namely sulfuric acid, anodic O3 liberation is observed; O2 the mechanism seems to be (cf. pp. 302–303 in Vol. 1) OH − !− OH ! HO3 !+ O3− !− O3 . In −e −e −H slow oxidation of elemental phosphorus in contact with air, during glow many reactions occur such as 2P + O2 = P2O + O, P4O + O2 = P4O + O + O (subsequent O + O2 = O3). The ozone formation at high temperatures (due to O2 = O + O) is likely but only short-lifed under the conditions of the reactions (see Rubin (2007) for history). 216 Gilberts Annalen = Annalen der Physik (see comments under references).

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explains in a wonderful poetically communication (Mohr 1854) the word as onomatopoeia “oz–zo,” derived from όζω (I smell) and όδμή or οσμή (odor). In a letter sent in 1840 to François Arago and submitted to the French Academy of Sciences, Schönbein suggests that ozone could belong to the chemical group of chlorine or bromine. The Swiss physicist Auguste Arthur de la Rive (1801–1873) argued that this smell is derived from lost metallic particles (de la Rive 1841, pp. 402–405). Schönbein (1858), who never identified the constitution of ozone, proposed the existence of another form of reactive oxygen species which he called antozone. He believed that ozone and antozone were both formed under ozone-producing conditions (quiet electric discharges of air) and react together to give oxygen217 hence explaining the low yield of ozone by its destruction by antozone. He first believed that this new substance is bonded together with hydrogen, and a body similarly to bromine and chlorine, and later identical with hyponitrous or nitrous acid, after revising this view, he stated that ozone is a higher compound of oxygen with hydrogen, but different from Thénard’s hydrogen peroxide (see Table 2.13). Schönbein also ascribes the smell occurring together with lightning strokes, since the antiquity described as “sulfurous,” to this new substance ozone. In a letter to Justus von Liebig from 5.9.1853, Schönbein emphasized the role of ozone in the earth atmosphere (Kahlbaum and Thon 1900, p. 10): Geneigt zu glauben, das atm. Ozon spiele im Haushalte der Erde eine wichtige Rolle, halte ich es fuer wünschenswerth, dass möglichst zahlreiche, sowie grosse Zeiträume als bedeutende Laenderstrecken umfassende, untereinander vergleichbare Beobachtungen ueber die Veränderungen des Ozongehaltes der Atmosphäre angestellt werden. . . [Inclined to believe that atmospheric ozone plays an important role in the earth’s budget, I think it is desirable to carry out as many as possible as well as big periods and comprehensic major routes comprising observations on the variation of the atmospheric amount of ozone, comparable with each other. . .].

On the nature of ozone In 1845, Auguste de la Rive communicates in a postscript “Sur l’ozone” that together with the Swiss chemist Jean-Charles de Marignac (1817–1894) they produced ozone from pure and dry oxygen, and suggested that ozone is a form of oxygen: l’ozone ne provient que de l’oxygène (de la Rive 1845, p. 1291). This was the first correct view on the nature of ozone. The US American chemist Thomas Sperry Hunt (1826–1882), professor at MIT, was the first who proposed speculative in 1848 the formula O3 (cited after Rubin 2001).218 Jean Auguste Houzeau (1829–1911), French agriculture chemist in Rouen, first proved by careful experiments this chemical composition (only consistent from oxygen): n’est pas un oxide d’hydrogène (Houzeau 1855, 1856). This was soon later supported by Thomas Andrews (1813–1885), professor for chemistry at the Queen’s

217 Later described as O3 + H2O2 → H2O + O2. 218 Morcedal Rubin (1924–2012) Israel chemist, published a series of articles on the history of ozone (Rubin 2001, 2002, 2007).

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College in Belfast, studying the decomposition of ozone together with Peter Guthrie Tait (1831–1901), and not detecting water in (Andrews 1856, Andrews and Tait 1860), and confirmed later by Soret (1863) and von Babo (1865). The English chemist William Odling (1829–1921) suggested in his “manual of chemistry” (Odling 1861) that the formula of ozone is O3 based on the volumetric experiments by Andrews and Tait. The German physicist Rudolf Julius Emanuel Clausius (1822–1888), who discovered the second main of thermodynamics, explains the formation of ozone from oxygen through electric discharge by the dissociation of both atoms of the molecule [Trennung beider Atome eines Moleküls], and the observation that only a small amount of ozone is gained, by recombination of single atoms [Wiederverbindung der einzelnen Atome]; hence only a small part remains separated and forms ozone [kleiner Theil bleibt vereinzelt und bildet Ozon] (Clausius 1858). Lambert Heinrich Clemens Karl Freiherr von Babo (1818–1890), who studied medicine in Heidelberg and Munic, but begun a carrier in chemistry at Liebig in Gießen and since 1844 at the University in Freiburg (Breisgau), constructed an apparatus to produce ozone (Babo 1861), and conducted experiments to proof that ozone does not contains hydrogen (the formulas HO, HO2 and HO3 have been discussed before) and that oxygen can be converted completely into ozone (Babo 1863). Babo also stated that the oxidizing properties of ozone only are observed in presence of water (Babo 1865). In 1868 the Swiss chemist Jacques-Louis Soret (1827–1890) in Basel, determined the density of ozone gas using Graham’s law of diffusion, and found the ratio 3 to 2 for ozone to oxygen. He established quantitatively that ozone is an allotropic form of oxygen: OOO or O3 (oxygen dioxide). Soret also conducted several experiments on the consumption of ozone in different chemical reactions. The well-known Scottish organic chemist Alexander Crum Brown (1838–1921), who never studied atmospheric ozone to my knowledge, wrote a short paper (Brown 1869), summarizing the knowledge in an excellent scientific style: Andrew and Andrew and Tait established that ozone is merely a form of oxygen, and that oxygen can be transformed into ozone, and ozone into oxygen, without the production of any other substance. Soret’s experiments seem further to prove that ozone is denser than oxygen, in the proportion of 3 to 2. Common oxygen can be transformed into ozone by means of the silent electric discharge, oxygen is ozonized in the course of many slow processes of oxidation, and particularly by the slow oxidation of certain volatile oils. These processes undoubtedly occur to a great extent in nature.219

219 Ozone formation during autoxidation is possible (see p. 245 in Vol. 1), however, in the case of organic compounds containing double bonds (such es turps), ozone would be added (ozonolysis) and the decaying ozonide (see p. 415 in Vol. 1) forms reactive oxygen species that additionally react with the alkenes. The formation of ozone while slow oxidation of oils such as turpentine, was already doubt by Kingzett (1874); he clearly states that (ibid., p. 520) “When oil of turpentine is exposed to air or oxygen in presence of moisture, it oxidises, producing an agent which resembles ozone and peroxide of hydrogen,…”.

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This phrase can be transformed into the reaction scheme energy

O2

O+O

2 O2 energy (–2 O2)

2 O3

(2.1)

The source of energy to produce ozone was either electric discharge in the laboratory or in the atmosphere during thunderstorm; the energy for ozone decomposition has been regarded generally as heat (radiation energy to photolyze the molecules have been regarded only in the 1920s). Brown, however, was wrong with the statement that ozone is gained from oxygen in slow oxidation processes, later called autoxidation, discovered by Traube (1882) as a source of hydrogen peroxide (see next Section).220 This can be attributed to the close affinity between O3 and H2O2, confusing by same detection in air with the Schönbein paper and similar oxidative behavior, not knowing in that time that both compounds produce OH radicals, the “true” air cleanser. Brown further writes: Ozone is converted into common oxygen by heat, by contact with various substances which do not themselves undergo change in the process; such substances are peroxide of manganese [MnO2], peroxide of lead [PbO2], black oxide of copper [CuO], etc. Ozone acts upon a small class of substances as a reducing or deoxidizing agent; thus it reduces peroxide of hydrogen to water, being itself, at the same time, converted into common oxygen. Ozone acts on most substances as an oxidizing agent. Thus it corrodes organic matter, bleaches indigo, converts sulphuretted of lead into sulphate of lead, etc.

Basically, the ozone chemistry is well described phenomenological.221 The problems of detection of ozone in the air, Brown describes clearly: (a) by oxidation of iodide of potassium, (b) by oxidation of oxide of thallium, (c) by oxidation of sulphate of manganese, which is of brown colour. (c) is very characteristic, converting sulphate of manganese into peroxide of manganese [MnO2]; no other substance which can be supposed to exist in the air is known to have this action.

Brown then explains that the brown color is hard to differentiate concerns O3 levels and that the thallium paper is sensitive against CO2, gaining brown thallium 220 However, that the formation of H2O2 proceeds either from O2 according to Eq. (2.6) via photosensitizing or from O3 via the reaction of (O1D) with H2O (Eqs. (2.2) and (2.8)) became clear only 100 years later. 221 Peroxide of manganese was in that time the name for manganese dioxide (MnO2). The wellknown property of MnO2 and CuO (and other oxides) to decompose O3 goes via a catalytic surface mechanism, which have been understood 150 years later. Li et al. (1998) suggest the peroxide intermediate formation (S – surface of the catalyst): S + O3 = S–O + O2, S–O + O3 = S–O–O + O2, and S–O–O = S + O2 (slow). There is no direct reaction between O3 and H2O2 in the gas phase; reaction (5.33) on p. 279, Vol. 1 is rather unlikely. Indirectly, O3 reacts with OH (which can be produced from slow H2O2 photolyses, but rather from O3 photolyses itself) in air. In aqueous phase, H2O2 and O3 turn into OH radicals by separate reactions, thus itself converting into H2O and O3, respectively. Finally, the oxidizing capacity of O3 (with the exception of a direct reaction with olefins) results from the OH radical, gained in subsequent reactions.

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carbonate; the first methods results in violet-blue colors due to formation of free iodine and thus giving relative quantities of ozone in air, but are sensitive concerns humidity and all other oxidizing substances. Ozone measurements in the nineteenth century Ozone, as a natural component of air, was found in 1866 (Andrews 1867), despite the fact that the so-called Schönbein paper (ozonometry) had already been used in England in 1848 for atmospheric “monitoring”. Houzeau carried out the first atmospheric O3 measurements near Paris in 1856 and developed later a semiquantitative method, a paper involving a mixture of iodide of potassium and litmus together with a specific holder, where different colors correspond to certain ranges of the ozone concentration (Houzeau 1872); in 1857 he measured for the first time 10–8 (10 ppb) ozone (Houzeau 1872, p. 46). He presents the first systematic (relative) measurements 1861–1870, carried out in Paris and Rouen; as quantitative mean he called the number of hours with and without ozone in air. The seasonal cycle of ozone (maximum in May and June, minimum in December and January) Houzeau contributed to causes of natural variation [réveil de la nature] and separated a very active and nonactive season in link with sunshine and vegetation, but also speculates that the less rainfall in summer maybe a cause. Furthermore he found that the atmospheric amount of ozone is largest when the air in Rouen comes from south to south-west and smallest from west (by a factor of 3–4). Houzeau is also the first who found that the concentration of ozone is at night lower than daytime (most other observers found it vice versa, see below). Based on his measurements in different cities of France, Houzeau (1872, p. 26) writes the remarkable phrase: . . . evidence l’influence des localités sur la manifestation de l’activité chimiques de l’air.

At that time, nothing was known about the atmospheric formation reactions of O3 and H2O2 and which chemical mechanisms existed between both species in the gas and aqueous phases. The formation of ozone, hydrogen peroxide and nitric acid in air had been attributed generally to “variations in the electrical condition of the atmosphere” (Fox 1873). Thus, Houzeau (1872, p. 62) concluded that ozone is a natural constituent of the air222: . . . dans la nature et permettent à l’électricié atmosphérique d’ozoniser l’oxygène de l’air.

The atmospheric electricity, Houzeau writes, is also permanent in air. Houzeau (such as Schiefferdecker, Reslhuber, see below) found that on rainy days the ozone

222 It should be noted that in that time the photochemical ozone formation in the troposphere was negligible due to very small NO2 concentrations, lilely below 0.5 ppb (approximately derived from the ratio of nitrate in rainwater today and that before 1870); thus the chemical regime was rather ozone consuming. The only source of ozone – such as today unchanged – was the transport from the stratosphere down (hence providing a maximum in spring). Therefore, transport and nearsurface removal processes were dominant causes for observed ozone variations.

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level is larger than on “nice” days (38 days with ozone to 100 days with rain and 28 days with ozone to 100 “nice” days). Engler (1879, p. 51) presents a remarkable explanation; rain and snow washes out dust particles from the atmosphere and thus reduce ozone decomposing substances; as already stated by Fox (1873, p. 74): The washing out of the air of the impurities continually passing into it, in the oxidation of which the ozone was previously consumed.

The period 1850–1880 of uncounted ozone measurements using the Schönbein paper has often been criticized and it is likely that apart from ozone, also nitrous acid223 and mostly hydrogen peroxide were also responsible for the blue coloring of the paper. The objection to Schönbein’s ozonometer (potassium iodide on starch paper) and to Houzeau’s ozonometer (potassium iodide on red litmus paper) lies in the fact that their materials are hygroscopic, and their indications vary widely with the moisture of the air; the intensive “ozone reaction” near places with intensive water evaporation, for example, waterfalls have been wrongly interpreted as an ozone source. Later Emil Schöne provided the results of an extended series of experiments on the use of thallium paper for approximately estimating the oxidizing material in the atmosphere, whether it be hydrogen peroxide alone, or mixed with ozone, or perhaps also with other constituents hitherto unknown. Thus, his findings may indicate an oxidizing species, but with our present knowledge it is possible to conclude that the “ozone reaction” is due to hydrogen peroxide in air. Whereas no definite reagents were available for ozone detection, H2O2 was clearly detectable in solution (e.g., rain water) in the presence of ozone and nitrous acid (Schöne 1893). Gottfried Wilhelm Osann (1797–1866), German chemist in Dorpat, Erlangen, Jena and professor for chemistry and physics in Würzburg, found in 1853 that each snowflake falling on a paper coated with potassium iodide is followed by a “Schönbein reaction”. Which substance other than H2O2 could it be? Thus many so-called ozone observations may be attributed to H2O2. Joseph Georg Boehm (1807–1868), director of the observatory in Prague, observed that the majority of thunderstorms are accompanied by a simultaneous increase in the depth of the color in tests (Boehm 1858).224 Remarkable is the observation that thunderstorms without or little rain did not show an “ozone reaction” (Schiefferdecker 1855). Augustin Reslhuber (1808–1875), director of the observatory Kremsmünster (Austria), states that “with thunderstorms, the amount of ozone [we should turn it now into hydrogen peroxide] is dependent upon the amount and kind of the aqueous precipitations which accompany them” (Reslhuber 1856). Finally it is cited by Houzeau (after Fox, 1873, p. 72) “ . . . that ozone is more frequently present in the air 223 Before 1850 this acid was wrong attributed to be NO2 or N2O4; note that sulfurous acid was SO2 and no difference with the acid anhydride was made (e.g., SO2 + H2O). 224 Fox (1873) cites many other observers in his book on pp. 70–72 concerning increased “ozone” in connection with rain, fog, and snow.

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during days of rain than during days of fine weather”. Moreover, Robert Joseph Henri Scoutetten (1799–1871), professor and head of medicine at the military hospital in Metz, found that rain and fogs determine different affects, according to their conditions of production of “ozone reactions” (Scoutetten 1856): If rain follows a storm, and returns after a temporary reappearance of blue sky, the test-paper exhibits deep tints. If, on the contrary, the rain is fine and continuous, and the temperature is slightly elevated, there is little ozone.

However, we can deduct from the humidity dependence of “ozonometers” that the “ozone reaction” is a result of interfacial chemistry of O3 and H2O2 onto wetted surfaces (see Section 5.2.5 in Vol. 1). The results and conclusions by the two following observers confirm it, but are worth for citing because of a beginning “chemical climatology”. Wolfgang Schiefferdecker, physician in Königsberg, conducted “ozone measurements” 1853–1854 and draw the following conclusions (Schiefferdecker 1855): – Schönbein’s method is unreliable; wind and humidity show a large crosssensitivity, – the amount of ozone in towns vary considerable so that single measurements make no sense, – the amount of ozone outside the city is rather constant and larger. – the amount of ozone is at night and in winter larger,225 and – is larger on days with snowfall than on days with rainfall, and on those again larger than on nice days,226 – increases sometimes during thunderstorm, – humidity in air favors the “ozone reaction”.227 Michael August Friedrich Prestel (1869–1880), director of the “Naturforschende Gesellschaft zu Emden,” systematically investigated the ozone concentration in Emden between 1857 and 1864 (Prestel 1865). Remarkable is Prestel’s “ozonometric wind rose” we now call air pollution climatology228 (Figure 2.5). Prestel (1872) wrote that (cited after Lender 1873b, p. 28)

225 This observation can be explained by the fact that ozone at daytime and in summer is photochemically destroyed (note that photochemical ozone production was yet unimportant). 226 This observation can be explained similarly (depression of photochemical activity) and, as cited in the text, by the wet removal of particulate matter that provides a surface for catalytic ozone removal (but much less effective than photochenmical ozone removal under low NOx conditions). 227 This is surely the reaction of O3 on the wetted paper surface, giving radicals and hydrogen peroxide which results in a stronger “Schönbein reaction”; moreover, absorption of H2O2 is favored. 228 In German, Immissionsklimatologie. The term Immission – not known in English (only emission)– is deduced in analogy to emission (entry of matter into the atmosphere), however, it does not describe the discharge (which is referred to as deposition), but the concentration of a matter at the effective location, a somewhat spongy definition.

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Fig. 2.5: Annual variation of the “ozone reaction” and ozonometric wind rose according to observations in Emden, Bern, Kremsmünster, and Prague (Prestel 1865).

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. . . die Feststellung des periodischen und nichtperiodischen Auftretens des Ozons ein wesentliches Moment für die Climatologie [. . . the determination of the periodic and non periodic occurrence of ozone be a relevant moment for the climatology].

Matthias Eugen Oskar Liebreich (1839–1908), physician, chemist, pharmacologist, and toxicologist, in 1872 successor of the chair for pharmacology at the Berlin Charité, hold before by the chemist Eilhard Mitscherlich (1794–1863), writes (In: Deutsche Medizinische Wochenschrift 6 (1880) 24): Der erste Fehler beginnt damit, dass man überhaupt Ozonmessungen vornimmt und veröffentlicht, und dass Balneologen von einer ozonreichen Luft sprechen und einen besonderen Wert darauf legen. Es ist zu verwundern, dass sich nicht jemand gefunden hat, der gegen solche Dinge ankämpft [The first mistake starts with that one at all conduct measurements of ozone and published them, and that balneologists talk on air rich of ozone, and put a special emphasis on it. It is to be wondered that nobody find to fight against such things].

French Chemist Albert Lévy (1844–1907) used the chemical method suggested by Thenard (1872)229 to observe the abundance of ozone almost continuously from 1877 to 1907 at the municipal Observatory of Parc Montsouris in Paris. This newly aspirator method is based on bubbling the ozone containing air through a solution of potassium arsenite (AsO33 − ) and iodide of potassium (KI) where the arsenite is transformed into arsenate (AsO44 − ) and estimated by titration with iodine solution. Volz and Kley (1988) as well as Anfossi and Sandroni (1997) analyzed the Paris data and present reconstructed annual means of being around 10 ppb. Carl Oswald Viktor Engler (1842–1925)230 in Halle, coined the term “air cleanser” for oxidative substances such as ozone and hydrogen peroxide – hundred years before Paul Jozef Crutzen231 (Crutzen 1986) coined the phrase “detergent of the atmosphere” to describe this important cleansing role of OH (O3 and H2O2 are the OH precursors); Engler (1879, p. 65) writes in his book Historisch-kritische Studien über das Ozon [historic-critical studies on ozone]: . . ., dass in unserer Atmosphäre und auf der Oberfläche der Erde eine grosse Zahl von Bedingungen für die Bildung derjenigen Atmosphärilien – Ozon, Wasserstoffsuperoxyd, salpetrige Säure und Salpetersäure – gegeben ist, die wir unter der Bezeichnung “Luftreiniger” zusammenfassen [. . . that in our atmosphere and on the earth surface a lot of conditions exist for the formation of such substances – ozone, hydrogen peroxide, nitrous and nitric acid – which we summarize under the term “air cleanser”].

229 Not to confuse with Louis-Jacques Thénard or his son Paul Thénard. 230 German chemist, studied in Karlsruhe, promotion at Carl Weltzien in Freiburg 1862, professor for chemistry in Halle 1872 and since 1876 in Karlsruhe; “father” of petrochemistry (after 1885). 231 Born 1933; Dutch Nobel prize winning atmospheric chemist; worked at the Stockholm University, University of California, Georgia Institute of Technology and 1980–2000 director of the Department of Atmospheric Chemistry (MPI) in Mainz (successor of Christian Junge).

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First reliable measurements of ozone have been conducted end of the nineteenth century using UV spectrometer and since the 1930s (see Section 4.4.7) by fluorescence measurements; however, until the 1970s, wet-chemical methods (iodometry) remained the only routine procedure. Table 2.12 list (likely complete for the nineteenth century) books, reviews, and extensive studies on ozone until end about of the 1950s.

Tab. 2.12: Books and essays on ozone. year

publication



Johann Rudolf Wolf: Ueber den Ozongehalt der Luft und seinen Zusammenhang mit der Mortalität. Verlag Huber & Comp., Bern,  pp.



Wilhelm Schiefferdecker: Bericht über die vom Verein für wissenschafliche Heilkunde in Königsberg in Preussen angestellten Beobachtungen über den Ozongehalt der atmosphärischen Luft und sein Verhältnis zu den herrschenden Krankheiten. In: Sitzungsberichte der Kaiserlichen Akademie der Wissenschaften. Mat.-Naturwiss. Classe. XVII. Band II. Heft, Jahrgang  – Juli, Wien, pp. –



J. Pless and Viktor Pierre: Beiträge zur Kenntnis des Ozons und des Ozongehalts der atmosphärischen Luft. In: Sitzungsberichte der Kaiserlichen Akademie der Wissenschaften. Mat.-Naturwiss. Classe. XXII. Band. I. Heft, Jahrgang  – October, Wien, pp. –



Joseph Georg Boehm: Untersuchungen über das atmosphärische Ozon. In: Sitzungsberichte der Kaiserlichen Akademie der Wissenschaften. Mat.-Naturwiss. Classe. XXIX. Band II. Heft, Jahrgang  – Juli, Wien, pp. –



Georg Meissner: Untersuchungen über den Sauerstoff. Hahn’sche Hofbuchhandlung, Hannover,  pp.



Gustav Dachauer: Ozon. Eine gedrängte Zusammenstellung bisher gewonnener Resultate. Verlag E. H. Gummi, München,  pp.



Michael August Friedrich Prestel: Die jährliche, periodische Aenderung des atmosphärischen Ozons und die ozonoskopische Windrose als Ergebnis der Beobachtungen zu Emden von  bis . E. Blochmann, Dresden,  pp.



Georg Meissner: Neue Untersuchungen über den elektrisierten Sauerstoff. Dieterische Buchandlung, Göttingen,  pp.



Constantin Lender: Das atmosphärische Ozon, nach Messungen in Marienbad, Mentone, Meran und Wiesbaden. Separat-Abdruck aus Göschen’s “Deutscher Klinik” No. . G. Reimer, Berlin,  pp.



Constantin Lender: Das atmosphärische Ozon. II. Theil. Separat-Abdruck aus Göschen’s “Deutscher Klinik.” G. Reimer, Berlin,  pp.



Cornelius Benjamin Fox: Ozone and antozone. Their history and nature. When, where, why, how ozone is observed in the atmosphere? J. & J. Churchill, London,  pp.

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Tab. 2.12 (continued ) year

publication



Johann Hammerschmied: Das Ozon vom chemischen, physiologischen und sanitären Standpunkte. In: Schriften des Vereines zur Verbreitung Naturwiss. Kenntnisse, Band , Wien, Gerold, pp. –



Carl Engler: Historisch-kritische Studien über das Ozon. Heft XV, Leopoldina, Halle,  pp.



Albert Ripley Leeds: Lines of the discovery in the history of ozone, with an index of its literature, and an appendix upon the literature of peroxide of hydrogen. Annals of the New York Academy of Sciences. Vol. , pp. –.



Paul Hautefeuille and Joseph Chappuis: Recherches sur l’ozone. In: Annales Scientific de l’Ecole Normale Supérieure. e série, Tom , Gauthier-Villars, Paris, pp. –.



Carl Engler and J. Weissberg: Kritische Studien über die Vorgänge der Autoxidation. Fr. Vieweg, Braunschweig,  pp.



Viktor Ehrlich and Franz Russ: Über den Verlauf der Stickstoffoxydation bei elektrischen Entladungen in Gegenwart von Ozon. In: Sitzungsberichte der Kaiserlichen Akademie der Wissenschaften. Mat.-Naturwiss. Klasse. CXX. Band. VII. Heft, Abteilung IIb, Wien, pp. –



Henry Le Chatelier: Les Classiques de la Science. III. Eau Oxygénée et Ozone (Memoirs de Thénard, Schoenbein, De Marignac, Soret, Troost, Hautefeuille Chappius). Libr. Armand Colin, Paris,  pp.



Ewald Fonrobert: Das Ozon. Chemie in Einzeldarstellungen (Ed. J. Schmidt), IX. Bd., F. Enke, Stuttgardt,  pp.



Carl Dietrich Harries: Untersuchungen über das Ozon und seine Einwirkung auf organische Verbindungen (–). J. Springer, Berlin,  pp.



Max Moeller: Das Ozon. Sammlung Vieweg Tagesfragen aus den Gebieten der Naturwiss. und der Technik, Heft , Fr. Vieweg & Sohn, Braunschweig,  pp.



Alexander Vosmaer: Ozone. Its manufacture, properties, and uses. Van Nostrand, New York,  pp.



Eric K. Rideal: Ozone. Van Nostrand, New York,  pp.



Frederick E. Fowle: Atmospheric ozone: its relation to some solar and terrestrial phenomena. Smithsonian Inst., Washington,  pp.



Rupert Wildt: Ozon und Sauerstoff in den Planetenatmosphären. In: Nachrichten von der Gesellschaft der Wissenschaften zu Göttingen. Mathematisch-Physikalische Klasse, Neue Folge, Band , Nr. , Weidmannsche Buchhandlung, Berlin,  pp.



Berichte des Deutschen Wetterdienstes in der US-Zone. Nr. . Ozona, Bad Kissingen,  pp.



Kaare Langlo: On the amount of atmospheric ozone and its relation to meterological conditions. In: Geofysiske Publikasjoner. Vol. XVIII, No. , Grøndal & Søns, Oslo,  pp.

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Tab. 2.12 (continued ) year

publication



Friedrich Renger and Otto Lucke: Über die meteorologischen Bedingungen der Ozondichte in bodennaher Luft. In: Abhandlungen des meteorologischen und hydrologischen Dienstes der Deutschen Demokratischen Republik. Nr.  (Band II), Akademie-Verlag, Berlin,  pp.



Friedrich Teichert and Wolfgang Warmbt: Ozonuntersuchungen am meteorologischen Observatorium Wahnsdorf. In: Abhandlungen des meteorologischen und hydrologischen Dienstes der Deutschen Demokratischen Republik. Nr.  (Band V), Akademie-Verlag, Berlin,  pp.



Wolfgang Warmbt: Luftchemische Untersuchungen des bodennahen Ozons –. In: Abhandlungen des meteorologischen und hydrologischen Dienstes der Deutschen Demokratischen Republik. Nr.  (Band X), Akademie-Verlag, Berlin,  pp.

a This volume contains the lectures held at a conference “Ozon” in Tharandt 1944, and 4 papers by Regener and Hedweg (1941).

2.2.8.2 Hydrogen peroxide Hydrogen peroxide (H2O2) was discovered by Louis-Jacques Thénard (1777–1857)232 in 1818 while treating barium peroxide with sulfuric acid (Thénard 1819). He called it l’eau oxygénée (oxygenated water). William Prout first proposed its presence in the atmosphere and he called it deutoxide of hydrogen.233 In his famous book “Chemistry, Meteorology and the Function of Digestion” he writes (Prout 1834, p. 569): . . . that a combination of water and oxygen is a frequent, if not a constant, ingredient in the atmosphere. This ingredient, which we suppose to be a vapour, and analogous to (we do not say identical with) the deutoxide of hydrogen,234 may be imagined to act as a foreign body, and thus to be the cause of numerous atmospheric phenomena, which at present are very little understood. . . The oxygen and vapour in this combination are so feebly associated,. . .

It is notable that Prouts ideas were established before the discovery of ozone by Schönbein in 1839 (Schönbein 1844). The study of H2O2 in air was closely connected with studying the chemistry of O3 in the nineteenth century (Engler 1879, Rubin

232 French chemist and professor at École Polytechnique in Paris; he published a textbook, and his Traité de chimie élémentaire, théorique et pratique (4 vols., Paris, 1813–1816), which served as a standard for a quarter of a century. 233 This term was introduced by the Scottish chemist Thomas Thomson (1773–1852). It was subsequent termed “peroxide of hydrogen”. It was called in German oxydiertes Wasser (oxidized water) and Sauerstoffwasser (oxygen water), and later (before the 1960’s) as hydrogen superoxyd as well as hyperoxyd. 234 Hence we can speculate that also the hydroxyl radical (OH) is meant without any knowlegde on it . . .

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2001). It is remarkable that the existence of H2O2 in air (as gas as well as dissolved in hydrometeors) was definitely established before 1880 but the existence of O3 in the atmosphere was still discussed around 1880. On the nature of hydrogen peroxide and antozone Already Thénard had recognized that one oxygen atom is only weakly bonded in H2O2 and that the molecule easy decomposes. Remarkably soon after its discovery it was known that H2O2 oxidizes sulfurous acid into sulfuric acid without formation of free oxygen (Gmelin 1827, p. 240), a mechanism, recognized to be important in air chemistry almost 150 years later (Hoffmann and Edwards 1975, Penkett et. al. 1979, Möller 1980) as the most important pathway in oxidation of dissolved SO2 in hydrometeors. Mader (1958) was the first to study the kinetics of this process. The apparent contradiction that water, even with the strongest oxidant, may not be oxidized to H2O2, was explained by Schönbein (“antozone theory”) in that oxygen exists in three different modifications: negative active (ozone O–), positive active (antozone O+) and ordinary inactive oxygen (O2), consistent with both positive and negative active ones (Table 2.13). H2O2 was attributed to be an “antozonide” with the formula HO by Schönbein. The German chemist Carl Weltzien (1813–1870) was the first (Weltzien 1860) who fought against the antozone theory and proved that hydrogen peroxide also has reductant properties. Babo (1863, p. 290) writes: So wahrscheinlich es die schönen Untersuchungen Schönbein’s und Meißner’s machen, dass neben Ozon auch stets sogenanntes Antozon gebildet wird,. . . durch die Electricität allein kein Körper von den Eigenschaften des sogenannten Antozons aus reinem Sauerstoff entstehen kann [So presumably the beautiful experiments Schönbein’s and Meißner’s do it that beside ozone always the so-called antozone forms,. . . through electricity solely no body with the properties of the so-called antozone can gained].

Tab. 2.13: Different “historical” oxygen species. observer

designation

formula

Thénard Schönbein Schönbein Schönbein Schönbein Soret Meissner Meissner Engler and Nasse

peroxide of hydrogen ordinary inactive oxygen negative active oxygen (ozone)a positive active oxygen (antozone) antozonide ozone electricized oxygen atmizoneb antozone

HO O O– O+ HO O ?

a

Consistent with both positive and negative active ones. Soon later by Meissner identified as antozone.

b

HO

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Meissner concluded from his studies (Meissner 1863) that (Meissner 1869, p. 3): . . . unter der Einwirkung elektrischer Spannung neben dem Ozon ein zweiter Zustand des Sauerstoffs oder eine zweite Sauerstoffmodification entsteht, welche vor Allem dadurch ausgezeichnet und characterisiert ist, dass sie, nachdem das Ozon durch gewisse oxydierbare Substanzen absorbiert ist, den Wasserdampf ohne Mithülfe einer Temperaturerniedrigung zu Nebelbläschen zu condensieren vermag [... under the impact of electric discharge beside ozone a second state of oxygen is gained, which is especially characterized through the capability – after absorption of the ozone by certain oxidizable substances – to condense the water vapor without decrease of the temperature].

Thus, Meissner concluded that ozone not favored the formation of fog but “antozone”. Meissner also state that “electricized oxygen” can oxidize free nitrogen (N2), but ozone not.235 Finally, he defined antozone as this modification of oxygen, which is able to oxidize water into hydrogen peroxide.236 Soon later Weltzien (1866) believed that the so-called antozone is simply the “peroxide of hydrogen” (H2O2), soon confirmed by Engler and Nasse (1870). Engler (1879, p. 18)237 writes: . . . dass das sogenannte Antozon nur dann entsteht, wenn Ozon in Gegenwart von Wasser zerstört wird, so dass die Annahme nahe lag, das Antozon sei. . .weiter Nichts als Wasserstoffsuperoxyd [. . . that the so-called antozone only be formed if ozone in presence of water decomposes, so that the assumption was likely that antozone. . . is nothing else than peroxide of hydrogen].

Bieber (1911, 1912) conducted interesting experiments on condensation of water vapor in the presence of ozone with the aim to characterize the chemical nature of “blue fog”; the course of such fogs (blue haze in today’s termination). Bieber correctly interpreted Meissner’s antozone as free oxygen atoms, which appear during formation and decomposition of ozone.238 Later (beginning of the 1880s) Moritz Traube (1826–1894) proved the antozone theory to be wrong and that H2O2 is not “oxidized water” but a reduced form of the 235 This is known from oxygen atoms according to Eq. (5.150) in Vol. 1: N2 + O = N + NO (slow reaction). 236 This is known from O(1D) + H2O = 2 OH with subsequent formation of H2O2 via HO2 radicals (see Section 5.2.3.1 in Vol. 1). 237 This small booklet “Historisch-kritische Studien über das Ozon” (Halle 1879) is to my mind the best history on all aspects of ozone and includes all literature concerns discovery and nature of ozone, formation, production, properties, detection, and determination, ozone in the atmosphere, its sanitary role and technical use. 238 The observation of fog formation (not always) of almost all scientists of the nineteenth century during experiments with ozone must be interpreted as homogeneous nucleation process (formation of CCN in a reaction between OH and precursor molecules such as SO2, NOx and VOC) and formation of haze or (at high humidity) fog. NOx was always produced while O3 formation with electric discharges, ammonia, and organic substances were always in air and likely not completely removed by air washing of the treated air. In such conditions of ozone production it is to be expected that OH is gained simultaneously.

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oxygen molecule (Traube 1882, 1887). First, Traube (1887) showed that water electrolysis in acid solution (never in alkaline solution) always first produces H2O2 when oxygen is bubbling around the cathode and then hydrogen. He explained it by a reaction between in statu nascendi hydrogen (H) and molecular oxygen and concluded the formula H–O = O–H (2H + O2) in contrast to H–O–O–H for H2O2. That could be interpreted as the first (not yet clear) idea on the reaction H + O2 → HO2. H2O2 formation in autoxidation processes was proposed by Traube (1882) despite nothing being known on formation mechanisms. Years before, Schönbein (1866) had detected the formation of H2O2 from essential oils and turpentine oil under sunlight. Marcellin Berthelot (1827–1907), who studied the reaction between potassium permanganate and hydrogen peroxide, proposed as intermediate239 trioxide d’hydrogene HO3 (now H2O3, see pp. 304–305 in Vol. 1); the formula of hydrogen peroxide (in that time in French named l’eau oxygéne) he present as HO2 (Berthelot 1880). Some years later Dmitrii Ivanovich Mendeleev [Дмитрий Иванович Менделеев] (1834–1907) proposed the intermediate H2O4 (Mendeleev 1895, cited after Plesničar (2005)); Leopold Gräfenberg (1878–1962)240 named it ozone acid (H2O·O3) (Gräfenberg 1902, 1903). Measurements of hydrogen peroxide in the nineteenth century It was known in that time that O3 reacts very slowly with permanganic acid (HMnO4) (in old German Uebermangansäure) whereas H2O2 fast reacts, what was used for its analytical separation. Georg Meissner (1829–1905)241 provided the first evidence of H2O2 in rain during a thunderstorm242 in 1862 (Meissner 1863). Schönbein (1869) confirmed this observation and Heinrich Wilhelm von Struve (1822–1908)243 detected it in snow soon later (Struve 1869). Struve even proposed in 1870 that H2O2 is produced during all burning processes in air (Struve 1871). The German chemist Emil Hermann Schöne (1838–1896),244 however was the first scientist who studied atmospheric H2O2

239 In analogy to the known trisulfide H2S3 (Berthollet writes HS3). 240 Born in Göttingen, he obtained a Ph.D. degree based on experimental work “Contributions to the Knowledge of Ozone” done at the Göttinger Institute of Walter Nernst. Immigrated 1933 to Palestine. 241 German anatomist and physiologist; University Professor at Basel (from 1855), Freiburg (from 1857) and Göttingen (from 1860 to 1901). 242 Zuo and Deng (1999) believed to be the first authors (!) to establish lightning induced H2O2 production in a Florida thunderstorm. 243 Генрих Васильевич Струве: German-Russian chemist, born in Dorpat (now Tartu in Estonia), worked 1849–1867 in Sankt Petersburg and from 1867 in Tiflis; in 1876, Struve became a member of the Russian Academy of Sciences in Petersburg. Son of Friedrich Georg Wilhelm von Struve (In Russian, his name is often given as Vasilii Yakovlevich Struve [Василий Яковлевич Струве]; the Struve family were a dynasty of five generations of astronomers from the 18th to 20th centuries. Members of the family were also prominent in chemistry, government, and diplomacy. 244 Шене, Эмиль Богданович: German chemist, born in Halberstadt, studied in Halle, Berlin and Göttingen; changes to Moscow in 1863 and worked since 1864 at the Petrowskaja Agricultural and

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in detail in rain, snow, and air near Moscow (Petrowsko-Rasumowskaja, an agriculture research station) in the 1870s (Schöne 1874, 1878, 1893, 1894). Schöne noted the following remarkable observations: – in showers the H2O2 concentration was higher than in drizzle, – in rain from southern air masses H2O2 was higher than in rain from polar air masses, – the H2O2 concentration decreases strongly from July until November, and – in snow less H2O2 is found than in rain during the same season. Schöne also used an artificial dew and frost sampler made from glassware and found H2O2, which had to be co-deposited from the gas phase. In this way, he detected a diurnal variation and found H2O2 to be largest at noon. Under comparable conditions, he also found that the amount of deposited H2O2 is largest when the temperature is highest, there is more sunshine and less relative humidity. During rain, he found no H2O2 in his “sampler” and concluded correctly that “rain washes out all H2O2 which is vaporous in air.” He further concluded (Schöne 1874, p. 1708) . . . dass bei der Entstehung des atmosphärischen Wasserstoffhyperoxyds das Sonnenlicht eine hervorragende Rolle spielt [that sunlight plays a singular role in the formation of atmospheric hydrogen peroxide].

These results were later confirmed by Kern (1878). Schöne was the first to state that H2O2 is a permanent natural constituent of our atmosphere. His statement that the existence of H2O2 in air is due to the influence of solar radiation (onto water) was proven through observations by Thiele (1907), Tian (1911), Chlopin (1911) and Kernbaum (1911). These authors’ experiments show that the ordinary moist air of a room, after subjection for a few minutes to the action of ultra-violet light, shows the presence of ozone, hydrogen peroxide, and nitrogen trioxide. Hence the formation of H2O2 during electric discharges in air and water vapor was established at the beginning of the twentieth century which explained its excess occurrence in rain from thunderstorm. However, the formation mechanisms were not known. Chemistry of hydrogen peroxide German chemist (Nobel prize in 1927) Heinrich Otto Wieland (1877–1957) and his student Wilhelm Franke (1903–?), after World War II professor for enzyme chemistry at the University Cologne, studied the kinetics of H2O2 formation in autoxidation processes (Wieland and Franke 1929).

Forest Academy (Петровская земледельческая и лесная академия), founded in 1865, where he became in 1875 a professor for chemistry. He deceased in Moscow. Member of the Deutsche Chemische Gesellschaft (German Chemical Society).

2.2 Discovery of air chemical composition

133

Between 1876 and 1890, several authors believed they could prove the existence of H2O2 in plants.245 However, because of insufficient analytical methods, there were doubts about such claims (Machu 1937). After the turn of the nineteenth century, the Russian-Soviet biochemist Alexei Nikolajewitsch Bach [Алексей Николаевич Бах] (1857–1946) and the Swiss botanist Robert Hippolyte Chodat (1865–1934), wellknown for its oxygenase-peroxidase theory, found evidence for H2O2 in living plants (Bach and Chodat 1902). Twenty years later it was confirmed by Gallagher (1923), and Tanaka (1925) proved that H2O2 was a primary product in respiration.246 Because of the significance of biological processes, H2O2 formation was also found (in the late 1930s) under visible and UV light influence in different aqueous suspensions containing plant parts (Gmelin 1966). Water containing organic substances produces H2O2 under (visible) light influence (Blum and Spealman 1933). As mentioned above, formation of O3 (and H2O2) has been explained in the nineteenth century by quiet electric discharges including O2 dissociation. That is not incorrect based on the fundamental ozone formation reaction (O + O2 → O3) but can hardly apply to explain the peroxide formation. Schönbein (1861) first observed the formation of H2O2 while slow oxidation of metals in air and oxygen.247 Traube assumed (in contrast to Schönbein who stated the dissociation of the oxygen molecule) that the O2 is reduced to H2O2 via water degradation. Bach (1897) and Engler and Weissberg (1904) stated that the whole O2 molecule is uptaken under formation of a peroxide. Both statements, O2 reduction and the O2 transfer into H2O2, are amazingly correct. The “water degradation” mentioned by Traube, may today be interpreted by the reaction chain still unknown at that time (see Vol. 1, Section 5.2.3): hν

H2 O

O3

HO2 + H2 O

! H2 O2 ð+ H2 OÞ. O3 ! O1 Dð+ O2 Þ ! OHð+ OHÞ ! HO2 

(2:2)

The HO2 radical also can be produced within this reaction chain (2.2) and explains the fact that the “whole oxygen molecule” (O–O) is transferred into H2O2. During the 1930s, the radical gas-phase H2O2 formation mechanism was described in combustion processes (Hinshelwood and Williamson 1934, Jost 1939) where peroxide O2 radicals are formed according to H ! HO2 . Bates (1933) and likely independently Bodenstein and Schenck (1933) proposed the reaction HO2 + HO2 ! H2 O2 + O2 , but not before 1995 were the kinetic fully understood in its dependency from pressure and water vapor (Stockwell 1995):

245 Schönbein (1864) was the first person to detect H2O2 in the human body. 246 Even the redox behavior of H2O2 produces it during the photosynthesis in the step of formation of oxygen from water to be an important intermediate (Halliwell and Gutteridge 1984). In cells it is both a source of oxidative stress and a second messenger in signal transduction (Georgiou and Masip 2003). 247 The “hydrogen peroxide theory” while rusting of iron was established by Dunstan et al. (1905), see Section 4.5 Vol. 1.

