The Science of Sustainable Energy 9780470626122, 4114214224, 0470626127

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The Science of Climate Change

Scrivener Publishing 100 Cummings Center, Suite 541J Beverly, MA 01915-6106

Publishers at Scrivener Martin Scrivener ([email protected]) Phillip Carmical ([email protected])

The Science of Climate Change

M. R. Islam and M. M. Khan

This edition first published 2019 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA © 2019 Scrivener Publishing LLC For more information about Scrivener publications please visit www.scrivenerpublishing.com. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions. Wiley Global Headquarters 111 River Street, Hoboken, NJ 07030, USA For details of our global editorial offices, customer services, and more information about Wiley products visit us at www. wiley.com. Limit of Liability/Disclaimer of Warranty While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials, or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Library of Congress Cataloging-in-Publication Data ISBN 978-0-470-62612-2 Cover Image: All supplied by Dreamstime.com; Electricity: Anigoweb I Refinery: Steve Stedman I Black refinery: Kodym I Earth Bubble Landscape: Rolffimages Cover Design Kris Hackerott Set in size of 11pt and Minion Pro by Exeter Premedia Services Private Ltd., Chennai, India Printed in the USA 10 9 8 7 6 5 4 3 2 1

Dedication Authors would like to dedicate this book to the scientists of the Islamic golden era that personified research for sake of discovering the truth. Their true scientific approach is dearly missed in today’s culture of ‘science’ of tangibles.

Contents Foreword 1

xiii

Introduction 1.1 Opening Statement 1.2 Summary 1.3 Chapter 2: State-of-the Art of the Climate Change Debate 1.4 Chapter 3: Forest Fires and Anthropogenic CO2 1.5 Chapter 4: Role of Agricultural Practices on Climate Change 1.6 Chapter 5: Role of Biofuel Processing in Creating Global Warming 1.7 Chapter 6: Role of Refining on Climate Change 1.8 Chapter 7: Scientific Characterization of Petroleum Fluids 1.9 Chapter 8: Delinearized History of Climate Change Hysteria 1.10 Chapter 9: The Monetization the Climate Science 1.11 Chapter 10: The Science of Global Warming 1.12 Chapter 11: Conclusions

1 1 6 6 8 9 10 11 11 12 13 16 18

2

State-of-The-Art of the Climate Change Debate 2.1 Introduction 2.2 The Anthropogenic Climate Change (ACC) 2.3 The Climate Change as a Natural Process 2.4 Conclusions

3

Forest Fires and Anthropogenic CO2 3.1 Introduction 3.2 The Science of Forest Fires 3.2.1 Role of Water and Carbon 3.2.2 Combustion and Oxidation 3.2.3 From Natural Energy to Natural Mass 3.2.4 Causes of Forest Fires 3.3 Climate Change and Forest Fire 3.4 Setting the Stage to Discover a CO2 Effect 3.5 Conclusions

37 37 38 39 42 57 68 71 89 101

4

Role of Agricultural Practices on Climate Change 4.1 Introduction 4.2 Climate-Water-Food Nexus

103 103 104

vii

19 19 20 27 35

viii Contents

5

6

4.3 Biofuel 4.4 Pathway Analysis of Biofuels 4.4.1 Chemical Fertilizers 4.4.2 Pesticides 4.4.2.1 Toxin Related to Pesticide 4.4.3 The Heavy Metals 4.4.3.1 Lead 4.4.3.2 Chromium 4.4.3.3 Arsenic 4.4.3.4 Zinc 4.4.3.5 Cadmium 4.4.3.6 Copper 4.4.3.7 Mercury 4.4.3.8 Nickel 4.4.3.9 Overall Effect of Heavy Metals on Life Cycle and Ecosystem 4.4.4 The Mechanism 4.4.5 Bioethanol 4.5 Conclusions

112 119 119 130 136 142 145 146 147 150 151 151 152 153

Role of Biofuel Processing in Creating Global Warming 5.1 Introduction 5.2 The Process of Biodiesel Manufacturing 5.2.1 Variables Affecting Transesterification Reaction 5.2.1.1 Effect of Free Fatty Acid and Moisture 5.2.1.2 Catalyst Type and Concentration 5.2.1.3 Molar Ratio of Alcohol to Oil and Type of Alcohol 5.2.1.4 Effect of Reaction Time and Temperature 5.2.1.5 Mixing Intensity 5.2.1.6 Effect of Using Organic Co-Solvents 5.2.2 Catalysts 5.2.2.1 The Effects of Homogeneous Catalyst in Biodiesel Production 5.2.2.2 Effect of Heterogeneous Catalysts 5.2.2.3 Future Trends and the Impact on the Environment 5.2.3 Greening of the Biodiesel Process 5.3 Conclusions

181 181 183 185 186 188 190 193 194 195 197 198 207 225 229 234

Role of Refining on Climate Change 6.1 Introduction 6.2 The Refining Process 6.3 Additives and Their Functions 6.3.1 Platinum 6.3.2 Cadmium 6.3.3 Lead 6.4 Science of Nanaoscale 6.4.1 Connection Between Subatomic and Bulk Properties

235 235 236 246 246 250 254 258 264

153 165 176 180

Contents ix 6.4.2 The Correct Formulation 6.5 Zeolite as a Refining Catalyst 6.5.1 Gasoline Pool 6.5.2 Linear Paraffin Isomerization 6.5.3 Isobutane–Butene Alkylation 6.5.4 Fluid Catalytic Cracking (FCC) 6.5.5 Reforming 6.5.6 Hydrocracking 6.6 Conclusions

270 277 281 282 282 283 286 287 291

7 Scientific Characterization of Petroleum Fluids 7.1 Introduction 7.2 Organic and Mechanical Frequencies 7.3 Redefining Radiation and Energy 7.3.1 Radiation 7.3.2 Flames and Natural Frequencies of Flames 7.3.3 Energy 7.3.4 Conversion of Energy Into Mass 7.4 Role of Petroleum Sources 7.4.1 Organic Origin of Petroleum 7.4.2 Implication of the Abiogenic Theory of Hydrocarbon 7.4.3 Effect on Reserve 7.5 Scientific Ranking of Petroleum 7.6 Conclusions

293 293 297 298 298 304 308 319 324 325 327 331 333 341

8 Delinearized History of Climate Change Hysteria 8.1 Introduction 8.2 Climate Change Hysteria 8.3 The Energy Crisis 8.3.1 Are Natural Resources Finite and Human Needs Infinite? 8.3.2 The Finite/ Infinite Conundrum 8.3.3 Renewable vs Non-Renewable: No Boundary-As-Such 8.4 Conclusions

343 343 345 349 349 357 358 361

9 The Monetization the Climate Science 9.1 Introduction 9.2 The Nobel Laureate Economist’s Claim 9.3 Historical Development 9.3.1 Pre-Industrial 9.3.2 Industrial Age 9.3.3 Age of Petroleum 9.3.3.1 High-Acid Crude Oils and Opportunity Crudes 9.3.3.2 Oil From Tight Formations and From Shale Formations 9.3.3.3 Natural Gas 9.3.3.4 Heavy Oil 9.3.3.5 Tar Sand Bitumen 9.4 Petroleum in the Big Picture 9.5 Current Status of Greenhouse Gas Emissions

363 363 366 375 377 377 382 385 386 387 388 389 390 401

x Contents

9.6 9.7

9.8 9.9

9.5.1 CO2 Release to the Atmosphere 9.5.2 Linking with GDP 9.5.3 Different Trends in the Largest Emitting Countries and Regions Comments on the Copenhagen Summit The Parise Agreement 9.7.1 Connection to Nordhaus 9.7.2 The Agreement Carbon Tax: The Ultimate Goal of Climate Change Hysteria Conclusions