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2 History of investigation and understanding the climate system

H2 O

HO2 + HO2 ! H2 O2 + O2 .

(2:3)

However, the role of the superoxide anion (O2− ) in autoxidation processes became clear only after the 1950’s, interestingly because of studying bleaching processes. Mirosław Kernbaum (1882–1911), who worked at the research school of Marie Curie (1867–1934) in the Paris faculty, also studied the influence of UV radiation (Kernbaum 1909), electric discharges (Kernbaum 1910) and metals (Kernbaum 1911) on water decomposition and was one of the pioneers of H2O2 formation from water. The formation of H2O2 due to electric discharges in air containing water vapor was first proposed by Boehe (1873)248 and confirmed by Fischer and Ringe (1908). Duane and Scheuer (1913) first studied H2O2 formation in water during irradiation with α radiation (from Rn ampulla). The German radio-chemist Otto Karl Hermann Risse (1895–1942) first studied the influence of X-rays on water (Risse 1929). In all these studies, H2O2 formation was confirmed but hydrogen often did not escape and was instead dissolved in water with sometimes oxygen even being evolved (Fricke 1934). However, X-rays do not produce H2O2 in oxygen-free water (Risse 1929, Bonét-Maury and Lefort 1948). All these early observations are consistent with the modern view of H2O2 radiolysis through radioactive radiation. Liquid water photolysis under the formation of H2O2 was first proven by Tian (1911) for wavelengths 

– – – 

heavy naphtha’s kerosene fraction diesel fractiona atmospheric residues

gjet engine fuel

– – – >

vacuum oil medium oil heavy oil vacuum residues

g

vacuum (~ %)

diesel fuel, heating (heavy fraction)

engine oil

tar, asphalt, residual fuel

a

Also named gas oil (250–350 °C) and lubrication oil ( > 300 °C).

increase the yield of gasoline (petrol). From 1996 to 2000, the share of fuel oil decreased from 26% to 11% whereas the percentage of the light and middle fraction increased from 58% to 68% (BP 2009); it is expected that in future it will be used exclusively for engine fuels. Natural gas consists primarily of methane (Table 4.10). It is found in association with fossil fuels, in coal beds, and together with oil. Gas present in contact with and/or dissolved in crude oil is coproduced with it. Nonassociated gas is found in reservoirs containing no oil; in dry wells but also as clathrates under frozen conditions or under high pressure at the deep sea bed. Before natural gas can be used as

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4 A changing climate system

Tab. 4.10: Chemical composition of natural gas (in vol-%); data adapted from Matar and Hatch (2001), Guibet and Faure-Birchem (1999), Leverson (1967). compound CH CH CH CH CH CH N CO HS He H

mean (methane) (ethane) (propane) (butane) (pentane) (hexane)

~ ~. ~. ~. ~. ~. ~. ~. ~. ~. ~.

range – – – – 95% completeness) and means from 1-h samples for solutes, resp. period

– – –

gas-phase concentration in ppb SO

NO

NO

O

. ± . . ± . . ± .

. ± . . ± . . ± .

. ± . . ± . . ± .

. ± . . ± . . ± .

cloud-water concentration in µeq L–

– – –

SO2– 4

NO–3

NH4+

Ca+

. ± . . ± . . ± .

. ± . . ± . . ± .

. ± . . ± . . ± .

. ± . . ± . . ± .

4.2 Humans historic perspective

433

that it is caused due to the photochemical steady-state relationships between NO, NO2 and O3. At all, there is no trend in NOx and O3 at the Brocken site after 1993. Small Eastern German cities surrounded of Berlin (Figure 4.24) show a trend of slight decrease in NO2 from (averaged) 20 (1993) to 15 (2002) µg m–3; the number of stations 1991 and 1992 is too small to get a statistical provided regional mean. This is similar to the total trend in NO2 from 30 (1995) to 20 (2016) µg m–3 as averaged German city background value according to UBA data. As discussed above, >60% of NO was emitted through high stacks not contributing to local near-ground NO2 concentrations in the GDR. The NO2 concentration trend reflect generally the NO emission trend (Table 4.19), being roughly 50% in west and east between 1989 and 2010. 45 NO2 concentration in μg m–3

40 35

mean 18.2 ± 4.9 μg m–3

30 25 20 15 10 5 0 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 year

Fig. 4.24: Trend of mean annual NO2 concentration at 15 different urban sites in the State Brandenburg; black line – mean of all stations (in µg m–3). Data from LUA (2002a).

The most vigorous emission decline happened concerns particulate matter. From a few measurements before 1990 (Figure 4.26) a rural background mean value of 30–35 µg m–3 can be derived, consistent with early data after 1990 at Melpitz being 35 µg m–3 (Figure 4.28) and as German rural background value 1990 from UBA network to be 30 µg m–3. However, PM values before 1990 represent total suspended matter (TSP)552 including also giant particles which can significant contribute to total mass but are almost insoluble silicates. Many studies result in a percentage being 50–60% of PM10 to TSP; only at remote background sites the percentage of PM10 increases to 80–90% of TSP. Hence there is no correlation between PM (as well TSP) and dust precipitation. Thus the TSP value for 1992 (60 µg m–3) in Figure 4.29 corresponds with 30–35 µg m–3 PM10. Figure 4.29 shows distinct the air quality “plateau” 1994–1996 for SO2 and PM as discussed concerns the emissions trend (cf. Figure 4.12).

552 Also denoted SPM – suspended particulate matter

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4 A changing climate system

35 30

NO2 (in ppb)

25 20 15 10 5 0 1992

1995

1998

2001 year

2004

2007

2010

0 35

330

30

30 25 20

300

60

15 NO2 (in ppb)

10 5 0

270

90

5 10 15 20

240

120

25 30 35

210

150 180

Fig. 4.25: Daily NO2 concentration at Mt. Brocken (1993–2010). Own data until 1995 and later from Landesamt für Umweltschutz Sachsen-Anhalt.

It is notable that after 1990 until 2016 no change in O3 concentrations was observed (Figure 4.29); a likely greater decrease in NO2 due to closing of power stations occurred only between 1989 and 1993 (no data available between 1989 and 1991); further continuous but small downward trend until 2008 (from 20 to 13 µg m–3) corresponds to the general trend of NOx emissions.

4.2 Humans historic perspective

435

Neuglobsow (Mecklenburg) 50 40 30 20

mean 1969 – 1989 (TSP) 36.1 ± 4.7 mean 1990 – 1998 (TSP) 26.8 ± 3.7 mean 1999 – 2003 (PM10) 16.3 ± 1.3

10 0 1965

1970

1975

1980

1985

1990

1995

2000

2005

1995

2000

2005

Mt. Schmücke (Thuringia) 40 30 20 10

mean 1979 – 1988 (TSP) mean 1989 – 1998 (TSP)

30.3 ± 2.7 20.6 ± 3.4

mean 1999 – 2003 (PM10) 12.0 ± 1.2

0 1965

1970

1975

1980

1985

1990

Fig. 4.26: Annual means of particulate matter at two baseline stations Neuglobsow (Mecklenburg) and Mt. Schmücke (Thuringia). Data before1990 from Meteorological Service of the GDR and after 1990 from UBA (until 1996 TSP and after 1996 PM10).

So-called dust precipitation (deposition), collected by an open gauge (for example the German Bergerhoff sampler)553 and given in mass per square and time (e.g., mg m–2 d–1) includes almost PM > 10 µm (diameter) due to sedimentation. In the 1970s, from 45 measurement sites in the Cottbus district the dust precipitation was estimated to be averaged 800 (450–2,500) mg m–2 d–1 (at that time given in g per 30 days and m2), BHI (1979). After 1990, this value declined from 360 (in 1991) to 105 (in 1999) mg m–2 d–1 (LUA 2002b). As known, Bitterfeld was the most polluted area in the GDR; Zierath (1981) estimated the annual mean dust precipitation (1976–1979) to be 1,800–2,500 mg m–2 d–1. From this dust precipitate, 25% was soluble (gaining pH = 5.35) and consisting almost (to 98%) of CaSO4. It remains speculative to assume whether CaSO4 was primary emitted or generated airborne from primary SO2 and CaCO3. Own studies (Paucke et al. 1975, 1979) have shown that soils in a nearby pine forest area (Dübener Heide) was untypical alkaline (up to pH 6.2) due to dust deposition suggesting that at least a part of primary dust emission was alkaline as CaO and CaCO3. These extreme dust pollutions 553 Bergerhoff, H. (1956) Staubpegelzonen nach Sedimentationsmessungen der Landesanstalt für Bodennutzungsschutz des Landes Nordrhein-Westfalen, Bochum. Heinz Bergerhoff (living dates unknown) wrote his dissertation 1928 „Untersuchung über die Berg- und Rauchschädenfrage mit besonderer Berücksichtung des Ruhrbezirkes (Landwirtschaftliche Hochschule Bonn-Poppelsdorf).

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4 A changing climate system

were only observed close to sources; sedimentation reduced atmospheric dust concentration quickly with distance from the source. Figure 4.30 shows an excellent correlation between dust precipitate and dust emission in the State Brandenburg (1991–1999) suggesting a “natural” deposition of about 100 mg m–2 d–1 as annual average. Much less is the decrease of PM (Figures 4.27 to 4.30) in relation to dust emission. In Section 4.4.13 it is discussed that PM10 (and even more PM2.5 which has a percentage of 70–80% to PM10) is composed to about 30% from secondary aerosol that has gaseous precursors such as SO2, NOx, NH3 and VOC (see also Section 3.6.2.2 in Vol. 1). After the year 2000, rural background of PM10 declined to around 15–20 µg m–3 comparing with 40–50 µg m–3 before 1990. Therefore, it can be concluded that today’s airborne dust values approaches already natural levels.554 From the available data (Table 4.24 and Figures 4.16 to 4.20), the following annual mean characteristic SO2 concentrations can be derived for the GDR (in µg m–3); in winter season it can be several times higher (see also Table 4.25). – – – – – 10 years) is essential. Table 4.28 shows the annual means of Mt. Brocken cloud water chemical composition. The mean concentrations are LWC-weighted according to  n  P LWCi cij cj = iP (4:1) n ðLWCi Þ i

442

4 A changing climate system

LWC – liquid water content of individual sample i (1 – n), c – concentration of specific ion j in individual sample i, n – total number of samples in averaging period. In contrast to arithmetic means, weighted means are less sensible against extreme values (large c due to low LWC or polluted air). As an example here the statistics for sodium (Na) is presented in terms of arithmetic mean, standard deviation, minimum and maximum value, and LWC weighted mean (in µeq L–1) for the whole period 1993–2009; note that the sample number for weighted means is smaller because of missing LWC data: arithmetic mean: weighted mean:

.±. (.–.) .

n = , n = ,

It is remarkable that (as a “mathematical” result of the large variation of LWC and concentration) the difference between the arithmetic and the weighted mean is considerable. In literature, often only arithmetic means are used (because of missing information on LWC and/or R) but only the weighted mean represents the “true” chemical averaged in sense of collecting samples continuously over the whole period in a “bottle” and analyzing the cumulated solution (adopting no changes due to storage). Another important point is that the volume-based cloud water concentration (cf. Eq. (3.64)), the product of LWC and aqueous-phase concentration, is more robust and shows less variation than the liquid-phase concentration (cf. Figure 4.34).557 It represents the residual or – assuming that the regarded substance is totally dissolved (scavenging efficiency = 1) – the concentration of the compound in aerosol particles (PM). It must therefore be concluded that any climatologically statements can only be drawn after long-term monitoring having a large timely representativeness. We normally collected from April to October every year gathering about 80–90% of all cloud events of this period at the summit; note that the overall cloudiness is larger because of higher clouds. As already said, cloud chemical composition is more regional (meso-scale) representative than wet deposition (precipitation chemistry). Even with the large number of available cloud water samples and the long period (over 17 years) it is not simple to classify “cloud chemistry” according to trends and variation of air pollution, trajectories and cloud physical parameters because all “effects” overlay and varies often by different reasons. Not discussing the relationships here in detail (see cited literature), it is evident that cloud microphysics and dynamic (including cloud transport and cycles, that is, evaporation, precipitation, nucleation) determine dominantly the chemical

557 Note that each single value (based on the water sample) must be calculated from LWC and aqueous-phase concentration with subsequent averaging according to the regarded period. This mean is different from the product of averaged LWC and averaged concentrations, based on different averaging periods. It is a mathematical phenomenon: LWC only can be arithmetically averaged but the annual mean concentration is based on single LWC weighted values.

443

4.2 Humans historic perspective

composition (likely through the droplet size distribution which we only measured during campaigns). Of second importance are the air mass characteristics (maritime, continental, pollution level, precipitation events, and so on). For any cloud chemistry monitoring it is crucial to include a minimum of cloud physics, such as LWC, height above cloud base, duration of cloud and cloud-free events. It would be desirable also to monitor the droplet size distribution (since a few years a robust and not expensive technique is available). Table 4.29 shows different factors affecting the chemical composition of cloud water. Event 3 is clearly maritime influenced by NW air masses otherwise alike concentrations of all other ions with event 1 which is more from SW air masses. In contrast, event 2 is of continental SE origin with enhanced concentrations of non sea salt components. The relatively low LWC and namely the large standard variation tell us that cloud water from the lower cloud (cloud base events) with some entrainment was collected gaining scavenging of NH4NO3 and CaSO4. Tab. 4.28: Annual and total LWC weighted mean concentrations (in µeq L–1) of cloud water constituents at Mt. Brocken, n – number of samples (total 22,841), LWC – liquid water content (annual mean). year                   meana

n

LWC

Cl–

NO–3

SO2– 4

NH4+

Na+

K+

Ca+

Mg+

H+

pH

                 

                 

                 

                 

                 

                 

                 

– –                

                 

                 

                 

. . . . . . . . . . . . . . . . . .

–





















.

a

From annual means; note the large difference to the total mean (229) from all single event data.

The mean LWC frequency distribution is shown in Figure 2.8 in Vol. 1; the yearly distributions are very similar and do not vary large; the monthly means also vary not large (Table 4.29). The years 1993 and 2003 (both characterized by hot summers) show significant lower LWC compared to average; characterizing the air masses by

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4 A changing climate system

Tab. 4.29: Characteristics of three continuous cloud events concerns LWC (in mg m–3), TIC (total ionic content without H+) and selected ions (in neq m–3). event   

..–.. ..–.. ..–..

LWC

TIC

SO2– 4

NO–3

NH4+

Ca+

Na+

Cl–

 ±   ±   ± 

  

  

  

  

  

  

  

Tab. 4.30: Statistics of LWC in Mt. Brocken cloud monitoring program (in mg m–3), based on sampling periods (about 80% of all cloud events). Period – – – – –

arithmetic mean

weighted mean

 ±   ±   ±   ±   ± 

    

– May June July August September October

arithmetic mean  ±   ±   ±   ±   ±   ± 

sea salt loading, 1993 was “continental” (lowest NaCl) and 2003 was “maritime” (highest NaCl). If this explanation is true, however, the low concentrations of “pollutants” (sulfate, calcium, and nitrate) in 1993 are hard to explain in continental (i.e., easterly) air masses. The LWC of 80% of all clouds (“in-station”) is in a range of 10 to 400 mg m–3; maxima are between 1,100 and 1,400 mg m–3. However, LWC can vary extreme during single cloud events. With increasing altitude above the cloud base, LWC increases approximately linear (from 0 to 800 mg m–3 from the cloud base up to 500 m in clouds, cf. Figure 2.6 in Vol. 1) and the droplet spectrum shifts to larger droplets (Wieprecht et al. 2000). Based on our ceilometer measurements, we sampled cloud water almost (about 40%) between 50 and 150 m above the cloud base; the cloud layers between 0–50 m and 150–200 m contribute each to around 15%. However, deep clouds can attain the foot-hill site (500 m down). Based on visual observation by the Weather Service, the Brocken summit is on average 50% within clouds (note that the occurrence of total cloudiness is around 90%) where cumuli are most frequent. The preferential wind directions are between SW and NW; this sector has a much larger probability having clouds then cloud-free conditions; the situation is conversely in all other directions. Hence, cloudy air masses from south to east are unusual. There is no trend between 1992 and 2010 concerns the signal “station-in-cloud” as well as for the yearly hours of sun shine (1,423 ± 166 h). As one would expect, between both quantities exist a high correlation (r2 = 0.8). Despite large variations between the years, the cloud base increased by about 150 m (yearly mean) from 1992 (about 350 m) until 2010 (about 500 m), Figure 4.31.

mean cloud base above Brocken summit (in m)

4.2 Humans historic perspective

445

600 550 500 450 400 350 300 250 1990

1995

2000

2005

2010

2015

year Fig. 4.31: Mean cloud base above Mt. Brocken (in m) derived from observations and ceilometer monitoring.

On the relationships between LWC and TIC (total ionic content) as well as specific ions we reported elsewhere (Möller et al. 1996a), best correlated by power functions (Figure 4.32 as example for sulfate). With decreasing LWC, in other terms, near the cloud base, TIC varies extreme due to droplet evaporation and condensation processes (Wieprecht et al. 2000). For long-term observations in sense of cloud climatology and air pollution characteristics, it is essential to collect cloud water not below 50 m above the cloud base. Because of the dependency between LWC and ionic content, it is essential to measure LWC in cloud chemistry programs and to construct weighted aqueous-phase concentration means. A trend in LWC is not seen, however, it seems that after the year 2003, LWC is significantly lower than in all periods before (Table 4.28 and 4.30). To conclude on “climate change” is not serious because LWC is an integrated parameter, whereas droplet size and droplet number are directly climate relevant. It is discussed (e.g., Junkermann et al. 2011) that due to “warming” and air pollution abatement the number of potential CCN increases, especially below 0.1 µm (nanoparticles), but the droplet sizes decreases. As a possible consequence, more cloudiness and less precipitation could results. However, any conclusion on changing LWC is impossible. Assuming (and there is no reason not to assume it) that the number of activated CCN (and newer results show that natural sources are likely dominant) remain unchanged but the absolute humidity for nucleation became less, the number of cloud droplets will not change but its size decreases – this would mean that LWC decreases. Smaller droplets enhance uptake of soluble gases (see Section 3.6.5 in Vol. 1) but that is not longer important under clean air conditions, that is, low concentrations of SO2, NH3 and HNO3. The origin of TIC in cloud water is now determined through the nucleation process from CCN.

446

4 A changing climate system

3000 1994 (n = 1074) 2500 2000

cloud water sulfate concentration (in μeq L–1)

1500 1000 500 0 0

100

200

300

400

500

600

700

800

900

1000

3000 2004 (n = 1615) 2500 2000 1500 1000 500 0 0

100

200

300

400

500

LWC (in mg

600

700

800

900

1000

m–3)

Fig. 4.32: Scatter plot of sulfate and LWC for two selected years.

A very strong correlation between ions exists only between Na and Cl (Figure 4.33) – as it is expected for sea salt – but weaker correlation are found for the following relationships (note that in cloud events and short-term periods the correlation coefficient is much higher; based on microequivalents). We can conclude that magnesium is to a large extent of sea salt origin and (what is not surprising) ammonium, sulfate, and nitrate are interlinked via particle formation as described in Section 3.6.2 in Volume 1 and providing an important percentage of CCN. ½Na +  = 4.9 ½Mg2 +  − 18.5

r2 = 0.86

½SO24 −  = 0.5 ½NO3−  + 82.5

r2 = 0.67

1.7 ½SO24 −  + 2.8 0.9 ½NO3−  + 90.8

r2 = 0.81

½NH4+  ½NH4+ 

= =

r2 = 0.80

4.2 Humans historic perspective

447

400 Na concentration (in μeq L–1)

350 (r2 = 0.97)

[Na] = 1.0 [Cl] + 1.5

300 250 200 150 100 50

monthly means (n = 96)

0 0

50

100

150

200

250

300

350

8000

Na concentration (in μeq L–1)

7000 [Na] = 1.0 [Cl] + 3.6

(r2 = 0.95)

6000 5000 4000 3000 2000 1000 all samples (n = 23,803) 0 0

1000

2000

3000

4000

5000

6000

7000

8000

Cl concentration (in μeq L–1) Fig. 4.33: Correlation between sodium and chloride in Brocken cloud water (in µeq L–1) based on monthly weighted means (n = 96) and all data (1993–2009, n = 23,803 1-h values).

From Table 4.28 is seen that the years 1997, 1999, 2001 and 2003 were over proportional influenced by sea salt: 236 µeq L–1 NaCl in cloud water in contrast to the other years having on average 148 µeq L–1 NaCl. The “maritime” years show higher nitrate (256 µeq L–1 versus 219 µeq L–1) and lower calcium (44 µeq L–1 versus 65 µeq L–1), typically for NW European air masses. All other compounds show no significant difference. It seems that the nitrate/calcium ratio could by a proxy for air mass characteristics (maritime versus continental). There is no change in the Na/Cl ratio (in contrast to rainwater, see next section) and it is also notable that this ratio is much larger than in rainwater, suggesting that in clouds no excess chloride is found, indeed missing chloride, as discussed in Section 5.7.2, Volume 1, for “clean” maritime air masses passing the continent.

448

4 A changing climate system

Taking into account the molar cloud water composition we are able to “reconstruct” the salty composition to be (in parenthesis “volatile nitric acid”): NaCl + MgCl2 + NaNO3 + ðNH4 Þ2 SO4 + CaSO4 + NH4 NO3 ð + HNO3 Þ. From the mass budget, the volatile HNO3 amounts to around 30 µeq L–1 or in other terms only 3 eq-% of cloud water composition. The total inorganic salty mass, recalculated on the air volume, shows a continuous decrease after the year 2000 (mean 2002–2009: 9.4 ± 1.5 µg m–3) but no trend between 1992 and 2001 (12.8 ± 1.9 µg m–3). A value of 7.2 µg m–3 corresponds to the sum of water-soluble inorganic ions of PM10 measured at the Fronauer Tower (320 m a.s.l.) in suburb Berlin in 2001–2002, representative for a tropospheric background (Beekmann et al. 2007), which is slightly lower then the Mt. Brocken residual. The percentage of ions contributing to the total mass did not changed significant between both periods. It is remarkable that only the nitrate and sulfate percentage are very different between the Mt. Brocken residual (42% and 24%, resp.) and the Frohnau Tower PM10 (25% and 47%, resp.) supporting that sulfate dominates air in Berlin and nitrate air at Mt. Brocken around the year 2000. Ammonium, nitrate, and sulfate contribute to 80–90% of soluble ions in atmospheric particles. Sulfate in cloud water is originated from – CCN and therefore of large-scale characteristic and – SO2 scavenging (local to meso-scale characteristic). SO2 abatement was very efficient between 1990 and 2000 (but 1990–1995 less comparing to dust decline) – it is logical that sulfate change in cloud water is consequently smoothed and smaller then in rainwater where below-cloud scavenging additional increases sulfate loading. Sulfate only decreased by 17% (in rainwater by 72%), Table 4.25 and Figure 3.34 show the sulfate climate statistics.558 The trend in sulfate decrease (Tables 4.28, 4.31 and 4.35; Figure 4.34) continues despite since the year 2000 no change in SO2 emission is observed (see also Section 4.2.5). The trend consists from different components, the yearly mean and the standard variation as well as the number of exceedance (extreme values). From Figs. 4.32 and 4.34 it is seen that the number of samples with very large sulfate concentrations significantly declined. When looking into more detail (Figure 4.34), the sulfate picture is similar to that of gaseous SO2 (Figure 4.21); three characteristics can be seen, – the number and quantity of events with high sulfate concentration (>800 µeq L–1) were significantly larger before the year 2000,

558 Figure 4.34 only shows cloud water sulfate values larger than 300 µeq L–1 (the average over the whole period amounts 200–300 µeq L–1, depending on the type of averaging). Concentrations larger than 800 (up to 2,800) µeq L–1 after the year 2000 are likely originated by cloud microphysical and dynamic processes.

4.2 Humans historic perspective

449

4800 cloud water (average 229±288) sulfate concentration (in μeq L–1)

4300 3800 3300 2800 2300 1800 1300 800 300

sulfate concentration (in μg m–3)

50

residual (average 2.9±3.0)

45 40 35 30 25 20 15 10 5 0 0

5000

10000

15000

20000

running sampling (July 12, 1992–October 10, 2009, n = 23,807) Fig. 4.34: Trend of sulfate in Brocken cloud water (in µeq L–1) and the “residual” (in µg m–3) based on all 1-h samples (1992–2009), n = 23,807. Residual is calculated as the product of aqueous-phase concentration and LWC of each sample and represents as mass per air volume the particulate matter.

– a “typical background 1,800 µeq L–1) are either pollution events (eastern air masses) or (very few only) events with specific microphysical characteristics. The most significant change in cloud water composition at Mt. Brocken is the decrease of calcium (by 33%) and H+ ions (by 41%). Calcium in cloud (and rain) water originated from dust (here flue ash from lignite fired power plants), emitted in the time before 1995 from high stacks in Eastern Germany and therefore direct “injected” into long range transport. This also is the explanation why nitrate – gained from power plant NOx emissions – in easterly air masses, crossing the border to west, was

450

4 A changing climate system

Tab. 4.31: Trend in cloud water sulfate at Mt. Brocken. year

air-volume related concentration, so-called residual (in µg m–) from all samples

                

. ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± . . ± .

aqueous-phase concentration (in mg L–)

from annually weighted means . . . . . . . . . . . . . . . . .

from all samplesa weighted mean

arithmetic mean

                

 ±   ±   ±   ±   ±   ±   ±   ±   ±   ±   ±   ±   ±   ±   ±   ±   ± 

a

This data set comprises only samples where LWC is available to compare the weighted mean exactly with the arithmetic mean; in Figure 4.34 arithmetic mean is calculated from all data available including samples with missing LWC (1994: 300 ± 396 and 2004:179 ± 166).

larger than in westerly air masses. The “calcium abatement“ (this was also the case for all other dust compartments) was very efficient in the early 1990s and resulted direct in equivalent reduction of air pollution due to particulate matter. Despite larger percentage of Ca control comparing to SO2 in the period 1990–1995, the mean ratio calcium/sulfate is significantly larger in this period than after 2000. This is not in coincidence with the (mean) result that acidity (in terms of H+) was higher in this period. However, taking into account the large standard variation (monthly variation, seen in Figure 4.35) and the pH distribution (Figure 4.36) one can drawn the conclusion that in the period before 1996 different air masses occurred having significant different chemical climate due to pollution; today the differences are small and only caused by meteorological transport characteristics. Concerning acidity change (Figures 4.35 and 4.36), we first look on the budget and compare it with the period mean H+ concentration (Table 4.27). The difference A–B corresponds to [H+] – when there are no other constituents contributing to the acidity budget. With respect to the uncertainty, we can state that the difference [H+]–(A–B) does not show a change (23–28 µeq L–1), and is likely attributed to carbonate CO23 − which was not analyzed but associated with alkaline particulate

H+ concentration (in μeq L–1)

4.2 Humans historic perspective

200 180 160 140 120 100 80 60 40 20 0

451

dashed: average 1993–1995 (96 ± 48) solid line: average 1997–2000 (68 ± 36) dotted line: average 2001–2009 (40 ± 23)

1993

1995

1997

1999

2001 year

2003

2005

2007

2009

Fig. 4.35: Variation of monthly weighted means of H+ concentration (in µeq L–1) in cloud water at Mt. Brocken 1993–2009 (April/Mai – October/December yearly variable; n = 96).

matter containing calcium, magnesium, and potassium (Möller and Zierath 1986). There is a good correlation between sulfate and calcium, however, a few years (1992, 1994 and 1999 – all having large exceedance in calcium above average) show remarkable deviation. The mean molar sulfate to calcium ratio amounts 2.4 ± 0.3 for these three exceptional years whereas it amounts for all other years 5.6 ± 0.6. As known, calcium was a proxy for polluted air masses from Eastern Germany and Europe. In the period before 2000, eastern and western air masses still had a different chemical climate. It shows that averaging might result in masking different effects. As discussed later (Section 4.2.5.4) for precipitation chemistry at Seehausen, the years 1994–1995 also show an increased acidity in Brocken cloud water (Figure 4.35), very likely because of the stronger abatement of alkaline dust than of acidic gases (where only SO2 was important). This effect, however, were obviously only measurable in easterly air masses. Figure 4.36 shows frequency distributions of pH for selected years. Climate parameters normally are unimodal distributed (Gauss distribution) but often showing a skewness. Most years here show a clear bimodal pH distribution with to separate maxima; only few years (1994, 2002, 2004, 2005, 2006 and 2009) show a skewed distribution and the year 2007 approximately a symmetric distribution. The pH minimum was in 1994 (pH 3.9) and than increased until 2002 (pH 4.4), further on remaining constant. However, the change of pH classes, respectively pH frequency distribution (Figure 4.36) is more significant than the change of mean pH. The number of very acid cloud events drastically decreased: from 11.5 ± 1.8% (230 h yr–1, resp.) in 1994–1996 to 2.6 ± 1.5% (35 h yr–1, resp.) in 1999–2009. In cases of bimodal pH distributions, the first maximum is around pH 4–5 (only in the years 1994 and 1995 it was slightly less around pH 4) and the second pH maximum moves from 5.5–6.0 in the period 1993–1997 to around 6–7 after 1998 but showing a second maximum only in 2008 whereas in the years 2002–2007 and 2009 no second maximum is

452

4 A changing climate system

40 35

1994

30 25

pH = 3.89

20 15 10 5 0 40 35

1995

30 25

pH = 3.98

relative frequency (in %)

20 15 10 5 0 40 35

1999

30 25 pH = 4.29

20 15 10 5 0 40 35

2004

30 25

pH = 4.39

20 15 10 5 0

A

B

C

D

E F G H I center of pH class

J

K

L

Fig. 4.36: Frequency distribution of pH in cloud water at Mt. Brocken for selected years. Center of pH classes: A – 2.25, B – 2.75, C – 3.25, D – 3.75, E – 4.25, F – 4.75, G – 5.25, H _ 5.75, I – 6.25, J – 6.75, K – 7.25, L – 7.50.

453

4.2 Humans historic perspective

Tab. 4.32: Period mean concentrations (based on annual means) of acidic and alkaline contributors as well hydrogen ion (in µeq L–1).

– –

A = [Cl–]+[NO–3 ]+[SO2– 4 ]

B = ([NH4+ ]+[Na+]+[Ca2+]+[Mg2+]+[K+]

A–B

[H+]

 

 

 

 

seen. The rainwater pH shifted in the last years (see Tables 4.35, 4.41 and 4.44) to around 6 (from about 4.5 before 1995). We conclude that clouds are on average more acidic than rain (due to cloud processing and acid formation) and that the second (less frequent) maximum represents the “clean” background; when clouds precipitate, the pH evolution (pH increase) is due to dilution by growing droplets in the cloud–rain transformation and subsequent below-cloud scavenging of (less acidic) dust particles. Long-term cloud water sampling and analyzing is very laborious and costly. In spite of meanwhile existing longer time-series in the world, the Brocken program is unique for Europe, covering the period of significant air quality changes in the early 1990s. Our monitoring program likely also comprised the world-wide largest time-resolution of cloud water samples and availability of accompanying chemical and physical data.559 At the end, however, we miss information on aerosol particles (CCN, PM) and droplet size distribution (automatic sensors are available only since a few years), important parameters for climate change. Many more data can be measured during field campaigns560 getting deeper insights into cloud chemistry and physics despite limited time and often unwanted weather situations. Changing air quality, in our opinion, can be monitored simpler on appropriate elevated sites by total sampling (e.g., using scrubbers) of soluble species in place of droplet sampling; unalterable would be sampling of particulate matter and additional gaseous species. Finally, we do not recommend continuing long-term cloud water monitoring without parallel chemical gas phase and particulate species measurements and droplet size distribution recording. However, to do that, it would consume huge financial and human resources asking the question whether it is equivalent to the gained information. Information on trends of air pollution and specific cloud parameter can be obtained also from different sites having selected monitoring systems.

559 Data on the chemical composition of all individual cloud water samples are now saved in the PANGAEA databank: Möller, D., Acker, K., Auel, R., Hofmeister, J., Kalass, D., Wieprecht, W. (2019) Cloud Chemistry Monitoring at Mt. Brocken, Germany (1992–2009). Brandenburg University of Technology Cottbus-Senftenberg, PANGAEA, https://doi.pangaea.de/10.1594/PANGAEA.909620. 560 Beside carrying out several field campaigns at Mt. Brocken (1991, 1993, 1995, 1998, 1999, 2000), my group participated at different cloud chemistry field campaigns, such as Great Dun Fell (UK, 1993; Choularton et al. 1997), Mt. Szrenica (Krkonoše, PL, 1995 and 1996; Acker at al. 1999a) and Mt. Schmücke FEBUKO experiment (Thuringian Forest, 2001 and 2002; Herrmann 2005, Acker et al. 2003).

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4 A changing climate system

Tab. 4.33: Rainwater investigation in the former GDR (Möller and Lux 1992), concentrations in µeq L–1. pH

Cl–

SO2– 4

NO–3

NH4+

Na+

K+

Ca+

Mg+

– . . . . . . . . . .

  –        

          

          

          

  –        

–  –        

          

  –        

Wahnsdorf (–)a GDR mean (–)b Cottbus (–)c Seehausen (–)d Greifswald (–)d Oberbärenburg (–)e Tharandt (–)e GDR mean (–)f Leipzig (–)f Cottbus (–)f Wiesenburg (–)d

a

Mrose (1966). 9 stations, pseudo-wet-only, Zierath (1981), see also Table 4.34. c Bulk samples, Heinz Jursch (Hygiene Institute Cottbus), person. commun. (1990); the concentrations seem to be too large for rainwater (exceptional ammonia), likely influenced by dust precipitation. d Marquardt, pers. communication (1990), wet-only sampling. e Erzgebirge, wet-only sampling (Herbert Lux), n = 133 (Oberbärenburg), n = 223 (Tharandt); the low ammonia concentration at Oberbärenburg cannot be explained. f 32 stations, weekly bulk samples, Meteorological Service of the GDR. b

4.2.5.4 Change of concentrations in rainwater at Seehausen Sampling and analyzing of rainwater (such as dust precipitation) is simple comparing with measurements of airborne gaseous compounds, cloud water, and particulate matter suspended in air. Thus, in the history of air pollution and atmospheric chemistry, these studies begun first and very early (see Section 2.4.5). Several studies and later monitoring of rainwater chemistry were carried out in the GDR, beginning 1958 with few measurements by Mrose (1966), Table 4.33. Not listed are measurements which were made in forests from the forestry institutes in Tharandt (Herbert Lux, born 1937) and Eberswalde (Klaus Westendorff, born 1949 and KarlHermann Simon, 1930–2011), see Möller and Lux (1992) for more details. The best data set on rainwater chemistry concerns data quality, time resolution, and additional information from former GDR and Eastern Germany (and likely in Europe) comes from the station Seehausen (1982–2002), see below. A few others, including some occasionally rainwater samples exist, for example from the Hygiene Institute Cottbus. The former Meteorological Service built up a large network from 32 stations operating since 1988; the background station Neuglobsow was belong EMEP earlier (1978) in operation. Despite much lower data quality (due to the sampling procedure – but that was “standard” at these time in all countries), a unique

4.2 Humans historic perspective

455

Tab. 4.34: Mean concentrations in rainwater at different stations in the former GDR (1976–1978), in mg L-1 (Zierath 1981); Neugl. – Neuglobsow (data from Meteorological Service), background – average from 4 stations not showing large differences (Altglienicke /Berlin, Keula/Mühlhausen, Freiberg, Neubrandenburg); e.v. evaporation residue, – no measurements, n number of samples. Bulk sampling procedure: 1 m2 funnel with water collecting unit until about 2.5 L for analysis (2–4 samples per month), daily cleaning of the funnel.

n pH Na+ K+ NH4+ Ca+ Mg+ ClNO–2 NO–3 SO2– 4 HCO–3 FPO3– 4 Fe Zn Mn Cu Pb Cd Ni e.v.

Bitterfeld

Halle

Torgau

Cottbus

background

Greifswald

 . . . . . . . . .  . . . . . . . . . . 

 . . . . . . . . .  . . . . . . . . . . 

 . . . . . . . . .  . . . . . . . . . . 

 . . . . . . . . .  . . . . . . . . . . 

 .–. . . . . . . . .  . . . . . . . . . . 

 . . . . . . . . .  . . . . . . . . . . 

Neugl.  . . . – . – . – .  – – – – – – – – – – –

Bitterfeld – most polluted area in GDR (chemical industry) Halle – very polluted area in GDR, close to Leuna (petrochemical complex) Torgau – small city at the Elbe River near Leipzig, agricultural background Greifswald – Baltic Sea cost Neuglobsow – background site in central Mechlenburg, Lake Stechlin (now UBA station) Cottbus – 129 km southeast of Berlin, surrounded by coal-fired power plants

historic data set was created by Zierath (1981) from 8 different sites in the GDR (1976–1979),561 Table 4.34. According to the huge air pollution in a few larger cities surrounded by industrial complexes, sulfate (SO2 precursor), calcium, and magnesium (dust precursors) were extremely enlarged comparing to the background (Table 4.36). With the 561 The monitoring was done between end of 1976 and middle of 1979, within the first about 1.5 years nearly wet-samples were taken and within the remaining 1.5 years bulk samples; here only the (pseudo) wet samples are presented.

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4 A changing climate system

exception of Bitterfeld, nitrate and ammonium show no significant regional differences. At present no significant differences in rainwater chemical composition are found between the cities listed in Table 4.36 and the background. The decline after 1990 is between a factor of 2 (ammonium) and 40–100 (sulfate and calcium) at heavy polluted sites and 4–5 for the background, respectively. The former meteorological station Seehausen562 represents the North German Plain, situated close to the former border between East and West Germany. In 1982 rainwater chemistry monitoring (Table 4.35) begun to study the different acidity from western and eastern air masses.563 At that time, depending on the trajectory, Tab. 4.35: Annual weighted-mean concentrations (in µeq L–1) of chemical composition of precipitation at Seehausen; R – annual precipitation amount (in mm or L m–2 yr–1, resp.), n – number of samples (based on 4-h wet-only sampling). year a                    

n

R

pH

H+

Na+

K+

NH4+

Ca+

Mg+

Cl–

NO–2

NO–3

SO2– 4

                    

                    

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . .

. . . . . . . . – – – – – – – – – – –

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . .

a

Begin of monitoring in October 1982.

562 52 °06´N, 12 °24´E, 21 m a.s.l., mean precipitation 556 mm; about 40 km west of Salzwedel, 100 km north-westerly of Magdeburg and 150 km northeast of Mt. Brocken. 563 Established by the former Institute for Energetics (Leipzig), continued from 1992 by the Institute for Troposheric Research (Leipzig) and since 1996 by the Chair for Atmospheric Chemistry and Air Pollution Control (Cottbus) until ending the monitoring in 2002. The chemical analysis was carried out from 1982–1995 by Dr. Erika Brüggemann (Leipzig) and from 1996 to 2002 by Dr. Renate Auel (Berlin) with highest quality standards. No change of any sampling procedure and data classification has been made over the whole period.

4.2 Humans historic perspective

457

Tab. 4.36: Mean concentrations in rainwater (in µeq L–1) at different stations in the former GDR, see Tables 4.32 and 4.33.

Bitterfeld Halle Leipzig Cottbus backgrounda backgroundb

– – – – – –

SO2– 4

Ca+

Mg+

NO–3

NH+

     

     

     

     

     

a

Remote northern parts of GDR. Seehausen (representing often western air masses).

b

high concentrations of sulfate in southern Sweden were accompanied by greater or lesser carbon as black or white episode, respectively (Rahn et al. 1982). The former East Germany (GDR) was known to be the second largest SO2 emitter (after UK) in Europe but based on lignite combustion instead of hard coal, used dominantly in Western Europe. It was expected that long range transport from GDR is associated with high sulfate but also high calcium and therefore less acidity in contrast to air masses from UK to Scandinavia. Therefore, wet-only sampling on 4-h basis was established to attribute chemical composition to air masses characterized by backward trajectories to classify rainwater samples according to entry sector, Table 4.37 and Figure 4.37 (Marquardt and Ihle 1988a, b, Möller et al. 1996b, Marquardt et al. 1996, 2001). Tab. 4.37: Entry sectors at Seehausen. F G H I J K L

 °–  °  ° –  °  ° –  °  ° –  °  ° –  °  ° –  °  ° –  °

N NE–E SE SW W NW NNW

remote air from Scandinavia and Baltic Sea continental polluted (Poland) continental polluted (GRD, Czech Republik) continental (West Germany) continental polluted (West Germany) continental polluted and maritime (West Germany) maritime from North Sea

The variation between single samples (or events, but due to 4-h sampling time, longer lasting rain events were characterized by several samples) is huge, the maximum concentration is 10–20 times larger than the mean and the minimum goes toward zero (Table 4.38). The reasons for the large variation are manifold: rainfall rate (determining droplet sizes and amount), air mass origin, time with and without rain before sampling, and local contamination. The longer the dry period persists before the rain event, the higher the ionic concentration (up to 2–3 times) due to atmospheric accumulation. Conversely, the longer the rain event persists, the

458

4 A changing climate system

F L Greifswald G

K S

Cottbus

Brocken

J I

H

Fig. 4.37: Entry sectors at station Seehausen for rainwater sample classification (Marquardt and Ihle 1988a).

Tab. 4.38: Statistics (arithmetic mean of all samples, maximum concentration, number of samples n, standard deviation σ; note minimum → 0) of the Seehausen rainwater data set (in µeq L–1, rounded). Ion +

H Cl– SO2– 4 NO–2 NO–3 NH4+ Na+ K+ Ca+ Mg+

n    a      

mean

σ

max

. . . . . .  . . .

. . . . . . . . . .