411 421 422 423 429 429 430 435 444

10 The Science of Global Warming 10.1 Introduction 10.2 Current Status of Greenhouse 10.3 The Current Focus 10.3.1 Effect of Metals 10.3.2 Indirect Effects 10.4 Scientific Characterization of Greenhouse Gases 10.4.1 Connection to Subatomic Energy 10.4.2 Isotopes and Their Relation to Greenhouse Gases 10.5 A New Approach to Material Characterization 10.5.1 Removable Discontinuities: Phases and Renewability of Materials 10.5.2 Rebalancing Mass and Energy 10.5.3 Energy: Toward Scientific Modeling 10.5.4 The Law of Conservation of Mass and Energy 10.5.5 Avalanche Theory 10.5.6 Simultaneous Characterization of Matter and Energy 10.6 Classification of CO2 10.6.1 Isotopic Characterization 10.6.2 Isotopic Features of Naturally Occurring Chemicals 10.6.3 Photosynthesis 10.6.4 The Effect on Carbon (114C and δ13C) 10.7 The Role of Water in Global Warming 10.7.1 Water as the Driver of Climate Change 10.8 Characterization of Energy Sources 10.8.1 Environmental and Ecological Impact 10.8.2 Quality of Energy 10.8.3 Evaluation of Process 10.8.4 Final Characterization

445 445 447 456 456 460 467 467 471 487

11 Conclusions 11.1 Concluding Remarks 11.2 Conclusions of Chapter 2: State-of-the Art of the Climate Change Debate 11.3 Conclusions of Chapter 3: Forest Fires and Anthropogenic CO2 11.4 Conclusions of Chapter 4: Role of Agricultureal practices on Climate Change

537 537

491 491 493 495 495 499 503 504 515 518 522 527 529 533 533 533 534 535

541 541 542

Contents xi 11.5 11.6 11.7 11.8 11.9 11.10

Conclusions of Chapter 5: Role of Biofuel Processing in Creating Gobal Warming Concludsions of Chapetr 6: Role of Refining on Climate Change Conclusions of Chapter 7: Scientific Characterization of Petroleum Fluids Conclusions of Chapter 8: Delineraized History of Climate Change Hysteria Conclusions of Chapter 9: The Monetization the Climate Science Conclusions of Chapter 10: The Science of Global Warming

542 543 543 544 544 545

12 References

547

Index

619

Foreword In the name of ‘science’, there has been a growing trend of dogmatic solutions forced on the world by the ruling elite. Upon the election of President Donald Trump to the most powerful office on the planet, this modus operandi has reached an unprecedented hype. Among the vast majority of the ‘scientific’ world, there is a natural tendency to mock President Trump, much like they do in liberal states, such as California, New York, etc. For them, anyone advancing any argument against the so-called ‘97% consensus’ is immediately identified as a suspect and climate change denier, and, therefore, is worthy of being intellectually lynched by categorizing him/her as a Trump supporting, MAGA hat-wearing hillbilly. At this point, anything the ‘scientist’ would say, no matter how egregious, be it manufacturing cow-free burgers and milk or dimming the sun with toxic chemicals, would pass for ‘science’ while anyone advancing ‘alternate’ explanation would be ridiculed. This is not a scholarly forum, where real science can survive1. As such, this book, titled, “The Science of Global Warming” is a remarkably courageous undertaking. It is no surprise that this book starts with the deconstruction of existing ‘settled’ science. It exposes the hollowness of New Science in general and climate change hysteria in particular. The book reminds the readership, that it is New Science that has made the following transition in the past and is poised to continue along the same path. In the 70s, there was this coming of second ice age; In the 80s, acid rain was considered the villain that was ruining the planet earth; In the 90s, global warming was said to bring the earth at the brink of the tipping point;  In the 2000s, climate change was declared real and carbon designated the enemy; In the 2010s, engineering the earth began, and the natural ecosystem, carbon, water, sunlight were designated the enemy; In 2019, we prepare for the 2020s, in which an apology to acid rain is being offered and the plans are underway with billions of dollars of funding to “dim” the sun with acid and let the entire world wear toxic sunglasses - all funded by universal carbon taxes.  This is the much-dreaded environmental scheme propped up by institutions such as the United Nations. Yet, the science that others have been working with have no avenue to evaluate, let alone critique, the only ‘scientific’ recourse being promoted. It is as if the world 1

Kraychik, R., 2019, Greenpeace Founder: Global Warming Hoax Pushed by Corrupt Scientists ‘Hooked on Government Grants’, Breitbart. March 7

xiii

xiv Foreword has gone insane and cannot fathom the fundamental question as to what is wrong with carbon, water, or sunlight. This book not only asks those questions, but it goes beyond giving satisfactory answers to each of these questions, showing the lunacy of the schemes that promote ‘new wave’ nuclear energy as the panacea while vilifying natural resources as ‘evil’. In a society in which Judges and lawyers cringe at the thought of asking the ‘why’ questions, medical doctors are utterly clueless about why diseases occur, and scientists are engineers would not touch those questions in fear of losing funding, this book is as revolutionary as it gets. At the end, this book leaves no question regarding the global climate unanswered and recommends fundamental changes that can offer hope for the future. The solutions will not make more money for to do the corporations or tax-happy big governments, but who said those things have anything with proper science? The book lives up to the expectation of the name the ‘Science of Climate Change’. You have to read the book to appreciate how real science is different from dogmatic nonsense that we have been indoctrinated to believe as ‘science’. G.V. Chilingarian University of Southern California

The Science of Climate Change. M. R. Islam, M. M. Khan. © 2019 Scrivener Publishing LLC. Published 2019 by John Wiley & Sons, Inc.

1 Introduction

1.1

Opening Statement

The evolution of human civilization is synonymous with how it meets its energy needs. Few would dispute the human race has become progressively more materially advanced with time. Yet, for the first time in human history, an energy crisis has seized the entire globe and the very sustainability of this civilization itself has suddenly come into question. If there is any truth to the claim that humanity has actually progressed as a species, it must exhibit, as part of its basis, some evidence that overall efficiency in energy consumption has improved. In terms of energy consumption, this would mean that less energy is required per capita to sustain life today than, say, 60 years earlier. Unfortunately, exactly the opposite has happened. We used to know that resources were infinite, and human needs finite. After all, it takes relatively little to sustain an individual human life. Things have changed, however, and today we are told, repeatedly: resources are finite, human needs are infinite. What’s going on? Some Nobel Laureates (e.g., Robert Curl) and environmental activists (e.g., David Suzuki) have blamed the entire technology development regime, except certain disciplines of their choosing. For instance, Robert Curl would not see anything wrong with chemicals and David Suzuki would actually make living out of selling solar panels, calling them ‘renewable’ (it is these panels that guzzle cancer causing SiO2 fume that are far worse than car exhaust). Others have the blamed fossil fuel and chemical industries. It was a common saying over a century ago, that we would run out of coal; therefore, coal needs to be replaced with petroleum. Ever since the politics-related oil crisis of 1970s, we have 1

2

The Science of Climate Change

heard the declaration that the end of the global reserve is near. It was widely believed that oil price would rise to $200/bbl by 2000 and we must seek an alternate source of energy because petroleum will soon become out of reach. The opposite happened during the Clinton era, with peace dividend due to cessation of the cold war (due to dismantling of the Soviet Union), economy flourished and oil price hovered around $10/bbl. A new crisis had to be invented. Starting from the Clinton era, another concern has been added; that is, the environmental concern. With former Vice President, Al-Gore’s newfound contempt for fossil fuel and love for anything not carbon (including nuclear technology, which was curiously synonymous with Tennessee – a state Al Gore1 once represented), the world started to believe carbon was the enemy. This drumbeat against petroleum continued even during the Bush 43 era and President George W. Bush talked about ‘oil addiction’ (Islam et al., 2010). Even his most ardent detractors embrace that comment as some sign of deep thinking. Then came the Obama era – the era of contradictions and paradoxes (Brown and Epstein, 2014). If President Clinton gained notoriety by admitting to doing drugs but not inhale, Obama could admit to get ‘high’ and yet maintain his saintly aura. The Obama era is marked with unprecedented surge in oil and gas production activities that catapulted USA to energy solvency (Islam, 2014), looking to an unprecedented position of net exporter of energy (CNBC, 2018). In a paradoxical move, however, Obama increased investments in so-called renewable projects, painting the US administration as environment-friendly, with the fundamental premise that oil is not sustainable but renewable energies, such as solar, wind, biofuel are. The president who ran on the slogan ‘yes we can’, invested heavily on promises of a vast network of high-speed rail, a "smart" electric grid, a million electric cars on the roads, a "clean energy economy" creating millions of new green jobs. The ‘yes we can’ slogan turned out to be ‘no he cannot’ after spectacular failure of his promises (Editorial, 2017). After spending over $105 billion on a road system he called the "largest new investment in America's infrastructure since President Eisenhower built the Interstate Highway System," the American Society of Civil Engineers graded the state of the nation's overall infrastructure when from a "D" to a "D+." In other words, it went from poor to only slightly less poor. In fact, the Transportation Department reports (USDT, 2018) that highway congestion was worse in 2016 (4 hours 43 minutes) than it was in 2008 (4 hours 20 minutes). It is the same for electric cars that saw heavy subsidies and generous tax breaks only to see a $8 billion investment see only a tiny niche market, subsidized by millions of taxpayers who have no interest in owning one (Editorial, 2017). Similarly, Obama’s high-speed rail fantasy that was supposed to take root in 10 regions ended up being a ‘California’ dream with a price tag of $8 billion in stimulus package and $3.5 billion in grants from the federal government. This is the same California ranked no. 32 in overall ranking among 50 states (USNews, 2018), the same California that became a national disgrace for its ‘cruel’ and ‘inhuman’ homelessness crisis (Bendix, 2018). Obama’s most spectacular failure was in renewable energy spending. He spent billions of taxpayer dollars subsidizing windmills and solar plants as part of his vision of a "clean energy" future. However, despite his repeated claims about a huge increase in renewable energy production, renewables today make up just 11% of the nation's total energy production, according to the Energy Information Administration. Figure 1.1 shows how it was oil and

1

Al Gore shared the Nobel Peace Prize with IPCC in 2007 (Schiermeier & Tollefson, 2007)

Introduction

3

Quadrilliion Btu 3

2

1

0 2000

2002

2004

2006

2008

2010

2012

2014

2016

2018

Natural gas (dry) production Crude oil production Coal production Nuclear electric power production Natural gas plant liquids production Total renewable energy production

Figure 1.1 Primary energy production (from EIA, 2018).

Picture 1.1 This big solar project in Arizona is just one of the large clean power plants enabled by the Energy Department's Loan Program Office. Credit: Courtesy of NRG.

gas production that met the bulk of the energy need of the USA. In mid-1983, the share of energy production comprised of renewables was 11%. The biggest shift in energy under Obama came not from a government program, but from fracking, which vastly expanded the supply of domestic oil and natural gas. But, what all these have to do with the science of climate change? One would think scientists are the first ones to recognize inherent flaws in political decisions, involving billions of public funding. The sad reality is that scientists have abandoned objective research. In this case of energy policy and climate change strategies, 97% of scientists have pandered the liberal line, that is carbon is the enemy and as long as an energy source is not carbon, we are safe (Nuccitelli, 2018). Before we talk about the 3% who at least opposed the 97%, let us review some of the public reaction to Obama’s no-carbon policy. Biello (2015) painstakingly described how Obama’s energy policy was actually a ‘seed of clean-energy revolution’. Biello proudly displays a picture of a giant collection of 5.2 million solar panels, A blue-black field of 5.2 million solar panels (Picture 1.1) turning 300 megawatts of silicon photovoltaics (PV) into electricity. He (Biello, 2015a) connects to equally glamourous feat of a giant wind farm equipped with wind turbines (Picture 1.2) to green energy, totally oblivious of the facts

4

The Science of Climate Change

Picture 1.2 Few realize wind turbines are inherently unsustainable and nowhere close to being renewable.

that these technologies are not renewable, efficient (Chhetri et al., 2008) or safe for the environment (Islam et al., 2015). To cap it up, the loans from the U.S. Department of Energy’s Loan Programs Office (LPO) is flaunted as if this public fund that made the projects possible is a testimony that the project is a scientific marvel. To be clear, this loan program was attached to innovative technologies, defined as "new or significantly improved technologies as compared with commercial technologies" (with commercial defined as used in three or more other projects over more than five years). Some $16 billion was available before September 2011 on top of the $56 billion already available – all in name of innovative technology. So, one must wonder what great innovation these huge loans were connected to? Those innovations range from the basic layout of solar farms of more than 100 megawatts to storing sunshine in molten salts and using lens to concentrate it and improve photovoltaic efficiency. Translation? As long as it does not involve petroleum, it is innovative. Inherent to all these is the premise, is that anything related to carbon is unsustainable whereas anything related to solar, wind, or socalled ‘renewable’ is sustainable or ‘green’. As pointed out by former President Barack Obama, “There is such a thing as being too late when it comes to climate change," President Barack Obama said in unveiling the administration’s Clean Power Plan at the White House on August 3, "The science tells us we have to do more." All of a sudden, a president with law degree sanctifies ‘science’ and none of the 97% scientists could ask the research questions: 1. What is the long-term consequences of the ‘renewable’ energy? 2. What is the real cause of global warming? Instead of seeking to answer these research questions, the debate now moves on to the phase, where the research question become 3. How the economics of ‘renewable’ energy can be improved? 4. How can we reduce our ‘oil addiction’? Not surprisingly, the solution becomes Carbon tax, so the ‘oil addiction’ is minimized and with added revenue more can be spent to offset the poor economy of ‘renewable’

Introduction

5

energy sources or worse, some absolutely preposterous idea. What could be more preposterous than taxing people to offset so-called renewable energy sources that account for less than 20% of the total energy? Well, it seems scientists lived up to the insanity that would make flat earthers look logical. In 2018, Smith and Wagner came up with the ‘brilliant idea’ that the solution to global warming is to spray the stratosphere with aerosol, containing sulfates – the very kind that contributed to the current crisis. It is reminiscent of Stephen Hawking’s claim that the solution to global crisis that is a fruit of colonization is to colonize the Mars. But, at least Stephen Hawking didn’t have an axe to grind. He wasn’t waiting to cash in a large grant out of his insane comment. For Smith and Wagner, it is a lucrative business. They propose developing a new, purpose-built high-altitude tanker with substantial payload capabilities. That’s a great ticket to instant cash considering that a 15 year span for the spraying project is proposed. These are the scientists that give credibility to politicians, who have been vocal about academic ‘corruption’ akin to corporate greed2. As Sen. Rick Santorum said, “If there was no climate change, we’d have a lot of scientists looking for work. The reality is that a lot of these scientists are driven by the money that they receive," if one consensus that’s worth a mention it is the fact that scientists have made funding to be their primary motivator. The response of the 3% ‘disbeliever’ scientists have been first denial that global warming exists, then challenge the prospect of replacing fossil fuel with a workable alternative, arguing that the economics of scale offered by fossil fuel cannot be overcome with alternative energy sources. This line of argument buries the possibility of answering pivotal Questions 1 and 2. This book brings back real science to answer the most important questions regarding climate change. These questions have eluded both sides of the Climate change debate. Because one side of the debate (the 97%) starts off the premise that ‘Carbon is the enemy’ and this book starts off the premise that carbon is essential to life, this book may appear to be taking side of the 3% ‘climate change denier’. This perception is inaccurate. In this book, the mistakes of both sides are corrected and, as such, it opposes both current views of climate change. The only stance the book backs is the pure logic – free from dogmatic assertions. As such, it criticizes all dominant physics and chemistry theories that have been built on illogical, aphenomenal and unnecessary premises. It is, however, found that mainstream scientists have resorted to take a stance that can be considered liberal (antiCarbon). We see no excuse for such bias other than ‘monetary axe to grind’. In this process, economists have played a role in what we call monetizing ignorance or bias. This is not just an economics problem (Islam et al., 2018a), this is also a scientific integrity problem. This book will show how every time the most logical options have been avoided in explaining natural phenomena, instead resorting to dogmatic solutions that would support the desired conclusion. Whenever someone critiqued this process and pointed out obvious fallacies, he/she has been a target of attack by people who have little or no understanding of fundamental processes at play. In that process, even the likes of US President has not been spared (Nuccitelli, 2018). In the meantime, it has become fashionable even to promote nuclear energy pitting against fossil fuel and that too by the likes of Al Gore

2

US Sen. Rick Santorum recently claimed that climate scientists "are driven by the money that they receive." (See Burke, 2018 for details)

6

The Science of Climate Change

and even Crown Prince of Saudi Arabia (Frantzman, 2018). This book brings back logic and isolates politicking from science and delivers scientific findings in their purest forms.