         

a

Only before 1991.

smaller (by a factor 0.3–0.8) the ionic concentration due to wet removal with the exception for sea salt NaCl and hydrogen ions (Marquardt and Ihle 1988a). Thus a larger number of samples are required to draw conclusions in relation to air pollution; moreover the concentrations should be precipitation-weighted and the samples should be classified according to entry sectors, based on back trajectory calculations (Figure 4.37). Moreover, timely changes due to seasonal and interannual variations occur because of variations of meteorological conditions, air mass

4.2 Humans historic perspective

459

Tab.4.39: Mean concentrations in rainwater from different entry sectors (in µeq L–1) at Seehausen 1983–2001; note the total number is much smaller than those listed in Table. 4.38 because some samples could not be classified to sectors.

F G H I J K L

n

H+

Cl–

      

. . . . . . .

. . . . . . .

SO–  . . . . . . .

NO–

NO–

NH+

Na+

K+

Ca+

Mg+

. . . . . . –

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

Tab. 4.40: Mean concentrations in rainwater from different entry sectors (in µeq L–1) at Seehausen for periods 1983–1990 (90) and 1999–2001 (2000).  F G H I J K L

 F G H I J K L

n

H+

Cl–

      

. . . . . . .

. . . . . . .

n

H+

Cl–

      

. . . . . . .

. . . . . . .

n

H+

Cl–

      

. . . . . . .

. . . . . . .

SO–  . . . . . . . SO– 

NO–

NO–

NH+

Na+

K+

Ca+

Mg+

. . . . . . –

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

NO–

NO–

NH+

Na+

K+

Ca+

Mg+

. . . . . . .

– – – – – – –

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

SO– 

NO–

NO–

NH+

Na+

K+

Ca+

Mg+

– – – – – – –

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

. . . . . . .

460

4 A changing climate system

Tab. 4.41: Means of rainwater concentration at Seehausen from different characteristic regions and three periods (in µeq L–1); data rounded. period

n

H+

Cl–

SO– 

NO–

Na+

K+

Ca+

Mg+

  

  

  

  

  

  

  

  

  

  

NH+

F – north remote (northern Germany, Baltic Sea and Scandinavia) – – –

  

  

  

  

  

L – northwest maritime (northwest Germany and North Sea) – – –

  

  

  

  

  

G + H – east continental (East Germany, Poland, Czech Republic) – – –

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

  

I + J – west continental (West Germany) – – –

  

  

  

characteristic and air chemistry. Furthermore, this data set shows a trend (see below) with the result that averages over periods are meaningful (Table 4.40). To pronounce the influence of different air masses, in Table 4.41 some entry sectors are condensed and separated in periods before and after 1990. The data set shows imposingly the changes in chemical composition of precipitation due to emission changes in the period before and after 1990 as well as significant differences between “west” and “east.” As already discussed, pollution proxies are sulfate and calcium (SO2 and flue ash from coal combustion), ammonium (NH3 from agriculture) and nitrate (NOx from power plants and traffic). It was widely shown that sulfate, ammonium, and calcium decreased everywhere with air pollution abatement in Europe and Northern America but nitrate not or only little. There are other interesting changes in chemical composition of precipitation from east (Figure 4.39). Substances, normally associated with natural sources, such as potassium (soil dust), magnesium (sea salt and soil dust), sodium and chloride (both sea salt) were found in large excess in precipitation before 1990 (and hence

461

4.2 Humans historic perspective

also in PM).564 The molar ratio [Na]/[Mg] is much less (2.6 before 1990 and 3.8 after 1990) than expected (molar 9.8) assuming that all Mg is sea salt. It must be concluded that Mg found in precipitation is also from other primary sources of dust (such as Ca). Obviously, Mg, K, and Na (apart from Ca) were emitted with flue ashes from lignite-fired power plants. We cannot exclude it also for Cl (the so-called westElbe coal was salty) but much of HCl was emitted from potash industry. Excess chloride accounted to about 50% to total chloride before 1990 and decreased significant until 2002 but obviously still exists. Interestingly, the data demonstrate that at present – despite lower emissions from Eastern Germany than from west – eastern air masses contain significant higher atmospheric concentrations for sulfate, nitrate, and ammonium as well as calcium but no different concentrations of sea salt constituents (sodium, chlorine and magnesium); Table 4.41. It is fact that (with the exception of local activities such as building) sea salt and soil dust remain as sources of alkali and alkali earth metals (Na, Mg, Ca, and K). These higher concentrations found in precipitation (and also particulate matter) with easterly trajectories (Tables 4.41 and 4.43) are not longer a result of the often cited still higher emissions in southeastern countries (Poland, Czech Republic, and Ukraine) but a result of long range transportation. Clouds and precipitation occur much less with eastern air masses than with western air masses; in other terms, the time interval between “wet events” is large. Sulfate, nitrate, and ammonium, however, are secondary produced from gaseous SO2, NOx and NH3 via gas-to-particle conversion and cloud scavenging – this needs time, synonymously with transport distances which is favor in continental eastern air masses. Hence concentrations increase due to missing wet deposition; especially particulate matter (secondary aerosol), exceeding EU limits of 50 µg m–3 (see also Section 4.4.13). In case of precipitation, associated with easterly trajectories, higher wet deposition is Tab. 4.42: Estimations and change of excess chloride in precipitation (in µmol L–1) at Seehausen, based on two different sea salt reference values for [Na]sea/[Cl]sea (see for details on the sea salt Na/Cl ratio Möller 1990). period

– – –

[Na+]

 ±   ±   ± 

[Cl–]

 ±   ±   ± 

R = [Na]/[Cl]

. ± . . ± . . ± .

Clexcess calculated on Rsea = .

Rsea = .

  

  

564 Before 1990, PM was only monitored concerns total mass (TSP) and dust precipitation. There was not yet scientific interest and ingredients (heavy metals and benzo[a]pyrene) were analyzed only because of legal requirements.

462

4 A changing climate system

found. In western air masses, many precipitation (and cloud) events occur during transport from Atlantic or North Sea which remove (and transform) gases and particles until they can deposited in Eastern Germany (and further eastern). Similar, calcium that today is dominantly derived from soil dust, is accumulated during transportation without precipitation (concentration of potassium is so small that variations are analytically not significant). Above we have seen that sodium as well chloride was exceeded in relation to sea salt NaCl in rainwater before 1990 due to anthropogenic emissions. Normally, chloride is depleted in continental rain resulting in ratios Na/Cl > 0.86 (see Section 5.7.2 in Volume 1 and Möller 1990). Table 4.42 and Figure 4.38 show clearly an increase of Na/Cl at Seehausen from 0.4 to 0.8 between 1982 and 2002 despite extreme interannual variations. Rainwater analysis from other German sites around the year 2010 (Tables 4.33 and 4.34) indicated Na/Cl > 1.

3.6 all samples (n = 200) 3.2 2.8 2.4 2.0 1.6 1.2

Na/Cl equivalent ratio

0.8 0.4 0.0 1984

1986

1988

1990

1992

1994

1996

1998

2000

1.2 annual means (not weighted) 1.0 0.8 0.6 0.4 0.2 0.0 1985

1990

1995

2000

year Fig. 4.38: Na/Cl ratio in rainwater at Seehausen (based on equivalent concentration) from sector H (GDR): based on all samples (n = 200) and monthly arithmetic means (1983–2001).

4.2 Humans historic perspective

463

120 magnesium 100 80 60 40 20 0 1882 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 rainwater ionic concentation in μe L–1

1200 calcium 1000 800 600 400 200 0 1882 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 350 chloride 300 250 200 150 100 50 0

year

Fig. 4.39: Trend (1982–2002) of magnesium, calcium and chloride rainwater concentration (in µeq L–1) at Seehausen from sector H (GDR).

Obviously, potential high acidity derived from sulfate was neutralized by calcium from alkaline flue ash emission in “eastern” air masses. Hence, in the period before 1990 no large differences in acidity (expressed as H+) can be seen from different trajectories (Figure 4.41). In the period after 1995, the pH rose from about 4.3 (before 1990) to 4.8 (east trajectories) and 5.0 (west trajectories). However, in the period 1991–1995 an acidity increase up to levels twice as before 1990 was observed

464

4 A changing climate system

Tab. 4.43: Change of equimolar concentration ratios in precipitation at Seehausen before and after 1990; [NH4+ ]/[cations]] = [NH4+ ]/([Ca2+]+[Mg2+]+[Na+]+[K+]), [N]/[S] = ([NO–3 ]+[NH4+ ])/[SO2– 4 ]. before a

concentration ratio

[N]/[S] [NH4+ ]/[cations]

after b

trajectory east

all data

trajectory east

all data

. ± . . ± .

. ± . . ± .

. ± . . ± .

. ± . . ± .

[N]/[S] 1983–1989 and [NH4+ ]/[cations] 1983–1991. [N]/[S] 1991–2000 and [NH4+ ]/[cations] 1992–2000.

a

b

(Figure 4.41), following by a sharp decrease after 1996. The simple explanation is that air pollution abatement first concerned particulate matter (better filter techniques and particularly its continuous operation).565 For the remaining power plants, flue-gas desulfurization was completed only after 1995 with a sharp decrease in SO2 (Figure 4.12 on p. 414). Note that not the absolute concentration (or emission) but the relative percentage of compounds having acidifying and/or neutralizing properties, is essential in determination of the acidity budget. This is also illustrated by the long term rainwater pH trend of a site south of Cottbus (Figure 4.40) where industrial growth results in increasing alkaline rainwater (up to pH > 6) between 1983 and 1988 followed by pH decrease gaining a minimum around 1993 (pH ~ 4.6) and succeeding again small increase. pH 7

6

5

4 1983

1985

1987

1989

1991 year

1993

1995

1997

1999

Fig. 4.40: Trend (1983–1999) of annual mean pH of rainwater at station Lauchhammer, a former very polluted industrial site about 50 km southwest of Cottbus; data from LUA (1995, 2002a).

565 It was (but not officially) known that electrostatic precipitators in GDR power stations not operated permanently to economize electricity.

4.2 Humans historic perspective

465

250 entry sector I (“west”) 200

rainwater hydrogen ion concentration in μe L–1

150 100 50 0

1882 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002

250 entry sector H (“east”) 200 150 100 50 0

Fig. 4.41: Trend (1982–2002) of hydrogen ion rainwater concentration (in µeq L–1) at Seehausen from sector H (“east”) and I (“west”).

For Central Europe, Winkler (1982) stated that an average pH of 4.2 in rainwater was not changing since 1937. This was likely valid until end of the 1980s; from our long-term monitoring at Seehausen the pH changed from 4.3 to 4.8 end of the 1990s in less then 10 years. It is remarkable that ammonium decreased between the two periods by a factor of two whereas nitrate remains constant. Thus is also supported by changing rainwater composition at a former extreme polluted site, Lauchhammer (Figure 4.43). It is remarkable that the sulfate trend follows the two-step decline in SO2 (cf. Figure 4.12 on p. 414). In Figure 4.42 the sulfate trend at Seehausen is compared between “west” and “east.” It follows the SO2 emission changes as discussed above, earlier in West Germany (and west Europe) between 1986 and 1989, followed by the Eastern German decline (1990–1996). Between 1996 and 2002, a further small decline in sulfate is observed, which seems to be stabilized around 2000. The most significant change is seen in the sulfate/nitrate ratio from 3.4 to 1.0. Concerns total inorganic nitrogen (nitrate + ammonium), the S/N ratio was between 1.0 and 1.2 before 1990 (east to west) and decreased to 0.4 to 0.5 after 1995. In other words, the chemical climate changed from sulfur to a nitrogen regime.

466

4 A changing climate system

1000 900 800

entry sector I (“west”)

700 600

rainwater sulfate ion concentration in μe L–1

500 400 300 200 100 0 1882 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 1000 900 800

entry sector H (“east”)

700 600 500 400 300 200 100 0 year

Fig. 4.42: Trend (1982–2002) of sulfate rainwater concentration (in µeq L–1) at Seehausen from sector H (“east”) and I (“west”).

4.2.5.5 Emissions versus concentrations: chemical climatology (summary) “Climate change” can be expressed in changing air chemical composition and (now increasing) temperature, intercorrelated through different direct and indirect radiation effects. However, we discussed in Section 2.3.3 in Volume 1 that climate change is not only due to changing temperature and subsequent changing meteorological/climatological elements but also due to changing chemical properties of the atmosphere. Aerosol–cloud interactions constitute the single largest uncertainty in anthropogenic radiative forcing. However, decreasing emissions of chemically reactive substances (almost entirely SO2, NOx, NH3, HCl, VOC) and hence air pollution is normally nonlinear (or better expressed complex) and associated with changing atmospheric chemistry in terms of acidity and oxidation capacity. These listed gases are also precursors of CCN; therefore, likely one of the most important question is that upon changing size depending chemical composition of atmospheric particles and droplets. With respect to cloud formation, CCN number (likely decreasing; see Birmili et al. 2016) and humidity (likely increasing, see McCarthy et al. 2009) is most significant. A review on long-term observations of CCN number

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sulfate

100

20

0

0

19

19

19

99

2

19 97

40

95

4

19 91 19 93

60

89

6

19 87

80

19 85

8

sulfate concentration (in mg L–1)

120

nitrate calcium ammonium sulfate

10

19 83

concentration (in mg L–1)

12

year Fig. 4.43: Trend (1983–1999) of annual mean nitrate, sulfate, calcium, and ammonium rainwater concentrations at station Lauchhammer, a former very polluted industrial area about 50 km southwest of Cottbus; data from LUA (1995, 2002b).

concentrations, particle number size distributions and chemical composition from 12 sites on 3 continents is recently given by Schmale et al. (2018) showing very large variations. As expected, CCN characteristics are highly variable across site categories. However, they also vary within them, most strongly in the coastal background group, where CCN number concentrations can vary by up to a factor of 30 within one season. In terms of particle activation behavior, most continental stations exhibit very similar activation ratios (relative to particles >20 nm) across the range of 0.1–1.0 % supersaturation. At coastal sites the transition from particles being CCN inactive to becoming CCN active occurs over a wider range of the supersaturation spectrum. On the other hand it is discussed (e.g., Junkermann et al. 2011) that due to “warming” and air pollution abatement the number of potential CCN increases, especially below 0.1 µm (nanoparticles), but the droplet sizes decreases. As a possible consequence, more cloudiness and less precipitation could results. Junkermann et al. (2016) have shown the surprisingly result that from “modern” coal-fired power stations a large number of ultra-fine particles (UFPs) were emitted; in plumes they find 60,000–80,000 cm–1 and 10–40% of rural countryside of Germany are continuously covered with UFPs in the range 15,000–80,000 cm–1 around one to two orders above continental background. We have found no LWC trend at Mt. Brocken between 1993 and 2009 which results in three possible explanations: 1. no change in droplet size distribution, 2. less but bigger droplets or 3. more but smaller droplets.

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Unfortunately, no data on cloud drop size distribution are available for that period to give evidence for one of this assumption. Only since a few years, automatic monitoring of droplet size is possible to study this relationship even over longer periods (e.g., Spiegel et al. 2012, Sarna and Ruschenberg 2016) and case studies (e.g., Li et al. 2017) support the principal relationship between humidity, particulate matter, and droplet size. The observed trend of increasing cloud base height at Mt. Brocken, however, is consistent with observed trends of increasing planetary boundary layer height over Europe, which is associated with decreasing surface relative humidity and increasing surface temperature at most stations (Zhang et al. 2013). The data from Mt. Brocken reflect the general trend of air pollution in relation to emission, found also at many other stations. To compare cloud with rainwater chemistry, in Table 4.44 two periods, which characterize the period of strong changes of emissions before 1996 and the period after 1996 were selected. Because of the evolution of rain from clouds, the relationship between its chemical compositions is complex and remains unclear. In polluted areas (mainly in past), sub-cloud scavenging has to be regarded as an important source to rain chemistry. As seen, changes are less in cloud water comparing with rainwater. The changes should not be overestimated but in rain all compounds decreased by around 30% whereas in clouds only sulfate, calcium, ammonium, and potassium decreased somewhat less than 30%. The period 1997–2004 is characterized with significant higher sea salt (~200 µeq L–1 NaCl) whereas the periods before (1993–1996) and (2005–2008) have much lower but same sea salt loading (~144 µeq L–1 NaCl). Tab. 4.44: Comparison of cloud (Brocken) and rainwater (Seehausen) chemical composition; weighted means (in µeq L–1). LWC – liquid water content (in mg m–3) and R – yearly rain fall amount (in L m–2) as mean over the period; n – number of samples. Period

n

LWC/R

Cl–

NO3–

SO24 –

NH4+

Na+

K+

Ca+

Mg+

H+

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

cloud water – – rainwater – –

It is remarkable that the concentrations (related to around the year 2000) of magnesium and potassium are both exactly 5 times higher in cloud comparing to rainwater whereas calcium is only slightly higher (by a factor of 1.7) in cloud water. It is [Ca] = [Mg] + [K] in cloud water but [Ca] = 3([Mg] + [K]) in rainwater. As discussed, cloud water represents west European air mass characteristics whereas in rainwater

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Tab. 4.45: Change of emissions and concentrations over the period 1990 to 2000 (approximated decrease in % if not other indicated); 0 no change, ? unknown (no data available), + increase. Note that “dust” includes several types of PM. emission

gaseous concentrations

aqueous concentrations

near-ground

Mt. Brocken

cloud

rain “east”

SO dust

 

– –

 ?

NOx NH HCl O

  a –

 ? ? +

 ? ? +c

Ca Mg K Na NO–3 NH4+ Cl–

       

H+ pH

 +.b

SO2– 4

“west”

     +    +.

         +.

a

Estimated. PH units. c Maximum around 2002 and further decrease until 2009 from 42 ppb to 35 ppb; the low annual values in the early 1990s were discussed due cloud chemistry effect resulting in extreme low winter season values. b

sub-cloud scavenging of particulate matter remains obviously important. It is known that North Africa accounts for 50–70% and Asian deserts contribute 10–25% of global dust emission, and is enriched in calcite. Countries in Europe, which are closer to these sources, are more affected by alkaline dust (Lajtha and Jones 2013). Locally derived dust (for example from the Hungarian puszta) can also contribute to neutralization of precipitation acidity. In the background of climate change, we also may look back to different chemical climates in past, which were the result of changing sources of particulate matter and gaseous precursers (note only compounds are listed that are relevant for CCN): a) permanent sources over geological periods: volcanism, sea salt, and soil dust b) biogenic sources from sea: DMS, NH3 c) biogenic sources from vegetation and soils: NH3, NOx, NMVOC d) era of intensive agriculture: NH3 e) era of coal combustion: SO2, NOx, industrial dust f) era before coal combustion: NH3 from putrefaction In discussing the relation between CCN and cloud droplets, in following some simple questions and principal answers will be given.

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– Represents the chemical composition of cloud water the nucleus? Partly – the more polluted the atmosphere with gases (NH3, SO2, HNO3 – other trace gases play no role in the mass budget), the more substance the droplet can scavenge after nucleation. Particles that are not acting as CCN, can be taken up through collision by cloud droplets – even insoluble particles such as soot. – Can we conclude from cloud water chemical composition on the nucleus? Only from single droplet analysis – mean cloud water composition corresponds to the chemical mixture of all nuclei. – What is the typical cloud water composition? (1) sea salt components (Na, Cl, Mg, and sulfate), (1) ammonium, nitrate, and sulfate from gaseous and particulate precursors, (3) soil dust components Ca and K, (4) organic matter (widely unspecified); note that many minor species are found such as carbonate, phosphate, iodide, and so on, and trace metals. – What types of nuclei (CCN) we may expect? (1) sea salt particles, composing mainly from Na, Mg, and Cl (if there is Cl loss, it is replaced by nitrate and/or sulfate), (2) ammonium-nitrate-sulfate particles (from the gaseous precursers NH3, HNO3 and SO2 through gas-to-particle conversion), (3) secondary organic particles (oxygenated and thus hygroscopic and likely often modified through surface reactions with SO2 and NOy), (4) soil and industrial dust particles: oxides and carbonates of Ca and Mg (modified by SO2 partly to sulfate) and potassium (likely from plant guttation). – Plausibility test: cloud water from Mt. Brocken contains on average totally 30 mg L–1 solutes (50% sea salt, 10% soil dust and 40% ammonium-nitratesulfate); with mean LWC being 0.5 · 10–6 and a mean droplet radius of 5 µm, it follows for the “residue” (CCN and soluble gases, where only NH3 and HNO3 are important in the mass budget) about 15 µg m–3 and from the mass budget (assuming a density of 2 g cm–3) of the dissolved matter a nucleus with a diameter of 0.5 µm. – What is the relation between nucleus and droplet? The number of activated CCN determine the number of cloud droplets; the type of the nucleus determines the chemical composition of the droplet. In the following, the relations between emissions and concentrations are summarized; this concerns the period 1990–2000 and the time before 1990 and after 2000 respectively: – The decrease of near-ground SO2 concentrations is close to that of SO2 emission decrease; however, 30–40% of measured SO2 is caused through long-range transport from other countries which had less emission reduction (see below). – The less percental reduction of SO2 concentrations at Mt. Brocken is due to dominant influence of western air masses (Mt. Brocken represents the transport layer in the upper mixing layer in summer and almost upper the mixing layer in winter).

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– The much less reduction of dust concentration comparing to its emission reduction is due to the fact that many dust sources are not considered in the emission statistics (such as soils) and dust is to a large extent provided through long-range transportation. – Calcium reduction is associated with SO2 abatement from coal-fired power stations. Considering calcium as proxy for dust, it is overproportional reduced in rainwater and much less in cloud water; hence atmospheric calcium is removed to a large extent from particulate matter through sub-cloud scavenging. – As for calcium, also sodium, magnesium, and potassium, which have been identified as constituents of man-made dust emissions, were likely quantitatively removed through precipitation (via sub-cloud scavenging). – In cloud water, however, concentrations of sodium, magnesium, and potassium did not change, suggesting that PM and namely CCN at higher atmospheric levels is exclusively caused by sea salt and other natural sources (soils), representing a large-scale airborne background. – The significant reduction of calcium in cloud water shows that Ca was the dominant cation in dust emission from coal-fired power plants (several times larger found is flue ash comparing to Na, Mg, and K) and that Ca has no other notable sources (sea salt and soils dust) in contrast to Na, Mg, and K. – The decrease of NOx emission in the 1990s was only due to power plant abatement (high stack emission) whereas traffic related NOx emissions increased; after the year 2000, decrease of NOx emissions occurs only from ground-based sources (traffic and domestic). Note that about 90% of primary emission is NO. This resulted in a net effect of no change of gaseous NOx (measured as NO and NO2). – In rainwater, no change of nitrate is observed. However, in rain from eastern air masses, nitrate increased by 25% whereas in rain from western air masses nitrate decreased by 15% – In cloud water, the data suggest a trend in aqueous phase nitrate but care is taken due to large interannual variations. However, period means of cloud water nitrate are significant different being 251 ± 38 µeq L–1 (1993–2001) and 196 ± 36 µeq L–1 (2003–2009), respectively. The reduction of nitrate is expected from NOx reduction in the upper mixing layer and hence reduced NOy formation (HNO3 and particulate nitrate). – It is not unlikely that HNO3 replaced SO2 in interaction with ammonia in gasto-particle conversion. – However, the NO2/NO ratio decreased, suggesting a smaller conversion of NO into NO2 in troposphere and subsequent of airborne gaseous HNO3, the precursor of aqueous nitrate. – Ammonia, important for gas-to-particle conversion in formation of aerorol particles of sulfate and nitrates and hence CCN precursor, shows also no clear trend

472

– –

–

– –

4 A changing climate system

in emission and cloud water concentration but also significant differences in period means: 303 ± 29 µeq L–1 (1993–2001) and 271 ± 52 µeq L–1 (2003–2009). The molar ratio ammonium to nitrate remains constant (being 1.28), supporting the idea of large scale particulate ammonium nitrate (and CCN) formation. The emissions of chlorine (as gaseous HCl) decreased likely to the same extent as SO2. Continues HCl measurements are absent but in rainwater chloride decreased by 65%. No chloride change occurs in cloud water, indicating that cloud water chloride is caused from particulate sea salt. Gaseous HCl is scavenged through rain, thus contributing to rainwater chloride. The acidity (in terms of H+) decreased in cloud and rainwater as well, somewhat less in eastern rainwater comparing to western rainwater. This resulted from more reduction of acidic precursors (SO2 and NOx – HCl is negligible in the budget) then alkaline (NH3 and cations, mostly Ca). Cloud water is more acidic than rainwater. Nitrate becomes the dominant anion, replacing sulfate.

In the countries, located southern and eastern of East Germany (Poland, Czech Republic, Austria and Hungary) the decrease in SO2 emissions between 1990 and 2000 amounted around 55% (most in Czech Republic with 65%) which explains now gaining sulfur to the German budget. In the Czech Republic, sulfate in rainwater decreased similar to the emission change to 65% (from 125 to 42 µeq L–1) whereas nitrate decreased insignificant to 10% (from 61 to 54 µeq L–1); Hůnová et al. (2004). This is slightly higher than in rainwater (as total mean; note large differences in rainwater between east and west air masses) at Seehausen: 40 and 35 µeq L–1 for nitrate and sulfate, respectively. In the USA, between 1992 and 2010, SO2 emission and particulate sulfate (as large scale and annual averages) decreased both by about 50% (Hand et al. 2012). A similar “linear” relation was found for Europe, where SO2 emissions decreased by about 50% and particulate sulfate by 59% between 1985 and 2000 and 20% respectively 32% between 1995 and 2000 (Berglein et al. 2007). Trends in sulfate and H+ in precipitation in the USA were close to stoichiometric ratio found in a record between 1978 and 2010 (Lajtha and Jones 2013), but not in Europe, especially Eastern Europe. In Europe, alkaline Ca containing dust and ammonia levels were substantially higher until the beginning of 1990s and declined only in the 1990s. The strong Ca decline in eastern European Countries owing to coal-fired power plant air pollution control counteracted the decline in H+ expected from concurrent SO2 emission decline as discussed by Hedin et al. (1994) and Hedin and Likens (1996). In Europe, however, the emission pattern was inhomogeneous and different in trends; in Western Europe, decrease begun already in the early 1980s whereas in Eastern Europe only after 1990. Hence, monthly and even more annual concentration averages masks the differences between different polluted air masses, which were still typical in the 1990s. This is indicated by a high standard

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deviation (or fluctuation of daily concentration means). Adjustment of air pollution between western and eastern air masses after the year 2000 led to much less timely variation and less extremes. However, secondary PM such as sulfate, ammonium and nitrate will be still enriched in easterly air masses due to long range transportation associated with less wet removal via precipitation (note it is not necessarily caused due to higher emissions from Eastern Europe). Further changes in cloud and precipitation chemical composition even with coal exit will not be expected significant in absolute values; power-plant emissions of SO2, NOx, and flue ash are already to a large extent controlled. However, because coal combustion remains the only important SO2 source, further decline of gaseous SO2 concentrations and sulfate in PM and aqueous-phase is anticipated. Atmospheric NOx and nitrate levels will certainly only decline with a change of current traffic technologies to electromobility. Thus, in the future precursors of atmospheric acidity will be unimportant. Assuming that ammonia will not significant further decline because of agricultural activities, an alkaline precipitation (pH ≥ 6) is likely in the future, creating a new-type environmental problem, “alkaline rain”.

4.3 Emission of atmospheric substances An emission represents a flux (amount of a compound566 per time). Concerning the source characteristics, we separate emissions from – point sources (volcanoes, fumaroles, factories, and more), – specific sources (plants, animals, vehicles, and so on), and – diffuse sources (surfaces such as soils, lakes, landscapes, and so on). The flux can be related to an area (a standard area such as ha and m–2) and is then termed a specific emission. The matter state is – gaseous (volatile elements, molecules), – solid (particulate matter) or – liquid (droplet spray). An emission inventory is a database that lists, by source, the amount of air pollutants discharged into the atmosphere of a community during a given time period

566 Normally the amount of a substance is given as mass but could also be given in mole or equivalent. The substance can be undefined (such as dust or any particulate matter) and than given in mass (eventually specified in categories such as size range) or lumped (such as reduced sulfur compounds or VOC) and must be given in mass element (here S and C, resp.). Unfortunately, nonchemists (no chemist would do it because the definite amount of a substance is a base principle in chemistry) publish NOx emission values in mass (by convention the mass is related to NO2). A special case are VOC emission values in mass – if that is in mass carbon, it is definite but in mass VOC the question remains, whether this value is based on the sum of all individual VOCs.

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(Friedrich and Reiss 2004). Emissions as flux (mass per time) of substances in the atmosphere are the parameters for atmospheric chemistry – they determine the initial air concentration (the key parameter for the reaction rate) and the composition (the key parameter for the reaction mechanisms).

4.3.1 Introduction: estimation of emissions Beginning with estimates of global values of a high degree of uncertainty 30–40 years ago, now emission (or better, source) processes are described for diurnal, weekly and annual cycles with the aim to achieve a better temporal resolution for global inventories (Table 4.46). By using geographical statistical data, the sources and emissions are spatially resolved, from the 1 ° · 1 ° normally used in global models down to 1 · 1 km2 in local models. It is another question how reliable the temporal and spatial resolved estimates are. The Global Emissions Inventory Activity (GEIA) aims to provide global gridded emissions inventories to science and policy communities for all trace gases. GEIA was created in 1990 in frame of IGAC (International Global Atmospheric Chemistry Program) to encourage the development of global emission inventories of gases and aerosols emitted into the atmosphere from natural and anthropogenic sources (Galbally 1989). The long-term goal is to provide inventories of all trace species relevant to global atmospheric chemistry (Graedel et al. 1993). Emission inventories are available for the following species: – acidification: NOX from soils and lightning; NH3 from natural soils, oceans, and wild animals, – aerosol formation: SO2 from volcanoes; DMS from oceans, – climate change: CH4 from wetlands, termites, oceans/hydrates; N2O from natural soils and oceans, CO2 from fossil fuel combustion, – tropospheric ozone: CO from vegetation and oceans; CO soil sink; NMVOC from vegetation, – major reactive chlorine compounds: CH3Cl, CHCl3, CH2Cl2, C2HCl3, and C2Cl4 from oceans; CH3Cl and CHCl3 from land-based sources; HCl and ClNO2 from sea salt dechlorination. Several estimates exist for historical emissions. The Carbon Dioxide Information and Analysis Center (CDIAC) presents a good estimate of historical CO2 emissions from fossil fuel combustion for the period 1950–1990 on a 1 ° · 1 ° grid based on United Nations (UN) energy data (Andres et al. 1996). Andres et al. (1999) report on an exercise similar to that described in this paper to extend their data sets of energy consumption on country levels back to 1751. Gschwandtner et al. (1986) estimated emissions of sulfur and nitrogen oxides by the United States for the period 1900–1980, partly on a subnational (state) level. The Environmental Protection Agency (EPA) develops an annual

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Tab. 4.46: List of selected global and regional emission inventory activities. RIVM – Rijksinstituut voor de Volksgezondheid (Bilthoven, Netherland) MPI – Max-Planck-Institute (Mainz, Germany), LSCE – Laboratoire des Sciences du Climat et l’Environnement (Paris, France), IER – Institut für Energiewirtschaft und Rationelle Energieanwendung (Stuttgardt, Germany). inventory

spatial cover and resolution

GEIA (IGAC) global,  ° ·  ° or per country EDGAR . global,  ° ·  ° or (RIVM) per country EDGAR per sector and v.. country AEROCOMN global,  ° ·  ° (MPI/LSCE) POET global,  ° ·  ° RETRO global, . ° · . °

EMEP GENEMIS (IER) TNO ABBI REAS

Europe,  ·  km Europe, Germany,  ·  km Europe,  ·  km Asia,  ° ·  ° Asia

temporal cover and resolution

remarks

, 

natural and anthropogenic (EDGAR) emissions

–

only anthropogenic emissions

–

time series and grids

, 

natural, anthropogenic, and “effective” secondary aerosol POET emission WP extended EDGAR and GEIA RETRO is about modeling intraannual trends in tropospheric chemistry

– global emissions – –, h h

anthropogenic emissions, based on official reporting of countries and experts assessment production on demands for selected episodes

 hour – –, , 

Asian biomass burning inventory regional emission inventory for Asiaa

a For China, three emission scenarios have been developed: REF (reference case), PSC (Policy Success Case), and PFC (Policy Failure Case).

report, titled the “Inventory of U.S. Greenhouse Gas Emissions and Sinks”, that tracks U.S. greenhouse gas emissions and sinks by source, economic sector, and greenhouse gas going back to 1990 (EPA 2018). Mylona (1996) presented sulfur emissions for several European countries (including Russia and Turkey) for the period 1880–1990. A detailed global study of sulfur emissions from 1850 to 1990 with data per country and for some sectors has been presented by Lefohn et al. (1996, 1999). The EDGAR (Emission Database for Global Atmospheric Research) project is a comprehensive task carried out jointly by the Netherlands National Institute for Public Health and the Environment (RIVM) and the Netherlands Organization for Applied Scientific Research (TNO) (Bouwman et al. 1997, Olivier et al. 1999a, 1999b, 2005, Olivier and Berdowski 2001, Olivier 2002, Janssens-Maenhaut et al. 2012, 2017). This set of inventories combines information on all different emission sources, and it was

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used over the past few years as a reference database for many applications. The work is linked into and part of the Global Emissions Inventory Activity (GEIA) of IGBP/IGAC. The last version of EDGAR v4.3.1 (January 2016) provides calculated global annual man-made emissions for direct greenhouse gases (CO2, CH4, N2O, and 22 halogenated compounds), ozone precursor gases (CO, NOx, CH4, NMVOC), acidifying gases (NH3, SO2, NOx) and PM10 for the period 1970–2010. This new database structure allows calculating emissions by country, sector, and includes specific technologies for combustion/processing and emission abatement measures. Furthermore, to facilitate both the use of EDGAR data in air pollution and climate modeling on different scales the country emissions are allocated to a 0.1 ° · 0.1 ° grid using newly developed 0.1 ° grid maps for a large variety of emission sources. EDGAR datasets have also been used in IPCC assessments, both on source strengths and on spatial distribution of emissions in the development of emission scenarios (Nakicenovic et al. 2000). These SRES scenarios, as they are often termed, were used in the IPCC Third Assessment Report (TAR), published in 2001, and in the IPCC Fourth Assessment Report (AR4), published in 2007 (IPCC 2001, 2007). Apart from the large international activities in emission inventories (Table 4.46) there are several substance- or source-related emission estimates; for example, for mercury in Europe (Pacyna et al. 2001) and the world (Pacyna and Pacyna 2002, Pacyna et al. 2003, 2006), global carbonaceous aerosol inventory 1860–1997 (Junker and Liousse 2006), and trace metals (Nriagu 1979, 1989). Moreover, many countries (almost all developed) provide national emission inventories. There are two general methodologies used to estimate regional to global emissions; bottom-up and top-down. Bottom-up methodologies apply the following general equation to estimate emissions: Ei = Ai ðEF Þi P1i P2i .......

(4:2)

where Ei emission (for example, kg sulfur hr–1), Ai is the activity rate for a source (or group of sources i, for example, kg of coal burned in a power plant), (EF)i is the emission factor (amount of emission per unit activity, for example, kg sulfur emitted per kg coal burned), and P1i, P2i . . . are parameters that apply to the specified source types and species in the inventories (for example, sulfur content of the fuel, efficiency of the control technology). The uncertainties in anthropogenic emission inventory data are mostly due to inaccuracies of available data regarding fuel consumption and fuel chemical composition. Note that the estimation of uncertainty in emission inventory data is itself a challenging task: in particular, as different inventories are usually based (at least partly) on common sources of information, their intercomparison does not necessarily result in revealing all the uncertainties. A promising alternative approach to constrain emissions and to assess the uncertainty in available emission estimates is inverse modeling (Enting 2002); the key idea of this approach is to derive emission estimates from atmospheric measurement data

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by optimizing emissions coupled to a transport model. Such estimates are frequently referred to as “top-down,” in contrast to “bottom-up” ones based on emission inventories alone. The key steps of the method are (here given as example for CO2 estimation according to Konovalov et al. 2016) – inferring “top-down” estimates of the regional budget of anthropogenic NOx and CO emissions from satellite measurements of proxy species (NO2 and CO in the case considered) without using formal a priori constraints on these budgets, – the application of emission factors (the NOx-to-CO2 and CO-to-CO2 emission ratios in each sector) that relate fossil-fuel CO2 emissions to the proxy species emissions and are evaluated by using data of “bottom-up” emission inventories, and – cross-validation and optimal combination of the estimates of CO2 emission budgets derived from measurements of the different proxy species. Finally, “hybrid” estimates are based on both atmospheric measurements of a given proxy species and respective bottom-up emission inventory data. However, model transport errors are an important source of uncertainty in the analysis. It is therefore absolute curious that most authors publish values from computer printouts such as (as an example) 10356.67 Gg, disregarding that a minimum error of ±10% is impossible to undercut); hence this “value” should be rounded to 10,300 (or better 10,000) Gg (note that the last value looks like a rough estimate whereas the first value looks reputable, but this is a large mistake). In recent publications often a priori emissions, which are based on a detailed bottom-up inventory for the observation period are compared with a posteriori emissions from top-down estimates.567 Table 4.47 shows the significance of emitted substances to key properties of the climate system; all substances have natural as well as anthropogenic sources. Abatement strategies were applied successful but to very different degrees for all substances with the only exception being CO2 and with only limited reduction for NH3, CH4, N2O. Some substances were completely controlled in last few decades – or at least to an extent that they no longer play role (or more than a negligible role) in the climate system or as local pollutants, such as trace metals, smell-intensive substances, and CFCs. Behind NMVOC are so many organic compounds with 567 The top-down approach is based on the statistical probability that a hypothesis is true calculated in the light of relevant observations. This is the Bayes’ Theorem central insight — that a hypothesis is supported by any body of data it renders probable — lies at the heart of all subjectivist approaches to epistemology, statistics, and inductive logic. The probability of a (a priori) hypothesis H conditional on a given body of data E is the ratio of the unconditional probability of the conjunction of the (a posteriori) hypothesis with the data to the unconditional probability of the data alone. The prior is a probability distribution that represents the uncertainty over a value before sampling any data and attempted to estimate it. The posterior is a probability distribution representing the uncertainty over the value after sampling of the data. It is a conditional distribution because it conditions on the observed data.

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Tab. 4.47: Relevance of emitted substances to the climate system. + and – positive and negative significant, respectively, (+) less significant. CCN cloud condensation nuclei, i.e., influencing cloud and precipitation formation. species

global warming

global cooling

tropospheric ozone formation

stratospheric ozone depletion

secondary aerosol formation

acidifying

CCN

SO DMSf NOx NO NH CH PM sea salt NMVOC CO CO BC HCFC´sg HFC´s

– – – + – + – – (+)a + (+)a + (+) (+)

+b +b (+)b – +b – (+) (+) (+)b – – – – –

– – + – – + – (+)j + – – – – –

– – (+)d + – – – – – – – – + +

+ + + – + – – – + – – – – –

+ (+)e + – + – (+)h – – (+)c (+)a – – –

+b +b +b – +b – (+) + (+)b – – – – –

a

Via CO2 formation. Via (secondary) aerosol formation. c Weak acidity in global background. d From high-altitude aircrafts. e Via oxidation to SO2 and further to H2SO4. f Only natural emitted. g Synonym with CFC´s. h Partly acid-neutralizing if alkaline such as carbonates. j In sense of ozone depletion via heterogeneous processes. b

different properties that an assessment of the climate system relevance needs a compound-specific approach; however, as also seen from Tables 5.27 and 6.21 in Vol. 1, natural sources become more and more dominant with a further abatement of anthropogenic sources. Table 4.48 summarizes global natural emissions of gases. As seen, the uncertainties are large. Although the citation is from the year 2000 (which means that the data results from research around and before 1995) there is no reason not to use this data in comparison with anthropogenic sources for climate change. In recent years, the values of natural NMVOC emissions were corrected continuously to larger values (Friedrich 2009). It is worth noting again that man-made climate change (deforestation, warming, and more) has a feedback on natural emissions too. For example, the global NMVOC emission was estimated to be 717 Tg C yr–1 in 1986 and 778 Tg C yr–1 in 1995, that is, the increase amounts 8.5%.

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4.3 Emission of atmospheric substances

Tab. 4.48: Estimation of global natural emission of gases (in Tg element yr–1). Source: Watts (2000); reduced sulfur modified after Möller (2003). source ocean aquatic ecosystems soils and plants wild life biomass burninga volcanisms lightning secondary sources total

NH

NO

NO

CO

DMS

CS

SO

COS

HS

– – – – – – – –

– – – –  –  –

 – – –  – – –

c

– -c – , – – –

– ≤. – – – – – –

. . . – – 

 . .

 . .

 . .

 . .

 . .

Tab. 4.71: Composition of PM10 (in µg m–3) at Frohnau Tower (see also Figure 4.85).

PM total organic material (OC) elemental carbon (EC) Na + Cl nitrate (NO–3 ) sulfate (SO2– 4 ) ammonium (NH4+ ) K + Mg + Ca insoluble part

min

max

mean

n

. . . . . . . . .

. . . . . . . . .

. . . . . . . . .

        

50 Frohnau Tower 45 frequency (number of days)

40 35 30 street (Frankfurter Allee) 25 20 15 10 5 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 classes of concentration in 2 μg steps (in μg m–3) Fig. 4.84: Frequency distribution of PM10 at Frohnau Tower and a busy street (Frankfurter Allee) in Berlin.