1.2

Summary

Even though petroleum continues to be the world’s most diverse, efficient, and abundant energy source, due to “grim climate concerns”, global initiatives are pointing toward a “go green” mantra. When it comes to defining ‘green’, numerous schemes are being presented as ‘green’ even though all it means is the source of energy is not carbon. In fact the ‘left’, often emboldened with ‘scientific evidence’, blames Carbon for everything, forgetting that carbon is the most essential component of plants. The ‘right’, on the other hand, denies climate change altogether, stating that it is all part of the natural cycle and there is nothing unusual about the current surge in CO2 in the atmosphere. Both sides ignore the real science behind the process. The left does not recognize the fact that artificial chemicals added during the refining process make the petroleum inherently toxic. This book is aimed at examining science behind global warming and climate change. Avoiding the conventional approach of looking into ‘greenhouse gases’ that are recognized to be from anthropogenic activities, this book looks beyond the usual suspect of fossil fuel. By using a detailed pathway analysis, this book identifies flaws of various energy production schemes, including petroleum resource development. The source of alteration of CO2 quality that renders the CO2 unabsorbable by the ecosystem is identified for cases of forest fire, agricultural activities, fossil fuel as well as biofuel. The nature of CO2 emission from various processes, including biomass (during the agricultural process and beyond) is analyzed and decisions made as to what role it will play to the global scenario. CO2 emission data from the pre-industrial age all the way to current era are then analyzed, showing clear correlation between CO2 concentration in the atmosphere with ‘corrupt’ CO2 emission, which itself was a function of the fuel source, the path it travels, isotope numbers, and age of the fuel source. Various energy technologies are ranked based on their long-term sustainability. It is shown that petroleum is the most environmentally benign among the energy sources investigated, followed by biofuel, solar, wind, and nuclear. When the artificial chemicals are replaced with natural substitutes at various phases of petroleum processing, petroleum wastes become useful materials that can be recycled in the ecosystem in a zero-waste mode. Not only the by-products, including CO2 emissions, are benign, they are in fact beneficial to the environment. Each of these wastes can then become raw materials for value added new products. Finally the paper offers guidelines for ‘greening’ of petroleum operations as well as the economics of zero-waste petroleum production and longterm environmental sustainability.

1.3

Chapter 2: State-of-the Art of the Climate Change Debate

Politics has never been separated from science – at least not in the post-RCC (Roman Catholic Church) Europe. Of course, politics has been controlled by the Empire or the

Introduction

7

Church, but when it comes to science, it is entirely controlled by politics. Many argued that for reasons unknown and unjustified scientists are capable of looking at facts and impart objective judgement without regards to their political belief. As pointed out by Jaan Islam (2018), this arises from fundamental illogical assumption that scientists (or any human) can dissociate his/her conscience from any influence of the outside, particularly the one that will determine his/her financial status in the near future. This internal conflict was blown open during the Enron scandal of the 2003 and following years. In following years all the way through Obama’s second term, scientists took an unusual dip in terms of abandoning the path of objectivity. Each research project funded by the government and each commercial project sponsored with government blessing had invariably have the starting point that Carbon is the source of ‘vile’ and alternate energy sources were inherently beneficial. However, 97% of the scientists argued in favour of the liberal agenda whereas the 3% argued against the liberal agenda (Bolton, 2016). Once this premise is established, nothing can stop scientists from making statements, such as the one made by Sarah A. Green, a chemistry professor at Michigan Tech who said, "What's important is that this is not just one study -- it's the consensus of multiple studies" (quoted by Bolton, 2016). This is not a new paradigm but it was a paradigm Al Gore perpetrated decades ago, long before the climate debate even started. More significantly, this immediately gained traction when Democrats threw their support for the March for Science, asking Americans to vote climate change deniers out of office (Delk, 2018). The New Crusade began and new slogans became: “Accept reality”, “Ignoring experts is stupid”, “Climate denial is very expensive” – all making headlines in the mainstream media and popular science magazines. In justifying each side’s position, they did not correct each-others’ fundamental premises. As a result, the debate moved to a different topic and that is Scientists vs. Climate Change deniers. Of course, numerous publications purporting to discover the real mindset that make people so fixated on their position, some even suggesting deep divergence in psyche behind liberal and conservative stances (Laber-Warren, 2012). In all practicality, there was no science to be investigated as it has been universally established that climate change is the reality and carbon is the enemy. Then came the Trump phenomenon. No other president in US history exposed the role of politics in every affair, including science. In science, the biggest exposé was Trump’s energy policy that has been opposed by the Scientific community and even the judiciary has become involved. There has been this incessant ridicule that Trump has no regard for real science (Nuccitelli, 2018) in line with Nobel laureate economists’ joint concern that Trump economy would be an utter failure or even the great concern of psychologists that Trump is mentally incompetent to govern (Islam, 2018a,b). He was also ridiculed for withdrawing from the Paris Agreement. In the latest case, involving the controversial Keystone XL pipeline project, a federal judge temporarily blocked the construction on the basis that selective facts were chosen to grant a permit for the 1,200 mile long project designed to connect Canada’s oil sands fields with Texas’s Gulf Coast refineries (Barbash et al., 2018). Clearly, science has failed to deliver objective truth, let alone universal truth and politics has become the gatekeeper of research outcomes and ‘facts’. Chapter 2 reveals the nature of climate change debate. Both sides of the debate are exposed and their fundamental premises deconstructed.

8

1.4

The Science of Climate Change

Chapter 3: Forest Fires and Anthropogenic CO2

Global warming is synonymous with heat. In a natural system, fire is the most tangible source of temperature. It is no surprise that wildfires sweeping across various parts of North America, Europe and even Siberia have caught attention of the scientists, who are inclined to find any justification for their climate change theory. These fires are not only wreaking local damage and sending choking smokes, they are also affecting the climate itself in important ways that will have long-lasting impacts. Scientists see these wildfires as the source of carbon dioxide and other greenhouse gases. The underlying assumption is that these forest fires damage forests, thus removing CO2 from the air. In addition, they assume that the soot and other aerosols into the atmosphere that arise from wildfires will behave like artificial aerosols and carcinogenic chemicals, thus rendering the climate more adverse to human inhabitants. Even though until now it is recognized that the leading cause of global warming is overwhelmingly the burning of fossil fuels, forest fires are considered to be making the situation worse. In essence, global warming lengthens the fire season, drying and heating the forests, thus creating an environment more conducive to wildfires, a vicious cycle with the results of warming produce yet more warming. In fact, every time there is a wildfire (Picture 1.3 and Picture 1.4) , scientists become busy writing yet another research proposal in search of

Picture 1.3 The Woolsey Fire raged near the Ventura-L.A. County line, burning about 2,000 acres and forcing mandatory evacuations in several communities. Chatsworth West Hills area, California (Nov. 8, 2018).

Picture 1.4 Bush fire burns near Rocketdyne complex Simi Hills, California (Nov. 8, 2018).

Introduction

9

solutions to mitigate global warming. It is truly amazing how scientists do not see wildfires as part of the natural process and further conflate this fire with artificial fire, for instance the ones arising from fireworks. Yet, for millennia, humanity has seen wildfires as part of the natural process and considered it a blessing similar to floods that help renew the biological system. Indeed, changes in climate, atmospheric carbon dioxide concentration and fire regimes have been occurring for millennia in the global boreal forest without affecting the overall frequency of forest fires. Instead, scientists spend their time quantifying CO2 emitted from wildfires and assign those billions of tons of CO2 per year to the overall CO2 imbalance of the atmosphere. Immediately, this is taken up by researchers from both sides of the climate change debate. One side argues that wildfires release as much CO2 as cars, therefore that there is no point of even trying (Thompson, 2007). The other side argues that by introducing carbon-free cars, we can reduce the greenhouse effect to half. In the mean time, scientists look on as if they have no clue as to how to solve this puzzle (Bond-Lamberty et al., 2007). The research focus has been on assessing quantitatively the effect of changing environmental conditions on the net boreal forest carbon balance without regards to the nature of CO2 emitted from the forest fires. A great deal of publications have emerged, all confirming the same conclusion that was embedded in the first premise. Chapter 3 unravels the mysteries of forest fires and their link to global warming. Dominant theories are deconstructed and the science of real fire is presented. Thompson, A., 2007, Wildfires Release as Much CO2 as Cars, Live Science, Oct. 31. Bond-Lamberty, B. et al., 2007, Fire as the dominant driver of central Canadian boreal forest carbon balance, Nature, volume 450, pages 89–92.

1.5

Chapter 4: Role of Agricultural Practices on Climate Change

Climate change and global warming have been connected to agriculture and food production only through evaluation of impacts on crop production. The application of agriculture of crop involving biofuels has been considered to be entirely positive as an alternative to fossil fuel, which is the declared target of any global warming mitigation mission. Yet, there is widespread acceptance that climate change and agriculture are interrelated processes, both of which take place on a global scale. Factors that have been studied with relation to climate change are changes in average temperatures, rainfall, climate extremes, changes in pests and diseases, in atmospheric carbon dioxide, ground-level ozone concentrations; in the nutritional quality of some foods; and in sea level (Vermeulen et al., 2012). The most important link has been to food security and how it relates to economic aspect of farming. Many initiatives have been undertaken around the world, all missing one crucial aspect, that is how the use of chemical fertilizer, pesticide, and the latest use of GMO can impact the CO2 that the vegetation breathe out to the atmosphere or how these chemicals affect the photosynthesis

10

The Science of Climate Change

process. Not a single research study addresses the analysis of the entire pathway followed by a crop either through its consumption or its processing for biofuels. Not a mention has been made regarding the negative impact of chemicals on human health and related long-term consequences. Instead of answering these pivotal questions, the focus of the world scientific community has been to act as the rubber stamp in support of global policy-linked research, pontificating the third world about how to survive the onslaught of global warming – a phenomenon that has little to do with the third world. Chapter 4 answers the questions that have not been answered before. It presents the delinearized history of agricultural practices and how they can impact the CO2 concentration of the atmosphere, thus contributing to the climate change. It is shown that the practices involving agriculture can affect the global CO2 accumulation far more intensely than the burning of fossil fuels.

1.6

Chapter 5: Role of Biofuel Processing in Creating Global Warming

Ever since the Clinton era, biofuels have been considered to be sustainable alternatives to petroleum products. It has become a foregone conclusion that biofuels are inherently sustainable (hence the term ‘renewable’) and the debate moves on to how to produce biofuels cheaply. Because few are accustomed to questioning the first premise of any of these conclusions, even the ardent supporters of the petroleum industry find merit in this conclusion. Considerable funds have been spent in developing biofuel technology, and even the mention of negative impacts of food (e.g., corn) being converted into fuel was considered to be anti-civilization (Islam et al., 2010). The argument put forward is that plant and vegetable oils and animal fats are renewable biomass sources. This argument follows other supporting assertions, such as the idea that biodiesel represents a closed carbon dioxide cycle because it is derived from renewable biomass sources. Biodiesel has a lower emission of pollutants compared to petroleum diesel. In addition, it is biodegradable, and its lubricity extends engine life (Kurki et al., 2006) and contributes to sustainability (Kurki et al., 2006). Biodiesel has a higher Cetane number than diesel fuel, no aromatics, no sulfur, and contains 10–11% oxygen by weight (Canakci 2007). The negative aspects of biofuels are expressly limited to physical properties that are not amenable to instant combustion, as required in a combustion engine, its cost, and its use of edible sources. Based on this argument, alarms were sounded when oil prices dropped in fall of 2008, as though a drop in petroleum fuels would kill the “environmentally friendly” biofuel projects, thereby killing the prospect of a clean environment. As a remedy to this unsubstantiated and aphenomenal conclusion, waste cooking oils and non-edible oils are promoted to take care of the economic concerns. Not a single study thoroughly investigated the effect of chemical fertilizer, pesticide, or GMO on the long-term impact of the CO2 that would eventually be produced upon combustion of the biofuel. Not a single conclusive statement has been made in assessing the impact of the chemicals used to process biofuel. Both of these questions are answered in Chapter 5. It is shown that the process currently followed to refine vegetable oil to produce biofuel can lead to permanent contamination of biofuels.

Introduction

1.7

11

Chapter 6: Role of Refining on Climate Change

Refining has been synonymous with value addition, efficiency, and outright civility of the modern society. No fossil fuel today sees combustion in its crude form, always being subject to refining, processing with chemicals that are prepared separately and almost always artificially (as in synthetic chemicals or catalysts). It is no surprise that the most ardent supporters of climate change advocacy do not hold particular grudge against refiners or chemical industries that process crude oil into useable products. As for the ‘climate change deniers’, they see nothing different about the refining process from simple usage of a natural technology that is advancing the efficiency. They wonder, this must be a way to reduce their carbon footprint. This stance is visible in all walks of life. For instance, consider the headline: Refiners Aren’t To Blame For Climate Change (Rapier, 2018). The arguments made in support of such headline is: refiners did not cause climate change because all they did is to improve the efficiency of burning, how could that be harmful. In fact, a common argument is to say, if refining is harmful, why not pharmaceutical products or even agricultural products? After all, they are also using chemicals (mostly the same chemicals as the refining industry). New Science has no argument against this defence of the refining industry. Chapter 6 takes a fresh approach that looks at each of the major chemicals used during the refining process and evaluates the long-term impact of the chemicals. This chapter helps see how changes in trace elements can profoundly affect the CO2 character, thereby rendering it unabsorbable by the ecosystem.

1.8

Chapter 7: Scientific Characterization of Petroleum Fluids

Crude oil and natural gas are part of the global ecosystem (Figure 1.2). Because all systems in the global climate system are connected, adding heat energy causes the global climate as a whole to change. If this source of heat is artificial, it will have a different impact from the one in its natural state. It is the artificial component that creates

Figure 1.2 Heat is energy and when energy is added to any system, changes occur.

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The Science of Climate Change

imbalance. Yet, today all of produced oil and gas are subject to refining or processing with the aim of producing fuel that can be burned to produce energy. This refining or processing uses exclusively artificial chemicals, no matter what the crude form of the petroleum is. These products can be tar sand, heavy oil, light oil, or natural gas, they all end up being fuel first, leaving behind residues that form the feedstock for chemical products with a wide range of applications. Curiously, the heaviest part of the crude petroleum products becomes immune to climate change criticism as the main target is the fuel component that is readily burnt, instead of being a feedstock for the plastic, pharmaceutical, and numerous other useful products. As such, no study has focused on the effect of characterizing petroleum fluids in order to custom design applications. Yet, such characterization can have profound impact on both the currently estimated world reserve as well as on climate change itself. Chapter 7 presents a comprehensive scientific characterization of petroleum fluids and shows how the world petroleum reserve can be expanded vastly through proper characterization and appropriate applications. Refining and other processing means are proposed that would allow for sustainable application of petroleum and reverse the current global warming trends.