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events having high PM loading are combined with a large number of events corresponding to a standard normal distribution (Gaussian). From the normal distribution, “means” for the background levels and the pollution episode can be derived (Table 4.72). The stepwise difference from rural background to a busy road is due to local dust sources, mainly soil dust and resuspension on roads. The mean PM excess during “pollution episodes” is due to long-range transport and increases the mean PM level by around 60% at all sites – only on busy roads by “only” 40% (because of the permanent large resuspension percentage). It is remarkable that the mean of normal distribution (background levels) at Frohnau Tower is not very different from PM10 at a site in Birkenes in southern Norway, typically in the order 5–8 µg m–3, but during episodes with air passing from the European continent, concentrations in the order of 20–30 µg m–3 are seen between 2000 and 2001 in Norway (Tørseth et al. 2002). The timely variation of PM10 at Frohnau Tower (Figure 4.85) shows no seasonal or regular pattern according to any source characteristics; it is determined by air mass characteristics, meteorological parameters such as wind direction, precipitation, and so on, but complex and not well defined. Fairly good correlations exist between PM and the insoluble part, sulfate, ammonium and nitrate, but not to sodium and chloride (sea salt). As expected, very good correlations exist between Na and Cl as well between sulfate, ammonium, and nitrate, EC and OC but not between Na and K. Tab. 4.72: Statistics of the PM frequency distribution (in µg m–3). site Frohnau Tower rural background city background busy road

mean of normal distribution mean of excess to background level (background levels) (pollution episodes)  ±   ±   ±   ± 

± ± ±  ± 

4.5 Atmospheric substances: impacts on health Air pollution was identified for centuries, even for thousands of years (since controlling of fire by man) with smoke. Combustion of wood, organic waste and fossil fuels, mining and processing produce a wide range of particulate and gaseous substances that have different physical, chemical, and toxicological properties. However, we have mentioned that natural emissions also can lead to substantial atmospheric concentrations of trace compounds. Without considering catastrophic natural events such as volcanic eruptions and others (see Section 3.2.2.4), the ecosystems with its living organisms are balanced with abiogenic factors and within the climate system. For an example, soils of tropical rain forests can produce high

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70

PM10 (in μg m–3)

60 50 40 30 20 10 0 10

11

12

01

02 03 04 05 month (2000–2001)

06

07

08

09

Fig. 4.85: Daily PM10 at Frohnau Tower (in µg m–3), October 18, 2000 – September 24, 2001.

NH3, NOx, and VOC concentrations, however, to a large percentage the gases are scavenged by the canopy providing local closed nutrient cycles. Air pollution in European cities has been recognized since the early Middle Age. At the turn of the 19th century, many European and the US cities suffered under permanent air pollution levels larger by a factor of 100 and more than today. This situation did not change significantly until beginning of the 1950s. Since the 1980s air pollution abatement started in the USA and Western Europe and after 1990 in Eastern Europe, which was to a large extent completed around the year 2000. In Section 4.4 we have seen that classical air pollutants (SO2, NH3, NOx, NMVOC, dust) significant declined (however, by different extent) until now. The question must now be answered if there are still health effects verifiable (in air pollution controlled areas). On the other hand, “greenhouse” gases (CO2, CH4 and N2O) increased and will likely further increase for many decades. Impacts of air pollution can be classified as following: – direct impacts on humans (health: toxicity of gases and particles), – indirect effects on humans through direct impacts (loss of life quality and economic loss due to visible pollution, damages of vegetation and animals, corrosion), – indirect effects on humans through indirect impacts (loss of life quality and economic loss due to consequences of climate change: severe weather, change of temperature, sea level, solar radiation, precipitation, drought, and more), – direct impacts on plants and animals (health: toxicity of gases and particles), – direct impacts on ecosystems (changing biogeochemistry: effects on population density, nutrition, diversity), – depletion of the ozone layer through ozone depleting substances (increase of UV radiation and causing skin cancer and ecosystem problems),

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– indirect climate impact by influencing the number and efficiency of cloud condensation nuclei (effects on cloudiness and precipitation), – direct climate impact due to absorption of terrestrial radiation by “greenhouse” gases (radiative forcing: warming), – direct climate impact due to reflection of direct solar radiation by particulate matter (reduced radiation transfer: cooling). This section deals only with impacts on human health and will try to highlight the question whether air pollution is responsible for millions of deaths each year. The World Health Organization (WHO) claimed (http://www.who.int/gho/phe/outdoor_ air_pollution/en/) that in the year 2016, ambient air pollution was responsible for 4.2 million deaths. Worldwide, ambient air pollution is estimated to cause about 16% of the lung cancer deaths, 25% of chronic obstructive pulmonary disease (COPD) deaths, about 17% of ischaemic heart disease and stroke, and about 26% of respiratory infection deaths. In 2016, 55.3 million people died580 (UN 2017). On the other hand, the global mean life expectancy at birth (LEB) increased from 64.3 years in 1990 to 71.4 years in 2015, however, showing large differences between continents (62–79 years) and countries (50–84 years). In statistics, several causes of death are documented; however, studies at various academic institutions have found errors in cause and/or manner of death certification to occur in approximately 33% to 41% of cases (Brooks and Reed 2015). Principally, the following causes might be in relation to air pollution (in parenthesis number of global deaths in 106 decedents in 2016): cardiovascular diseases (17.65), cancer (8.93), respiratory diseases (3.53), and lower respiratory infections (2.38) Ritchie and Roser (2018a).581 It remains a mystery, how the 4.2 million deaths due to air pollution have been identified from these numbers. There are published diagrams showing age-standardized death rates from PM2.5 particular matter exposure per 100,000 people vs. average PM2.5 concentrations, e.g., by the Health Effects Institute (HEI); Ritchie and Roser (2018b). However, there are several points to reject such “estimations”: – the nonlinearity and large variation: the global mean death rate due to PM of 58 death per 100,000 people corresponds to a variation of 20–100 µg m–3 and vice versa, the level of 20 µg m–3 corresponds to a variation of a death rate from 22 to 82; – the estimation of PM2.5 levels for different countries is based on very approximated methods, hence very erroneous or unsure, resp.;

580 This number increases from year to year because birth rate > death rate until approaching a steady-state (birth rate = death rate); assuming steady state under present conditions of world population and life expectancy, the death rate would be around 100 million per year. 581 It is remarkable that the “natural” cause of death, senile decay is not documented (by law only one of listed diseases). Death rates are highest for those aged over 70 years old with nearly 1000 deaths per 100,000 people.

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– it is unclear how different causes of death are related to air pollution and especially to PM582 (despite the large error in causes of death). Concerns human health it seems that sciences meet religion583 and I try to figure out the question where all the “thousands additional annual deaths” due to air pollution are coming from. The answer can be given already at the beginning of this section: it is a finding based on wrong statistics, erroneous date and simple mathematical assumptions, not verified by true observations but wanted by governmental administrations (conflict between law and nature, see Immanuel Kant footnote). This conclusion does not exclude air pollution as cause for diseases and loss of life time. It seems, however, that other factors such as nutrition, alcohol and drug use, incidents, conflicts, homicides, suicides, and so on (totally 4.54 million deaths in 2016) and social behavior influence life expectancy much more. According to the WHO, “health is a state of complete physical, mental and social well-being and not merely the absence of disease or infirmity”. WHO further states that governments have a responsibility for the health of their peoples which can be fulfilled only by the provision of adequate health and social measures. It is important to understand that health is much more than absence of diseases and avoiding impacts by air pollution.

4.5.1 The basics There is no doubt that historical air pollution in terms of smokes, fumes, vapors, mist, and dust lead to severe health problems, excess morbidity and mortality. Several smog episodes in different European cities have been recorded since the middle of 19th century but the London fog episode 5–9 December 1952, associated with some thousands premature death was an exceptional occurrence, caused a rethinking of air pollution, as the smog had demonstrated its lethal potential. Because most of the victims were very young or elderly, or had pre-existing respiratory problems, it was the view until

582 Epidemiological studies (see later in this section) only show differences in the age of death of different cohorts from which years of life lost can be derived. 583 Immanuel Kant (1724–1894) deals in his essay (1794) The Conflict of the Faculties (Der Streit der Fakultäten) with the conflict between the “lower” faculty of philosophy, which is answerable only to individual reason; and the faculties of theology, law, and medicine, which get “higher” precedence in the world of affairs and whose teachings and practices are of interest to the government. He writes: “Although medicine is an art, it is an art that is drawn directly from nature and must therefore be derived from a science of nature”. However, he also states that “the biblical theologian (as a member of a higher faculty) draws his teachings not from reason but from the Bible; the professor of law gets his, not from natural law, but from the law of the land; and the professor of medicine does not draw his method of therapy as practiced on the public from the physiology of the human body but from medical regulations”.

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the 1950s that everyday levels of air pollution were acceptable (Thorsheim 2006, p. 170). However, since then new regulations were stepwise implemented. The SO2 concentration during this fog event was high (500–1,000 µg m–3 comparing to “normal” levels of around 250 µg m–3) but not unusual comparing to other historic pollution sites (see Sections 2.2.8, 2.5.5, 4.2.5.2 and 4.4.2). The London fog turned into a haze of concentrated sulfuric acid that burned airway tissue. The bronchitis death rate in England in the 1950s was several times larger than in other European countries. However, the life expectancy in England was around 2 years higher than in Germany between 1950 and 1960. Today it is the responsibility of any civilized government to implement measures to exclude harms by air pollution on people. In past that was not understood and air pollutants have been accepted as byproducts of industrialization. Under natural conditions, concentrations of atmospheric trace compounds were so low (or high, relatively said) that plants, animals and humans were not harmful affected by air constituents (but see Section 2.5.3 for volcanic “dry fog” event). In what follows we only will deal with direct impacts on humans through breathing. Principally it must be separated between uptake of toxic compounds by breathing and via skin. Another minor pathway is uptake of potentially toxic compounds by food and water, which was likely important too in past und still in underdeveloped countries. Contamination of skin (and eyes by lachrymatory agents) is negligible by air pollution with the exception of accidents (by poison gases). However, solar radiation (UV) will not only directly attack our skin but also produce oxidative compounds (ROS, see Section 5.2.3 in Volume 1),584 which can result in dermal cancer. The main pathway is uptake via breathing. The breathing volume of an adult is about 5–8 L min–1. In a day it amounts on average 10 m3. We breathe air to live and what we breathe has a direct impact on our health. Humans and mammals created a respiratory system depending on the environment in which they lived and on their evolutionary history. Hence soil and plant dust (having particle diameters larger than 1 µm) will be nearly completely separated in the upper airway. On the other hand, also smaller particles (a small percentage of sea salt and nucleation modes from vegetable VOC emissions, called “blue haze” as well as sulfate from volcanic SO2 emissions) occur at some sites, possibly influencing human health. However, since human settlement processes, such as combustion, mining, chemical conversions, and so on have been managed that lead to artificial products such as crystalline minerals (silica), fibers (asbestos), soot and coal dust, tobacco and industrial smoke, which are unknown in nature or occur only in negligible magnitude under natural conditions.

584 Reactive oxygen species (OH, O2− , H2O2) produced photocatalytic at wetted surfaces; this pathway is also the cause of bleaching and destruction of surfaces of materials under ambient conditions.

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When a pollutant gas is breathed, its transport through the highly branched tracheobronchial tree results in a unique internal distribution of concentration and uptake rates. A major factor complicating the study of these processes is the fact that gases with different molecular properties can exhibit different internal dose distributions. Highly water-soluble gases, such as sulfur dioxide (SO2), are essentially removed by the upper airways, the primary site of respiratory defense. A highly reactive gas of only moderate solubility, such as ozone (O3), can reach the tracheobronchial tree, where it reacts with the protective mucous layer and eventually damages underlying tissue in the small bronchioles. A gas that has limited aqueous activity but is highly reactive with hemoglobin, such as carbon monoxide (CO), is able to penetrate further to the respiratory zone and diffuse to the pulmonary circulation in quantity (Ultman 1988). The particle deposition fraction, DF, of inhaled aerosols varies by more than one order of magnitude – from less than 0.1 to almost 1 – depending on breathing pattern, structure of the respiratory tract, and particle characteristics such as size, shape, and hygroscopicity (Rissler et al. 2017). In the nose pharyngeal tract 80% of particles larger than 12 µm (all in aerodynamic diameter) and about 50% (DF = 0.5) of particles of larger than 5 µm are deposited; PM10 particles have a DF between 0.44 and 0.76 (Okunade et al. 2003). In the tracheobronchial tree all remaining particles larger than 1 µm are separated (Horn 1979). Particles smaller 1 µm penetrate to the lung. Deposition in the airways does not mean that all particles are long life accumulated – they mostly will be removed by different airway cleaning mechanisms. It is self-evident that all gases can principally penetrate to the lung; however, very soluble and reactive gases might be removed or destructed in the upper airway. In dependence of the breathing frequency a large fraction of the breathing air volume is unaltered exhaled. Particles entering the lower tract (bronchioles) and pass those to the lung alveoli, will be exhaled to a large extent through a selfcleaning mechanism585 that ensures the free flow of mucus together with deposited particles. It has been found that no more than 10% of the total inhaled dust is found in the lung at the end of life. Less soluble gases (O3, NO, VOCs) will be exhaled and only partly taken up by alveoli. Soluble anions such as SO24 − , NO3− , Cl– (which result also from dissolution of gases such as SO2, HNO3 and HCl) and cations such as Na+, K+, Mg2+ and Ca2+ are main constituents of particulate matter and will be quickly transferred into the bloodstream and are harmless.586

585 The mucosal layer, sometimes called the mucous membrane, contains ciliated epithelium and mucus-producing goblet cells, with additional mucus-pro-ducing glands located in the submucosal layer. In the lumen of these airways, cilia are surrounded by a low-viscosity periciliary fluid, above which high-viscosity mucus floats. The cilia beat in an organized unidirectional fashion, propelling this mucous blanket from the lower respiratory tract to the oropharynx with a daily clearance of about 100 mL (Ultman 1988). 586 It is sure that the amount of such ready-soluble ions, taken up by food and water is several times larger. Therefore, this part of PM is fully negligible concerns human health.

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Among air pollutants we distinguish between nontoxic, specific toxic, and unspecific toxic compounds. It is a fundamental principle in toxicology that the amount of toxic inhaled is a reference for impacts; this is called dose (“the dose makes the poison”). However, there are also limitations of this principle (the interested reader should refer textbooks on toxicology). Here is an example which also characterizes the difference between acute and chronic toxicology: – a person breathing for 5 min 2000 ppm NO2 will die within 2 days (see below): the dose corresponds to about 12 mg NO2; – a person who lives 50 years in a rural environment (10 µg NO2 m–3) will inhale about 2,000 mg NO2 and no any adverse health effect from NO2 exposure will be detected. The health effect of an airborne substance when breathing is also different: – specific toxicity due to reaction with biomolecules; they produce a specific action at a specific target site, – nonspecific acting toxicants are those which result in narcosis, defined as a generalized depression in biological activity (e.g., irritation and inflammation of the respiratory tract) which is almost reversible, – nontoxic substances that accumulate in the lower airway and lung (particulate matter) not having a direct toxic effect but decline the lung function over longtime exposure, – subsequent effects after chemical reaction in the respiratory tract, such as formation of acidity (free H+ ion) or radicals that attack biomolecules. A substance can be attributed to different modes of action. Acids (HNO2, HNO3, HF, H2SO4) and acidic precursors (SO2, NO2) can produce strong acidity as well have specific toxicity; moreover SO2, NO2 and HNO2 can produce under circumstances radicals. Other acids (HCl) and bases (NH3) have no known specific toxic effect but result in changing pH regime and serious cell damages at high concentrations. Low concentrations are buffered in the mucosa. Many atmospheric compounds show a specific toxicology but at very different limit concentrations (e.g., SO2, NO2, O3, H2O2, H2S, HF). Some very reactive air constituents occur at so low ambient concentrations (OH, HO2, H2O2, NO3, N2O5) that no human health impact result (reactive radicals would be destroyed in the nose); however, they can have (and had) impacts on plants. A large number of carcinogenic air pollutants including benzene, 1,3-butadiene, formaldehyde, vinyl chloride, perchloroethylene, and polycyclic aromatic hydrocarbons (PAHs) and dioxins and other gases (e.g., CS2, HCN, Cl2, halogenated organic compounds, acrylonitrile, aldehydes, phenols, and others) having specific toxic properties, have been identified and meanwhile controlled in ambient air. They are only relevant in case of industrial accidents and at working sites. Some compounds (CO, N2O) are toxic only at concentrations never obtained under ambient conditions. For other substances no direct impact on health is known (e.g., N2, NO, CH4, alkanes, novel gases).

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It is worth to note that in ambient air several compounds with individual changing concentrations are always breathed together, thus any possible impact is superimposed. Thus, any epidemiological study showing a relationship between health and a selected air pollutant (e.g., NO2 and PM) basically shows the impact of the mixture (cocktail) of all air pollutants on health and likely also nonlinear superimposed (synergistic) effects of atmospheric constituents. Actual risk of adverse effects depends on current health status, the pollutant type and concentration, and the length of exposure to the polluted air. There are three steps with increasing exposure: – irritation of the airways, coughing or difficulty in breathing, – decreased lung function, – aggravated asthma. High air pollution levels can cause immediate health problems including – aggravated cardiovascular and respiratory illness, – added stress to heart and lungs, which must work harder to supply the body with oxygen, – damaged cells in the respiratory system. Long-term exposure to polluted air can have permanent health effects such as – accelerated aging of the lungs, – loss of lung capacity and decreased lung function, – development of diseases such as asthma, bronchitis, emphysema, and possibly cancer, – shortened life span. In recent years, the theory of free radicals causing lung diseases from many different pollutants finds increased attention despite the idea of oxidative stress in aging comes already from the 1950s (Harman 1956) and the role of free radicals in diseases is known since decades (Halliwell and Gutteridge 1984). The production of free radicals, or factors possessing properties of free radicals, occurs during the activity of various oxidative enzymes. These radicals appear to play important roles in biological oxidation involving electron transfers. At normal rates of generation, some free radicals are useful in the human body. However, when free-radicals generation exceeds the capacity of antioxidant defenses, the result is oxidative stress. Free radicals are formed in greater amounts during almost all human diseases. In the respiratory system, ROS may be either exogenous from more or less inhalative gaseous or particulate agents such as air pollutants, cigarette smoke, ambient high-altitude hypoxia, and some occupational dusts, or endogenously generated in the context of defense mechanisms against such infectious pathogens as bacteria, viruses, or fungi. ROS may also damage body tissues depending on the amount and duration of exposure and may further act as triggers for enzymatically generated

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ROS released from respiratory, immune, and inflammatory cells (Domej et al. 2014). Oxidants such as superoxide anion, hydrogen peroxide, and myeloperoxidase from activated inflammatory cells in the lower respiratory tract contribute to inflammation and injury (Rom 2011). Etiologic agents include inorganic particulates such as asbestos, silica, or coal mine dust or mixtures of inorganic dust (e.g., cement) and combustion materials (Vallyathan et al. 1988, Tian et al. 2009, Vallyathan and Shi 1997, Friday et al. 2016). In quantifying the impact of air pollution on human health, morbidity (a measure for the rate of disease in a population) and mortality (a measure for the rate at which deaths occur in a given population) are frequently used and relate to life expectancy (LE). In mathematical terms, life expectancy587 refers to the expected number of years remaining for an individual at any given age. According to evolutionary theory, organisms that live for long periods manage to avoid disease, predation, and accidents due to their defense mechanism and lifestyle. The life expectancy at birth (LEB) can exactly be determined only for the past: for a past year (e.g., 2017) in a given population the number of passed persons are counted and related with the individual age at death. This can also be done for any period of age (e.g., for persons older than 65). In this way also life tables are gained that contain the mortality rate (number of death related to a fixed number of persons of a cohort). All these parameter are statistical values.588 The further life expectancy589 (how many years a person from today will life) is the projection from past mortality rates, adjusted by model parameters into future; it is a hypothetical statistical value. Years of potential life lost (YPLL) is a measure of premature mortality, defined as the number of years between the age at death (for those who die before age of LEB, e.g., 75 years) and the LEB. A number of factors influence life expectancy including gender, race, and exposure to pollution, education status, income level, and healthcare access. Modifiable lifestyle factors such as exercise, alcohol status, smoking status, and diet also influence life expectancy. Therefore, life expectancy is highly variable from one individual to another. However, epidemiologist and statisticians still note trends and patterns in terms of life expectancy across data sets obtained for various geographical areas. This is done by choosing different cohorts (smoker versus nonsmokers, rural versus city population, population in clean and polluted regions, for example) with the attempt to evaluate selected impact parameters.

587 Not to confuse with lifespan that refers to the maximum number of years that a person can potentially expect to live based on the greatest number of years anyone from the same data set has lived. 588 The variation of LEB is large: 11 years in Europe between different countries and 3 years in Germany between different states. 589 Healthy life expectancy (HALE) is a form of health expectancy that applies disability weights to health states to compute the equivalent number of years of life expected to be lived in full health.

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4.5.2 The problem Accurate estimates of human exposure to inhaled air pollutants are necessary for a realistic appraisal of the risks these pollutants pose and for the design and implementation of strategies to control and limit those risks. However, there are several problems in characterizing impacts on air: – No compound act separately in ambient air: it is a “cocktail” of substances with varying concentrations. It is principally impossible to get concentrations for all impacting species, hence so-called proxies have been selected (e.g., O3 and NO2 for photochemical smog, SO2 and PM for winter smog). – Used concentration data in epidemiological studies are always erroneous (what is not characterized); this uncertainty is mostly in the range of used differences (gradients) in air pollution which should result in different health effect (hence giving weak or no significance of the results). – Persons move permanent from one environmental regime to another: between indoor and outdoor environment and among remote air (rural), less polluted air (suburb), polluted air (urban area) and highly polluted air (traffic). It is impossible to record the different environmental situations and integrate them to a total stress factor. – In addition, available evidence indicates that personal pollutants exposure is not adequately characterized because the time people spend in different locations and their activities vary dramatically with age, gender, occupation, and socioeconomic status. – Information on toxic effects of compounds were obtained from clinical studies using concentrations much larger than in ambient air but much smaller than known from accidental events with extreme concentrations. – It is impossible to deduce on impacts at lower concentrations from clinical studies due to nonlinear relationships. – Epidemiological studies show extreme uncertainties and controversial results; the significance of the results is often equal or smaller than errors of input data. In other words, its scientific worth is questionable (almost all studies are based on the questionable approach by Pope et al. 1995, 2002). – The morbidity data used in such studies are not specific concerns pollutant impacts; they integrate all factors that govern the medical condition. – Since a few years it is “in fashion” to calculate years of reduced life expectancy due to air pollution exposure based on mortality. This is a pure mathematical approach having no physical sense; the life expectancy or in an other related terms mortality depends from so many individual and social factors that it is pure nonsense to obtain a mathematical relationship to air pollution (particularly at air pollution levels of the last few decades).

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For air quality control, threshold limit values have been introduced for a wide range of substances, based on clinical studies (taking into consideration security factors) and epidemiological studies. Epidemiological studies require long term observation of sample populations (cohort) with similar exposure over a number of years and comparison with a control group. The main problem of epidemiological studies concerns air pollution590 is the weak or missing significance because – differences in air pollution between selected cohorts are small and profound under levels of clinical effects, – indoor pollution is often much larger than outdoor, but never incorporated in such studies, – other parameters influencing morbidity and mortality (diet and exercise for example) result in large variation between individuals, – published values in terms of changing air pollution (µg m–3) versus changing life expectancy even with large correlation or probability parameter can be a purely mathematical result without relevance to the reality (the lower life expectancy of a cohort staying in a region with larger air pollution and vice versa can have many different reasons being more important than small differences in air pollution at low level). The absence of toxicological data and health relationships for humans is due to the ethic principles concerns experiments on humans. The relationship between soot and health (e.g., as lung cancer) is known for a long time but up to now there are controversial meanings. Results gained with experiments on animals; exposing rats under extreme concentrations (>1,000 µg m–3 life-long) lead to cancer but below 600 µg m–3 no cancer have been detected (Valberg and Crouch 1999); note that ambient soot concentration under traffic conditions amounts 2–5 µg m–3). On the other hand, hamster and mouse did show no effects. From that we learn two thinks, a) different animals show quite different effects and any conclusion on human effects is invalid and b) extrapolation to 100 times smaller concentration is impossible (unknown relationship). To calculate the age-specific death rates, different data groups that are believed to be associated with different mortality rates (such as smokers versus nonsmokers, for example) are considered separately. The data are then used to draw up a life table or actuarial table. These tables can be used to predict how likely it is that a person of a given age will die before their next birthday. From here, several points can be calculated, including:

590 It is self-evident that a cohort is classified concerns gender, age, and smokers. This is simple but to separate the population further (what seems to be necessary in evaluation of air pollution impact) with respect to health risks is more complicated due to extreme efforts and likely missing data.

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– the person’s probability of surviving to any given age, – the life expectancy remaining for people of various ages. From epidemiological studies different mortality hazard591 were derived: – 6% for change of 10 µg m–3 PM2.5 (Pope et al. 2002), – 0.6% for change of 10 µg m–3 PM10 (Anderson et al. 2004) Updated risk coefficients in relation to ambient exposure to PM and ozone were obtained for all-cause and cause-specific mortality and hospital admissions for respiratory and cardiovascular causes, however, studies from different European countries show positive as well negative correlations (Anderson et al. 2004). To give an example of accompanying factors, high O3 concentrations are often associated with heat waves that could impact more on health. Most studies have been carried out concerns on the effect of smoking on health – the epidemiologic evidence of harmful smoking is vast and well summarized in authoritative reports and historical accounts. Smokers loses at least one decade of life expectancy, as compared with those who have never smoked. After successful smog abatement, smoke from smoking remains the true plague (Office on Smoking and Health 2014): – more than 10 times as many US citizens have died prematurely from cigarette smoking than have died in all the wars fought by the United States; – smoking causes about 90% (or 9 out of 10) of all lung cancer deaths; more women die from lung cancer each year than from breast cancer; – smoking causes about 80% (or 8 out of 10) of all deaths from chronic obstructive pulmonary disease; – cigarette smoking increases risk for death from all causes in men and women; – the risk of dying from cigarette smoking has increased over the last 50 years in the US. It is unknown how many nonsmokers reduce their life expectancy due to wrong diet, missing exercise, stress, missing luck. Remember the definition of health given by the WHO, which is not changed since the 1950s. Democritus (500–497 BC) was to apply for relief to the gods: men ask for health in their prayers to the gods: they do not realize that the power to achieve it lies in themselves. Lacking self-control, they perform contrary actions and betray health to their desires (Yeraulanos 2016, p. 190). One of the most cited scientists, John Ioannidis from the Stanford University, states that most current published research findings are false. In our field of 591 It describes the ratio of events (e.g., death and diseases per period) under risk (air pollution) to that of a population without risk. A percentage of 6% means a ratio of 1.06. Not to confuse with the relative risk, the ratio of the probabilities (of a disease or death) between two groups. A value 1 means in both cases that there is no difference.

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epidemiological studies concern the impact of air pollution, the following arguments support that the research finding is less likely to be true when (beside others) effect sizes are smaller, when there is a greater number and lesser preselection of tested relationships, when there is greater financial and other interest and prejudice, and when more teams are involved in a scientific field in chase of statistical significance. Moreover, for many current scientific fields, claimed research findings may often be simply accurate measures of the prevailing bias (Ioannidis 2005). Albert Einstein should have said (nor authenticated): it is easier to break an atom than a prejudice. The prejudice reads “present air pollution reduces life expectancy”. Some of the answers by Sabine Hossenfelder, a physicist at the Frankfurt Institute for Advanced Studies in Germany, to the question why there is no progress in theoretical physics within the last 40 years, illustrate the situation in our field of research too (http://nautil.us/blog/thepresent-phase-of-stagnation-in-the-foundations-of-physics-is-not-normal): I am afraid there is nothing that can stop them. They review each other’s papers. They review each other’s grant proposals. And they constantly tell each other that what they are doing is good science. They hold conferences, they publish papers, they discuss their great new ideas. From the inside, it looks like business as usual, just that nothing comes out of it. Why should they stop? People can believe all they want - but it´s not science. Stop rewarding scientists for working on what is popular with their colleagues. I think that´s a discussion that belongs safely in the realm of philosophy.

4.5.3 Nitrogen dioxide (NO2) When inhaled, NO2 reacts with the moisture in the respiratory tract, resulting in the formation of nitrous acid (HNO2) and nitric acid (HNO3)592: 2 NO2 + H2 O ! HNO2 + HNO3 .

(4:11)

At low concentrations, NO2 reacts with moisture in the upper respiratory tract, but as the exposure concentration increases, NO2 penetrates into the lower respiratory tract. An increasing respiratory rate, such as might result from exercise, also results in higher amount of NO2 and its products reaching deeper areas of the lung.593 It is unclear whether this reaction proceeds only via N2O4 (! NO2 + NO2) or threemolecular as written in eq. (4.11); there are arguments (see Section 5.3.5.2 in Vol. 1) that interfacial NO2–NO2 adducts must be formed, suggesting that the reaction is not fast.

592 I thank Jörg Kleffmann (University Wuppertal) for a critical review of this Section and helpful comments. 593 In contrast, nitric oxide (NO) is known as inhalation therapy. Nitric oxide (NO) is a naturally occurring vasodilator produced by vascular endothelial cells. Physiological effects are reduction of pulmonary vascular resistance, reversal of hypoxic pulmonary vasoconstriction in unobstructured airways and improvement of oxygenation (Siddons et al. 2018).

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Reaction (4.11) is described as equilibrium (K = 4.3 · 105 Mol2 L–2 atm–2), that is, at ambient NO2 concentrations (for example 20 ppb), the nitrite concentrations is very low (about 0.2 nM). However, it is questionable whether equilibrium is gained because of the low reactions rate (which is unknown) of (4.11) and the subsequent biochemical reactions of nitrite after absorption in blood and tissues. With 50 µg m–3 NO2 in air, a person is breathing about 350–550 µg NO2 per day. On average, an adult holds 5–6 L blood which circulates at a flow rate of about 7 m3 per day. Assuming that less than 1% of NO2 from inhaled air is turned into nitrite, it results in 0.6–1 nM in blood, which is not very different from the above equilibrium estimate. In reality, the concentration of nitrite in blood should be less because of decomposition of nitrite in blood and uktake though tissues. Such concentrations of nitrite likely expected through NO2 exposure are less than 1% of natural nitrite levels found in blood: nitrite is a permanent constituent of blood in humans and all animal species at concentrations that vary considerably with diet; in human blood there is about 150–300 nM of nitrite (Dejam et al. 2005) and 50–100 µg L–1 in tissues (Kim-Shapiro and Gladwin 2014). Nitrite was once thought to have little physiological relevance. Nitrite, long considered a biologically inert metabolite of NO oxidation, is now accepted as a physiological storage pool of NO that can be reduced to bioactive NO in hypoxic conditions to mediate a spectrum of physiological responses in blood and tissue (Shiva 2013). Moreover, nitrite is now being increasingly recognized as a therapeutic or possibly even physiological precursor of nitric oxide (NO) that is utilized when needed to increase blood flow (Patel et al. 2011, Siddons et al. 2018). Once inhaled, NO2, or its chemical derivatives, can either remain within the lung or be transported to extrapulmonary sites via the bloodstream. Increased levels of nitrates have been reported in the blood and urine following exposure to NO2, indicating that NO2 reacts to produce nitrates (EPA 1993). It is known from different studies in the 1980s (IPCS 1996 and citations therein) that inhaled nitrogen oxides are fast transformed into nitrite and nitrate, but this exposure gives only 1.3 mg nitrate per day. A person with western diet takes up daily a minimum of 50 mg nitrate. The major toxic effect of nitrite poisoning at elevated concentrations is its reaction with hemoglobin to form methemoglobin (MetHb). That reaction has important health implications because MetHb is an ineffective oxygen carrier. Transformation of hemoglobin to MetHb can increase health risks to vulnerable individuals who have hypoxia associated with pulmonary and cardiac disease. A major acute toxic effect from nitrite is development of methemoglobinemia, a condition where more than 10% of the hemoglobin is transformed into methemoglobin. When the conversion exceeds 70% the condition can be fatal. The lethal oral dose of nitrite for adults has been variously reported to be between 0.7 and 6 g nitrite (approximately 10 to 100 mg kg–1 nitrite); IPCS (1996) and cited literature therein. Human volunteers given sodium nitrite intravenously produced a maximum methaemoglobin level of 7% after a dose of 2.7 mg kg–1 nitrite and 30% after a dose of 8 mg kg–1; this

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indicates a lethal dose within the range reported above. Symptoms of nitrite poisoning and MetHb formation after ingestion ranged from 0.4 to >200 mg kg–1 bw (body weight), expressed as nitrite ion (WHO 2006b). Thus exposure to NO2 may lead to protein damages through protein radical formation and tyrosine nitrations, lipid peroxidation and the potential formation of nitrated lipids (Keszler et al. 2008 and citations therein). Nitrite have been made responsible for formation of poisoning nitrosamines (studies concerns exceeded nitrite concentrations in potable water, namely to infants) and can damage DNA by cross-linking via diazotation of aming-groups (Kirchner and Hopkins 1992). Nitrite may also cause sudden fall in blood pressure due to its vasodilating properties. These effects are reversible. The major concern of possible long-term effects of exposure to nitrate and nitrite is associated with formation of nitroso compounds, many of which are carcinogenic. This formation may take place wherever nitrite and nitrosable compounds are present, but it is favored by acidic conditions or the presence of some bacteria. There are no reports that suggest that nitrate as such has toxicological effects. Now, comparing reported relations between nitrite doses and poisoning with nitrite gained from exposure to NO2 in air, we can conclude that this atmospheric pathway is totally negligible for the nitrite and nitrate budget of humans. The obtain physiological effects from NO2 exposure, the air concentration must be severel orders of magnitude larger than found presently in urban air. There have been numerous reviews on the toxicity of NO2 (NRC 1977, WHO 1977, EPA 1982, 1993). Most have focused on the health effects associated with exposures to high concentrations of NO2. Certain groups might be more sensitive to the effects of NO2 exposure than others; those groups are persons with pre-existing cardiopulmonary problems and children. Lower concentrations of NO2 might affect those groups more than healthy adults, or the severity of an effect at a given concentration might be greater. In what follows, some literature data from clinical studies and accidents on the effect of different NO2 concentrations will be presented (NRC 1998 and citations therein, EPA 1993, 2016); it is worth to emphasize that all concentrations used in such studies were much higher than actual maximum traffic related NO2 concentrations (Table 4.73). For the most severely exposed, death can occur immediately or be delayed. Exposure above 150 ppm for 30 min to an hour results in fatal pulmonary edema or asphyxia and can result in rapid death. Exposure to NO2 at concentrations of 150–300 ppm can result in bronchiolitis fibrosa obliterans accompanied by restrictive and obstructive ventilatory defects that might lead to death in 2 to 3 weeks. Such exposures would likely produce permanent injury in those surviving the exposure. The LC50 (the lethal concentration for 50% of those exposed) for a 1-hr exposure for humans has been estimated to be 174 ppm. From 50 to 100 ppm for a 30-min exposure, pulmonary edema, and bronchiolitis with focal pneumonitis are likely to develop and last from 6 to 8 weeks; recovery is often spontaneous. Individuals exposed for 30 min

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Tab. 4.73: Statistics of NO2 concentrations in Germany 2017 from 397 stations (in µg m–3). Data source: UBA. Note: annual mean limit 40 µg m–3 and 1-h maximum limit 200 µg m–3 that can be exceeded 18 times per year (note 1,880 µg m–3 = 1 ppm NO2 under standard conditions). n

site characteristics –

city, traffic (> µg m and exceedance) city, traffic (> µg m–) city, traffic (all)a city, urban backgroundb city, suburban ruralc rural, remote

      

c  ±   ±   ±   ±   ±  ± ±

min

max

      

      

a

1995: 50. 1995: 31. c 1995: 14. b

at concentrations between 25 and 75 ppm might develop bronchial pneumonia, acute bronchitis, dyspnea, cyanosis, chess pain, rales, headaches, eye irritation, a dry nonproductive cough, and vomiting. Such effects usually are resolved in hours but sometimes are followed by a relapse with shortness of breath, cough, cyanosis, and fever. A 5-min exposure to NO2 at 25 ppm caused slight-to-moderate nasal discomfort in 5 of 7 volunteers and chest pain in 3 of the 7. Threshold values for impairment of dark adaptation were reported to be 7 ppm after 5 min inhalation of NO2 by mouth or after 25 min inhalation through the nose only. Below 1 ppm, short-term exposures (2 hr or less) do not appear to cause adverse effects in healthy subjects, at least as indicated by traditional measurement of pulmonary function. In clinical studies using asthmatic subjects, most significant responses have been associated with short-term (1 to 3 hr) exposures to NO2 and low concentrations ranging from 0.2 to 0.5 ppm. Those effects are not seen at higher concentrations (i.e., up to 4 ppm). That indicates that the observed effects fail to follow a normal concentration-response relationship. In most human clinical studies of healthy individuals, exposures to NO2 at concentrations less than 4 ppm do not cause symptoms or alter pulmonary function. In healthy individuals, exposures in the range of 1.5 to 2 ppm may increase airway responsiveness; similarly, exposures in the range of 1 to 2 ppm NO2 induce mild airway inflammation. A number of studies have shown effects on lung lymphocytes, but there is a lack of consistency among these studies (EPA 2016). Most epidemiological studies (Faustini et al. 2014) that have examined populations for adverse responses to NO2 have looked at either changes in normal lung function or increases in respiratory illness, especially in children. Although some studies suggest a possible association between NO2 exposure and an increase in

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respiratory disease in children, the concentrations of NO2 in such environments were usually very low (0.1 ppm or less). Other investigators have not been able to repeat those findings. The difference in findings has led to the conclusion that if an effect exists, it is subtle and difficult to distinguish from other environmental effects (EPA 1993). A similar conclusion has been drawn from those epidemiological studies examining the effects of NO2 on pulmonary function (EPA 1993). Because of the low exposure concentrations of NO2, the extended exposure durations, and the presence of other toxic chemicals in the air, evidence from epidemiological studies is of little value for establishing short-term exposure limits for accidental releases of NO2. The current US air quality standard for NO2 was initially adopted in 1971 and was last reviewed in 1995 (EPA 1993, 1995). It is an annual standard of 53 ppb (100 μg m–3) calculated as the arithmetic mean of the 1-h NO2 concentrations; this limit is smaller for California (30 ppb). The value is based in part, on epidemiological studies where investigators reported decreased in lung function for children (ages 7 to 8) living in areas with relatively high (greater than 60 ppb) annual average NO2 levels. However, follow-up studies by the same investigator could not support these initial findings. From the clinical studies it is seen that no effects result from NO2 concentrations less than 1 ppm (it is 20 and 50 times the annual US and EU limits, respectively). Some (but some not) epidemiological studies show for sensitive persons irritations for less than 0.1 ppm NO2 but that is likely not because of NO2 but rather of the air pollution mixture. As discussed, likely all adverse effect of NO2 result from nitrous acid (HNO2) and nitric acid (HNO3), gained according to Eq. (4.11) which shows a square relationship in kinetics to NO2. It means, that with decreasing (ambient) concentration of NO2 (e.g., from 100 to 10 ppb) the amount of body impacting HNO2 and HNO3 formed by Eq. (4.11) also decrease quadratically (not by a factor of 10 but by a factor of 100). Hence, linear extensions of health effects from NO2 concentration levels used in clinical and epidemiological studies are not meaningful. Traffic related concentrations between 9 and 42 ppb (Table 4.73) are thus out of any health relevance. The current small (!) exceedance of the EU limit (40 μg m–3 which is about 21 ppb), see Table 4.73, results in political hysteria. The dubiousness of limits can be seen in the following comparison. Acute health impact by SO2 is stronger than that of NO2 (it is simple to explain due to much stronger acidity gained after breathing) cited above: 50–100 ppm strong irritation of eyes and respiratory tract; 400–500 ppm human lethal toxicity after 1 min (BASF 2016). The US National Institute for Occupational Safety and Health (NIOSH) still recommend the IDLH values (Immediately Dangerous to Life and Health Concentration) by Henderson and Haggard (1943): the maximum concentration for exposures of 0.5 to 1 h is considered to be 50 to 100 ppm and it has been reported that 400 to 500 ppm is considered dangerous for even short periods of exposure. However, European limits for SO2 are higher compared for those for NO2 (in µg m–3, in parenthesis those for NO2): 350 (200) for 1 h and 125 (40) for 1 year.

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An interesting historic example on speculative ideas how air pollution causes diseases is the claim by Samuel Latham Mitchill (1763–1835) “to have discovered the demon of all epidemies, particularly that of yellow fever, reigned by virtue of the principle of acidity in the earth, air, and water, causing corruption everywhere” (Kealing 1879, p. 70). Mitchill proposed his theory in 1795 (Anonym 1799) soon accepted by followers, for example, the physician Samuel Brown (Brown 1800). The proof for existence of atmospheric acidity and “effects of poisonous atmosphere” was argued by iron rusting, the “leaves of trees, often became spotted, and turned to mortification” and “ . . . white cotton . . . spread to dry after washing, . . . when this mist prevailed . . . afterwards, by twice boiling in alkaline lie”.594 Mitchill´s theory is denoted to be untenable by Christoph Wilhelm Hufeland (1762–1831); (Hufeland 1804). In 1803, an article appeared in the Medical Repository,595 having the title “Dr. Chalmers on the Acidity prevalent in the Atmosphere of South Carolina” giving some extract from Chalmer (1776): “ . . . exhalations near the Atlantic do not consist of simply aqueous particles . . . One of the most predominant of these is an ACID, or some other saline principle. The proofs of which acidity in the atmosphere are, the speedy rusting of polishes metals . . . For these strongly attracting this salt from the air etc”. This is a remarkable indication of gaseous HCl release from sea salt – without any experimental proof. However, it is worth to cite from Brown (1800) some interpretations of Mitchell´s acidity theory, particularly on septic acid (HNO3) in air. This seems to me the first published idea on atmospheric NOy and other trace constituents in relation to health, or in historical words, “from bad air has been believed that malignant and pestilential diseases derived their origin”. Brown writes “the septic acid, generated by putrefaction, is always on the earth surface, and it vapours never rise to a great height above it. From these exhalations, the water of dews, mists and fogs, precipitated when the atmosphere is cooled, particularly during night, receives a portion of the same acid . . . From chemical combination of these (seption and oxygene)596 acting upon different parts of the body, seem to spring the common symptons fecers, dysenteries and plagues . . . ; that of syphilis from phosphorous, blended with the septon and oxygene; that of measles, from a combination of sulphur, that of pertussis, or croup, from the addition of the unknown radical of the muriatic acid [HCl], forming a nitro-muriatic oxyd”.597 As sources of atmospheric trace substances, Brown notes marsh exhalations (miasma), animal and vegetable putrefaction, and human effluvia. Today, Mitchill is forgotten but in that

594 Lye (lie – spelling error?): metal hydroxides obtained by leaching of ashes, containing largely potash (K2CO3). 595 Vol. 6, pp. 92–93 (this is the first scientific journal in the USA). Lionel Chalmer (1771–1777), American physician. 596 Without knowing, it is NOy meant. 597 It could be nitrosylchloride NOCl.

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time, the US Navy was following his idea to protect sailors by impregnating ships with alkaline solutions (basically a nice idea: neutralization after dry deposition that even increases due to reduced surface resistance). Summary: – Nitrite in human blood and tissues plays an important biological role. – Natural nitrite concentrations in human blood are at least 2 orders of magnitude higher than those expected from exposure to ambient NO2. – The acute poisoning from NO2 is likely only due to chemical burn of the respiratory tract at NO2 concentrations at least 3 orders of magnitude higher then present ambient levels. – Limits given for NO2 in ambient air are a lot of times less than “true” values being in relation to medical effects. 4.5.4 Particulate matter (dust) First we state that the PM levels have been reduced by several hundreds of μg m–3 over the last 100 years. The difference between PM2.5 and PM10 is mainly due to insoluble soil dust (mostly silicates) and resuspension. Resuspension is important only close to streets. City background PM2.5 of about 15 μg m–3 consists to about 15% of soot, 50% of secondary inorganic ammonium, sulfate, nitrate, and sea salt (NaCl) and 1/3 of organic matter (OM). Contribution of biogenic compounds to OM depends from season and location. Measurements of toxic organic compounds and heavy metals show concentrations far less than resulting in any health effects. Soot (2–3 μg m–3) is obviously due to traffic, mainly diesel exhaust. Soot itself is nontoxic (there is no limit fixed) but it is associated with potential toxic organic compounds; moreover soot is accumulated in the deeper airways. Long-time exposure in occupational environments to certain PM such as soot, coal, asbestos and minerals is well-known to cause serious lung diseases. Whereas silicosis was known since the 19th century, black lung disease was not well described until the 1950s. It is also known as coal workers’ pneumoconiosis (CWP), comes from inhaling coal mine dust that is usually less severe than silicosis. The other disease, silicosis, is caused by inhaling crystalline silica dust from crushed rocks. Black lung and silicosis often appear together because coal seams are found between rock layers that contain silica. Another type is asbestosis, an asbestosrelated illness to develop, it usually takes years of regular asbestos fibers exposure, followed by a latency period that may last decades before symptoms present. All these types of particulate matter (fibrous asbestos, black carbon, and crystalline minerals) do not occur under natural conditions. This type of pulmonary fibrosis, a condition in which the lung tissue becomes scarred over time, is usually not diagnosed until decades after the exposure occurred. It is obviously not only the amount

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of particulate matter598 inhaled but the particle structure where the airways have no efficient self-cleaning protection developed. Results from many investigations support four basic mechanisms in the etiology of CWP and silicosis (Castranova and Vallyathan 2000): 1. direct cytotoxicity of coal dust or silica, resulting in lung cell damage, release of lipases and proteases, and eventual lung scarring; 2. activation of oxidant production by pulmonary phagocytes, which overwhelms the antioxidant defenses and leads to lipid peroxidation, protein nitrosation, cell injury, and lung scarring; 3. activation of mediator release from alveolar macrophages and epithelial cells, which leads to recruitment of polymorphonuclear leukocytes and macrophages, resulting in the production of proinflammatory cytokines and reactive species and in further lung injury and scarring; 4. secretion of growth factors from alveolar macrophages and epithelial cells, stimulating fibroblast proliferation and eventual scarring. In fact the issues surrounding the big three (coal, asbestos, and quartz) have never been fully resolved and there remain many unanswered questions in conventional particle toxicology (Donaldson and Seaton 2012). It seems that freshly mined crystalline silica provides breaking of Si–O bonds and subsequent formation of superoxide and hydroxyl radicals: O2

½Si − Op ! ½Si¯ − Op ! O2− + ½Si¯ − Op

(4:12)

½Si¯ − Op + OH − ! OH + ½Si − Op

(4:13)

From freshly mined coal dust and emitted diesel soot, relative long-living carboncentered radicals are known (Vallyathan and Shi 1997, Tian et al. 2009). Mineral dust (asbestos, silica, coal) contains iron and other transition metals (such as Mn, Cu, Cd, and more) that convert H2O2 (subsequent product of superoxide) to OH (Fenton reaction). However, aging of dust particles reduces the ability to generate radicals. This explains why long-term and continuous exposure to mining dust is essential for detection of health impacts. Short-term exposure is compensated by the capacity of antioxidant defenses, which, however, is different among individuals and weakens with age. Long-term generation of free radicals by etiologic agents accelerates the process of human aging. Cigarette smoke certainly exceeds “the big three” in terms of the ill health that it has caused. From the point of view of toxicology the relationship between the main pathological consequences in the lungs and particulate versus the gaseous

598 Desert people such as the Tuareg´s have life-long exposure of Sahara dust but these particles are polished and rounded, supporting airways self-cleaning.

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and organic phases is not resolved and particles themselves may not play the primary role (Donaldson and Seaton 2012). However, the tumorigenic effect of cigarette tar is clearly cumulative; the lifetime cumulative tar exposure (total amount of tar available for inhalation) is between 1 kg and 9 kg (20–60 years smoking); Zang and Wynder (1992). The cigarette tar content decreased by 50% between 1960 and 1990 (to around 18 mg) and now to 10 mg and less. Studies over the past few decades have showed a clear association between cigarette smoking and the development of chronic airway obstruction. Yet, only a minority of smokers is affected so that in many, even heavy, smokers, pulmonary function remains within normal limits (Bohadana et al. 2004). However, Life expectancy for smokers is at least 10 years shorter than for nonsmoker; quitting smoking before the age 40 reduces the risk of dying from smoking-related disease by about 90% (Jha et al. 2013). It is worth to mention the exposure values for workers and miners and comparing that with ambient PM. There is a strong trend in declining dust concentration for miners in the USA (NIOSH 2011); in µg m–3: 2500–6500 (1967–1969), 2000 (1979–1977) and 1500 (1978–1987). Between 1980 and 2010 mean levels of respirable quartz dust and coal mine dust amounts 40–60 μg m–3 and 500–700 μg m–3, respectively (NIOSH 2011). Mortality from CWP of persons aged 25–64 years led to an average of 8.8 (5–12) years of potential life lost (YPLL); Mazurek et al. (2018). CWP typically takes least 10 years after initial exposure; total exposure time is between 30,000 and 70,000 h. The exposure of miners to coal dust (often given in gramhours per cubic meter: g h m–3) from 9 studies between 1970 and 2014 (USA, UK, Germany) is between 12 g h m–3 and 183 g h m–3 (Beer at al. 2017).599 Hence, taking into account the mean breathing volume (see above), a miner breathes long-life between about 5 g and 80 g dust. This is significant less than long-life breathing of cigarette tar, even assuming that only 10% of cumulative tar exposure in inhaled. The permissible exposure limits (PEL) in the USA (OSHA)600 are (in µg m–3) 10,000 for respirable quartz, 2400 for respirable fraction with less than 5% SiO2, 5,000 for total respirable fraction and 15,000 for total dust. In Germany, the limit (MAK) amounts 4000 µg m–3 for the total respirable dust fraction and 1,500 µg m–3 for alveolar dust fraction. These values have been set up for 40 h per week and 40 years working as maximum without expecting adverse health effects. It follows a long life maximally cumulative exposure of around 2,500 g h m–3. For ambient

599 The following comment of the authors highlights the “quality” of papers dealing with CWP: “The literature search resulted in a total of 2665 unique articles. Based on title or abstract 2440 articles were excluded. After reading of 225 full papers, eight articles were regarded suitable for data extraction. It is evident that major methodological limitations are present in most studies”. It is worth to note that from the selected studies it remains unclear whether the coal miners have been separated into smoker and nonsmokers (so much to the quality). 600 Occupational Safety and Health Administration

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PM (limit 40 µg m–3) it follows for 65 years life a maximally cumulative exposure of only 24 g h m–3. Urban dust will presently have a potential of about 3 μg m–3 soot. A person would be exposures over 65 years with 1.7 g h m–3 of this sooty PM. However, it is notable that comparing total exposure of different dust fractions with respect to health impacts is scientifically unsound because of different particle sizes, different toxicological agents and other accompanying substances being potentially toxic. Under the aspect of evolutionary adaption of humans to a dusty environment and the different self-cleaning processes of the airways, it seems that a certain amount of cumulative dust – proved for cigarette tar (see above) – can be accepted without measurable health effects. What could be concluded is that the respiratory system can be likely exposed to an amount of ambient PM several times larger than inhaled under ambient conditions without serious health impacts (Möller 2008a, 2009). In other words, the ambient air quality standards for PM are much too low comparing the workplace permissible exposure limits. The literature related to specific PM types (e.g., coal dust) also shows responses only at high concentrations (>4 mg m–3). The studies show that effects would be expected with any inhaled particle (Wyzga and Rohr 2015 and citations therein). The question must be answered why PM at levels more than hundred times smaller and changes of PM levels being consumption because of losses. It is a challenge to achieve production ≈ consumption both from resource management and climate control.

596

5 Climate change mitigation: global sustainable chemistry

The steady-state economy is an entirely physical concept. Any nonphysical components of an economy (e.g., knowledge) can grow indefinitely. But the physical components (e.g., supplies of natural resources, human populations, and stocks of human-built capital) are constrained and endogenously given. An economy could reach a steady state after a period of growth or after a period of downsizing or degrowth. However, the technical man also uses materials (nonorganic such as minerals and elements) with life-cycles being extremely small comparing to its geochemical recycling. Even in a steady-state economy, simple reproduction consumes materials not being in time scale of natural reproduction. Hence, sustainable economy also leads on long-term scale (thousands of years) to an irreversible degradation. The technical society remains therefore always a factor in global chemical weathering and dissipation. The challenge of sustainable chemistry is looking for replacement of inorganic through organic (hence reproducible) materials and substances; the carbon-based economy is later described in Section 5.3.1.

5.2 The carbon problem: out of balance From the analysis of the history of anthropogenic trace compounds in the atmosphere, its impacts on the climate system – so far we understand the processes of climate change – and recognizing the introduced abatement, few atmospheric environmental problems remain that are connected with the compounds N2O, CH4, and CO2. The carbon dioxide problem is by far the most serious. There is no or only very little hope that global CO2 emissions will significantly decrease in the next two or three decades. In contrast to N2O and CH4, the atmospheric residence time of “anthropogenic” CO2 is orders of magnitudes larger (Section 5.2.2); in other words, even when there would be a zero CO2 emission world soon, the subsequent “greenhouse” effect will still last several hundreds of years. However, there are ways to solve the problem (Section 5.3.1). That part of N2O and CH4 linked with fossil fuels will “automatically” be solved together with the CO2 problem. Hence, because the remaining sources of N2O and CH4 are linked with agriculture and food production (Section 4.2.3), they are likely to become the dominant residual problem in 100 years, but with a far lower impact factor than today. In the following two subsections, the “carbon problem” is characterized in terms of the budget, residence time, and global equilibrium. Climate scientists have warned that to have a 50-to-50 chance of limiting global warming to not more than 2 °C above the average global temperature of preindustrial times throughout the twenty-first century cumulative carbon emissions between 2011 and 2050 need to be limited 300 Gt C (Allen et al. 2009, Meinshausen et al. 2009). Recent calculations suggest that this necessitates one-third of oil reserves, half of gas reserves, and over four-fifths of coal reserves to remain untapped from 2010 to 2050

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(McGlade and Ekins 2015). With business as usual, global warming leads to unacceptable degrees of peak global warming, around 5 °C. This highlights the urgency and scale of the climate policy challenge. Van der Ploeg and Rezai (2017) estimate of the optimal time paths for the carbon tax significantly curb cumulative fossil fuel use to 670 Gt C. As a consequence, peak temperature reduces to 2.2 °C in their baseline scenario but ranges between 1.2 °C and 3 °C across scenarios with cumulative emissions ranging from 30 to 1430 Gt C. These results illustrate how previous estimates of the carbon budget for 2 °C (usually cited at around 300 Gt C) have been too pessimistic.

5.2.1 The carbon budget Since the beginning of the Industrial Revolution, humans have emitted about (365 ± 30) · 1015 g CO2–C from the combustion of fossil fuels and cement production, and about (180 ± 80) · 1015 g CO2–C from land-use change, mainly deforestation (period 1750–2011, IPCC 2013). Vegetation biomass and soils not affected by land use change, stored 150 ± 90 Pg C (IPCC 2013). Hence, the net effect was an emission of 355 Pg C into the atmosphere for the 1700–2011 period (350 Pg C for the period 1750–2000 after Minnen et al. 2009). The atmospheric increase amounts (240 ± 10) · 1015 g CO2–C and the oceans take up (155 ± 30) · 1015 g CO2–C and the residual terrestrial uptake amounts (150 ± 90) · 1015 g CO2–C. The world carbon stocks for about 1990 are (Scurlock and Hall 1991), in 1015 g C: – in plant biomass (80% in trees) 560, – in ocean 75 m surface layer 725, – soil carbon content 1,515, – deep ocean carbon 38,000, and – fossil fuel resources (92% as coal) 5,900. In 1750, the atmospheric CO2 level was 278 ± 5 ppm, which increased to 390.5 ± 0.1 ppm in 2011 (Ballantyne et al. 2012). Since 1950 these sources have amounted to about 400 · 1015 g CO2–C, that is, 70% of the total carbon release. Measurements and constructions of carbon balances, however, reveal that less than half of these emissions remain in the atmosphere (Prentice et al. 2001). The anthropogenic CO2 that did not accumulate in the atmosphere must were taken up by the ocean, by the land biosphere, or by a combination of both. The fraction of CO2 remaining to the atmosphere from fossil fuel combustion was 59% (Thoning et al. 1989). Hence, with constant increases expected the atmospheric CO2 mixing ratio is predicted to grow to 500 ppm in 2050 and to 700 ppm in 2100. There is no doubt that CO2 was increasing since the Industrial Revolution and has reached a concentration unprecedented for over more than 400,000 years.

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It is easy to calculate the amount of CO2 accumulated in the atmosphere. Between mass and atmospheric mixing ratio x, the following relationship is valid. The changing air concentrations of trace compounds do not influence the value of the total mass of the atmosphere in any detectable way. mass of CO2 = xðin ppmÞ10 − 6

mol mass of CO2 mass of the atmosphere mol mass of air

(5:3)

The mass of human cumulated CO2 in the atmosphere at a given year i is m = ð1 − αÞ

t X

Qi

(5:4)

i=1

where Q emission for year i = 1 until i = t and α fraction (0 . . . 1) of up taken anthropogenic CO2. It follows for the atmospheric CO2 concentration (taking into account the values for the parameters in eq. (5.3); Q in Pg CO2-C (Gt): xðtÞ = xð0Þ +

t 1−αX Qi 2.15 i = 1

(5:5)

This is equivalent to the regression shown in Figure 5.1. The point of intersection for zero emission amounts x(0) = 286 ppm in sense of a “pre-industrial level” (see Section 4.4.3.1). The slope ð1 − αÞ=2.15 ≈ 0.20 represents the atmospheric CO2 increment (in ppm) per Pg (1015 g) of total emitted CO2. It follows from eq. (5.5) α = 0.57, that is, 57% of emitted anthropogenic CO2 is removed by the biosphere; ð1 − αÞ represents the airborne fraction (0.43). As seen from Figure 5.1, the slope (which corresponds to the airborne fraction) varies over the whole period 1850–2010, giving ð1 − αÞ between 40% and 60%. On average, 50% of the cumulative emissions were absorbed by the environment assuming, of course, that the carbon source is entirely

CO2 mixing ratio (in ppb)

410 390

[CO2] = 0.0002Q + 286 (r2 = 0.99)

370 350 330 310 290 270 0

100000 200000 300000 400000 500000 cumulative CO2 emission Q (in Gt C)

600000

Fig. 5.1: Relationship between cumulative total anthropogenic CO2 (from fossil fuel use and landuse change) and atmospheric CO2 mixing ratio (data source see Figs. 4.45 and 4.49).

5.2 The carbon problem: out of balance

599

human (there is no doubt). This means that the emitted carbon dioxide is directly “partitioned among reservoirs”. By 2016, CO2 mixing ratio (404 ppm) corresponds to 869 · 1015 g CO2–C: taking into account the total mass of the atmosphere (5.2 · 1021 g; Table 1.2 in Vol. 1) it follows that607 atmospheric CO2 − C mass = 0.0404 ½vol% · 10 − 2 ·

12 · 5.2 · 1021 = 869 · 1015 g 29

where 12 is the molar mass of carbon and 29 the molar mass of air. Hence, the “reference” level of 285 ppb (related to about 1850) is equivalent to 613 · 1015 g CO2–C; the total added CO2 mass since 1850 is, therefore, 256 · 1015 g CO2–C, less than half (43%) of the total emitted carbon (591 · 1015 g: 422 from fossil fuels and 169 from land-use change 1850–2016). In other words, the airborne fraction amounts as mean over the period 1850–2016 about 0.57. Without ocean and land uptake, the atmospheric CO2 concentration would have increased to 566 ppm, if it had all stayed there. Bolin et al. (1981) estimated a “pre-industrial” atmospheric CO2 content of 614 Pg (290 ppm) assuming a constant airborne fraction of 0.54. The airborne fraction will increase if emissions are too fast for the uptake of CO2 by the carbon sinks (Raupach 2013). It is thus controlled by changes in emissions rates, and by changes in carbon sinks driven by rising CO2, changes in climate, and all other biogeochemical changes. However, the percentage of CO2 injected into the atmosphere from human activities that remains in the atmosphere has remained pretty much constant for the last 50 years (Ballantyne et al. 2012). Knorr (2009) extended his analysis back 150 years, and concluded that the airborne fraction of carbon dioxide had remained constant over that longer period as well. Thus, identifying the mechanisms and locations responsible for increasing global carbon uptake remains a critical challenge in constraining the modern global carbon budget and predicting future carbon–climate interactions. From eq. (5.5) we can simply calculate the future CO2 concentration assuming different CO2 emission scenarios based on the slope608 given by Figure 5.1 and assuming (which is not self-evident) that the airborne fraction (~50%) also remains constant in future. In Figure 5.2, two different emission scenarios are presented:

607 Expressed in other terms, it follows that per ppm CO2 the atmospheric increase amounts 2.150 Gt CO2–C; Prater et al. (2012) use a “conversion factor” to be 2.120 Pg per ppm. 608 It is remarkable that the linear fit (r2 = 0.996) only begins at 1850. The period before (Fig. 4.50) is characterized by several distinguished positive and negative trends in CO2. Between 1600 and 1800 there is a CO2 minimum plateau (~270 ppm). This period is called the little ice age (LIA). It is generally agreed that there were three minima, beginning about 1650, 1770, and 1850, each separated by intervals of slight warming. Beginning around 1850, the climate began warming and the LIA ended. We may assume that natural CO2 exchange was dominant and that the anthropogenic signal masked before 1850.

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5 Climate change mitigation: global sustainable chemistry

500

CO2 mixing ratio (in ppm)

measurement until 2016

450

without CCS with CCS

400

350

300 1950

1970

1990

2010 year

2030

2050

Fig. 5.2: Two scenarios of future atmospheric CO2 development (see text for assumptions).

a) a further but slowing down increase of CO2 emission (3% until 2020, then 2% until 2030 and further 1% growth); land use change and biomass burning 3 Gt CO2–C yr–1 constant until 2040 and further 2 Gt CO2–C yr–1, no carbon capture; and b) the continuous increase of CO2 emission, but with a faster slow down (3% until 2010, then 2% until 2015 and 1% until 2020), from 2020 carbon capture (1% yr–1 increase until 2015 and then 5% yr–1 until 2050). Scenario (b) seems to be very optimistic – it results in a constant CO2 mixing ratio of 450 ppm after 2050. It is more likely that carbon capture and sequestration/storage (CCS) technology (Section 5.2.3) becomes important only after 2030 and will capture a maximum of 50% of the fossil fuel-released CO2. It is also unlikely that the yearly consumption of fossil fuels will be more reduced before 2050 because of the increasing alternative energy source percentage of the total energy consumption. Hence, in 2050 a value between 450 and 500 ppm CO2 seems to be more likely. The most important reservoir is the backmixed surface layer of the ocean (Table 5.1). The anthropogenic emissions are added to the atmosphere, continuously increasing the equilibrium carbon content of the surface layer as a result of the increasing partial pressure of the carbon dioxide in the gas phase (see Section 4.4.1.6 in Volume 1). The further transport of anthropogenic carbon from the surface to the ocean bulk (deep sea) is believed to be extremely slow (thousands of years) and hence the limiting step. A first quantification of the oceanic sink for anthropogenic CO2 is based on a huge amount of measured data from two international ocean research programs; the cumulative oceanic anthropogenic CO2 sink for 1994 was

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estimated to be (118 ± 19) · 1015 g CO2–C (Sabine et al. 2004). The cumulative uptake for the 1750–2011 period is ~ (155 ± 30) · 1015 g CO2–C from data-based studies (IPCC 2013), about 30% of the total cumulative anthropogenic CO2 emission. Similar results were obtained by DeVries (2014) using a global steady-state ocean circulation inverse model, estimating the oceanic anthropogenic carbon storage to be 160–166 Pg C in 2012, and the oceanic anthropogenic carbon uptake rate averaged over the period 2000–2010 is 2.6 Pg C yr−1 or about 30% of current anthropogenic CO2 emissions. This result implies a residual (primarily terrestrial) anthropogenic carbon sink of about 1.6 Pg C yr−1 for the same period. Ballentyne et al. (2012) estimated the uptake by a combination of land and ocean carbon reservoirs to be 2.4 ± 0.8 Pg C yr−1 in the 1960s and 5.0 ± 0.9 Pg C yr −1 in the 2000s.

Tab. 5.1: Global carbon budgets (in 1015 g C yr−1) . (Denman et al. ) s

process

(Sabine et al. )

– – – total cumulative

. ± . . ± . .b .b

 ±  −

 ±   ± 

d e

sum

.

−





atmospheric increase

. ± . . ± .

 ± 

 ± 

f

difference (biospheric uptake)

.

−





ocean uptake terrestrial uptake

. ± . . ± . .c .c,e

 ±  –

 ±   ± 

g 

industrial CO emission land-use change

a

.

.

a

From fossil fuel use and cement production. Range 0.5−2.7. c Range 0.9−4.3. d 1751−2005 (Boden et al. 2015). e 1850−2005 (Houghton 2008). f Calculated from the difference 384 to 280 ppm CO2. g To be assumed 50% of cumulative industrial CO2 emission. e Forest sequestration for the period 1993−2003 has been estimated to be 0.3 · 1015 g C yr−1 (IPCC 2007). b

The total oceanic dissolved carbonate carbon (Table 3.9 on p. 327) corresponds to 0.028 g L−1 as carbon in seawater taking into account the volume of the world’s oceans (Table 3.2 on p. 303). The experimentally estimated seawater standard carbonate carbon is 0.0244 g L−1 seawater (Dickson et al. 2007). In the first 200 m of the ocean, the total deposited anthropogenic CO2 (Table 5.1 and assuming that 30% is within this layer) only contributes to 3% to dissolved inorganic carbon (DIC). Hence, it is very

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5 Climate change mitigation: global sustainable chemistry

difficult to measure trends in the DIC because of man-made changes (see Fig. 4.10 in Volume 1). The kinetic processes of exchange and transport have a characteristic time of a few years for the system atmosphere – the mixed surface layer of the ocean – whereas the exchange time with the deep sea is between 500 and 2,000 years (Wagener 1979). Variations in surface concentration are related to the length of time that the waters were exposed to the atmosphere and the buffer capacity for seawater, as expressed by the Revelle factor. This factor represents the ratio of the instantaneous fractional change in the partial pressure of CO2 (Δp/p0) exerted by seawater to the fractional change in total CO2 dissolved in the ocean waters (ΔΣCO2/(CO2)0), where the subscript 0 denotes the reference status and ΣCO2 denotes all forms of DIC (see Section 4.4.1.6 in Volume 1). Changes between ocean sediment and deep water play no role on a time scale of a few hundred years of anthropogenic perturbation of the surface layer CO2. But over thousands of years nearly all anthropogenic CO2 will be captured by the ocean. The impact of global climate change on future carbon stocks is particularly complex. These changes might result in both positive and negative feedbacks on carbon stocks. For example, increases in atmospheric CO2 are known to stimulate plant yields, either directly or via enhanced water use efficiency, and thereby enhance the amount of carbon added to soils. Higher CO2 concentrations can also suppress the decomposition of stored carbon because C/N ratios in residues might increase and because more carbon might be allocated below ground. Predicting the long-term influence of elevated CO2 concentrations on the carbon stocks of forest ecosystems remains a research challenge (Prentice et al. 2001). The severity of damaging humaninduced climate change depends not only on the magnitude of the change but also on the potential for irreversibility. Solomon et al. (2009) show that climate change that takes place because of increases in carbon dioxide concentration is largely irreversible for 1,000 years after emissions stop. The question of how large the residence time of anthropogenic CO2 in the atmosphere is will be discussed in next Section 5.2.2. There are strong arguments that the anthropogenic-caused CO2 increase is largely irreversible; hence, stopping emissions will not solve (though might smooth) climate change problems. As a consequence, CO2 capture from the atmosphere remains the challenge for climate sustainability (Section 5.2.3). The oceans have certainly been identified as the final sink of anthropogenic CO2 but after thousands of years; moreover, the seawater uptake capacity will decrease and oceanic acidification will result in serious ecological consequences.

5.2.2 Atmospheric CO2 residence time As mentioned already, the CO2 cycle has one major problem in the atmosphere – there is no direct chemical sink. In nature, CO2 can only be assimilated by plants

5.2 The carbon problem: out of balance

603

(biological sink) through conversion into hydrocarbons (Section 3.2.2.3) and stored in calcareous organisms, partly buried in sediments but almost completely turned back into CO2 by respiration; hence, CO2 partitionates between the biosphere and atmosphere. The only definitively carbon sink is the transport of DIC to deep ocean – when the ocean–atmosphere system is not in equilibrium, that is, in the case of increasing atmospheric CO2 levels (due to anthropogenic and volcanic activities). The CO2 source term by volcanic exhalations is very uncertain but is likely to be a value much less than 0.1 · 1015 g yr−1 carbon (see Section 6.3.3.3 in Volume 1). Hence, with respect to time periods being of interest for humankind (from decades to hundreds of years), this natural biogeochemical recycling can be regarded to be closed or, in other words, the net flux is zero. Consequently, all concentrations (pools) in the biosphere and atmosphere remain constant (we should not consider short-term variations because of seasonal and interannual fluctuations). The only driving forces behind removing CO2 from the atmosphere are dry deposition (including plant uptake) and wet deposition (CO2 scavenging). As discussed, the marine and terrestrial earth surface can be assumed to be carbonate saturated. This equilibrium is only disturbed by the yearly increase of the CO2 level due to anthropogenic emissions. Hence, the physical (not the biological) surface resistance is very large and no physical dry deposition flux results (Section 2.6.1 in Volume 1 for details). Therefore, the only abiogenic removal pathway from the atmosphere is CO2 scavenging by clouds and finally precipitation. We can easily calculate the DIC in precipitation (assuming equilibrium; see eq. (4.87b) in Volume 1). Thus, we get 0.21 and 0.28 mg L−1 carbon for 280 and 383 ppm CO2, respectively (pH = 5.6 and at 10 °C). By using the global precipitation (Table 6.1 in Volume 1) it results in a very small total of wet removal fluxes (in 1015 g yr−1 carbon): – 280 ppm CO2 (preindustrial): 0.08 and 0.02 for marine and terrestrial precipitation, respectively and – 400 ppm CO2 (today): 0.10 and 0.03 for marine and terrestrial precipitation, respectively. The river run-off (Tables 6.3 and 6.4 in Volume 1) is about 0.46 · 1015 g yr−1 carbon and is much larger than the total wet-deposited carbonate (0.13 · 1015 g yr−1 carbon). The global volcanic CO2 emission is uncertain and there is given a value (Table 6.29 in Volume 1) of 0.02 · 1015 g yr−1 carbon. We state that the global carbon wet removal is significantly larger (by about a factor of 6 − 7) than the annual volcanic CO2 release. Hence, it is likely that biogenic CO2 is precipitated, but this amount is extremely small compared with the assimilation flux (about 0.1 · 1015 g yr−1 carbon). Moreover, the river run-off is much larger than the total continental wet removal flux (by a factor of ~15). It is likely that it comprises biospheric carbonate from soils but we cannot exclude anthropogenic CO2. We can summarize that the maximal physical removal fluxes are 0.13 · 1015 g yr−1 carbon wet deposition and 0.46 · 1015 g yr−1 carbon river run-off.

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5 Climate change mitigation: global sustainable chemistry

The residence time τ in sense of a turnover from one reservoir (atmosphere) to another (biosphere) is generally described by (cf. Section 2.7 in Volume 1): τ=

m Fsink

(5:6)

where m mass of the compound in the reservoir. The CO2 mass in the preindustrial atmosphere amounts to about 600 · 1015 g yr−1 carbon with a global assimilation rate (Fig. 3.8) of about 200 · 1015 g yr−1 carbon, meaning the turnover time (a “pseudoresidence time”) of natural CO2 amounts to about three years. Some climate skeptics (Segalstad 2009) use this time quantity (enlarged because of rising atmospheric CO2 mass to about four years) to explain that after the cessation of anthropogenic CO2 emissions the recovery of the atmospheric CO2 concentration will soon be expected (within less than 10 years). However, this is misinterpreting the conception of budgets and fluxes (Prather 2007). As discussed above, it follows that the natural removal is balanced with the new yearly input by respiration. In Section 2.7 in Volume 1 we define the residence time mathematically and see that eq. (5.6) is valid only for removal processes, which can be described by a first-order rate equation (cf. eq. 5.7): Fsink =

dm =k·m dt

(5:7)

Because almost all chemical reactions can be described as pseudo-first order (see Section 4.2.3 in Volume 1) and dry deposition (so far it is driven by physicochemical sorption) as well wet deposition can also described mathematically as first-order rate, removal of most atmospheric trace constituents can be described by eq. (5.6). However, CO2 assimilation must be considered as a zero-order process, that is, the removal rate is constant and (largely) independent from the atmospheric CO2 concentration. This becomes reliable when considering the global biosphere as heterogeneous uptake process, only depending on the plant amount. This consideration should not be fully valid but explains that application of eq. (5.6) is invalid. The above estimated “pseudo-residence time” of CO2 is the time when all atmospheric CO2 (assuming no CO2 source via respiration) is completely consumed and the “reaction” (photosynthesis) abruptly stops. However, because respiration brings about at the same rate CO2 back to the atmosphere, the “pseudo-residence time” of CO2 becomes infinite. Only burial of organic matter (lignin-derived organic matter, relatively nonbiodegradable) in sediments, representing a small excess of photosynthesis over respiration, is important over million of years for control of CO2 and O2 (Berner 2005, Beerling and Berner 2005). The CO2 measurement clearly shows that the accumulative CO2 increase is due to anthropogenic emission without fully balancing it by a sink. We have discussed in Section 5.2.1 that only about 50% of annual anthropogenic CO2 is taken up by the biosphere and ocean. The remaining 50% builds up the carbon stock in the atmosphere (“airborne fraction”) and can only be removed physically.

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605

Taking the present anthropogenic CO2 mass in the atmosphere (Table 5.1) of about 225 · 1015 g carbon, and assuming that the river run-off represents the maximum physical removal rate, it follows from eq. (5.6) that there is a residence time of about 500 years. Taking into account only the atmospheric wet removal flux (0.13 · 1015 g yr−1 carbon), the residence time is 1,700 years. Moreover, the residence will increase with increasing airborne CO2. Having a mixing ratio of 500 ppm (corresponding to about 300 · 1015 g carbon) by 2050, the residence time increases to 650 and 2,300 years, respectively. It is, therefore, likely that the removal capacity of our climate system for the recovery of anthropogenic atmospheric CO2 is in the order of 1,000 years. Then, the removal flux amounts to 0.2 · 1015 g yr−1 carbon, only 2% of the present man-made emission flux.

5.2.3 Direct air capture (DAC) The idea of DAC (CO2 extraction from air) as climate control strategy is now accepted and seriously considered in global ecological (e.g., Cao and Caldeira 2010) and economic models (e.g., Edenhofer et al. 2006). Keith (2009) writes: Air capture is an industrial process for capturing CO2 from ambient air; it is one of an emerging set of technologies for CO2 removal that includes geological storage of biotic carbon and the acceleration of geochemical weathering. Although air capture will cost more than capture from power plants when both are operated under the same economic conditions, air capture allows one to apply industrial economies of scale to small and mobile emission sources and enables a partial decoupling of carbon capture from the energy infrastructure, advantages that may compensate for the intrinsic difficulty of capturing carbon from the air.

A complete air capture system requires both a contactor and a system for regenerating the absorbing solution. However, with the exception of CCS, which is presently transferred to larger technical equipment being tested in pilot plants, DAC and CCU (carbon capture and utilization) still only exist in laboratory or only on conceptual levels, characterized by different approaches.609 Recently, the world’s first commercial DAC plant for supply and sale of CO2 opened on May 31, 2017 near Zurich in Switzerland. The commercial-scale DAC plant uses technology patented by Swiss company Climeworks that filters and captures pure carbon dioxide. The filter material is made of porous granulates modified with amines, which bind the CO2 in conjunction with the moisture in the air. This bond is dissolved at temperatures of 100 °C. The idea of CO2 capture from ambient air using alkaline solution is not new (Tepe and Dodge 1943, Spector and Dodge 1946, Greenwood and Pearce 1953) and

609 A critic of the American DAC Report also comes from the Climeworks Company, which is doing solar-thermal CO2 capture and conversion in cooperation with the Professorship of Renewable Energy Carriers, Institute of Energy Technology at ETH Zurich (Switzerland).

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5 Climate change mitigation: global sustainable chemistry

was used as a pretreatment before cryogenic air separation. In general, air capture includes all processes of CO2 fixing and sequestration. In the past it focused on biomass (Marchetti 1977, Keith 2000, Metzger and Benford 2001), but it remains an option today and for the future too. Bio-energy with carbon storage is the term referring to a number of biofuel technologies, which are followed by carbon sequestration and yielding “negative emission energy” (Read and Lermit 2005). However, the key factor in CO2 removal from the atmosphere is the specific carbon flux per time and square. Plant assimilation needs time and a large area, whereas bringing biomass (almost always wood) to biofuel power plants also needs energy. However, it is important to study all practical measures to slow down climate change and ensuring the safety of risky geo-engineering (Lenton and Vaughan 2009). The large-scale scrubbing of CO2 from ambient air was first suggested by Lackner et al. (1999). Zeman and Lackner (2004) write: It is not economically possible to perform significant amount of work in air, which means one cannot heat or cool it, compress it or expand it. It would be possible to move the air mechanically but only at speeds that are easily achieved by natural flows as well. Thus, one is virtually forced into considering physical or chemical adsorption from natural airflow passing over some recyclable sorbent.

The basic principles of CO2 capture from ambient air with respect to a climate strategy were described in Elliott et al. (2001), Dubey et al. (2002), Keith et al. (2005), and Keith (2009). Almost all these authors suggested techniques based on sodium hydroxide, whereas sodium carbonate is converted back into NaOH by “causticization”, one of the oldest processes in the chemical industry. Different absorbers were proposed such as large convective towers (Lackner et al. 1999), packed scrubbing towers (Zeman 2007), and a fine spray of the absorbing solution in open towers (Stolaroff et al. 2008). CaO–CaCO3 cycles have also been proposed using solar reactors (Nikulshina et al. 2009). Holmes and Keith (2012) adapt technology used in large-scale cooling towers and waste treatment facilities, which are designed to efficiently bring very large quantities of ambient air into contact with fluids. The design they present assumes that absorber fluid is an aqueous solution that absorbs CO2 from ambient air (typically of a 1–2 M NaOH solution) with flux across the surface of the liquid film of order 1 mg m−2 s−1, and that, under typical operating conditions, each kilogram of solution absorbs about 20 g of CO2 before it is returned for regeneration. A new generation of polymeric resins, containing specific primary amine functionalized based sorbents, have been developed (Buijs and Flart 2017 and literature therein). They are completely regenerated at temperatures in the order of 100 °C and show a low H2O adsorption of 1.5 mol kg−1. Generally, it is a huge challenge to believe that direct CO2 extraction from air can be achieved in quantities approaching an order of several Gt C yr−1. Note that about 50% (about 4 Gt C yr−1) of technically emitted CO2 comes from small and mobile

5.2 The carbon problem: out of balance

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units, a percentage likely to increase further in the future. Additionally, about 1–2 Gt C yr−1 comes from land use change and wood fuel use, which are categories that should diminish in the future. Some 4 Gt C yr−1 is absorbed by the biosphere (ocean and forest) but with an anticipated decreasing capacity. This “uptake capacity” is not constant but at a certain percentage (likely non-linearly) of the total CO2 release into the air. Hence (assuming full CO2 capture from stationery large sources), there is a requirement of at least 2 Gt C yr−1 air capture. A compensation of atmospheric CO2 buildup through engineered chemical sinkage was proposed by Elliott et al. (2001). They calculated the CO2 removal from air by asking for the area needed if this was a perfect, flat sink with a dry deposition velocity of 1 cm s−1. It is a hundred thousand square kilometer value, which constitutes an upper limit for absorbing the annual anthropogenic CO2 input. Roughness elements and vertical fences could increase the transfer velocity (by reducing the atmospheric residence) and increase the specific absorbing area per horizontal air column surface. A total square reduced by a factor of 10 might be able to be reached. Technically, CO2 is extractable from air by cryogenic techniques. However, based on 400 ppm CO2, an air volume of about 10 km3 must be processed daily to get 0.1 Mt C d−1 (this rate corresponds to about 30 “capture units” globally to achieve a yearly capture of 1 Gt C). Today’s high-performance cryogenic air separation plants have an air capacity of about 0.02 km3 d−1. In other words, more than 10,000 these plants would have to be in use to provide CO2 capture of 1 Gt C yr−1 from air. The nonuse of other gases from air separation would also not to be conform to a sustainable approach. However, new air separation techniques will eventually make it possible to generate only carbon dioxide and water from air and to increase the daily capacity by a factor of 10. In that case, “only” 1,000 of these plants will be needed for the extraction of 1 Gt C yr−1 from air, less than the global number of coal-fired power stations. Carbon dioxide capture can be applied both in closed technical plant systems as well as in an open-field technology (geo-engineering). The processed air volume is large (107 km3 because of about 40 t CO2–C km−3), but corresponds to the air volume passing through about 100 cooling towers of large power plants. Assuming CO2 solvents having a surface resistance being zero, the atmospheric (dry deposition) flux is determined only by the quasi-laminar and atmospheric resistance (see Section 2.6.1 in Volume 1), and a value between 0.4 and 1.2 kg CO2-C m−2 d−1 can be estimated. This corresponds to an uptake rate of about 2,000 t C ha−1 yr−1; at least 50 times more than most manipulated algal aquacultures will yield.610 610 Algal productivity rates between 5 and 10 g C m−2 d−1 have normally been cited (Drapcho and Brune 2000), but were reported to be up to 15 C m−2 d−1 in highly modern farming systems (Shelef et al. 1978). Again, to achieve 0.1 Mt C d−1, a farming area of about 7,000 km2 is needed or 210,000 km2 globally, which corresponds to an area roughly 50% of the size of Germany. Surely there is a research needed to optimize (and maximize) CO2 capture by industrial biofarming in sun-belt

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To “capture” 1–2 Gt CO2–C yearly, a square (assuming 50% scrubbing efficiency) of 104 km2, smaller than the State Brandenburg, is (“only”) needed. However, in contrast to CCS in this approach it is not the aim, to extract CO2 in short time from a given volume of gas (air) but to reach a saturation of the CO2 solvent for further desorption and solvent cycling. Design and synthesis of new CO2 absorbing materials is the key for applications of DAC. The argument of large costs will limit the technology can be overcome when the costs for climate change is included into energy price. It is self-evident that only solar energy is used for DAC. In the Section 5.3.1 we will see that DAC is a basic technology for the carbon economy similar to biogenic assimilation. From today’s perspective, it seems that as a result of the extremely low concentration of CO2 in the air, the technical and economic solution of direct atmospheric CO2 reuse is not very likely (DAC 2011). However, any technical solution in our concept is based on the paradigm change to establish a zero-carbon budget (not zero emissions!), and to no longer measure the effect on energy efficiency (solar energy is in “excess”) but on budget, with respect to climate sustainability. The “price” of CO2 emitted from fossil fuels (and hence fossil fuel costs) must include climate change affects; this would encourage energy transition and also DAC technologies.

5.3 The energy problem: the last industrial revolution The first Industrial Revolution (nineteenth century) is now characterized as the period of mechanization using water and steam power, followed by the second Industrial Revolution (first half of the twentieth century) using electricity for mass production via assembly that transferred to the end of the twentieth century to the third Industrial Revolution using computers and automatization (digitalization). This phase surely is going on with cyber physical systems (also called fourth Industrial Revolution). However, since the second Industrial Revolution, electricity is based up to present on fossil fuel burning. In my opinion, we expect a fifth Industrial Revolution by providing electricity solely based on solar radiation (second half of twenty-first century). Together with that a sixth Industrial Revolution is inevitable, the use of carbon as material and energy carrier from the atmosphere, the CO2 cycling. This could be the last industrial revolution reaching global steady states and gaining sustainable societies.

countries. For example, nutrients for biofarming could be taken from municipal wastewater of nearby “solar cities” and/or recycled from the biomass conversion process into CO2 (note that fixed CO2 is the aim rather than biofuel).