1.9

Chapter 8: Delinearized History of Climate Change Hysteria

When G. W. Bush laid out his action plan to declare ‘war on terror’, he used the now infamous rhetoric ‘you are either with us or against us’. Not a single western state questioned his motive and it was unanimously agreed that the war on terror must start with Afghanistan. When it comes to politics, people seem to have very short memory. How could they forget what happened to Socrates, who was also condemned by the 500-man jury? Some fantasize that such nonsense does not apply to science, particularly not after New Science was launched, allegedly after shedding the lunacy of religious Dogma. The ‘civilized’ version certainly is enlightened. After all, they are not blinded with faith and other inconveniences that obstructed the real inquisitive nature of humans. These people are either not paying attention to facts or are incapable of seeing anything beyond their first premise. Marc Morano (2018), the author of the book: The politically incorrect guide to climate change circulated a video with over five million viewers on Facebook, he was ridiculed as the real-world fossil fuel industry version of Nick Naylor (Nucitelli, 2018a). The title of the Guardian article read: Facebook video spreads climate denial misinformation to five million users Nucitelli, himself a faithful believer of Climate change agenda,3 points out that Morano was working for Rush Limbaugh, followed

3

Dana Nuccitelli is an environmental scientist at a private environmental consulting firm in the Sacramento, California area. He has made a career out of promoting ‘the 97% consensus’.

Introduction

13

Figure 1.3 The propagandizing of consensus.

by a job at Cybercast News Service where he launched the ‘Swift Boat’ attacks on 2004 Democratic presidential candidate John Kerry. In 2006, Morano was further discredited through his association with Oklahoma Republican Senator Jim Inhofe, who was himself ridiculed for his characterization of global warming as “the greatest hoax ever perpetrated on the American people.” So, what evidence does Nucitelli provide in support of such vitriol attack and characterize Morano as the perpetrator of Fakenews? Nucitelli comes up with the fact that as early as 2004, the consensus was 100%. As shown in Figure 1.3, each consensus study have been reporting over 90% consensus. At no time, it occurred to them that consensus has no meaning when it comes to establishing veracity of a natural occurrence. It is clear that the only question that is allowed to ask is as hysterically posed by Griffin (2015): Can Civilization Survive the CO2 Crisis? It is already decided that CO2 is the enemy and the debate must revolve around how much more we can extract from the unsuspecting public to feed the scientists who can foment more fear as the Establishment sells another round of fear mongering. Chapter 8 makes a bold assessment of the Climate Science researchers and propaganda con artists, ranging from politicians to scientists. A delinearized history brings forth key questions that needed to be answered but for some reason no scientist dared ask, instead debating over peripheral issues. This chapter exposes the reasons behind the incessant propaganda that has become the trademark of climate change activism. By analysing each historical landmark events, the chapter shows how scientists failed to even ask the questions that would have the faintest chance to expose the hollowness of the fundamental premises they promoted as facts. This sets stage for the next chapter that shows the motivation behind the ‘science’ of climate change hysteria.

1.10

Chapter 9: The Monetization the Climate Science

Hypocrisy aside, New Science has been solely motivated by financial gains and that too in the shortest possible timeframe (Islam et al., 2018a). Economics, in that case, has become the driver of the inanity that has become the hallmark of New Science. This is perhaps nothing new, what is new during the Trump era is the exposure of the sinister

14

The Science of Climate Change Decision Disinformation Opacity Justification

Figure 1.4 This is the inevitable outcome of the ‘original’ sin model that reverses the cognition process, and thereon corrupts the entire humanity. Unfortunately, there is no exception that we can cite in the entire history of modern Europe (From Khan and Islam, 2016).

forces that once had the protection of crying ‘conspiracy theory’. As the German economist, John Komlos, famously said, "The media is inundated with pundits analyzing the unexpected rise of demagoguery. I would like to add my own: the establishment’s utter loss of credibility. Abraham Lincoln’s warning, 'you cannot fool all of the people all of the time,' has now come back to haunt them with a vengeance" (Parramore, 2016). After Trump, the world has come to know how the mainstream media, political establishment, and the financial establishment have been working together to influence science and economics simultaneously, feeding back the narration that the Establishment is always right (Islam et al., 2018). The model used in making policies is the one shown in Figure 1.4. In this model, the decision is made before collecting facts, let alone turning facts into useful information that eventually leads to knowledge-based decision making. With this model, there is no decision making outside of the policy room and in this process, scientists and journalists work toward creating opacity and giving justification to the decision, in turn contributing to propagandizing. In the context of climate change, the decision is to extract carbon tax and after that everything else is cursory. This is nothing but the secular version of the Dogma model from the dark ages of the Roman Catholic Church. This is what we call the “trinity model” in which the original sin doctrine gave birth to the trinity model of religion. This trinity model, based on a lack of appreciation for humanity and involvement in the material (societal, political economic) sphere of life, fuelled the alternative material trinity that developed: the government, society, labour, all based on devotion to money. Nothing supports the ‘money god’ devotion better than the climate change ‘crisis’. The recent proclamation (synchcronized with Economics Nobel prize given to ‘Climate change’ economist and a world bank former operative) of IPCC that universal carbon tax feeds right into this corporate culture that continues to create economic extremism (Islam et al., 2018a). In the mean time, New Times (2018) headline reads: “Climate Change will take a bite out of US Economy.” US under the leadership of President Trump, of all places, is expected to succumb to this grand scheme. Of course, anyone non-conforming to this new Dogma will be quickly marginalized, as evident from CNN headlines that continue to ridicule President Trump and even otherwise timid Canadian press (CBC, 2018): chimes in: “Trump rejects findings of U.S. government climate change report.” Today, there is no

Introduction IS NOT

GOVERNMENT SON

IS

FATHER CORPORATION

15

IS

SI

IS N

OT IS N

OT

MONEY GOD

CHURCH HOLY SPRIT

Figure 1.5 The Material Trinity (from Khan and Islam, 2016).

Christian dogma, but the existence of the material trinity found in Figure 1.5 flourishes with even greater fervor. Today, Climate change advocates start off with the premise that CO2 is the cause of all disaster and then make a religion out of this premise, thus benefiting the establishment while lining their purse. In this process, false premises are introduced by scientists and economists. Then, they feed each other to create an illusion that collectively they are making progress. Consider the fact that Nobel peace prize was given to Al Gore and IPCC in 2007. Over a decade later, the economics Nobel prize was given to two economists: one a climate change crusader and the other is a spin doctor for the World Bank. This is the era that saw liberalism and conservatism descending upon Neoliberalism and Neoconservatism, respectively. In the mean time, most people do not have a clue what Neoliberalism and Neo-conservatism are but they are quite sure they don't like them. It is entirely lost on them that Neoliberalism has exactly nothing to do with being liberal and Neo-conservatism has pretty much nothing to do with Conservatism. Yet, they are told this is the only option they have – thanks to the intellectual laziness of the academia (Komlos, 2017). Chapter 9 shows how every major scientific project and economic strategy worked to establish and prop up the false narrative that would support the long-sought bounties through carbon taxes and other freebees for boosting the agenda of the environmental activists. These projects have nothing to do with science but everything to do with

The Science of Climate Change

16

covering up and justifying the climate change hysteria. All their efforts have been spent on turning science of reality or truth into science of ‘controlling reality’, commonly known as disinformation with an ulterior motive, which is monetization of ignorance. Science no longer serves the purpose of uncovering the truth, it has merely become the convenient tool of policy justification and weaponizing falsehood.

1.11

Chapter 10: The Science of Global Warming

Before we even discover the true cause of global warming or climate change, all alarms are triggered and climate change is perpetrated as an international emergency. Millions of dollars are doled out to research how we can adapt to the new reality, which is of course – ‘climate devastation because of carbon’. That fear mongering is accentuated with a new fear, that is, climate change is a health emergency for all of humanity. Climate change is not just hurting the planet – it is a public health emergency (Figueres, 2017). There is this rush to doing something and anything but there is absolutely no appetite to find facts, let alone solutions that actually remedy. It seems there is no need to find a sustainable solution because we already know that the solutions will not do anything beyond offering a very short-term reprieve. This point was made by Jordan Peterson, a psychology professor at Toronto University. Recently, Jordan Peterson gained notoriety (or fame from the climate denier) when he showed the helplessness of the current civilization. He said in a gathering on climate change and climate policy at the Cambridge Union: “It’s difficult to separate science from the politics and even if the claims are true and… anything we do right now when you can’t even measure the consequence of your actions how is that even possible, and besides that, what’s the solution? Switch to wind and solar? Try and see what happens!”