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5.3.1 The carbon economy: CO2 cycling Mining and combustion of fossils fuels now results in geological reservoir redistribution of carbon close to (or even passing?) the “tipping point”. In the last two decades, we observed an acceleration of CO2 release due to economic growth, which presently seems to go further on a constant level. The large CO2 residence times in air and seawater avoid reaching a steady-state (global cycle in-time) and a recovery (climate restoration) also after full stop of fossil fuel use. Therefore, much more forced by climate change than by fossil resource limits, we need the transfer into the “solar era” as soon as possible. Nuclear power may concern as “bridging technology”, but risks may not be longer accepted by society. Secondary “renewable” energy, for long time already in use (and we should not forget, it was the only significant source of energy before first Industrial Revolution), such as water and wind, will probably never contribute on global scale to fit the energy demand (this not excludes national and regional solutions, at presently proposed for Germany). Hence, only direct use of solar energy as it is proposed, for example, by the Desertec conception, can realistically solve the global energy problem and fully replace fossil fuels. Without any doubt, electricity is the unique form of energy in future and its direct application (also for mobility and heating) will increase – and can replace to a large percentage traditional fuels based on fossil resources. The Desertec consortium was a splash with its ambitious plans to harvest huge amounts of solar energy from the Sahara Desert, but the dream did not die – such technology is not unlikely to apply in next few decades to replace fossil fuels remarkable – if political (and thus financial) willingness is given. However, there are some open questions that have to be answered and transferred into technical solutions to establish the solar era. – Electricity will be produced not constant over time and not correlated with the demand of energy; hence, it must be stored, likely best by transfer into “chemical energy”, to manage energy supply. – Due to safety reasons, excess energy must be stored (e.g., in water reservoirs, but this way is limited), again best way seems to transfer electricity into “chemical energy”, – There are technological processes (e.g., air traffic, long-distance street traffic, ship traffic, metallurgy) where electricity cannot be taken directly from nets or storage units and will be neither ecological neither economic. – Humans always need synthetic organic materials (polymers, drugs, chemicals, etc.). These can be produced not only from remaining fossil resources but also from biomass – and from CO2. Möller (2012) put forward an option to create a global closed anthropogenic carbon cycle by using only solar energy to (a) stop further increase of CO2 emission and to

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get a global zero-carbon budget, (b) to solve the problem of electricity storage based on CO2 utilization, (c) to provide carbon-based materials only form CO2 utilization, and (d) to use further the infrastructure developed for the fossil fuel era, termed SONNE611 conception (“Sonne” is the German word for sun). The SONNE conception (Möller 2016) will interlink solar electricity conceptions such as Desertec with CO2 utilization to overcome the above-mentioned open problems after the fossil fuel era. In other words, SONNE build a man-made carbon (CO2) cycle in analogy to the natural assimilation-respiration carbon cycle (Figure 5.3). CO2 is recycled within hybrid power plants (see Figure 5.4) and captured from ambient air. It is replaced from waste (emission) to resource; process energy is taken from solar energy.

seawater CO2

atmospheric CO2 traditional technology (fossil fuel era) fossil fuel mining

combustion

CO2 emission

CCS technology (carbon capture and storage)

flue gas CO2 capture

CO2 storage for sequestration

solar fuels

CO2 utilization

sequestration for climate restoration

dynamic CO2 storage

CCC technology (carbon capture and cycling) ambient CO2 capture

Fig. 5.3: Scheme of energy transition from fossil to solar era including a CO2 economy (SONNE conception). Three overlapping systems: fossil fuel burning without (grey box) and with carbon capture (dotted box) as well solar fuel production/use and global carbon cycling. The driving force is exclusively solar radiation; hence, the CO2 economy is interdependent with solar electricity conceptions such as DESERTEC. Elements of this concept can be introduced parallel with further use of fossil fuels aimed by its stepwise replacement.

The specific approaches put together in this “CO2 economy” are already known and/or proposed, but to my knowledge, the creation of a man-made carbon cycle in such an integrative approach and with these rigorousness in linking energy with material economy adopting the principle of natural cycling but not copying natural

611 SOlar-based maN-made carboN cyclE.

5.3 The energy problem: the last industrial revolution

oxyfuel combustion

electrolyzer H2O Wel, in

O2

H2

methanization

611

O2 storage CH4 storage

combined cycle power plant

Wel, out

CH4 CO2 recycling solar electricity storage by CO2 utilization (hybrid power plant)

Fig. 5.4: Schema of a “hybrid power plant”: chemical storage of “renewable” energy (preferably solar electricity) by CO2 utilization (likely best by methanization) and internal CO2 recycling (likely best by oxyfuel combustion); Wel, in – direct solar electricity, Wel, out – indirect energy solar energy (electricity/heat) “on demand”. The energy efficiency is negative (e.g., in the case of CH4 production from CO2, only 30% of electricity input can be reused).

processes,612 as suggested here, is world-wide unique and new (even much more complex than the “methanol economy”). CO2 is unique,613 – as final oxidation product of all organic matter and materials, – because of its globally cycling and homogeneous distribution in the atmosphere, – as resource for organic materials concerns carriers of energy and functional materials, – carbon is the only element forming complex molecules and substances and being within a global dynamic614 cycle and gaseous compounds on lowest (CH4) and highest oxidation state (CO2), – the only environmental problem of CO2 is its rise in atmosphere (and seawater) with climatic implications; hence controlling its level on acceptable values will overcome the environmental problem.

612 For illustration, some scientists’ dream from the artificial leaves to transform CO2 into (solar) fuels. Our approach consists in “secondary” use of solar energy in terms of electricity and heat in large industrial operational units, which principally already are known. 613 In a certain sense, hydrogen (H2) can also play this role when we adopt the natural water splitting process, which was already proposed as “hydrogen technology” in the early 1980s. But there are several problems, (a) safety in storage and transport, (b) leakage and atmospheric implications, and (c) missing material supply. Water electrolysis will play an important role in SONNE for oxyfuel combustion (O2 supply) and CO2 reduction (H2 supply). 614 In (biogeochemical) cycles move all elements and its compounds – but often on geological time scale (beside carbon only sulfur and nitrogen are in similar dynamic cycles).

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5 Climate change mitigation: global sustainable chemistry

It is evident that through the realization of these principles a CO2 “zero-budget world” rather than a “CO2 free world” can be reached because there is a closed anthropogenic carbon cycle (we call it CO2 economy). All CO2 still emitted – and also cannot be technically captured in future from mobile and small equipment’s – will be captured from air and cycled for reuse; I call it “Carbon Capture and Cycling” (CCC) technology. With this in mind, CCS technology (CCS/sequestration) makes (more) sense – despite of the controversially discussed CO2 storage problems – and provides considerable incentive because CO2 storage is now only temporary (we call it dynamically) until it is recycled from waste to feedstock. The proposed CCC technology allows a stepwise replacement of coal and other fossil fuels by solar fuels but keeping the carbon-based infrastructure such as pipelines, tankers, storage facilities, engines, and allows the continuous use of other available technical applications developed in last hundred and more years, but within a CO2 neutral closed loop. A closure of the carbon cycle, however, is only possible when CO2 will be extracted from natural reservoirs such as the atmosphere and seawater (DAC, see previous Section 5.2.3) because a complete “industrial” CO2 capture will be impossible with regard to many small and mobile sources. Principally, the SONNE conception is not aimed for the very near future but for the solar era with “unlimited” access to useable solar energy, likely after 2050. However, because CCS will be an essential technology in “internal cycle” of hybridtype power plants (Figure 5.4), CCC could be introduced to some extent parallel with further use of fossil fuels and stepwise replacing them until full establishing the SONNE cycle. The principal scheme of CO2 use in solar electricity storage (valid also for other “renewable” energy such as wind) could be soon realized. The socalled oxy-fuel combustion would provide high purity CO2 as exhaust gas, which can be recycled without energy-intensive capture (Figure 5.4). We can set 10 mission statements or principles: 1. further use of fossil fuel combustion in large stationary units but only with CO2 capture (CCS technology) until the full transfer into the solar fuel world: capture CO2 from combustion units as much as possible; 2. replacement of fossil fuel use in small stationary and mobile units as far as possible (electricity-based and hybrid techniques): reduce carbon carriers as fuels as much as possible; 3. sequestration of carbon (not CO2) on medium- and long-term scale for buffering the further CO2 emission increase in next decades and climate sanitation in far future; 4. developing technologies for CO2 extraction from natural reservoirs (ambient air, seawater) to achieve a global man-made carbon cycle while allowing CO2 emissions into the atmosphere from mobile and small sources: atmospheric CO2 is considered as the only carbon reservoir for chemical CO2 utilization (CCU); 5. developing technologies for CO2 reduction but applications only with renewable energy, namely, solar radiation (solar fuel production);

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6. introduction of large solar thermal power plant units for electricity generation; 7. developing technologies for electricity conversion into chemical energy carriers (solar fuels used in hybrid power plants); 8. build-up a solar fuel infrastructure (widely on the basis of the existing fossil fuel infrastructure); 9. developing technologies for electricity conversion into large central heat storage units (based on molten minerals); and 10. economic paradigm change: solar energy is “in excess” (comparing with the global human demand) and is naturally dissipated in the atmosphere; hence, large energy consuming conversion processes and DAC can be carried out for resource generation and climate sustainability: a new economy-thinking based on sustainability (or closed carbon cycle) is needed. In other terms, not energy but material efficiency becomes the key factor. Human’s evolutionary responsibility should also consider the retransfer of emitted CO2 into geological stocks, for example, as elemental carbon for safe sequestration and stepwise but long-lasting climate recovery. All CO2 still emitted will be captured and cycled for reuse. Naturally, the energy needed for CO2 reduction comes from renewable sources. The proposed CCC technology allows a stepwise replacement of coal and other fossil fuels by solar fuels. Finally, there is a closed carbon cycle similar to the natural photosynthesis, a respiration cycle (Figure 5.3). Carbon-based solar fuels solve the problem of energy storage and allow the continuous use of available technical applications to provide products for materials, and are within a CO2 neutral closed loop. Olah (2005) proposed the “methanol economy”, but in the SONNE concept, CH3OH is only one possible product among C1 chemicals; the Fischer-Tropsch synthesis (from CO + H2) basically offers a wide range of organic compounds including liquid fuels. Our “CO2 economy” includes the “CH3OH economy”. Recently it was provided that the energetic efficiency of the overall energy conversion-storage system (see Figure 5.4) including CH3OH as a storage medium is only 17.6% in contrast to 29.7% for CH4 (Rihko-Struckmann et al. 2010). However, taking into account ambient CO2 capture, the overall energetic efficiency will drastically lower. Such as in nature (the photosynthesis efficiency concerning solar light is only 2–3%), we realize a closed carbon loop only with large energy input (in other words low energetic efficiency), but based on incoming solar radiation, 1,000 times higher than present global human energy demand. Still unanswered is the question, however, what are the limits of solar use without getting other climate implications. It is remarkable that establishing the SONNE conception (CO2 economy), we first see that sun-belt countries, many of them are privileged by natural oil and gas reservoirs, will provide “solar sites” for electricity generation and likely CO2 processing (Figure 5.5). On the other hand, future use of fossil fuels is mainly in the

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non-sun countries in the Northern Hemisphere, which should become responsible for ambient CO2 capture (there are good reasons, to establish DAC units more in the north because CO2 absorption processes needs low temperature and DIC in seawater is significantly higher in cold areas). For example, Northern Europe will capture ambient CO2 and transport them to Northern Africa as “fuel feedstock” for solar processing (Figure 5.5). Thus, a social win–win situation with many positive political and educational effects may be created.

solar radiation

CO2

transportation

CO2 CO2 fuel plant

power plant

solar fuels

electricity

transportation

decentralized use

ambient air capture

direct use

hybrid power plant

transportation

solar plant (sun-belt country)

Fig. 5.5: Solar plant complex (solar-to-electricity and CO2-to-fuel conversion in sun-belt countries), interlinked with transportation of fuels, chemicals and materials, and electricity to Northern Hemispheric countries (to be used there) and back transport of CO2 captured from ambient air to solar plants (getting a geo-economics equilibrium and political interdependence as win–win situation). Note that the whole system dissipates solar energy as it happens in the climate system by natural processes. Therefore, the energy efficiency plays a minor role (but should be maximized in singular technical process); the key for a sustainable economy (socioecological system) is the closed cycling of matter (here carbon, but this is true for all element to be used).

At this point, it is important to state that SONNE is based on ideas already known and further investigated (e.g., CCS, CCR,615 CCU, DAC) at many scientific institutions worldwide. As mentioned, a key idea of CCC technology is the capture of CO2 from the atmosphere (and its dynamic storage) to close the man-made global carbon cycle analogously to the biosphere. The CO2–carbon economy is the adaption of the biospheres’ assimilation–respiration cycle by humans, the only long-term sustainable way of human’s surviving. From today’s perspective it seems that due to the extremely low concentration of CO2 in air, the technical and economic solution of direct atmospheric CO2 reuse is not very likely (DAC 2011). However, any technical solution in our conception is based on 615 R stands for recycling.

5.3 The energy problem: the last industrial revolution

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the paradigm change to establish a zero carbon budget (not zero emission!) and measuring the effect not longer on the energy efficiency (solar energy is in “excess”) but on the matter budget with respect to climate sustainability. The “price” of CO2 emitted from fossil fuels (and hence fossil fuel costs) must include climate change affects; this would force the energy transition and also DAC technologies.

5.3.2 Solar fuels: carbon as a material and energy carrier The idea of using CO2 as a chemical raw material is not new (Aresta and Forti 1987, Edwards 1995, Aresta and Aresta 2003, Park et al. 2004, Olah 2005, Wu 2009, Aresta 2010). However, when using CO2 from fossil-fuel gases, it is only climate sustainable if the products are “sequestrated”, for example, by long-term use in carbon materials such as polyurethanes. CO2 captured from fossil-fired power plants and “utilized” for storage of excess electricity (e.g., from wind power) may help to improve the energy efficiency (because the excess electricity cannot be used on demand) but not solve the climate problem. Zeman and Keith (2008) also suggested synthesizing carbon neutral hydrocarbons from air-captured CO2. This term (in fact CO2 neutral) is inconsistent, and in its place we will use “solar fuels” to express that the supply of process energy for the chemical reduction of captured CO2 must be based on solar energy processing instead of fossil (geothermal heat is another option). In last years considerable progress was achieved in the catalytic hydrogenation of CO2 (methanization). The possible synthesis of C1-chemicals (CO, C, CH4, CH3OH, and HCHO) from CO2 and directly further to C3 in analogy to the assimilation process (see also Fig. 6.13 in Volume 1) leads to a variety of important basic chemicals being available for either direct combustion or material use (industrial synthesis in organic chemistry); we now call them solar fuels. The possible synthesis of methanol and formic acid from CO2 leads to important basic chemicals for industrial synthesis in organic chemistry. However, a global CO2 economy must not only provide chemicals in the order of hundred million tons but also an amounts of 1–2 orders of magnitude more gaseous and liquid fuels. By using high-temperature chemical processes (which were known for many years but due to the high energy consumption have hardly been mentioned before) based on solar thermal energy it is also possible to remake “coal chemistry” (gasification and liquefaction) via CO2 reduction. Namely, carbon monoxide (CO) and elemental carbon may be produced and inversely transformed. For example, elemental carbon could be stored better than carbon dioxide (for sequestration aiming climate abatement) but could also be reused directly in an early stage of the CCC technology. It is known that in hightemperature processes of conversion of carbon compounds to elemental carbon the yield of polymeric carbon structure (fullerenes) are large and unforeseen changes in creating new carbon materials are made possible. It is self-evident that all energy

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for processing is solar based. It is out of the focus of this book to review the chemical processes of CO2 utilization – this section will present only the basic ideas of chemical conversion in sense of the chemical evolution sustained by humans – and the reader is referred to (as examples) Aresta and Aresta (2003), Park et al. 2004, Grimes et al. (2007), Rajeshwar et al. (2008), and Varghese et al. (2009). There are several modular technical systems for realizing the CCC conception (Figure 5.5) where the solar (desert) site in sun-belt countries (module A) plays a key function by providing solar-based electricity (and heat for on-site chemical processing). Principally, it is possible to combine the solar site with other modules (B – air capture and CO2 supply and C – CO2 processing), but there are arguments to localize air capture close to CO2 storage (module E) to avoid transportation to sites where climatic conditions support large CO2 absorption (see above) and/or to sites of CO2 processing. Solar power plants are decentralized close to urban and industrial areas (module D). Solar fuel (in contrast to CO2) can be easily transported and stored using traditional infrastructure for liquids and gases. Processing sites (module C) must have access to solar (or non-fossil) energy. Then, by using high-voltage direct current transmission lines (Desertec conception), they can be sited several thousands of kilometers from the solar thermal power plants. An interesting site would be Iceland, which might be able to provide power from geothermal heat and cold carbon-rich seawater for CO2 extraction as well as air capture because of the large temperature differences in rich and lean CO2 loading. Captured CO2 could be reduced on site to solar fuels that are transported by tank ships to Central Europe. There is no need for long-range transportation of hydrogen (which is one feedstock for CO2 reduction) because electricity (according to the Desertec conception) can be transported advantageously in comparison to H2. Hydrogen can also be produced at any site by water electrolysis (also using renewable sources other than direct solar electricity). There are clear advantages to CO2 reduction close to the solar fuel consumers including the avoidance of the expensive transportation of CO2 back to the sun-belt countries and the possibility of mixing solar fuels directly with oxygen from the water electrolysis to create “oxyfuels”. Oxyfuels can be burned in stationary power plants with the result that the flue gas is almost all pure CO2. However, there is an interesting aspect for back transportation of CO2 from industrial to sun-belt countries. The solar site depends on the delivery of feedstock CO2. Thus, a geopolitical equilibrium can be reached in sense of a win–win situation. As mentioned, the world’s infrastructure is based on fossil fuels and products derived from coal and petrochemistry. The following groups of substances are delivered from fossils fuels and can be also produced from CO2 using solar-based processes: – gaseous hydrocarbons (CnH2n+2 with n < 6); methane as a key substance; all substances with n > 2 are easily liquefiable; – liquid hydrocarbons (CnH2n+2 with n > 5) such as alkanes but also oxygenated liquid compounds from C1 upward (e.g., methanol);

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– gaseous CO (the typical town gas in the past); and – elemental carbon (C in different modifications). Energy use is simply combustion in different burners and engines with, ideally, transformation back into CO2. Reaction enthalpies are different and thereby provide possible usable energy. CH4 + 2 O2 ! CO2 + 2 H2 O + 802 kJ mol −1   Cn H2n + 2 + ð3n + 1Þ=2 O2 ! n CO2 + ðn + 1Þ H2 O + 2, 214 kJ mol −1 for n = 3

(5:8) (5:9)

CH3 OH + 1.5 O2 ! CO2 + 2 H2 O + 727 kJ mol −1

(5:10)

CO + 0.5 O2 ! CO2 + 283 kJ mol −1

(5:11)

C + O2 ! CO2 + 393 kJ mol −1

(5:12a)

C + 0.5 O2 ! CO + 110 kJ mol −1

(5:12b)

Despite the lower energy yield, it is evident that hydrogen-free carbon carriers such as CO and C have the large advantage of consuming much less oxygen and producing only CO2, when considering oxyfuel technology in the future. That could be an important feature in establishing the carbon cycle and turning CO2 back into the feedstock for solar fuels. In the production of group one and group two compounds in the list above, some progress has already been made toward CO2 hydrogenation (reactions 5.13 and 5.14). Catalytic CO2 methanization is carried out at 160 °C and below 100 °C at pressures of 80 kPa (Abe et al. 2009). Reaction (5.13) has already been discovered by Paul Sabatier in the nineteenth century. CO2 + 4 H2 + 618 kJ mol −1 ! CH4 + 2 H2 O

(5:13)

CO2 + 3 H2 + 523 kJ mol −1 ! CH3 OH + H2 O

(5:14a)

CO + 2 H2 + 308 kJ mol −1 ! CH3 OH

(5:14b)

What must be considered in carrying out reactions (5.13) and (5.14) is the source of H2. It is clear that “traditional” reactions (water–gas shift and CH4 reforming) cannot be used and that H2 must be generated via water electrolysis using renewable energy sources such as solar radiation. Thus, the argument that it is preferable to use H2 directly as a fuel is inconsistent with our aim of carbon cycling. Moreover, carbon carriers provide a range of products that are better suited to the available infrastructure than H2. Overall, the photosynthesis-like reactions (5.15) and (5.16) are carried out. CO2 + 2 H2 O + solar energy ! CH3 OH + 1.5 O2

(5:15)

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n CO2 + n H2 O + solar energy ! ðCH2 OÞn + n O2

(5:16)

The formation of methanol from CO2 hydrogenation is known as the CAMERE process (Melián-Cabrera et al. 1998, Joo et al. 1999). In the past, a thermochemical heat pipe application was proposed (Edwards 1995), which is based on reaction (5.17a), where CO2/CH4 reforming (using solar energy) gives CO/H2 gas, which can be converted back (5.17b) in an exothermic reactor with an equivalent energy output. However, this technology needs an entirely new infrastructure. CH4 + CO2 + energy ! 2 CO + 2 H2

(5:17a; b)

The CO/H2 gas (also termed water–gas) – depending on the CO:H2 ratio – can also be converted (using the Fischer-Tropsch synthesis) to alkanes, alkenes, and alcohols. Preferably, substances should be generated for applications in known technical systems such as liquefied petroleum gas or low-pressure gas and gasoline as well as natural gas. The production of solar substitutes for diesels and oils (C > 8), that is, petrol products from the fractional distillation of crude oil between 200 °C and 350 °C, is also possible, but offers no advantages in the solar fuel cycle and its stepwise replacement by gases and gasoline should be foreseen. An interesting way of generating solar fuels can be seen in two “classical” inorganic carbon carriers: CO and carbon itself. The gasification of carbon (5.18a) produces CO (generator gas) in the so-called Boudouard equilibrium: C + CO2 + 172 kJ mol −1 ! 2 CO:

(5:18a; b)

The inverse reaction (5.18b) opens the way to finally convert CO2 to elemental carbon via reactions (5.13) and (5.17a). Alternatively, CO can be produced by the hightemperature electrolysis of CO2: CO2 + energy ! CO + 0.5 O2 :

(5:19)

where the overall reaction represents the inverse reaction (5.12a). High-temperature electrolysis using solid oxide electrolytic cells offers absolute new synthesis pathways. In contrast to reaction (5.19), the electrolysis of CO2/H2O leads to CO and CH4: CO2 + H2 O + energy ! CO + H2 + 1.5 O2 ;

(5:20)

CO2 + 2 H2 O + energy ! CH4 + 2 O2 :

(5:21)

For long-term space missions, these reactions were considered to provide a closed cycle of production of oxygen and consumption of respiratory CO2. A final pyrolysis reaction (5.22) recycles hydrogen, but more interesting for earth applications is the formation of elemental carbon according to the gross conversion process shown in eq. (5.23).

5.3 The energy problem: the last industrial revolution

CH4 + energy ! C + 2 H2

619

(5:22)

Reactions (5.19) and (5.21) provide the following overall reaction: CO2 + H2 O + energy ! C + 2 H2 + 2 O2 .

(5:23)

This set of reactions based on solid high-temperature electrolytic CO2 reduction shows that more advantages are likely at desert solar sites than the conversion processes in detail decisions will be ever made. The general budget is described by CO2 + H2 O + solar energy ! solar fuels ðC, CO, CH4 , H2 , O2 , etc.Þ,

(5:24)

independent of the detailed conversion processes. In inverse reaction (5.24), solar fuels reconvert into CO2 and H2O via the combustion or electricity in fuel cells and set the energy free, primarily as heat, for energetic use.

6 Final remarks With settlement, humans begun to produce local pollution that rose after industrialization to global air and marine pollution, which, together with land use change, lead to human health problems, modifying biogeochemical cycles, reducing biodiversity, and changing our climate. Although urban air pollution was recognized already in the Middle Age and culminated around 1900, global pollution was not realized before the 1960s. Pollution (soot plague) was visible and smellable, damages to vegetation noticeable, health effects to humans verifiable, and climate change now observable. Realizing these effects by the society finally resulted in significant reduction of air pollution (so-called greenhouse gases remain as a challenge) and large scientific achievements were made. Understanding the chemical composition (and finally its variations and changes) of the atmosphere was, is, and will be the aim of atmospheric chemistry. Needless to say that many other scientific disciplines evolved and linked together within earth system research. The great period of atmospheric chemistry begun after World War 2 and lasted until about the year 2000. Within this half century, 18 books on atmospheric chemistry (Table 6.1) appeared. In the century and a half before, 11 books appeared but not exactly on the science of atmospheric chemistry, more exactly on the gases in the atmosphere. After the year 2000, eight books appeared (until 2017), which is about the same per time then in the period before; note that the number of published proceedings and editorial works exceeds the monographs several times. The authors of the books, which appeared after 2000, are well-known atmospheric chemists, almost emeriti and senior scientists, that is, they spend most of their research before 2000. However, in the period 2000–2017, many new insights in atmospheric chemistry were achieved, excellently summarized in the report “The future of atmospheric chemistry research: remembering yesterday, understanding today, and anticipating tomorrow (2016)” published by many US scientists.616 All atmospheric chemists, being leading in the 1980s, are now retired and many schools (not only in Germany) no longer exist or were converted. However, science is never ending and after obtaining the fundamental insights and relationships in the second half of the twentieth century, current scientists are going deeper and deeper into details, for example, concerns aerosol particle chemistry and physics, interfacial chemistry, and feedbacks from chemistry to physical processes that determine global transportation, circulation, and hence our climate. Some of the younger generation of atmospheric chemists (Abbatt et al. 2013) emphasized the importance of the three-legged stool to be balanced in atmospheric chemistry: laboratory, ambient observations, and modeling studies to address the most pressing

616 Editor: National Academy of Science, Engineering, and Medicine. Committee Co-Chairs: Robert A. Duce and Barbara J. Finlayson-Pitts, 226 pp. https://doi.org/10.1515/9783110561340-006

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6 Final remarks

Tab. 6.1: Books (monographs and textbooks only, not edited books) on air composition and chemistry (not listed are books, written mainly on meteorological and physical aspects of air); note that all books published before 1960 are either on selected gases only or air composition but little or not on chemical processes in air. Only first edition given. Note the number of proceedings and editorial book in the field of atmospheric chemistry is several times larger. Year

Author(s)

 Joseph Priestley  Carl Wilhelm Scheele

 Robert Angus Smith  Cornelius Benjamin Fox  Arthur Petermann and Jean Graftiau

 Henry Henriet

 William Ramsay  Hans Blücher

 Francis Gano Benedict

 Arthur John Berry  Christian E. Junge

 Philipp A. Leighton  Christian E. Junge  Samuel S. Butcher and Robert J. Charlson

Biography Experiments and observations on different kinds of Air. W. Bowyer and J. Nichols, London (Vol. )a Chemische Abhandlung von der Luft und dem Feuer. Nebst einem Vorbericht von Torbern Bergman. Upsala & Leipzig Magn. Swederus,  pp. Air and rain – the beginning of a chemical climatology. Longmans, London,  pp. Ozone and antozone. Churchill, London,  pp. Recherches sur la composition de l´atmosphère. Acide carbonique, combinaisons azotèes contenues dans l´air atmosphèriquè. In: Mèmoires Courinnès et Autres Mèmoires publies part L´Academie Royale des Sciences, des Lettres et des Beaux-Arts de Belgique. Bd. XLVII, Brussels.  pp. Les gaz de L´atmosphère. Encylopedie Scientifique des Aide-Memoire, Guthier-Villars et Masson, Malicorne (France),  pp. The gases of the atmosphere. The history of their discovery. London, Macmillian and Co.,  pp. Die Luft. Ihre Zusammensetzung und Untersuchung, ihr Einfluss und ihre Wirkung sowie ihre technische Ausnutzung. Leipzig, Verlag Otto Wigand,  pp. The composition of the atmosphere with special references to its oxygen content. Carnegie Institution, Washington,  pp. The atmosphere. Cambridge Univ. Press,  pp. Atmospheric chemistry. In: Advances in geophysics. Vol. IV, Acad. Press. New York, (separate volume),  pp. Photochemistry of air pollution. Academic Press, New York,  pp. Air chemistry and radioactivity. Academic Press, New York,  pp. An introduction to air chemistry. Academic Press, New York,  pp.

6 Final remarks

623

Tab. 6.1 (continued) Year

Author(s)

 Julian Heicklen  John D. Butler  Ernö Mészáros  Валерий Алексеевич Исидоров  John H. Seinfeld  Barbara J. Finlayson-Pitts and James N. Pitts  Peter Warneck  Thomas Graedel and Paul Crutzen  Peter V. Hobbs  Peter Brimblecombe  John H. Seinfeld and Spyros N. Pandis

 Richard E. Goody  Guido Visconti  Галина Вячеславовна Сурковаc  Detlev Möller  Jacob G. Calvert, Richard G. Derwent, John J. Orlando, Timothy J. Wallington  Detlev Möller  Jack G. Calvert, John J. Orlando, William R. Stockwell, Timothy J. Wallington  Hajime Akimoto

Biography Atmospheric chemistry. Academic Press, New York,  pp. Air pollution chemistry. Academic Press, New York,  pp. Atmospheric chemistry. Fundamental aspects. Akadémiai Kiadó, Budapest,  pp. Органическая химия атмосферыb, СанктПетербург, Химиздат,  pp. Atmospheric chemistry and physics of air pollution. John Wiley & Sons, New York,  pp. Atmospheric chemistry: Fundamentals and experimental techniques. John Wiley & Sons, New York,  pp. Chemistry of the natural atmosphere. Academic Press, San Diego,  pp. (nd ed. , pp. ) Atmospheric change: An earth system perspective. W. H. Freeman, New York,  pp. Basic physical chemistry for the atmospheric sciences. Cambridge University Press,  pp. Air composition and chemistry. Cambridge University Press,  pp. Atmospheric chemistry and physics – from air pollution to climate change. John Wiley & Sons, New York,  pp. Principles of atmospheric physics and chemistry. Oxford. Univ. press.,  pp. Fundamentals of Physics and Chemistry of the Atmosphere. Springer,  pp. химия атмосферы, Издательство Московского университета,  pp. Luft: Chemie, Physik, Biologie, Reinhaltung, Recht. DyGruyter, Berlin,  pp. Mechanisms of atmospheric oxidation of the alkanes. Oxford Acad. Press.,  pp. Chemistry of the climate system. DyGruyter, Berlin,  pp. The mechanisms of reactions influencing atmospheric ozone. Oxford Uni. Press.,  pp. Atmospheric reaction chemistry. Springer,  pp.

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Tab. 6.1 (continued) Year

Author(s)

 Grant A. D. Ritchie

 Guy P. Brasseur and Daniel J. Jacob

Biography Atmospheric chemistry: From the surface to the stratosphere. Essential Textbook in Chemistry,  pp. Modeling of atmospheric chemistry. Cambridge Univ. Press.,  pp.

a

It is a six-volume work (1774–1786) in different editions. First printing: Observations on different kinds of air. In: Philosophical Transactions, Vol. 62, 1772, pp. 147–264. b English edition: Valerii Aleksandrovitsch Isidorov (1990) Organic chemistry of the Earth’ atmosphere. Springer, Berlin, 215 pp. Third Russian edition 2001, 352 pp. c Galina Vjatscheslavovna Surkova (textbook for students).

issues of our time. They further state that each leg of the stool is only as stable as the fundamental chemistry that underpins it is further studied. Unfortunately, that “fundamental chemistry” (studying properties and reactivity’s of molecules) is weakening in last 15 years. On the other hand, the three-legged stool (naturally not “tipping”) is rose to misbalancing due to more and more modeling studies relative to experimental work (theoria cum praxi drift apart). The reason is clear, because “fundamental research” needs much more funding than modeling studies. I agree with Abbat et al. (2013) that atmospheric chemistry (now to avoid the adjective “fundamental”) is increasingly focused on much more complex chemical systems. That is the answer to my question (academically) asked at this point in the first edition almost a decade ago: but why write 600 pages on climate chemistry? At this point, the reader might come to the conclusion that this book is in the long line with other books on atmospheric chemistry (Table 6.1). A total of 90% of this book deals with air chemistry, but the atmosphere represents 90% of the climate system. However, it is certainly not my aim to add another book belonging to Finlayson-Pitts and Pitts and Seinfeld and Pandis. Barbara Finlayson-Pitts is a great experimentalist and John Seinfeld a great theoretic chemist. Nonetheless, both combine theoria cum praxi. We do not need more than two columns, flanking the entrance into the science of air chemistry, namely, experiment (practice) and model (theory). If my book contributes something to atmospheric chemistry, which legitimates its publication in line with those books published before in this field, then it is the presentation of deeper insights into atmospheric aqueous and interfacial chemistry. It was my aim that the reader should understand that chemistry takes place in our climate system (or simply said our environment) simultaneously in all phases, namely, state of matter (aqueous, gaseous, and solid), and reservoirs, namely, sphere (atmosphere, hydrosphere, lithosphere, biospheres): this is climate system chemistry.

6 Final remarks

625

Tom Graedel and Paul Crutzen, if they could rewrite those books (Graedel and Crutzen 1993, 1995), would possibly rename them in global chemistry and earth chemistry. In this line down (global system → earth system → climate system) is climate chemistry. This is parallel to climate physics and both are the fundamentals of the very observational physical and chemical climatology. At the beginning of this book, we emphasized that it makes no sense to draw strong borderlines between the disciplines and this is valid too for the systems because they overlap and the most important processes likely occur at their interfaces. Therefore, chemistry of the climate system comprises atmospheric with water, soil, and biological chemistry. At the end, however, it is chemistry solely. Now, with the third edition, nearly 300 pages of the history of atmospheric chemistry is published, to my knowledge for the first time in these comprehensive form. I have mentioned it in the preface that it is not written from the point of a historian but from an atmospheric chemist who, already for many years, paid much attention and respect to our ancestors. If some of this history rubs off on others and eventually will help to justify own research, this new edition has also made sense. Furthermore, research on our climate system and climate change will not end while climate change now proceeds with increasing rate. At present, on the other side, we considerably understand our climate system to conclude that further “business-as-usual” brings us to different “tipping points” with social feedbacks out of economic rationality. However, there is no “tipping point” in climate change. The term “abrupt climate change” describes changes in climate that occur over the span of years to decades, compared to the human-caused changes in climate that are occurring over the time span of decades to centuries. I doubt that there is a climate change in less than a decade that affects people. Climate change is catastrophe in slow motion and many people do not know what it really amounts to, either due to unreliable sources or deliberate misinformation. So, why decisions makers are unable to draw the right decisions? The answer may be simple because of the “Renish Basic Law” (here in German): Es kommt wie es kommt – es ist noch immer gut gegangen [whatever will be, will be – so far, everything has always gone well in the end]. But this erroneous belief neglects the evolution of our climate system. In the final remark, the idea of global carbon dioxide cycling (fuels from atmospheric CO2 for further use of mobile combustion engines and small consumers) I have developed more than 10 years ago (Möller 2009c, 2011c, 2012). The DESERTEC conception died, the carbon capture and storage (CCS) died, the auto industry produces big and senseless cars (SUVs), the global confrontation increases, the global military expenditure ($1739 billion in 2017) not fell (likely a one-year budget would be sufficient for realization the global solar “energiewende” and the SONNE conception), the policy is without sustainable conception (e-mobility concerns private cars seems to me not sustainable) – I have rather pessimistic concerns about the future of my descendants. One thing that makes it possible to be an optimist, is the current

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children “Fridays for Future” climate demos “to save planet” – they do not know what is to do but that do know scientists and engineers; will get politicians the will?

Conclusions And finally I would present a few conclusions and recommendations that result from my work. – Substantial reduction of the number of routine measurement sites and favour a few selected long-term monitoring stations based on scientific approach and using sophisticated methods to document change in atmospheric chemistry, including substances such as H2O2, HNO2, HNO3, NH3, HCl and other (in gas, particulate and aqueous phase as well). – Better understanding and quantification of natural emissions, namely halogen compounds from ocean and their impact on tropospheric marine chemistry and the stratosphere. – Research on SOA formation from natural VOC to improve the PM budget, namely that of CCN; better understanding of CCN sources and budgets depending from regions and seasons. – Improvement of our knowledge on primary versus secondary sources of climate relevant substances. – To pay attention to future “alkaline rain” due to further decreasing acid precursors (SO2 and NOx) but likely unchanging or also increasing NH3. – Re-assessment of human health impacts from air pollution in view of complex factors affecting health. – Studying historic research before establishing new research programs. – Understanding that the “CO2 economy” (use of carbon as material and energy carrier from the atmosphere) based on solar energy is the only way to receive a sustainable society. – Paradigm change into zero carbon budget world (not zero emission). – Not the energy efficiency but the cycling of matter (zero matter budget) is the target in a sustainable economy based on solar energy.

Appendix I List of acronyms and abbreviations found in literature a.s.l. ABL ACC AD ASTM ATP BC BC BECS BGV BP Btu CCC CCN CCS CCU CDIAC CET CFCs CSP CTM DIC DM DMDS DMS DMSO DNA DOC DU EDGAR EF EJ EMEP ENSO EPA EU FAO FGD GAW

above sea level atmospheric boundary layer abrupt climate change anno domini (year after 0 of the Gregorian calendar) American Society for Testing and Materials (standard) adenosine triphosphate before Christ (year before 0 of the Gregorian calendar) black carbon (= soot) bio-energy with carbon storage Borde–Guth–Vilenkin theorem British Petro British thermal unit carbon capture and cycling cloud condensation nuclei carbon capture and storage (or sequestration) carbon capture and utilization carbon dioxide information and analysis center central European time chlorofluorocarbons (contain carbon and some combination of fluorine and chlorine atoms) concentrating solar thermal power (plant) chemisty-transport models dissolved inorganic carbon dry mass or dry matter dimethyl disulfide dimethyl sulfide dimethyl sulfoxide deoxyribonucleic acid dissolved organic carbon Dobson unit (total ozone column-concentration) emission database for global atmospheric research emission factor etajoule (1018 J) co-operative program for monitoring and evaluation of the long range transmission of air pollutants in Europe el Niño southern oscillation Environmental Protection Agency USA European Union Food and Agriculture Organization of the United Nations flue-gas desulfurization (plant) global atmospheric watch (WMO monitoring program)

Note: Often the plural is formed by adding “s,” for example: PSCs – polar stratospheric clouds. https://doi.org/10.1515/9783110561340-007

628

GCM GC-MS GCP GDR GEIA GEP GHG GPCP GPP Gt GW GWh Gyr HALE HBFCs HCFCs HFCs IGAC IGBP IPCC ITCZ kJ LE LEB LHB LMH LWC MEA MEGAN MOPITT MSA MSL Mt MW Myr NADP+ NADPH NASA NEO NEP NH NMVOC NOAA NOx NOy NOz NPP nss

Appendix I List of acronyms and abbreviations found in literature

general circulation model gas chromatography–mass spectrometry global carbon project German Democratic Republic (former East Germany) global emission inventory activity (within IGAC) gross ecosystem production greenhouse gases global precipitation climatology project gross primary production gigaton (109 tons) gigawatt (109 W) gigawatthours (109 Wh) gigayears (109 yr) healthy life expectancy hydrobromofluorocarbons hydrochlorofluorocarbons hydrofluorocarbons international global atmospheric chemistry (project within IGBP) international geosphere-biosphere program intergovernmental panel on climate change inter-tropical convergence zone kilojoule (103 J) life expectancy life expectancy at birth late heavy bombardment large molecule Heimat liquid water content monoethanolamine model of emissions of gases and aerosols from nature measurement of pollution in the troposphere methansulfonic acid marine sea level megaton (1012 g) megawatt (106 W) megayears (106 yr) nicotinamide adenine dinucleotide phosphate reduced NADP+ National Aeronautics and Space Administration (USA) NASA Earth Observations net ecosystem production Northern Hemisphere nonmethane volatile organic carbon National Oceanic and Atmospheric Administration, USA = NO + NO2 = NO + NO2 + N2O3 + N2O4 + HNO2 + HNO3 + NO3 + N2O5 + HNO4 + organic NOx + particulate NO2– and NO3– = NOy – NOx net primary production non-sea salt

Appendix I List of acronyms and abbreviations found in literature

NW OC ODP ODS OM OVOC PAR PBL Pg PM PM1 PM10 PM2.5 POP ppb ppm QA/QC QBO R REE RETRO RH RNA RNH2 ROS RSH SANA SCR SH SOA SONNE SPM SSA SSA STE SW TC TCM TFC Tg TIC toe TPES TPM TSP TW UBA UV

northwest organic carbon ozone depletion potential ozone depleting substance organic matter oxygenated volatile organic compound photosynthetically active radiation planetary boundary layer picogram (1015 g) particulate matter particulate matter with aerodynamic particle diameter ≤ 1 µm particulate matter with aerodynamic particle diameter ≤ 10 µm particulate matter with aerodynamic particle diameter ≤ 2.5 µm persistent organic pollutant part per billion (10–9) part per million (10–6) quality assurance and quality control quasi-biennal oscillation organic carbon radical rare earth element REanalysis of the TROposhperic chemical composition (emission inventory) hydrocarbon (= VOC) ribonucleic acid organic amines reactive oxygen species organic sulfides German research program on air pollution (1991–1995) selective catalytic reduction Southern Hemisphere secondary organic aerosol SOlar-based maN-made carboN cyclE suspended particulate matter (= dust, atmospheric aerosol) stratospheric sulfate aerosol sea salt aerosol stratosphere–troposphere exchange southwest total carbon (sum of organic and inorganic) tetrachloromercurate (SO2 measurement method) total final energy consumption terragram (1012 g) total ionic content ton of oil equivalent total primary energy supply total particulate matter total suspended matter (= PM) terawatt (109 W) Umweltbundesamt (Environmental Federal Agency, Germany) ultraviolet

629

630

VOC WEDD WHO WMO WSOC

Appendix I List of acronyms and abbreviations found in literature

volatile organic compound wet effluent diffusion denuder system World Health Organization of the United Nations World Meteorological Organization of the United Nations water-soluble organic compounds

Appendix II Quantities, units and some useful numerical values The SI (abbreviated from the French Le Système International d’Unités), the modern metric system of measurement, was developed in 1960 from the old meter-kilogram -second (mks) system, rather than the centimeter-gram-second (cgs) system, which, in turn, had a few variants. Because the SI is not static, units are created and definitions are modified through international agreement among many nations as the technology of measurement progresses, and as the precision of measurements improve. Long the language universally used in science, the SI has become the dominant language of international commerce and trade. The system is nearly universally employed, and most countries do not even maintain official definitions of any other units. A notable exception is the United States, which continues to use customary units in addition to SI. In the United Kingdom, conversion to metric units is government policy, but the transition is not quite complete. Those countries that still recognize non-SI units (e.g., the US and UK) have redefined their traditional non-SI units in SI units. It is important to distinguish between the definition of a unit and its realization. The definition of each base unit of the SI is carefully drawn up so that it is unique and provides a sound theoretical basis upon which the most accurate and reproducible measurements can be made. The realization of the definition of a unit is the procedure by which the definition may be used to establish the value and associated uncertainty of a quantity of the same kind as the unit.