Then the good professor pontificates, albeit with a touch of humanity, “These things are complicated, man!” So, what does he offer as a solution? After all, he has worked in the panel that set strategies for climate change actions. He continues: “So you know maybe if you increase child nutrition and you produce another 10 million geniuses as a consequence of that… it’s not a bad thing to increase the total sum of human brain power tripping so lightly… what everyone thinks that’s the biggest maybe it is but if you don’t have a solution to problems what are you gonna do about them? Feel good about being concerned about global warming? I don’t know. No one knows.”

It is always amusing how professors of all people can foam their mouth non-stop moving from one false premise to another. Jordan Peterson vibrates4 on the false premise that there is nothing inherently wrong with solar panels, wind turbines and even nuclear energy. None of them is, however, acceptable all because of their

4

In Islam et al., (2017) we describe the worst form of cognitive dissonance as incessantly moving from one false premise to another, termed as ‘vibrating’.

Introduction

17

economics or utility. For each of them, he gasps, "Good luck with that!" and lays out more hopelessness and continues, 'if burning coal is bad, what are going to do? Burn trees? Stop driving cars? So, so, no." He repeatedly says, he does not know what the solution is but he certainly speaks of nutrition for children that would create brain power necessary to find a solution. The depth of ignorance and height of hubris is breathtaking. Recall American Astrophysicist Neil deGrasse Tyson's notorious statement, “The good thing about science is that it's true whether or not you believe in it.” For Neil DeGrasse, no one dared cross him with the obvious question: “Would that be applicable to the Creator?” Then add to that Baroness Thatcher’s infamous ‘There is no alternative’ (TINA) line and one has the explanation for what’s wrong with today’s civilization. This is the unavoidable outcome of linear thinking that goes back to Dogma time but that became secularized after Newton. What we are being told is, we have only two options: False Premise 1; False Premise 2. Then, the cognitive dissonance kicks in and we debate over which premise would minimize the distance between premise and conclusion, no other option being open to us. Anything else is called radical and everyone that conforms to the system and agrees to disagree is called civilized and worthy of co-existence. Unfortunately, the current theories (both left and right) do not stop at predicting chaos or anarchy, it goes further and asserts that the chaos/anarchy model is the only model and there cannot be an alternative model. Zatzman and Islam (2007, p. 56) attributed this philosophy to Baroness Thatcher’s infamous statement, “There Is No Alternative”, calling it the TINA syndrome. This mindset has prevented scientists, philosophers and economists to even look anywhere. Only recently, with President Trump opening up the topic, some scientists started to speak out the obvious. In the past, few of reputation dared speak lest they be tainted as ‘climate denier’ – a cardinal ‘sin’. Professor Lindzen, of the Massachusetts Institute of Technology, argued that it was totally implausible for such a complex ‘multifactor system’ as the climate to be summarised by just one variable, global mean temperature change, and primarily controlled by just a 1–2 per cent variance in the energy budget due to CO2 (Wilkinson, 2018). He, however, barked up the wrong tree. He complained about “an implausible conjecture backed by false evidence repeated incessantly has become ‘knowledge,’ used to promote the overturn of industrial civilisation.” (Wilkinson, 2018). For him, he sees the 97% scientists as a threat to current civilization, but not to real science. Lindzen, however, correctly calls out the extravagant models for which climate scientists have become famous, likening them to ‘the formula for being an expert marksman: shoot first and declare whatever you hit to be the target.’ This is what we call the usage of the aphenomenal model (Figure 1.4) – a tactic that has made scientists turn into sheeple, incapable of seeing past their false first premise. Chapter 10 is devoted to answering the most crucial questions regarding climate change. It resorts to no dogma and starts with fundamentally sound premises. After deconstructing all existing theories and discarding them for their false start (through illogical premises), this chapter uses real science and shows how the root of the current climate change is in the usage of artificial chemicals. This chapter caps the much-needed

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The Science of Climate Change

scientific discussion that can answer all questions, related to climate change without resorting to dogma.

1.12

Chapter 11: Conclusions

In numerous occasions, this book has claimed to answer questions that eluded modern scientists and economists alike. Not only does this book raise those questions, it also answers them with logically consistent answers. These conclusions are not in line with any of the conclusions that have been made from the left or the right. In fact, these conclusions are bound to raise anger and disbelief from both sides of the climate change debate. It is also guaranteed that not a single hole can be punched in the arguments made in coming to these conclusions. For the first time in the Information Age, one can claim that science has been insulated from political influences and has been exclusively devoted to unearthing the objective truth.

The Science of Climate Change. M. R. Islam, M. M. Khan. © 2019 Scrivener Publishing LLC. Published 2019 by John Wiley & Sons, Inc.

2 State-of-The-Art of the Climate Change Debate

2.1

Introduction

The climate change debate has been lopsided in the sense that vast majority of scientific authorities have taken the position that manmade activities have been the driver of the current state of climate change. Repeatedly, this position has been stated in all IPCC (Intergovernmental Panel on Climate Change) reports, all claiming that based on the last 250 years of data and analysis of post industrialization (after 1750), there is a clear correlation between global warming and human activities, related to the use of fossil fuels, starting with coal and peaking with the ubiquitous usage of oil and gas. This side of the debate has fomented the ‘carbon the enemy’ slogan citing "grim climate concerns", recommending global initiatives all pointing toward a "go green" mantra. When it comes to defining 'green', numerous schemes are being presented as 'green' even though all it means is the source of energy is not carbon. In fact, the political 'left' in North American and European countries are often emboldened with 'scientific evidence’, forgetting that carbon is the most essential component of plants. Many in the political 'right', a minority in the scientific circle, on the other hand, deny climate change altogether, stating that it is all part of the natural cycle and there is nothing unusual about the current surge in CO2 in the atmosphere. This side cites historical evidence in geological time and argues that the modern day global warming is actually a cooling cycle, only if one considers the geological timeframe. This group 19

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The Science of Climate Change

also discredits the data acquisition techniques and questions the statistical methods that end up with the conclusion that anthropogenic climate change (ACC) is real. In this chapter, the arguments advanced from both sides are presented. Whenever appropriate, the scientific basis for the clams made is discussed either to consolidate the argument or to refute commonly held beliefs.

2.2

The Anthropogenic Climate Change (ACC)

Anthropogenic climate change refers to climate change resulting from the production of greenhouse gases emitted by human activities. This very wording implies that climate change is inherently related to anthropogenic carbon dioxide. Such naming bypasses the role of refining or any other process that is inherent to fossil fuel utilization. By using Pragmatism1, the proponents of ACC have relied on data on CO2 and ‘global’ temperature. By examining polar ice cores, scientists are convinced that human activity has increased the proportion of greenhouse gases in the atmosphere, which has skyrocketed over the past few hundred years. All IPCC reports continue to assert that the evidence of the post-industrial rise in greenhouse gases overwhelmingly suggests that these activities, and not natural mechanisms are responsible for the global temperature rise. What is remarkable in this narration is that today’s science does not discern between carbon dioxide (or any other greenhouse gas) of natural sources (e.g., organic matter) and carbon dioxide of artificial sources (e.g., combustion engines). The most potent of the greenhouse gases are carbon dioxide (CO2), methane (CH4) and nitrous oxide (N20). Today’s anthropogenic climate change, and the gases are allegedly at the highest levels for over 650,000 years. The IPCC Fourth Report (IPCC, 2007) confirms that over the past 8,000 years, and just before Industrialization in 1750, carbon dioxide concentration in the atmosphere increased by a mere 20 parts per million (ppm). The concentration of atmospheric CO2 in 1750 was 280ppm, and increased to 379ppm in 2005. For comparison, at the end of the most recent ice age there was approximately an 80ppm rise in CO2 concentration. This rise took over 5,000 years, and higher values than at present have only occurred many millions of years ago. Since 1750, it is estimated that about two thirds of anthropogenic climate change CO2 emissions have come from fossil fuel burning (coal and petroleum) and about one third from land use change (mainly deforestation and agricultural). Estimates are made routinely by the IPCC about the relative contribution of various greenhouse gases on the overall climate change (for instance, IPCC, 2014). The following are the principal contributors: Carbon dioxide (CO2): Anthropogenic climate change involves CO2 generated through use of fossil fuel, starting with coal in the 18th century,