Some useful definitions A quantity in the general sense is a property ascribed to phenomena, bodies, or substances that can be quantified for, or assigned to, a particular phenomenon, body, or substance. Examples are mass and electric charge. A quantity in the particular sense is a quantifiable or assignable property ascribed to a particular phenomenon, body, or substance. Examples are the mass of the moon and the electric charge of the proton. A physical quantity is a quantity that can be used in the mathematical equations of science and technology. A unit is a particular physical quantity, defined and adopted by convention, with which other particular quantities of the same kind are compared to express their value.

https://doi.org/10.1515/9783110561340-008

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Appendix II Quantities, units and some useful numerical values

The value of a physical quantity is the quantitative expression of a particular physical quantity as the product of a number and a unit, the number being its numerical value. Thus, the numerical value of a particular physical quantity depends on the unit in which it is expressed (Table A.1). Tab. A.1: The seven basic units of SI. quantity

name of unit

symbol

length mass time thermodynamic temperature amount of substance electric current luminous intensity

meter kilogram second kelvin mole ampere candela

m kg s K mol A cd

Other quantities, termed derived quantities, are defined in terms of the seven base quantities via a system of quantity equations. The SI-derived units for these derived quantities are obtained from these equations and the seven SI base units. Examples of these SI-derived units are given in Table A.2, where it should be noted that the symbol 1 for quantities of dimension 1 such as mass fraction is generally omitted (Tables A.3–A.5). Tab. A.2: Derived units (examples only; the list can be continued, e.g., for electric and magnetic quantities). quantity

name of unit

symbol

special definition

definition from SI

force pressure energy, work, quantity of heat power, radiant flux mass density dynamic viscosity moment of force surface tension heat flux density, irradiance frequency wave number area volume speed, velocity acceleration

newton pascal joule watt – – – – – hertz – – – – –

N Pa J W – – – – – Hz – – – – –

– N m– Nm J s– – Pa s Nm N m– W m– – – – – – –

kg m s– kg m– s– kg m s– kg m s– kg m– kg m– s– kg m s– kg s– kg s– s– m– m m m s– m s–

Appendix II

Quantities, units and some useful numerical values

633

Tab. A.3: Units outside the SI that are accepted for use with the SI. quantity

symbol

value in SI units

minute (time) hour day degree (angle) minute (angle) second (angle) liter metric tonb electronvoltc nautical mile knot hectare bar ångström curie roentgen rad rem

min h d ° ´ ´´ La t eV – – ha bar Å Ci R rad rem

 min =  s  h =  min = , s  d =  h = , s ° = (π/) rad ´ = (/)° = (π/,) rad ´´ = (/)’ = (π/,) rad  L =  dm = – m  t =  kg  eV = .·– J  nautical mile = , m  nautical mile per hour = (,/,) m s–  ha =  hm =  m  bar = . MPa =  kPa = , hPa =  Pa  Å = . nm = – m  Ci = .· Bq  R = .·– C kg–  rad =  cGy = – Gy  rem =  cSv = – Sv

a

This unit and its symbol l were adopted by the CIPM in 1879. The alternative symbol for the liter, L, was adopted by the CGPM in 1979 to avoid the risk of confusion between the letter l and the number 1. Thus, although both l and L are internationally accepted symbols for the liter, to avoid this risk the preferred symbol for use in the United States is L. b In many countries, this unit is termed “tonne”. c The electron volt is the kinetic energy acquired by an electron passing through a potential difference of 1 V in vacuum. The value must be obtained by experiment, and is therefore not known exactly.

Tab. A.4: Prefixes used to construct decimal multiples of units (SI). Y z E P T G M k h da d c

yotta zetta eta peta tera giga mega kilo hecto deca deci centi

          − −

634

Appendix II Quantities, units and some useful numerical values

Tab. A.4 (continued ) m µ n p f a z y

− − − − − − − −

milli micro nano pico femto atto zepto yocto

Tab. A.5: Some useful numerical values. name Boltzmann constant Avogadro constant Loschmidt constant gas constant Planck constant Stefan-Boltzmann constant Faraday constant elementary charge gravitational constant standard gravity speed of light a

symbol k NA no R h σ F e G g c

value

definition –

−

.· JK .· mol− .· m− . J K– mol− .·– J s− .·– J m− K− s− , C mol− .·− C .·– m kg− s− . m s− .· m s−

k = R/NA a b

R = k NA c

σ = πk/hc F = e NA d

G = f·r/mm e g = G·mearth/rearth f

Number of atoms in 0.012 kg 12C. Number of atoms/molecules of an ideal gas in 1 m–3 at 0 °C and 1 atm. c Planck-Einstein relation: E = hν. d Fundamental constant, equal to the charge of a proton and used as atomic unit of charge. e Empirical constant (also termed Newton’s constant) gravitational attraction (force f) between objects with mass m1 and m2 and distance r. f Nominal acceleration due to gravity at the earth surface at sea level. b

Appendix III Earth geological time scale eon

era

period

epoch Anthropocene

Cenozoic

Phanerozoic

Proterozoic

Archean

time ago (Myr) .

Neocene

Holocene Pleistocene Pliocene Miocene

. . . .

Paleocene

Oligocene Eocene Paleocene

. . .

Mesozoic

Cretaceous Jurassic Triassic

.  

Paleozoic

Permian Carboniferous Devonian Silurian Ordovician Cambrian

     

Neoproterozoic

Ediacaran Cryogenian Tonian

  ,

Mesoproterozoic

Stenian Ectasian Calymnian

, , ,

Paleoproterozoic

Statherian Orocirian Rhyacian Siderian

, , , ,

Neoarchean Mesoarchean Paleoarchean Eoarchean

Hadean

https://doi.org/10.1515/9783110561340-009

, , , , ,

636

Appendix III Earth geological time scale

The Geological Time Scale is hierarchical, consisting of (from smallest to largest units) ages, epochs, periods, eras, and eons. Each era, lasting many tens or hundreds of millions of years, is characterized by completely different conditions and unique ecosystems. Eras are divided into periods, which are divided into epochs, which in turn are divided into ages. The Geological Time Scale is followed as determined by the International Commission on Stratigraphy (ICS). The ICS has not finished its job and gaps remain, particularly in the Early Paleozoic. Where gaps occur, it is generally followed the Russian system for the Cambrian and the British system for the Silurian. Epochs are further subdivided into ages not listed here. The periods from Cretaceons and older subdivided into epochs and ages are not shown here.

References Comments to historical journal titles In the following list of references, the complete title of the Journal is given; however, normally abbreviations are used, which are not consistent in literature, dependent from the journal´s policy but also from the author. You can found many “lists” concerns abbreviations in the internet, also not consistent or incomplete. Publications, being originally in Cyrillic (from Russia and Soviet Union), are given in Latin-alphabet transliterations, which is also not consistent in literature; hence, the original Cyrillic spelling is additional given for names, journals and titles. In the Soviet Union, scientific results mostly have been published by the institute in Труды (+ name of the institute) [Trudy = Transactions]. In historical publications before 1900, citations are almost incomplete or even missing (often only the name of the person is mentioned). It is interesting that often no given name is printed but M. (monsieur) in French and H. or Hr. (Herr) in German is set before the family name. In France, almost all publications in the field of atmospheric research in the 19th century have been published in C. r., Compt. Rend. or Compte Rendu (Comptes rendus de l’Académie des sciences), complete title: Comptes rendus hebdomadaires des séances de l’Académie des sciences (1835–1965), edited from the French Academy of Sciences. The oldest chemical journal in France is Annales de Chimie, founded by Morveau, Lavoisier and others in 1789; the title of this journal changed: Annales de chimie ou recueil de mémoires concernant la chimie et les arts qui en dépendent (1789–1814), Annales de chimie et de physique (1815–1914), abbreviated as Ann. Chim. Phys. A third French journal is important in our field of research: Journal de Pharmacie et de Chimie (1842–1942), abbreviated as J. Pharm. Chim. that appeared in 9 series: sér. 1 Vol. 1–6 (1809–1814), sér. 2 Vol. 1–27 (1814–1841), sér. 3 Vol. 1–46 (1842–1864), sér. 4 Vol. 1–30 (1865–1879), and further in each 30 volumes over each 10 years from series 5–8 (1880–1939). In Germany, the following five journals were the most important in the field of atmospheric research in the 19th century (see following for details): – Annalen der Physik (Pogg. Ann., Wied. Ann., Ann. Phys.) 1795–1943 – Journal für Chemie und Physik (1798–1833) and Journal für praktische Chemie (J. pr. Chem.) 1834–2000 – Archiv der Pharmacie (Ar.) 1822 until present – Annalen der Chemie (Liebigs Ann.) 1832–1997 – Berichte der Deutschen Chemischen Gesellschaft (B.) 1868–1997

https://doi.org/10.1515/9783110561340-010

638

References

One of the most prestigious journals was Annalen der Physik, founded 1795 by Friedrich Albrecht Carl Gren, continued 1799–1824 by Ludwig Wilhelm Gilbert, 1824–1877 by Johann Christian Poggendorff, 1877–1899 by Gustav Heinrich Wiedemann, and 1899–1943 by Wilhelm Wien, Max Planck and Eduard Grüneisen, all together in 435 volumes. The title of this journal changed and different citations are in use: Journal der Physik, Vol. 1–8 (1795–1794), (Grens) Neues Journal der Physik, Vol. 1–4 (1795–1797), Annalen der Physik, Vol. 5–30 (1799–1809), Annalen der Physik, Neue Folge (Vol. 1–30), Vol. 31–60 der ganzen Folge [of the complete series] (1809–1818), Annalen der Physik, Neueste Folge (Vol. 1–16) = Annalen der Physik und physikalischen Chemie (Vol. 61–76 der ganzen Folge [of the complete series] (1819– 1824), 1799–1824 also called Gilberts Annalen (Gilb. Ann.), Annalen der Physik und Chemie (Vol. 1–60), Vol. 77–236 der ganzen Folge [of the complete series] (1824–1877), 1824–1877 also called Poggendorffs Annalen (Pogg. Ann.), Annalen der Physik und Chemie = Annalen der Physik, Vierte Folge (Vol. 1–69), Vol. 237–305 der ganzen Folge [of the complete series] (1877–1899), also called Wiedemanns Annalen (Wied. Ann.), Annalen der Physik, Vierte Folge (Vol. 1–87), Vol. 306–392 der ganzen Folge [of the complete series] (1900–1928), Annalen der Physik, Fünfte Folge (Vol. 1–42), Vol. 393–435 der ganzen Folge [of the complete series] (1929–1943). Another important German Journal is the Journal für Chemie und Physik that appeared with different titles, founded 1798 by Alexander Nicolas Scherer, 1803–1810 continued by Adolph Ferdinand Gehlen and 1811–1833 by Johann Salomo Christoph Schweigger; succeeded in 1834 by Journal für praktische Chemie: Allgemeines Journal für Chemie (Scherers Journal) in 10 Vol. (1798–1803), Neues allgemeines Journal der Chemie, Vol. 1–6 (1803–1806), Journal für die Chemie und Physik, Vol. 1–3 (1806–1807), Journal für die Chemie, Physik und Mineralogie, Vol. 4–9 (1907–1810), also called Gehlens Journal, Beiträge zur Chemie und Physik, Vol. 1–9 (1811–1813), Journal für Chemie und Physik, Vol. 10–30 (1814–1820), Journal für Chemie und Physik, Vol. 31–60 = Jahrbuch der Chemie und Physik, Vol. 1–30 (1821–1830), and Neues Journal für Chemie und Physik, Vol. 61–69 = Neues Jahrbuch der Chemie und Physik, Vol. 1–8 (1830–1833), all also called Schweiggers Journal.

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The Journal für praktische Chemie (J. prakt. Chem.) was 1828 founded by Otto Linné Erdmann as Journal für technische und ökonomische Chemie and 1834 renamed in Journal für praktische Chemie (1834–1869 in 108 Vol.), from 1870–1943 (163 Vol.) as Neue Folge continued. The Archiv der Pharmacie was founded in 1922 by Rudolph Brandes and appeared also under different names to the present: Archiv des Apothervereins im nördlichen Teutschland, Vol. 1–10 (1822–1824), Archiv des Apother-Vereins im nördlichen Teutschland für Pharmacie und ihre Hülfswissenschaften, Vol. 11–39 (1825–1834), Archiv des Apother-Vereins im nördlichen Teutschland (als Beilage zu Annalen der Pharmacie des Justis Liebig), Vol. 40–51 (1835–1838), Zweite Reihe Vol. 1 Archiv der Pharmacie, eine Zeitschrift des Apother-Vereins in Norddeutschland, Vol. 68–114 (1839–1850), Archiv der Pharmacie. Eine Zeitschrift des allgemeinen deutschen ApotherVereins, Abtheilung Norddeutschland, Vol. 115–200 (1851–1872), Zweite Reihe Vol. 65, Archiv der Pharmacie, Vol. 201–261 (1872–1923), Dritte Reihe Vol. 1. And finally an important journal concerns contributions on atmospheric composition is Annalen der Chemie, founded as Annalen der Pharmacie in 1832 by Rudolph Brandes and continued by Justus von Liebig; from Vol. 11 (1834) combined with Trommsdorffs Neuem Journal der Pharmacie: Annalen der Pharmacie (1832–1839) Vol. 1–32, Annalen der Chemie und Pharmacie (1840–1872) Vol. 33–164, Justus Liebig’s Annalen der Chemie und Pharmacie (1873–11874) Vol. 165–174, Justus Liebig’s Annalen der Chemie (1875–1944) Vol. 175–556. Finally, the most important source of chemical knowledge and likely the world’s most important journal in chemistry in the 19th century is Berichte der Deutschen Chemischen Gesellschaft (1868–1919), abbreviated often as B. or Ber.

Other German abbreviations Ann. Abh. Ber. ges. Nachr. Z.

Annales / Annalen Abhandlungen [Transactions] Berichte [Proceedings] gesamte [total] Nachrichten [News] Zeitschrift [Journal]

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Name Index Achard, Franz Carl 94 Acker, Karin 158, 248, 250, 256, 257, 413, 416, 439–440, 453, 533, 536, 543, 552, 553, 555, 561 Adelung, Johann Christoph 69–71 Adet, Pierre August 29 Adhémar, Joseph 289 Agricola, Georg 21, 323 Aitken, John 58, 60, 61, 65, 81, 241, 262, 263, 276, 278 Akimoto, Hajime 481, 624 Akimoto, Minoru 223 al-Bīrūnī, Aḥmad 50 al-Hikma, Kitab Mizan 50 al-Idrisi 267 al-Khazini, Abd al-Rahman 50 Anastasio, Cort 251 Anaxagoras 48, 49 Anaximander 17, 18, 47 Anaximenes 17, 18, 47, 48 Anderson, Valentine George 153, 197, 208, 209, 237 Andreae, Meinrath XII, 404, 407, 409 Andrews, Thomas 118, 119, 121 Aneja, Viney 247, 251 Ångström, Anders Knutsson 230, 290 ApSimon, Helen 250 Aquinas, Thomas von 51 Arago, François 118, 265 Archenhold, Friedrich Simon 66 Archimedes 49 Aristotle 4, 18, 19, 24, 42, 46–52, 57, 65, 66, 81, 142, 150, 152, 164, 257, 282, 330 Armstrong, George Frederick 106, 108 Arrhenius, Svante August 25 Aßmann, Richard 62, 65, 278, 438 Auel, Renate 425, 456 Aufray, Maurice 201, 204, 226, 237 Ayers, Greg XIII Babo, Lambert Heinrich von 119, 129 Bach, Alexei Nikolajewitsch 133 Balard, Antoine Jérôme 79 Bamber, Montague Kelway 196, 200, 203, 225, 237 Barnes, Charles 141 Barral, Jean-Augustin 153, 182, 189, 209, 210 https://doi.org/10.1515/9783110561340-011

Barrie, Len XIII Bauer, Karl Hugo 15, 27 Baumann, Anton 106 Baumhauer, Eduard Henrich von 183 Baur, Emil 134, 216 Becher, Johann Joachim 23, 87 Bechi, Emilio 200, 225 Becker, Karl-Heinz XII Becquerel, Antoine Henri 26 Beddoes, Thomas 175 Beethoven, Ludwig van 45 Bellmann, Klaus 414 Bellucci, Giuseppe 193, 225 Benedict, Francis 96, 97, 99, 100, 106, 107 Berger 61 Bergerac, Savinien Cyrano de 160 Bergman, Torbern Olof 173 Berljand, Mark Evseevič XII Berner, Axel XIII Bernhardt, Karl-Heinz XIII Bernstein, Basil X Bernoulli, Daniel 60 Bertels 153, 180, 181, 183, 224 Berthelot, Marcellin 26, 27, 131, 323, 361 Berthollet, Claude Louis 25 Berthollet, Marcellin 131 Bertrand, Gabriel Emile 218 Berzelius, Jöns Jakob 25, 29–31, 85, 86, 151, 175, 176, 191 Bezold, Wilhelm von 284 Binek, Bedřich X Bineau, Armand 112, 183, 189, 190, 199 Black, Joseph 12, 24, 83 Blagden, Charles 89 Blake, Robert Frederick 100–102 Blake, William Phipps 265 Blasius, Ewald 8 Blochmann, Georg Rudolf Reinhart 99, 100, 101, 105 Blücher, Hans 63, 110, 148, 622 Bobierre, Pierre Adolphe 190, 191 Boehm, Joseph Georg 12 2, 126 Boerhave, Herman 163 Bohlig, Franz Josef Dominicus 180, 209, 224 Bohr, Niels 26 Bolin, Bert 11, 148, 599 Borch, Ole. See Borrichius

748

Name Index

Borde, Arvind 293 Borovnikov, Alexander Moiseevich 242, 252 Borrichius, Olaus 17, 28, 167 Bottini, Ottaviano 153, 219 Bouguer, Pierre 61 Boussingault, Jean-Baptiste 264, 490 Boyle, Robert 12, 15, 37, 50, 52, 69, 71–73, 109, 239, 252, 258, 260 Bozo, László XII Brandes, Heinrich Wilhelm 57 Brandes, Simon Rudolph 177, 178, 209 Bretschneider, Paul 192, 199, 225 Brimblecombe, Peter 41, 43, 193, 195, 255, 272, 315, 325, 480, 504–506, 623 Broda, Engelbert 147 Brøgger, Waldemar Christofer 214, 265 Broglie, Louis-Victor Pierre Raymond de 26 Brown, Alexander Crum 119 Browne, Sir Thomas 167 Brown, Samuel 584 Brüggemann, Erika 456 Brugmans, Sebald Justinus 239, 240 Brünnich, Johannes Christian 201, 204, 206, 226 Bücher, Ludwig 145 Buchner, Johann Andreas 6, 8, 145 Builtjes, Peter XIII Bullister, John 529 Bunsen, Robert Wilhelm 25, 97, 98, 186, 191 Burkser, Evgenij Samojlovitsch 9, 10, 220 Butterfield, Herbert 41 Butte, Wilhelm 282, 283 Callendar, Guy Stewart 107, 108, 292, 515, 518 Calvin, Melvin 140, 141 Cantimpré, Thomas von 36 Carmody, Patrick 204, 226, 237 Carus, Titus Lucretius 257 Casali, Adolfo 198 Castelli, Benedetto 53 Castillo, Raymond A. 246, 247, 252 Cauer, Hans 9, 11, 222, 229, 232, 278, 426 Cavallo, Tiberius 95 Cavendish, Henry 13, 24, 59, 80, 82, 83–86, 88–91, 93, 95–97, 109, 138, 176 Chadwick, Edwin 92 Chalmer, Lionel 194, 584 Chamberlain, Thomas Chrowder 320 Chaptal, Jean-Antoine 85

Chardin, Pierre Teilhard de 354 Charlson, Robert 356, 622 Chatin, Gaspard Adolphe 182 Chaumerliac, Nadine XIII Chevallier, Jean-Baptiste-Alphonse 110, 113 Chladni, Ernst Florens Friedrich 164, 165 Chodat, Robert Hippolyte 133 Choularton, Tom 251 Churchill, Winston X Church, Sir Arthur Herbert 219 Clapham, Arthur Roy 353 Clarke, Frank Wigglesworth 319 Clausius, Rudolf Julius 60, 119 Cohen, Julius Berend 65, 238, 273–276, 508 Collett, Jeff 247, 251 Conrad, Viktor 64, 66 Conring, Hermann 167 Cossa, Alfonso 136, 187, 193, 225 Cotta, Heinrich 423 Coulier, Paul-Jean 60, 61 Coxe, John Redman 74, 78 Cox, Tony XIII Croll, James 289 Crosland, Maurice P. 27, 29, 85 Crowther, Charles 201, 207 Cruickshank, William 117 Crusius, Heinrich Wilhelm Leberecht 185 Crutzen, Paul 1, 3, 10, 125, 342, 355, 409, 489, 491, 496, 497, 625, 635 Cunningham, Robert M. 241 Curie, Marie Skłodowska 26, 134 Dachauer, Gustav 126 Dafert, Franz Wilhelm 187 Dallowe, Timothy 22 Dalton, John 25, 29, 30, 60, 84, 97, 177, 224 Damrath, Ulrich XIII D’Arcet, Jean Pierre Joseph 113 Darwin, Charles 4, 259, 265, 266, 351, 356 Däßler, Hans-Günther 272, 423 Daum, Peter H. 248, 252 Davy, Sir Humphry 25, 79, 109 Delmas, Robert 367, 484, 495, 515 Deluc, Jean-André (also De Lüc or De Luc) 65, 88, 89, 438 Democritus 578 Denison, Sir William 194 Descartes, René 54, 55, 65, 66 Des Voeux, Harold Antoine 276

Name Index

Dhar, Nil Ratan 216 Dianwu, Zhao XII Dickson, Henry Newton 287, 601 Dietze, Gerhard 426 Digby, Sir Kenelme 167 Dines, William Henry 64 Dittmar, Wilhelm (William) 8 Dobson, Gordon 14 Dobzhansky, Theodosius Grygorovych X Dorno, Carl 285 Dove, Heinrich Wilhelm 283, 284 Drebbel, Cornelius Jacobszoon 53 Driessen, Peter van 173 Drischel, Hans 198, 201, 204, 206, 216, 217, 222, 232 Drozdova, Valentina Ivanovna 228, 229, 252 Duce, Bob XIII Du Clos, Samuel Cottereau 69 Ducros, Hippolyte 14, 180, 181 Dumas, Jean-Baptiste André 25, 90, 97, 106 Dunstan, Wyndham 133, 209 Ebel, Adolf XII Ebelmen, Jacques-Joseph 348 Edelstein, Sidney 89, 91 Edrisi 267 Egnér, Hans Gabriel 11, 230 Ehhalt, Dieter 548, 552 Ehrenberg, Christian Gottlieb 39, 165, 265–268 Ehrenberg, Paul 147 Eichhorn, Carl Herrmann Alexander 192 Einstein, Albert 579 Emanuelsson, Arne 230 Empedocles 47 Engelmann, Theodor Wilhelm 140, 141 Engels, Friedrich 356, 365 Engler, Carl Oswald Viktor 125 Eriksson, Erik 148, 153, 198, 204, 206, 220, 222, 227, 230 Erdmann, Otto Linné Eugster, Werner 65, 251 Evelyn, John 109, 150, 161, 271, 276 Ewart, Alfred James 142 Fabricius, Thomas Balthasar 8 Fabri, Honoré 164 Fahrenheit, Daniel Gabriel 42, 53 Failyer, George H. 153, 196, 197, 200, 225 Faraday, Michael 25

749

Farman, Joe 14, 535 Farsky, Franz (František) 105 Faust, Bruce C. 251 Fay, Charles François de Cisternay du 57 Feilitzen, Carl Axel Hjalmar von 205 Feilitzen, Carl Henrik Jobst von 205, 231 Feister, Uwe 439 Ferdinand II of Toscana 53 Ferrel, William 284 Fiedler, Franz 413, 440 Filhol, Jean Pierre Bernard Édouard 190 Finlayson-Pitts, Barbara 621, 623, 624 Firmicus, Julius Maternicus 16 Fišák, Jaroslav 251 Fischer, Johann Carl 5, 73 Flammarion, Camille 59, 63, 164, 273 Fleming, James Rodger 41, 289, 292, 368 Flemming, Günther 424 Fodor, Jozef von 102, 112 Fonrobert, Ewald 127 Fontana, Felice 93 Fontenelle, Jean-Sébastien-Eugène Julia de 253 Formey, Ludwig 271 Fort, Charles 166 Fourcroy, Antoine François Comte de 5, 21, 25 Fowle, Frederick E. 127 Fox, Cornelius Benjamin 116, 121, 122, 126, 622 Frankland, Sir Edward 25, 194, 200 Franklin, Benjamin 288 Free, E. E. 258, 262, 269 Frenkel, Jakov Iljitsch 278 Fresenius, Carl Remigius 7 Fugger, Eberhard 64 Fulcanelli 157 Fuzzi, Sandro 245, 247–249, 251 Gaivoronskij, Iwan Iwanowitsch 228 Galbally, Ian 474 Galilei Galileo 42, 53 Gasparin, Adrien Étienne Pierre de 188 Gautier, Armand 80, 314, 317, 320, 551 Gay-Lussac, Joseph Louis 25 Geber. See ibn Hayyān Gehler, Johann Samuel Traugott 57, 58, 74, 281, 283 Gehlen, Adolph Ferdinand Georgii, Hans-Walter 197, 233, 248, 249, 490, 513 Gerhardt, Charles Frédéric 25

750

Name Index

Gersten, Christian Ludwig 57 Gest, Howard 140–142 Giacosa, Piero 193, 226 Gibbs, Josiah Willard 25 Giberne, Agnes 38, 63, 273 Gilbert, Joseph Henry 147, 184, 193, 199, 225 Gilbert, Ludwig Wilhelm Gilm, Hugo von 99, 105, 108 Girardin, Jean Pierre Louis 180 Girtanner, Christoph 29, 85, 90 Glauber, Johann Rudolf 21 Gmelin, Johann Friedrich 7 Gmelin, Leopold 7, 73 Godzik, Stefan XII Goethe, Johann Wolfgang von 40, 57, 438 Goldschmidt, Johannes 426 Gold, Thomas 309, 323, 344, 346, 361 Goppelsroeder, Christoph Friedrich 207 Göttling, Johann Friedrich August 7 Grabowski, Rostislav Ivanowitsch 229, 242, 252 Graebe, Carl 27 Graedel, Tom 625 Graftiau, Jean 100, 104, 106, 108, 198, 200, 225, 237, 622 Gräger 111, 189 Graham, Thomas 56, 119, 262 Grandeau, Louis Nicolas 198 Gravenhorst, Gode XII Gray, George 193, 221, 237 Gren, Friedrich Albrecht Carl 16, 17 Guericke, Otto von 55, 60, 65, 69, 438 Guth, Alan 293 Grüneisen, Eduard Haagen-Smit, Arie Jan 13 Haeckel, Ernst 282 Hager, Gisela XVI Hahn, Amandus 147, 148 Hahn, Otto 10 Haldane, John Burdon Sanderson 333 Haldane, John Scott 97, 101, 510 Hales, Stephen 12, 76, 81, 83, 84, 138 Hall, Alfred Daniel 112 Hammerschmied, Johann 127 Hann, Julius von 42, 64, 284, 286–289 Hänsel, Christian XIII Hantzsch, Arthur Rudolf 25 Hara, Hiroshi 229, 230

Harper, Horace J. 222, 223, 340 Harrison, John Burchmore 196, 200, 225, 237 Harting, Pieter 180 Hartle, James 293 Hassenfratz, Jean Henri 29 Haszpra, László XII Hawking, Stephen 293 Hawksbee, Francis 84 Hayes, Augustus Allen 8 Hegg, Dean A. 247, 248, 252 Heine, Heinrich 290, 438 Heinrich, Reinhold 200 Heisenberg, Werner Karl 26 Hellmann, Johann Georg Gustav 42, 438 Hellriegel, Herman 147 Helmholtz, Hermann Ludwig Ferdinand von 284, 330 Helmont, Johann Baptist van 21, 23, 40, 50, 54, 66, 68–71, 75, 80, 81, 83, 137, 141, 150 Helmts 177, 224 Hempel, Walter 97, 98, 101, 510 Henneberg, Wilhelm 198 Henriet, Henri 9, 115, 622 Henshaw, Thomas 167 Heraclitus 18, 48 Herder, Johann Gottfried von 281 Herodotus 46 Heron 81 Herrmann, Günther 422, 423, 424, 426, 427, 513 Herrmann, Hartmut 250, 453 Hessen-Rotenburg, Hermann von 63 Higgin, Robert 175 Hill, Robert 140–142 Hipparchus 281 Hippocrates 46, 280, 285 Hirasawa, Kenzō 224, 227 Hobbs, Peter Victor 247, 248, 252, 623 Hoefer, Ferdinand 26 Hoffmann, Michael 125, 241, 245, 247, 251 Hofmann, August Wilhelm von 25 Hofmeister, Jürgen XVI Högberg, Linus Vilhelm 230 Högbom, Arvid 290 Hohenheim, Theophrast von. See Paracelsus Homberg, Wilhelm 23 Homer 44, 46, 47, 164 Hook, Robert 53 Hornberger, Richard 9

Name Index

Horváth, László 199, 202, 232, 490 Hossenfelder, Sabine 579 Houghton, Henry Garrett 242, 244, 251 Houzeau, Jean August 116, 118, 121, 196 Houzeau, Jean-Charles 62 Howard, Luke 65 Hoyningen-Huene, Wolfgang von XIII Hube, Jan Michał 58 Hudig, Joost 201, 206, 226 Hudson, John 28 Hufeland, Christoph Wilhelm 584 Humboldt, Alexander von 2, 31, 32, 57, 71, 81, 84, 90, 96, 100, 265, 267, 282–285, 323, 361, 373 Humphrey, William Jackson 109, 288, 289 Huntington, Ellsworth 285 Hunt, Thomas Sperry 118 Hutchinson, W. L. 203 Hüttl, Reinhard F. 414 Hüttner, Eberhard XIII Ibn Hayyān, Jābir (Dschabir) 79 Ibn Sina, Abu Ali Al-Hussain 50 Igawa, Manabu 248, 251 Ihle, Peter 457, 458 Ingenhousz, Jan 93, 95, 138, 139 Ioannidis, John P. A. 578, 579 Isidirov, Valerij 499 Jacob, Daniel 251 Jaenicke, Ruprecht XII Jaeschke, Wolfgang 248, 251, 338 Jander, Gerhard 7, 8 John, Johann Friedrich 7 Johnson, Jacob 186 Johnston, James Finlay Weir 31 Jorissen, Paulinus 219 Julia, Jean-Sébastien-Eugène. See Fontenelle Junge, Christian 10, 11, 125, 233 Juran, Jacob 156 Juritz, Charles Frederick 201, 204, 226, 237 Jursch, Heinz 454 Kalass, Dieter Kamen, David 140, 141 Kämtz, Ludwig Friedrich 59, 60, 62 Kant, Immanuel 45, 281, 282, 283, 570 Katō, Takeo 223 Kazay, Endre 199, 201

751

Keeling, Charles David 520 Kekulé, August 25, 186 Kellner, Oskar 185, 187, 198 Kemp, Kenneth Treasure 111, 189 Kernbaum, Mirosław 132, 134 Kerr, Robert 15 Kesselmeier, Jürgen 500, 504 Khrgian, Aleksandr Khristoforovich 41, 242, 280 Kinch, Eduard 219, 225 Kind, Rudolf XIII Kirchhoff, Gustav Robert 25 Kirwan, Richard 75, 78 Klaproth, Martin Heinrich 8, 25 Kleffmann, Jörg 559, 579 Klemm, Otto 248, 251 Kley, Dieter 43, 125, 540 Klockow, Dieter XII Klossowski, Alexander Vikentievich 205 Kluge, Wolfgang 415 Knieriem, Johann Karl Woldemar von 186 Knight, David 28 Knop, Johann August Ludwig Wilhelm 13, 82, 146, 185, 191, 199, 202, 225, 253, 254 Knott, Cargill Gilston Köhler, Hilding 64, 66, 241 Kolbe, Hermann 25 König, Joseph 146, 147, 194 Konstantinova-Schlesinger, Maria Aleksandrovna 534, 541 Köppen, Wladimir Peter 60, 287, 288 Kopp, Hermann Franz Moritz 7, 16, 17, 26, 27, 174 Kopp, Johann Heinrich 7 Kossovitsch, Peter Samjonowitsch 148, 220, 221 Kratzenstein, Christian Gottlieb 55, 59 Kreil, Karl 283 Krogh, August 96, 97, 100, 106–108, 292 Krünitz, Johann Georg 40, 71 Kudryavtsev, Nikolai Alexandrowitsch 323, 361 Kühn, Gustav 185 Kunckel, Johann 23 Kupffer, Adolph Theodor 228, 283 Küppers 214 Kurzmann, Johann Philipp 267 Ladenburg, Albert 27 Ladureau, Albert 113 Laj, Paolo 250–251

752

Name Index

Lakatos, Imre 41 Lamarck, Jean-Baptiste 65 Lampadius, Wilhelm August 7, 37, 57–59, 152, 176, 179, 224, 239, 253, 282 Landriano, Marsilio 93 Lange, Johannes 161, 249, 265 Langlo, Kaare 127 Laozi 269 Lavoisier, Antoine-Laurent de 12, 15, 22–28, 37, 52–53, 65, 70, 84–89, 94–95, 109, 113, 138, 163 Lavrinenko, Rimma Fedorovna 228–229 Lawes, John Bennet 147, 184, 193–194, 199, 225, 254–255 Leather, John Walter 201, 204, 226, 254–255 Ledochovitsch, Aleksej Aleksandrovitsch 244 Le Chatelier, M. Henry 127 Leeds, Albert R. 127 Leeuwenhoek, Antoni van 152, 168 Leibniz, Gottfried Wilhelm 4, 36 Leighton, Philipp Albert 10, 14, 135, 231, 277, 622 Lejeune, Phocas 186, 506–507 Lelieveld, Jost 10, 429, 497, 527 Lémery, Nicolas 23, 25 Lenard, Philipp 264, 278 Lender, Carl Friedrich Constantin 116, 123, 126 Le Roy, Charles 55, 58, 65 Le Roy, Edouard 354 Letts, Albert Edmund 100–102, 106, 108 Lévy, Albert 41, 104, 106, 108, 112, 115, 125, 153, 195, 200, 225, 260–261, 483, 542 Libavius, Andreas 20 Liebig, Justus von 11, 25, 31, 81, 112, 118–119, 138, 141, 147, 151–152, 174, 179, 184, 186–188, 191, 193–194, 198, 210 Liebreich, Matthias Eugen Oskar 125 Liesegang, Wilhelm 215–216, 226 Likens, Gene 234, 472 Linde, Andrei 293 Lindgren, Waldemar 148 Lippmann, Edmund Oskar von 27 Liss, Peter Locke, John 72 Lockemann, Georg 16, 27 Loewy, Adolf 100, 285 Lomonossov, Michail Wassiljewitsch 22, 169 Lovelock, James 3, 356 Low, David 86

Luca, Sebastiano De 182, 225, 237 Lucke, Otto 128, 321 Ludwig, Friedrich Hermann 174, 330 Lundegårdh, Henrik Gunnar 106 Lunge, Georg 206 Lux, Herbert 453, 454 Macadam, Stevenson 182 Mach, Edmund 193, 225 MacMillan, Conway 141 Macquer, Pierre-Joseph 6, 74, 89 Magellan, Jean Hyacinthe de 95 Magnus, Albertus 51 Mahlmann, Wilhelm 283 Maimonides, Moses 270 Main, James 273 Mangin, Arthur 62, 63 Marcano, Vicente 196, 200, 203, 225, 237 Marchand, Eugène 180, 182 Marchand, Richard Felix 100 Marchi, Luigi De 287, 289, 290 Marggraf, Andreas Sigismund 13, 24, 151, 152, 161, 163, 169–173, 175, 176, 179, 188, 224, 237 Margules, Max 284 Margulis, Lynn 3, 330 Marié-Davy, Edme Hippolyte 102, 104, 106, 126, 195 Marignac, Jean-Charles de 118 Mariotte, Edme 143 Marquardt, Wolfgang 413, 415, 454, 457, 458 Marsh, Tony XIII Marti, Franquès, Antonio de 93 Martin 190, 209 Marum, Martinus van 117 Marx, Karl 2, 365, 373, 426 Matsudaira, Yasuo 223, 227 Matsui, Hideo 153, 224, 227, 230 Matthaei, Gabrielle 140, 141 Mauersberger, Günther XI, XII, XVI Mayer, Adolf Eduard 186 Mayer, Julius von 139, 141 Mayer, Roland Otto 423 Mayow, John 12, 23, 74, 81, 83, 84, 141 Megenberg, Konrad von 34–36, 51 Meissner, Georg 14, 126, 129–131, 134, 225 Melander, Gustaf 279 Menchikowsky, Felix 237 Mendeleev, Dmitrii Ivanovich 131, 323, 361

Name Index

Mensbrugghe, Gustave Léonard van der 64 Mészáros, Ernö 199, 235, 623 Meyer, Ernst von 17, 19, 27, 48 Meyer, Lothar 25 Meyrac, Victor 190, 209, 240, 253 Middleton, William Edgar Knowles 41, 42, 150 Mierzecki, Roman 27 Milanković, Milutin 289, 368 Miller, N. H. J. 112, 194 Miller, John XIII Mitchill, Samual Latham 29, 79, 584 Mitscherlich, Eilhard 25, 125 Miyake, Yasuo 153, 197, 201, 223, 224, 227, 230, 232, 242–244, 252 Mohnen, Volker 247, 252, 439, 440 Mohry, Herbert 418 Moleschott, Jacob 145, 151, 174, 182, 183 Monceau, Henri-Louis Duhamel du 69 Monge, Gaspard 88 Mons, Jean-Baptiste van 239, 240 Morley, Edward Williams 90 Morton, John Chalmers 194 Morveau, Gyuton de 28 Mosheim, Johann Lorenz von 158 Mrose, Helmut 233, 243, 244, 248, 249, 422, 423, 424, 426, 453 Mulder, Gerardi Johannis 176, 183, 186, 224 Müller, Carl Alexander 186 Muncke, Georg Wilhelm 57, 180, 268, 269, 273 Munger, William 251 Müntz, Charles Achille 139, 196 Muspratt, James Sheridan 8 Musschenbroek, Peter van 58 Nakazawa, Zenichi 230 Nehse, Claus Eduard 438 Neng-Huei (George) 251 Nernst, Walther 25, 131, 216 Neßler, Julius 185 Neumayer, Georg von 287 Newton, Isaac 4, 50, 52, 56, 167, 632 Odén, Svante 234, 415 Odling, William 119 Ogburn, William Fielding X Ogren, John 248, 251 Ogura, Yutaka 153, 223, 224, 227 Ohtake, Takeshi 244, 252 Okita, Toshiichi 230, 243, 244, 279

753

Okochi, Hiroshi 251 Oparin, Alexander Iwanowitsch 314, 333 Osann, Gottfried Wilhelm 122 Ostwald, Friedrich Wilhelm 25, 27, 264 Ostwald, Wolfgang 56, 216, 264 Owens, J. S. 277 Palissy, Bernard 1 Panopolis, Zosimos of 17 Paping, Bernard Joseph 152, 173 Paracelsus 20, 21, 23, 50, 67–70, 81, 137, 141, 154, 167 Parmenides 47 Partington, James Riddick 22, 27, 50, 69, 70, 89, 91 Pascal, Blaise 53, 81, 632 Passerini, Napoleone Pio 153, 197, 219, 225 Pasteur, Louis 81, 139, 260, 333 Pauling, Linus 26 Pauli, Simon 164 Pauli, Wolfgang Ernst 26 Peiresc, Nicolas Claude Fabri de 164 Péligot, Eugene Melchior 189 Penkett, Stuart XIII, 129 Périer, Florin 53 Perros, Pascal XIII Petermann, Arthur 100, 102, 104, 106, 108, 187, 198, 200, 225, 237, 622 Peterssson, Sven Otto 101 Petrenchuk, Olga Petrovna 229, 243, 244, 245, 440 Pettenkofer, Max 101 Petzholdt, Alexander 219 Pfaff, Christian Heinrich 8, 57 Pfeffer, Wilhelm 139, 142, 291 Pfeffer, Wilhelm 139, 142, 291–292 Pflüger, Eduard 139, 141 Philalethes, Irenaeus 161 Pierre, Joachim Isidore 174, 189 Pierre, Viktor 126 Pincus, Salomon 191, 192, 225 Pink, William E. 8 Plass, Gilbert Norman 292, 368 Platon 16, 19, 48 Planck, Max Platt, Ulrich 553 Playfair, Lyon 210 Plinius 45, 49, 107 Plutarch 16, 45

754

Name Index

Pollock, James Arthur 264 Popper, Karl X Poggendorff, Johann Christian Porta, Johann Baptista 56 Poseidonius 280 Pošepny, František (Franz) 143, 218, 229 Prestel, Michael August Friedrich 123, 124, 126, 265, 268, 269 Prévot, Edward William 219, 225 Priestley, Joseph 12, 24, 59, 80–83, 85–89, 93, 107, 109, 113, 138, 174, 179, 320, 622 Proctus 45 Proust, Joseph Louis 25 Prout, William 14, 25, 38, 59, 60, 110, 128, 166, 239 Pruppacher, Hans XII Ptolemy, Claudius 281 Puxbaum, Hans 248, 504 Pythagoras 47, 281 Radford, William H. 209, 241, 242, 251 Ram, Atma 153, 201, 216, 217, 227, 255 Ramazzini, Bernardino 152, 168 Ramsay, Sir William 9, 13, 73, 81, 83, 85, 88, 91, 92, 96, 272, 622 Raoult, François Marie 25 Rayleigh, Lord 13, 61, 80, 81, 91, 92, 263 Réaumur, René-Antoine Ferchault de 164 Reboul, Henri Paul Irénée 94 Reclus, Jacques Élisée 63 Redi, Francesco 168 Reichen, Charles-Albert 27 Reimann, Ernst Julius 36, 62, 529 Reinhold, Karl Leonhard 45, 163, 192 Reinsch, Edgar Hugo Emil 114, 115 Reiset, Jules 104–106, 108, 146, 147 Renger, Friedrich 128 Renner, Eberhard 413 Reslhuber, Augustin 121, 122 Rey, Jean 69 Richards, Eric Hannaford 200, 207, 226 Richter, Jeremias Benjamin 151 Rideal, Eric K. 127 Rink, Friedrich Theodor 282 Ripley, Sir George 157 Risse, Otto Karl Hermann 134, 135 Ritthausen, Heinrich 185 Rive, Auguste Arthur de la 116, 118 Robinet, Stéphane 182

Rodhe, Henning 11, 248, 413, 480 Rolle, Wolfgang 5, 118, 132, 413 Róna, Zsigmond 287 Rose, Heinrich 8 Rosing, Hans Anton 193 Rossby, Carl-Gustaf Arvid 11, 231 Rosset, Robert XIII Rössing, Adelbert 27 Rousseau, Jean-Jacques X Roussin, Albin Reine 267 Ruben, Samuel 140, 141 Rubin, Morcedal 117, 118, 128, 192 Rubner, Max 285, 288, 508, 513, 523 Russell, Colin Archibald XI Russell, Edward John 137, 194, 207, 209 Russell, Francis Albert Rollo 273 Russell, William James 264 Ruston, Arthur Gough 201, 207, 274 Rutherford, Daniel 12, 84 Rutherford, Ernest 26 Ryaboshapko, Alexey 480, 490 Sabatier, Paul 617 Sachs, Julius von 38, 39 Saint-Didier, Alexandre-Toussaint de Limojon de 156 Santorio, Santorio 42, 53 Saussure, Horace-Bénédict de 53, 56, 59, 60, 62, 65, 84, 97, 99, 139 Saussure, Nicolas Théodore de 110, 139, 141 Saxena, Vin 247, 252 Schaller, Eberhard 413 Scheele, Carl Wilhelm 12, 24, 264, 622 Schemenauer, Bob 251 Scherer, Alexander Nicolas Scherer, Johann Baptist Andreas Ritter von Schiefferdecker, Wolfgang 95 Schiller, Friedrich 45 Schlagintweit, Adolph 64, 65 Schlagintweit, Hermann 65 Schloesing, Jean-Jacques Théophile 100, 139, 141 Schmauß, August 56, 264 Schneider, Bernd XIII Schneider-Carius, Karl 42, 287 Schofield, Robert 88, 89, 91 Schönbein, Christian Friedrich 80, 81, 116–118, 120–123, 128, 129, 131, 133, 136 Schöne, Emil 14, 80, 122, 131, 132, 225, 544

Name Index

Schrödinger, Erwin 26 Schroeder, Johannes 206 Schroeder, Julius von 272 Schulze, Franz Ferdinand 104, 108 Schurath, Ullrich XII Schweigger, Johann Salomo Christoph 638 Schwartz, Stephen E. 229, 238 Schwinkowski, Kurt XIII Scott, Alexander 64, 90, 91 Scoutetten, Robert Joseph Henri 122, 123 Seilern, Carl Max Graf 198 Seiler, Wolfgang 413, 497 Seinfeld, John 623, 624 Selezneva, Evgenia Semenovna 228–229 Senebier, Jean 81, 95, 139, 141 Shaw, Peter 22 Shaw, Sir Napier 41, 42, 209, 276, 277 Shimizu, Mitsuo 223 Shmeter, Solomon Moiseevich 242, 252 Shopauskine, Dalia XII Shouw, Joakim Frederik 283 Shutt, Frank Thomas 201, 216, 226, 237 Silberschlag, Johann 61 Silvestri, Orazio 266 Simon, Karl-Hermann 453 Slanina, Jack 236 Smith, Robert Angus 11, 113, 114, 152, 209, 210, 211, 213, 218, 260, 384, 622 Snell, Willebrord van Roijen 36 Sobik, Mieczysław 251 Soret, Jean Louis 119, 127, 129, 136 Sprengel, Carl 138 Stahl, Georg Ernst 23, 24, 70, 87, 113 Stamp, Josiah Charles XI Starkey, George. See Philalethes Stark, William 152, 153, 174, 175, 224, 237 Steinhardt, Paul 294 Steinhauser, Ferdinand 232, 233 Stella, Tilemann 438 Stöckhardt, Julius Adolph 6, 81, 185, 214, 246, 272, 384, 423 Stoklasa, Julius 113, 153, 198, 200, 214, 215, 225, 237, 314 Stromeyer, Friedrich 78 Strunz, Franz 27 Struve, Heinrich Wilhelm von 131, 153, 205, 225, 237 Suess, Eduard 353 Sugawara, Ken 153, 227, 229

755

Svistov, Peter Filippovitsch 228, 229 Szabadváry, Ferenc 7, 27, 50, 167 Tait, Peter Guthrie 119 Takematsu, Okada 223 Takenaka, Norimichi XVII Takeuchi, Ushio 230 Tansley, Sir Arthur George 353 Tao Te Ching 269 Teichert, Friedrich 128 Thales 17, 18, 47, 48 Thénard, Louis Jacques 8, 97, 99, 109, 125, 127, 128, 129 Theophrastus 20, 49, 67 Thoms, George 186 Thomson, Thomas 17, 26, 32, 93, 97, 128 Thorpe, Sir Thomas Edward 27, 106, 108, 166 Tissandier, Gaston 263, 268 Torrent-Guasp, Francisco X Torricelli, Evangelista 42, 53, 81 Torstensson, Gunnar 202, 230 Trabezkoj, Pawel Peter 205 Tracy, S. M. 193, 203, 225 Traube, Moritz 120, 130, 131–133 Traube, Wilhelm 25 Trimble, Henry 8 Trommsdorff, Johann Bartholomäus 8, 26 Turner, Edward 31, 248 Turok, Neil 294 Tuxen, Christian Frederik August 193, 200, 225, 267 Tyndall, John 58, 262, 289, 290 Ulloa, Antonio de 61 Umlauft, Friedrich 36, 53, 63 Urey, Harold Clayton 135 van´t Hoff, Jacobus Henricus 25 van Roijen Snell, Willebrord 36 Várhelyi, Gabriella 480 Vaughan, Thomas 161 Vauquelin, Louis-Nicolas 7, 113, 253 Veraart, August Willem 66 Vernadsky, Vladimir Ivanovich 1, 9, 228, 286, 353–355 Vilenkin, Alexander 293 Ville, Georges 112 Vityn, Jan 220 Viviani, Vincenzo 53

756

Name Index

Voeikov, Alexander Iwanowitsch 228, 286, 287 Vogel, August 184 Vogel, Heinrich August 179, 184 Volta, Alessandro 89, 93, 96 Vonnegut, Bernard 66 Vosmaer, Alexander 127 Wackenroder, Ferdinand 174 Walcek, Chris XIII Walden, Paul 25, 27 Waldman, Jed 245, 246, 247, 251 Waller, Augustus Volney 62, 65, 138, 180 Wallerius, Johann Gottschalk 138 Walther, Reinhold von 163 Wang, Tao 251 Wankel, Georg Reinholdt 193, 237 Warburg, Emil Gabriel 140 Warburg, Otto Heinrich 140, 141, 237 Warington, Robert 194, 199, 200, 225 Warmbt, Wolfgang 128, 422, 426 Warneck, Peter 315, 317, 345, 346, 350, 480, 497, 623 Watanabe, Koichi 251 Watt, James 88, 89, 90, 632 Way, John Thomas 193, 194 Webster, George E. 8 Weedon, Thornhill 206 Weinschenk, Ernst 318 Weiss, Joseph 135 Welbel, Benzion Movscha-Morduchovitsch 197, 200, 220, 226, 255 Wells, William Charles 58 Welt, H. 146, 201, 206 Weltzien, Carl 116, 125, 129, 130 Werner, Abraham Gottlob 26, 282, 495, 496 Westendorff, Klaus 453 Wiedemann, Gustav Heinrich Wiegleb, Johann Christian 26 Wiegmann, Arend Friedrich August 179 Wiegmann, Arend Joachim Friedrich 177, 179 Wieland, Heinrich Otto 132 Wiegleb, Johann Christian 26

Wien, Wilhelm 638 Wienhaus, Hans 272, 423 Wienhaus, Heinrich 423 Wienhaus, Otto 423 Wieprecht, Wolfgang 444, 445 Wigand, Albert 264, 278, 622 Wildt, Rupert 127 Wilfarth, Hermann 147 Willard, Julius Terrass 153, 196, 197, 200, 225, 237 Willett, Hurd Curtis 66 Williamson, Alexander William 25 Wilson-Barker, David 209 Wilson, Benjamin Dunbar 201, 216, 222 Winkler, Clemens 144, 272 Winkler, Peter 234, 249 Wislicenus, Hans Adolf 247, 272 Wislicenus, Johannes Adolf 25, 272 Witting, Ernst 177, 224, 240 Wöhler, Friedrich 25 Wolff, Emil 185, 191, 198, 525 Wolffenstein, Otto 187 Wolf, Johann Rudolf 126, 402, 492, 493 Wolf, W. 191, 199, 202, 225, 254 Wollny, Ewald 191, 199, 225 Woodward, John 137, 141 Worm, Ole 164, 330 Wurtz, Charles Adolphe 25, 26, 187 Xenophanes 47 Zaizev, Vasili Aleksandrovitsch 225 Zavodsky, Dušan XII Zellner, Reinhard XII Zier, Manfred 233, 249, 422, 424, 426, 435, 454, 455 Zimmermann, Eberhard August Wilhelm von 144, 145 Zimmermann, Frank 249 Zimmermann, Wilhelm Ludwig 177 Zosimus 17, 154, 155

Subject Index a posteriori emissions 477 a priori emissions 477 abrupt climate change 365 accretion 299, 312 acetic acid – biomass burning emission 411 – historic terms 77 acetone – biomass burning emission 411 – global emission 503 – global sink 504 – secondary sources 503 acid deposition 234, 248, 415, 416 acid rain 180, 212, 230, 233, 351, 384, 415, 417, 479 acidity – and redox state 347 – atmospheric budget 417 – cloud 450 – human health 573 – rainwater 456, 464 – trend 472 aerosol – carbonaceous 476 – climate effect 351, 368 – history 264 æther 47 agricultural experimental station 185 agriculture – emission 402, 493, 496 – environmental impact 401 – land-use change 404 – rainwater studies 183 – waste burning 408 air chemistry see atmospheric chemistry air pollution – abatement 389, 413, 509 – and health 567 – and society 373 – books on history 41 – change 512 – climatology 123 – East Germany 453 – history 384 – human exposure 576 – in towns, historic 512 – in towns 270 https://doi.org/10.1515/9783110561340-012

– London, historic 390 – monitoring 235 – ozone 543 – rainwater monitoring 234 – rainwater studies 207 – Tokyo and Japan 224 – trend, East Germany 468 – trend, Europe 472 – urban 499, 564 – West Germany 428 air – alchemistic signs 67 – analysis 96, 111 – ancient views 18, 47 – chemical composition 96, 510 – cleanser, history 125 – different kinds 67, 82 – etymology 32 – goodness 92 – primordial composition 328 – self-cleaning 72, 144 Aitken dust counter 263 albuminoid 116 alchemy – airs and gases 71 – dew sampling 162 – history 15, 49 – water treatment 154 aldehyde – emission 501 – from biomass burning 409 alkaline air 110 alkaline rain 473 alkanes, emission 479, 498 alkenes, emission 479, 498 aluminum – in lithosphere 302 – in rainwater 182 ammonia hydrate 311 ammonia – air pollution 212 – animal emission factors 490 – biomass burning emission 479, 489 – early atmosphere 305, 326 – emission in Germany 416 – global emission 489 – historic terms 74

758

Subject Index

– history 110 – hydrate 300 – in air, first measurements 111 – in dew water 254 – in rainwater 199 – interstellar 311 – oceanic emission 479, 489 – origin 319 – photolysis 327 – plant fertilizer 139 – soil emission 479 – wild life emission 479 ammonia-water asteroid 312 ammonification 494 ammonium acetate 110 ammonium chloride 319 ammonium nitrate 172, 264, 415 ammonium nitrite 252 ammonium sulfate 81, 110, 114, 233, 278, 413 ammonium – deposition 489 – first detection in rainwater 177 – first determination in rainwater 189 – in cloud water at Mt. Brocken 443 – in dust, Berlin 566 – in fogwater 240 – in rainwater at Berlin, 1930s 216 – in rainwater at Rothamsted 194 – in rainwater at Seehausen 456 – in rainwater, history 179, 187 – in rocks 313 – loss in rainwater 171 anammox organisms 147 animal – ammonia emission 488 – biomass 352 – evolution 340 – feed 383 – manure 402 – methane emission 491 – sulfur emission 505 Annus Mirabilis 351 Anthropocene 591 anthroposphere 1, 355 antozone 118, 129 antozonide 129 Archean 326 argon – discovery 91

– in air 301 – in meteorite 308 – on Venus and Mars 325 aromatic compounds – biomass burning emission 409 – global emission 498 – in meteorites 307 – in space 306 asbestosis 585 aspiration method 111 asteroid 308 atmosphere – ancient views 46 – definition 12 – discovering periods 43 – etymology 36 – evolution 324, 341 – geographic quantities 303 – primordial 314 – secondary 314 atmospheric aerosol see dust atmospheric chemistry – definition 11 – first termination 9 – research topics 14 atmospheric potential oxygen 98 atomic theory 30 autotrophic 379, 501 autoxidation 131 balneology 218 Bergerhoff sampler 435 Berlin, air pollution 421, 437, 508, 565 bicarbonate – evolution 327 – from weathering 348 – in dew water 255 – in rainwater 220 – rainwater acidity 235 Big Bang 3, 293, 343 bioaerosol 267 bioclimatology 288 bioenergy 379 biogeochemical evolution 303, 335 biological evolution 4, 330 biological particles – in air 260 – in dust 261 – in rainwater 168

Subject Index

biomarker 335, 361 biomass burning – CH3CN as tracer 410 – climate impact 407 – combustion process 409 – emission factors 410 – emissions 411 – global carbon release 408 – global sulfur emission 505, 506 – of residues 404 – source categories 407 – VOC emission 500 biomass – definition 352 – energy 380, 401 – mineralization 346 biosphere, origin of the term 353 Bitterfeld, air pollution 424, 435, 456 bitumen 310 black episodes 415 black lung disease 585 black rain 268 black smoker 331 black snow 166 bleaching 79, 110, 134, 253 blue fog 130 blue haze 259, 262 borate, in seawater 327 boron 74 Boudouard equilibrium 618 breathing, air pollution 571 bromine – first detection in rainwater 180 – in seawater 327 – organic compounds 529 Bruckner cycle 289 butane, in natural gas 398 cadmium, in flue gas 394 calcium – dust decline 472 – in air, Mace Head 563 – in dew water 253 – in meteorite 302 – in rainwater, history 171 – in rainwater 180, 218 – in seawater 327 – rainwater analysis 101

Callendar Effect 292 Calvin cycle 140 carbides 318 carbon dioxide economy 610 carbon dioxide theory 289 carbon dioxide – air capture 605 – atmospheric accumulation 598 – atmospheric trend 519, 598 – background concentration 520 – biomass burning emission 412, 479 – capture and storage 593 – city dome 523 – climate change 368 – concentration variation 521 – cumulative emission 592, 599 – cycling 609 – discovery 83 – early atmosphere 349 – from cement production 484 – from earth degassing 320 – future trend 599 – global assimilation rate 604 – historic measurements 100, 108 – historic terms 76 – hydrogenation 617 – ice core records 518 – in natural gas 398 – in rainwater 183 – land-use change 405 – photolysis 329 – pre-industrial concentration 514 – residence time 372, 602 – seasonal variation 513 – urban excess concentration 524 – volcanic emission 348 – ice core records 366 carbon disulfide, global emission 479, 505 carbon monoxide – atmospheric concentration 531 – early atmosphere 323, 337 – from biomass burning 409 – historic terms 76 – in air of towns, history 508 – natural emission 479 – seasonal variation 532 – volcanic emission 315 carbon tetrachloride, in air 528

759

760

Subject Index

carbon – budget 291 – burial 337, 346, 350, 604 – capture and storage 592 – cycle 342, 349 – global budget 597, 601 – global-zero budget 610 – in coal 394 – in fossil fuels 344 – in petroleum 394 – inorganic cycle 345 – land-use emission 405 – man-made cycle 610 – reservoirs 344 carbonaceous meteorite – as CO2 source 290 – hydrothermal alteration 306 – late heavy bombardment 304 – matter deep in earth 344 – microfossil 331 – organic compounds 305 – origin 298 – SiC 318 carbonate – early Earth 322 – global wet deposition 603 – in dew water 253 – in meteorite 323 – in rainwater 603 – in rocks 343, 348 – in seawater 327, 601 – in sediments 343 – reservoir 344 – role in climate 291 – subduction 326 carbonization 310 carbonyl sulfide – atmospheric concentration 507 – natural emission 479, 504 catastrophic impact 351, 364 CCC technology 612 CCN – Aitken counter 263 – chloride 218, 229 – discovery 60 – dust particles 264 – history 65 – iodine oxides 279 – sea salt 241

– smoke particles 277 – sulfate 242 CCS technology 592 cell theory 331 chaos 70 chemical climatology 11, 81, 123, 466 chemical evolution 3, 4, 304, 307, 616 chemical meteorology 11 chemical weather 95 chemistry – analytical 7, 151 – aquatic 7 – as science 22 – etymology 16 – historic roots 17 – multiphase 7 – nomenclatura 30 – organic 25 chloride – distance from sea 222 – global deposition 229 – in air, Mace Head 563 – in cloudwater at Mt. Brocken 443 – in coal 420 – in meteorite 307 – in particulate matter 563 – in rainwater, history 207 – in rainwater 454, 462 – in rocks 319 – in sea water 326 chlorine – historic terms 76 – in stratosphere 540 – organic compounds 474, 528 – partitioning 563 chlorophyll 140 chondritic meteorite 306 city dome CO2 523 Clarke value 320 clathrate 344 climate 280, 362 climate change 363, 365, 466 climate elements 283, 287, 363, 365 climate system 352 climate variability 363 climate war 352 cloud base 445

Subject Index

cloud chemistry research – at Mt. Brocken 414 – in China 251 – in Europe 250 – in Germany 244, 437 – in Japan 242 – in the Soviet Union 244, 245 – in the USA 246 cloud chemistry – climatology 440, 441 – history 228, 238 – monitoring 443 cloud condensation nuclei see CCN cloud water – chemical composition 440, 444 – monitoring 453 – sampling 439 cloud – and fog 59 – classification 65 – colored 164 – Descartes view 54 – Greek mythology 37 – Greek philosophers 47 – Guericke’s experiments 55 – research goals 238 – research milestones 65 – seeding 66 coal chemistry 615 coal – ash 420 – carbon content 400, 485 – chemical composition 393 – consumption in China 482 – consumption 393 – flue ash 460 – mine dust 585 – power plant 395 – replacement 613 – reserves 597 coal-fired power station – desulfurization 421, 565 – flue gas composition 394 – ultra-fine particles 467 cohenite 318 collision – cosmic 301, 314 – Earth 333, 351, 358

colloid 262 combustion theory 87 comet 306, 308, 312, 323, 332 condensation nuclei see CCN condensation – ancient views 47 – historic theories 54 – on particles 60 convertibility 88 Cretaceous 341 cropland – carbon loss 406 – global area increase 404 – N2O emission 483 cross-mantle interchange 315 crust – continental 302 – degassing 315, 320 – depth and mass 303 – early Earth 301 – evolution 325, 329 – heat flow 375 – main elements 318 – oceanic 302, 341 – primordial 301 – temperature 376 – volcanism 317 cyanobacteria 337, 349 cycling of matter 142 Dansgaard-Oeschger warming 525 decay series 296 deep hot biosphere 334 deep sea – carbon transport 600 – clathrate 397 – mixing time 602 deforestation 405, 496, 597 degassing – from earth 315, 320, 348 – from particulate matter 562 – HCl from sea salt 108, 159, 173, 212 dehydrogenation 310 denitrification 483, 496 dephlogistigated air 86 dephlogiston 87 deposition gauge 161 deposition

761

762

Subject Index

– agricultural research 152 – agricultural studies 189 – by rainfall 189 – cloud water 247 – nitrate, trend 195 – nitrogen 192, 195 – rainfall 180 – sulfur in rainfall 223 Desertec 609, 616 detritus 325 deuterium 295 deutoxide of hydrogen 128 dew chemistry 7, 255 dew – alchemy 156 – bleaching property 109, 253 – chemical composition 256 – historic view 57 – HNO2 formation 556 – in the Bible 150 dialectic leap 4 diamond 309, 318 diatom 348 dimethyl sulfide – global natural emission 505 – oceanic emission 479, 491 – soil emission 479 dinitrogen monoxide – budget 494 – concentration trend 527 – from agriculture 404 – global increase 372 – historic terms 78 – in flue gas 395 – natural emission 496 – soil emission 479 direct air capture 605 distillation 154 Dobson unit 535 droplets – and vesicles 60 – dew 252 – historic terms 33 – historic views 55 – microphotographs 244 – microscopy 278 – nature 62 – size 62, 147, 178, 241, 263, 438, 439, 467 dry deposition 112, 256

dry fog 268, 288, 351 dust precipitation 435 dust – air pollution 416, 451 – atmospheric concentration 469, 565 – breathing 572 – chemical composition 263, 564 – definition 563 – different kinds 259 – emission in Germany 416 – emission 439, 564 – etymology 257 – fog and smoke 264 – from deserts 469 – history 257 – human health 585 – interstellar 295, 305, 332 – measurements 567 – particle-size fractions 564 – red 265 – resuspension 564 – volcanic 288, 351 earth crust see crust earth mantle see mantle earth-like planet 299 earthquake 317 economic growth 595 ecosphere 352 ecosystem 353 ecotope 353 EDGAR 475 element – abundance 295 – ancient view 44, 50 – crustal 318 – in meteorite 302 – radioactive 295, 374 – stellar origin 293 emission – bottom-up 476 – factor 476, 481 – from biomass burning 408 – inventory 473, 475 – top-down 476 energiewende 592, 625 energy consumption 381, 385, 399 energy fluxes on Earth 382 epidemiological studies 577

Subject Index

ethane, in natural gas 398 ethanol, as biofuel 407 eudiometer 93 EUROTRAC 249 evolution, definition 3, 293 exobase 328 exponential growth 593 extremophiles 330 faulting 317 feldspar 300 fertilizer, Liebig’s view 146 Feuerluft 86 firedamp 115 Fischer-Tropsch synthesis 613 flammable air 83 flue gas – chemical composition 394, 423 – CO2 capture 616 – desulfurization 394, 421, 481 fog chemistry research – in Europe 248 – in the USA 245 fog – and cloud 59 – and smoke 277 – chemical composition 239 – classification 66 – etymology 37 – historic studies 59 – London smog 570 – meteorological element 362 – sampler 241 forest – ammonia emission 490 – and CO2 602 – area 406 – burning emission 408 – burning 406 – land-use change 404 – NO emission 495 – VOC emission 500 formaldehyde – biomass burning emission 411 – early atmosphere 328 – global emission 503 – H2 source 552 – in air at Montsouris 115 – in air 216

763

– in dew water 255 – in dew 216 – in fog water 246 – in rainwater 216 formic acid, from CO2 reduction 615 fossil fuel – caloric and carbon content 400 – carbon stock 350 – CO2 emission 350, 398, 484 – energy amount 381 – energy and air pollution 390 – HCHO emission 503 – origin 310, 323 – reserves 379 fulvic acid 310 fusion in stars 295 Gaia hypothesis 3, 342, 355, 357 garnets 321 gas – analysis 97 – etymology 69 – explorer 83 – historic terms 74 – names in Latin 79 – sylvestre 70 – ventosum 71 gas-to-particle conversion 72, 172, 461, 471, 564 GEIA 474 geochemical cycling 358 geochemical evolution 303 geochemistry 6 geological evolution 3, 312 geothermal heat 358, 374 germs 260 giant molecular clouds 297 giant planet 334, 346 giant polymers 331 global warming 596 glyoxal, global emission 503 granite 313, 320 graphite 318 grassland – N2O emission 483 – NH3 emission 489 gravitational attraction 298, 305, 362 gravitational coalescence 318 gravitational force 374

764

Subject Index

Great Dying 352 Great Oxidation Event 338 Greenland ice core 312, 546 habitable 331, 356, 360 habitable system 4 Hadean 333 hail – as icy meteorite 312 – first sampling 180 – Greek view 48 health – and air pollution 567 – definition 570 helium – discovery 92 – exhausting from Earth 302, 346 – fusion to Be 343 – in meteorite 308 – in natural gas 398 – interstellar 294 – isotopes 301 Hill reaction 140 homeostasis 356 homopause 328 human evolution 4 humic substance 310 humus theory 138 hydrates 312, 474 hydrides 304 hydrocarbon – as solar fuel 616 – biogenic emission 500 – early atmosphere 329, 345 – fossil fuel formation 361 – from biomass burning 409 – in fossil fuels 398 – in lithosphere 309, 322 – in meteorite 306 – interstellar 304, 318 – solar fuel 593 hydrochloric acid 212 – East German emission 420 – emission 472 – explorer 79 – from sea salt 143, 212 – historic terms 76

– history 107 – in air, measurements 560 – in air 173 – volcanic emission 326 hydroelectricity 378 hydrogen fluoride, historic terms 74 hydrogen peroxide – and Schönbein paper 122 – explorer 128 – first evidence in dew 109 – from biomass burning 409 – from water radiolysis 134 – history 129 – in air, first evidence 132 – in air, first idea 110 – in air, measurements 546 – in air, trends 547 – in autoxidation 131 – in cloud water 248 – in Greenland ice core 546 – in ice core 517, 546 – in plants 133 – in rainwater, history 132 – in rainwater 230, 545 – in seawater 327 – in thunderstorm 131 – interstellar 297 – photocatalytic formation 135 hydrogen sulfide – early atmosphere 338 – emission 479 – global natural emission 505, 506 – historic terms 74 – in natural gas 398 hydrogen – early atmosphere 338 – first detection in air 551 – historic terms 75 – in natural gas 398 – in rocks 321 – interstellar 294 – lithosphere 309 – loss from Earth 302, 324, 346 hydrosphere – evolution 341 – origin 322 hydrothermal alteration 306 hydrothermal circulation 375

Subject Index

hydroxyl radical – atmospheric trend 550 – early atmosphere 328 – from HNO2 552 – in air, measurements 549 – interstellar 297 hygrometer 53

krypton – discovery 92 – early Earth 301 – in mantle 305 – on Venus and Mars 325 Kyoto Protocol 530

iatrochemistry 21 ice age 341, 363 ice core – carbon dioxide 365, 515, 518 – hydrogen peroxide 546 – methane 524 – N2O 527 – temperature record 367 icy ammonia hydrate 327 icy meteorite 312 IGAC 474 Industrial Revolution 387, 608 inflammable air 83 infusoria 153, 168, 267 injured air 85 interstellar chemistry 297 interstellar cloud 296, 332 interstellar dust 296 interstellar gas 318 iodine – first detection in rainwater 180 – in air at Paris 182 – in rainwater 190 – oxides from seawater 279 iodometry 126 iron – carbide 318 – earth core 301, 318, 322, 375 – meteorite 302, 308 – native 319 – oxidation 336, 346 – sediment 335 Isis 45 isoprene – from plants 500 – global emission 498

Laki eruption 240, 269, 288, 351 land use change 1, 404, 515, 597 Large Molecule Heimat 297, 628 late heavy bombardment 302, 628 law of conservation of mass 53 Leipzig, air pollution 514 life expectancy 575, 628 life – definition 330, 357 – origin 330, 333 liquid water content – at Mt. Brocken 443, 553 – historic estimation 64 – in clouds 441 – measurement in fog 246 – research in the USSR 242 lithosphere – carbon content 344 – geographic quantities 303 – temperature 375 litter 352, 494 London fog, historic term 273 London – air pollution 110, 113, 271, 274, 508, 513 – dust 264 – fog 64, 273, 274 – rainwater analysis 211 – smog 571 long-lived isotopes 296 long-range transport – acid deposition 234 – dry fog 265 – dust 471, 567 – first detection 214 Los Angeles smog 13, 513 Luft, etymology 34 LWC see liquid water content lye 584

kerogen 310 Kilauea eruption 317 Kola Superdeep Borehole 321

magma – ammonium content 313 – early Earth 301

765

766

Subject Index

– O2 supplier 345 – seawater uptake 326 – SiO2 content 316 magmatic gas 315 magnesium – chloride, and HCl 173 – dust 451, 455 – in air, Mace Head 563 – in cloud water 468 – in rainwater 177, 218, 461 – in seawater 327 – meteorite 308 – sea salt 224, 241, 446 – silicates 321 manganese – first detection in rainwater 177 – in lithosphere 302 – in rainwater 177 – oxide, and ozone 120 mantle – chemical composition 311, 320 – O2 production 322 – redox state 322 – seawater subduction 317 – temperature 376 Marenco curve 534 Mars, atmospheric composition 325 materia prima 19, 87, 154 Mauna Loa CO2 record 518 Melander hypothesis 279 mephitic air 83 mercury – alchemy 137 – in flue gas 394 metal smelting, SO2 source 482 meteorite – ammonia and methane 305 – carbonate 323, 344 – climate impact 351 – composition 302 – FeCl2 319 – icy 312 – organic compounds 308 – water 321 meteorological elements 11, 280, 362 methane – anthropogenic emission 491, 525 – clathrate 311 – early atmosphere 339

– hydrate 300 – in air, trend 526 – in natural gas 398 – natural emission 493 – oceanic emission 479 – lifetime 328 – photolysis 328 – wetland emission 479 methanol – from carbon dioxide 618 – global emission 502 methyl chloroform – in air, trend 529 – OH concentration tracer 549 miasma 72, 180, 260, 584 micrometeorite 308 Middle Ages 49 Milanković cycle 289, 368 Milky Way 296, 318 Miller-Urey experiment 305, 331 mineral – dust 564 – early Earth 300 – in earth mantle 320 – nutrition theory 138 mineralization 341 mist, etymology 38 molecular abundance 297 monoterpene, emission 498 Montreal Protocol 360, 528 Montsouris Observatory – ammonia measurements 112 – CO2 measurements 103 – formaldehyde measurements 115 – ozone measurements 125 – rainwater sampling 152, 195 moorland burning 269 morbidity 575 mortality 577 Mt. Brocken cloud chemistry program 437 Murchison meteorite 307, 318 muscovite 313 mutus liber 162 mysterium magnum 67 nannobacteria 307 natural gas 361, 398 neon

Subject Index

– discovery 92 – on Venus and Mars 325 Nessler’s reagent 185 net ecosystem production 361 new particle formation 259 nickel – in fog water 245 – in meteorite 302, 318 nitrate – aerosol 564 – agriculture 496 – first detection in air 167 – in air, Mace Head 563 – in cloud water at Mt. Brocken 446 – in cloud water, history 248 – in dew water 158, 256 – in fog water, history 245 – in rainwater, history 169, 171, 187 nitre 56, 72, 77, 156, 161, 259 nitric acid – and particulate nitrate 561 – history 109, 115 – in air, measurements 560 – in rainwater 199 nitrides 314, 327 nitrification 139, 208, 217 nitrite – in cloud water, history 244 – in cloud water 555 – in dew water 256 – in rainwater 197 – N2O source 496 – particulate 560 – photooxidation in rainwater 216 nitrogen dioxide – biogenic emission 495 – emission in East Germany 421 – emission in Germany 416 – health effects 579 – historic terms 78 – in air of towns, history 508 – in air of towns 514 – in air, Germany 582 – soil uptake 495 nitrogen monoxide – biomass burning emission 479 – global emission 483 – historic terms 78

– in flue gas 394 – lightning production 479 – soil emission 479 – Tunguska event 312 nitrogen – cycle 146 – discovery 82, 85 – early atmosphere 313 – fertilizer fate 403 – historic terms 78 – in natural gas 398 – in petroleum 394 – in rainwater, history 183, 188 – in rocks 319 – lithosphere 309 – organic 116, 180, 181, 194, 206 – plant nutrient 139 – residence time 311 – volcanic 314 nitrous acid – biomass burning 410 – historic terms 77 – history 115 – in air, measurements 552, 559 nitrous oxide see dinitrogen monoxide nitrous oxides, NOx 176 noble gas 305, 314, 317 noogenesis 354 noosphere 1, 5, 354, 356 nucleation 259, 264, 293 nucleation theory 62 ocean floor 331 ocean – chemical composition 327 – global sulfur emission 505, 506 – source of ammonia 490 olivine 300, 321 olivine bomb 314 Oparin-Haldane theory 332 organic acids – first detection in fog and rain 246 – in meteorites 307 – in natural oil 394 organic matter – airborne 260 – burial 604 – in dew water 253

767

768

Subject Index

– in dust fall 263 – in dust 268 – in meteorites 307 – in rainwater, history 171, 213 – in rainwater 177, 182, 192 – in rock 310 – in town fog 274 – interstellar 305 – sedimentation 342 – self-organizing 334 origin of life 4 orthosilicic acid 321, 348 oxidative stress 338 oxoacids 304 oxy-fuel combustion 612 oxygen – atmospheric concentration 335 – atomic weight, history 90 – discovery 82 – early atmosphere 337, 340 – electric discharges 117 – historic terms 74 – history 87 – in air 31, 92, 97 – in petroleum 394 – in rainwater 183 – reservoirs 344 – residence time 346 ozone acid 131 ozone hole 14, 535 ozone – at Mt. Brocken 538, 542 – change with altitude 540 – depletion in clouds 542 – diurnal variation 541 – global sources and sinks 535 – historic concentrations 535 – historic measurements 121 – history 117 – Hohenpeissenberg trend 538 – in air of towns, history 508 – long-term trend, Europe 534 – nature and formula 119 – seasonal variation 542 – source contributions 543 ozone-depleting substances 528 ozonometer 122 ozonometric wind rose 123 ozonometry 121

palaeoclimate 363 Paleocene 341 panspermia 330 particulate matter see dust peak oil 395 pentane, in natural gas 398 peridotite 321 pesticides, first detection in fog 246 petroleum 310, 323, 361, 391, 396, 618 pH – of cloud water, Mt. Brocken 443 – of cloud water, Mt. Washington 242 – of cloud water, Ontario 248 – of cloud water 243 – of dew water, Jerusalem 255 – of dew water, USA 256 – of dustfall, Bitterfeld 435 – of fog water, Los Angeles 246 – of rainwater, Archean 326 – of rainwater, GDR 233, 454 – of rainwater, historic 217, 219, 223, 232, 233 – of rainwater, Seehausen 456 philosopher’s stone 73, 88, 150, 154 phlogistigated air 87 phlogiston 23, 87 phlogopite 313 phosphate, discovery in rainwater 182 phosphine – historic terms 74 – history 115 phosphurated hydrogen 115 photosensitization 135 photosynthesis 140, 328, 337, 346 plant nutrition 137 PM1, PM2.5 and PM10 564 PM10, in air of towns 514 population growth 385, 388, 401 postaccrecationary period 299 potassium – in air, Mace Head 563 – in seawater 327 prebiotic soup 333 precipitation chemistry research – at Rothamsted 194 – at Seehausen 456 – global monitoring 236 – in East Germany 454 – in Germany 233

Subject Index

– in Japan 223, 230 – in Sweden 152, 230 – in the Soviet Union 229 primitive atmosphere 324 propane, in natural gas 398 Proterozoic 335 protoplanet 301 protosun 299 Pyrrhin 177, 179 quantum creation of universes 293 rain – acid 174 – alkaline 473 – colored 164, 265 – red 166 – tropical 196 rainwater – acidity 180, 207 – alchemy 154 – collection 169, 177, 208, 454 – distillation 168 – first photochemistry 216 – historic analysis 171, 182, 211 – in early atmosphere 326 – in volcanoe 314 – in weathering 336 – lead poisoning 173 – research milestones 152 red giant star 296 redox state 302, 322, 329 residence time 604 residual layer 541 respiration 82 Revelle factor 602 rime deposits 241 river – early Earth 325 – in weathering 348 rock – carbon content 343 – degassing 309, 320, 322 – early Earth 301 – silicate 321 – volatile gases 320 – volcanic 316 – water content 321 – weathering 347

769

Rosicrucians 154 Rothamsted – air analysis 112 – ammonia in dew water 255 – ammonium and nitrate in rain 199 – history 185, 193, 209 – rainwater sampling 152 rusting 133 salmiac 313 salt ammonia 110 salt cycle 143 saltpeter 71, 167, 171, 259 SANA research program 413 savanna burning 408 Scheidekunst 7, 150 sea salt hypothesis 278 sea salt – alchemy 107 – as CCN 218, 229, 241, 278 – cycle 142 – dechlorination 474 – distribution 220, 229, 231 – formation 143, 229 – fractionation 245 – in cloud water 446 – in coal 420 – in dew water 253, 255 – in particulate matter 562 – in rainwater, history 157, 167 – in rainwater 220, 460 – size range 564 seawater – carbon capture 592 – carbonate concentration 601 – chemical composition 326 – SiO2 solubility 348 – subduction 317, 326 secondary atmosphere 324 secondary organic aerosol 501 secondary sources – acetone and glyoxal 503 – carbon monoxide 479, 497 – dust 563 – HCHO and CH3OH 503 – NO, SO2, COS 479 seeder-feeder effect 250 Seehausen precipitation chemistry 414, 456 serpentine 300, 321

770

Subject Index

serpentinization 321, 337 Silent Book 157 silicon dioxide – in equilibrium with H2SiO4 321 – in magma 317 – in rocks 318, 320 – water solubility 348 – weathering 348 silicon – carbide 318 – in meteorite 302 silicosis 585 Silurian 336 smog – at London 570 – historic term 276 – in East Germany 427 smoke – and fog 273 – damage research 272 – plague 272, 389, 512 smoker and health 578 sodium 442 – in air, Mace Head 563 – in cloud water at Mt. Brocken 442 – in coal 420 – in rainwater, history 171 – in seawater 327 sodium carbonate 606 soil dust – emission 564 – history 265 – PM contribution 564 soil water 336 solar energy 380 solar fuels 615 solar nebula 299, 314 solar system 298, 300 solar wind 298, 314 SONNE conception 610 soot – black episodes 415 – black snow 166 – from biomass burning 408 – in fogwater 273 spiritus sylvestris 70, 83 star formation 295 stardust 318 steady state 511, 594

steady state economy 596 stellar evolution 295, 306 subduction 317, 326, 346, 348 sublimate 313 subnitride 319 sulfate – as CCN 279 – in air, Mace Head 563 – in CCN 278 – in cloud water at Mt. Brocken 450 – in dew water 253 – in fresh snowfall 214 – in rainwater at Manchester 210 – in rainwater, history 177, 207, 215 – in seawater 327, 338 – in volcanic dust 289 – sediment 338, 347 sulfite – in dew water 256 – in fog water 246 – in rainwater at Prague 214 sulfur dioxide – absorption on snow 214 – air pollution 273, 390 – emission from biomass burning 479 – emission from China 483 – emission from India 483 – emission in East Germany 417 – emission in Germany 416 – global emission 480 – historic terms 77 – history 113 – in air of East Germany 425 – in air of towns, history 508, 513 – in air, Prague 215 – in flue gas 394 – secondary production 479 – volcanic emission 479 – volcanic 351 sulfur – early atmosphere 325, 338 – rock degassing 322 – volcanic 315 sulfur hexafluoride 530 sulfur trioxide, historic terms 77 sulfuric acid – atmospheric aerosol 509 – early atmosphere 338 – historic research 113

Subject Index

– in air of London 110 – in air of Manchester 274 sulphonates, first detection in fog 246 super-carbonate 175 superoxide anion 134 sustainable chemistry 591 sustainable society 2, 373, 608 swamp gas 115 Tagish Lake meteorite 308, 310 temperature ice core record 367 tephra 316 terpenes, emission 479 The Great Stink 272, 508 Theia 301 thermometer, history 53 thunderstorm – acid rain 174 – hydrogen peroxide 131 – nitric acid 115, 169, 179, 217 – nitrogen fixation 196 – ozone 122 tidal energy 374 Titan 328 titanium dioxide – in rocks 320 – photocatalysis 135 total column ozone 535 town fog 273 town gas 617 transmutation 46, 65, 138, 162 tremolite 300 troilite 300 tundra, burning 408 Tunguska event 312 Twomey effect 356 ultra-fine particles 467 urban pollution – ozone 533 – sulfur dioxide 512 UV radiation – early atmosphere 305 – O2 increase early Earth 340 – OH correlation 549 – plant stress 494

– role in life evolution 329, 335 – water decomposition 134 vapor – alchemy 69 – condensation 62 – historic view 56 Venus, atmospheric composition 325 verdorbene Luft 87 vesicle 55, 60 vital air 83 vital force 25 volatile organic compound – biomass burning 409 – global emission 479, 498 – oxygenated 502 volcanic exhalation 314, 315 volcanic gas 320 volcanoes 315 Vostok station 365 Waldsterben 246 water controversy 88 water culture experiment 137 water cycle, ancient view 49 water energy 378 water – and carbon cycle 348, 359 – and life 329, 332, 334 – composition, discovery 89 – early atmosphere 324 – from comets 312, 322, 327, 331 – in meteorite 307 – in rocks 320, 321 – interstellar 304, 311 – on Mars 324 – photolysis 302, 328, 347 – radiolysis and photolysis 134 – reservoirs 344 – superheated 331 – transmutation 48, 162 – UV protection 336, 340 – volcanic 315 water-gas shift 617 weathering 347 wetlands – CH4 emission 493

771

772

Subject Index

– global sulfur emission 505, 506 white episodes 415 willow tree experiment 137 wind energy 376 wood – chemical composition 409 – fuel burning 408

– fuel 407, 607 xenon, discovery 92 zero-order removal 604

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Other error corrections in Volume 1 Page 141: Balthasar et al. (2005) replace by Balthasar and Frenklach (2005) Page 143: Rubner et al. (1907) replace by Rubner (1907) Page 220: Stumm and Morgan (1996) replace by Stumm and Morgan (1995) Page 276: Footnote j in Table 5.7 is referred to H2O5 Page 336: Golden and Smith (2000) replace by Benton and Moore (1970) Page 347: Burrey et al. (1983) replace by Baylis and Watts (1956) Page 347: Deláez et al. (2008) replace by Peláez et al. (2008) Page 348: delete (Burrey et al. 1983) Page 348: Ignaro et al. (1993) replace by Ignarro et al. (1993) Page 349 (footnote): Mirande (2005) replace by Fukuto et al. (2005) Page 349 (footnote): delete and Doctorivic et al. (2017). Page 352: Olah et al. (2009) replace by Olah et al. (1989) Page 358: (Youl et al. 2014) replace by (You et al. 2014) Page 417: (Koppmann 2008) replace by (Koppmann 2007)

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Page 421: O´Dowd et al. (1995) replace by O´Dowd et al. (2005) Page 431: Yeatts and Traube (1949) replace by Yetts and Traube (1949) Page 444: (Wannowius and Kaiser 2007) replace by (Wannowius and Kaiser 2004) Page 550: Doctorovich et al. replace the title by Nitroxyl (azanone) trapping by metalloporphyrins Page 567: Laszlo et al. insert (1998)