1

Pragmatism is a philosophical movement that essentially argues that an ideology or proposition is true if it works satisfactorily, that the meaning of a proposition is to be found in the practical consequences of accepting it, and that unpractical ideas are to be rejected. Islam et al., (2013) point out that Pragmatism is the modern version of ‘end justifies the means’ mantra

State-of-The-Art of the Climate Change Debate

21

then followed by oil and gas. Also considered is the CO2 imbalance due to human-induced impacts on forestry and other land use, such as through deforestation, land clearing for agriculture, and degradation of soils. Likewise, land can also remove CO2 from the atmosphere through reforestation, improvement of soils, and other activities. Methane (CH4): Agricultural activities, waste management, energy use, and biomass burning all contribute to CH4 emissions. Nitrous oxide (N2O): Agricultural activities, such as fertilizer use, are the primary source of N2O emissions. Fossil fuel combustion also generates N2O. Fluorinated gases (F-gases): Industrial processes, refrigeration, and the use of a variety of consumer products contribute to emissions of F-gases, which include hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulfur hexafluoride (SF6). In the above list, fossil fuel usage is considered to be the driver. It is so because both agricultural activities and F-gases are rooted in petroleum activities and/or raw materials sourced in petroleum. Of the emitted CO2, approximately 45% is considered to remain in the atmosphere, while approximately 30% is believed to be taken up by the oceans and the remainder taken up by the trees and plants. About half of the CO2 going into the atmosphere is removed over a time scale of 30 years; a further 30% is removed within a few centuries; and the remaining 20% will typically stay in the atmosphere for many thousands of years. Figure  2.1 Shows the distribution of major green house gases by sources. Global GHG emissions by gas: 65% is from carbon dioxide fossil fuel use and industrial F-gases 2%

Nitrous oxide 6% Methane 16%

Carbon dioxide (forestry and other land use) 11%

Carbon dioxide fossil fuel & industrial use 65%

Figure 2.1 Major greenhouse gases and their contributions (from IPCC, 2014).

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The Science of Climate Change

processes; 11% is from carbon dioxide deforestation, decay of biomass, etc.; 16% is from methane; 6% is from nitrous oxide; and 2% is from fluorinated gases. The following three major effects are considered (Karl et al., 2003): – Greenhouse gas emissions CO2, methane – Aerosols cooling – Land use cities, deforestation, agriculture, water “management” In recent decades, carbon emissions have continued to increase. Global annual fossil emissions increased from an average of 6.4 GtC/yr. Almost all arguments in favour of ACC are built on physical observations of global observation, the data of which exist from the early 1900 s Because the ‘golden era’ of petroleum started after that period, it is mostly asserted that any anomalous rise in global temperature must be due to petroleum production and usage. The criterion of this ‘anomaly’ is entirely based on numerical models that purport to capture global phenomena related to terrestrial behaviour of the water cycle. The water cycle itself being the driving mechanism behind climate change, the suitability of these numerical models is the most relevant discussion point. To-date, the known major forces that play a role in climate change are: – Greenhouse gases (GHG); – solar radiation; – volcanoes Many studies have made claims of capturing all these major forces and produced numerical simulation results that show acceptable match between physical observation of global temperature data and numerically predicted data (Stott et al., 2000; Meehl et al., 2003; Ammann et al., 2003; Broccoli et al., 2003). A general sweeping assumption made is that the response of the climate system to various factors is additive, such that the response to a combination of factors is equivalent to the sum of those factors (e.g., Cubasch et al., 2001). This assumption stems from Newton’s laws that impose automatic exclusion of factors other than the ones captured by each law. Studies that attempted to ‘verify’ the validity of this assumption did so by using Newtonian mechanics, thus introducing inherent bias to the modeling scheme. For instance, Meehl et al., (2004) conducted an ensemble simulation with a global coupled climate model that employs five dominating forces, considered to be driving the time evolution of globally averaged surface air temperature during the twentieth century. Two of these forces are natural (volcanoes and solar), for which human activities play no role. The other forces are: anthropogenic (primarily greenhouse gases), ozone (stratospheric and tropospheric), and the direct effect of sulfate aerosols. By using eight new combinations, Meehl et al., (2004) reported successful reproduction of century’s worth of climate data. Figure 2.2 shows temperature variations over the 20th century for observed and simulated under various options. Note that this figure shows temperature values as a departure from 30 years prior, during which period no manmade activities can be attributed to global climate change. Figure 2.2 shows that the globally-averaged temperature anomalies for prior to 1915 and after 1960 remain close to 0 °C. This is attributed to active volcanic

State-of-The-Art of the Climate Change Debate

23

)

e

0

0

Figure 2.2 Temperature variation (from Meehl et al., 2004). Billions of barrels 35 2010 Peak

30

2020 Peak

25 Actual

20 15

2005 Peak

10 5 0 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080

Figure 2.3 crude oil production during the 20th century and beyond (data from BP World report, 2018).

eruptions. From about 1910 to 1960, the lack of volcanic activity is correlated with in globally averaged temperature anomalies of around +0.05o to +0.15 °C, even though the volcanic temperature response remains mostly below the observed values after about 1930. In the 1940s, the temperature rose around 0.2 °C in the 1940s compared to the beginning of the century, followed by a relative cooling of about 0.1 °C in the 1950s–70s, and then increases to greater than 0.2 °C after approximately 1980. At this point, it is important to review the global crude oil production. Figure 2.3 shows global crude oil production for the 20th century and beyond. Also added are the figures that are often touted as an evidence for the existence of peak oil production. Note that the peak oil theory is itself a scientific debauchery as characterized by Speight and Islam (2016). This particular figure shows that the so-called peak never existed, prompting scientists that are obsessed with the concept to draw up different version of the peak. Here, three versions (2005 peak, 2010 peak and 2020 peak) are mentioned. With a short-term scope, the peak would have occurred in 1970’s as well as in some

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The Science of Climate Change

parts of 2000’s. This figure shows the need of taking a long-term approach in analyzing any scientific data. Figure 2.3 also shows that global oil production maintained an exponential growth with the exception of short-term ‘hiccups’. During the same period, global temperature is affected with inconsistent variability. Although Meehl et al., (2003) identified the temperature data to be uniquely influenced by solar and volcanic effects (with more focus on solar than volcanic), they attributed the late century decline in global temperature to the decline in volcanic activities. In other words, according to them, fluctuations can occur due to natural causes, even though during the same period oil production continued to rise exponentially. It is a remarkable conclusion considering the fact that solar radiation data during the same period were less than reliable (Wilcox, 2012). Sufficient accuracy in solar irradiance measurements only started from 1978 (Kyle et al., 1994). Wilcox (2012) summarized the shortcomings of previous data. The original serially complete data set for all sun-up hours for 239 stations. Because of expected changes in the roster of National Weather Service (NWS) sites, as well as the potential for adding NSRDB sites, the updated list of stations was not restricted to those same 239. Instead, Wilcox included as many stations and as much data as possible to increase the usefulness of the data set. His update provides data for 1,454 stations. In addition, following features were added New or modified solar models New gridded data product New station identification numbers New station classification scheme New data formats Different meteorological fields Revised uncertainty estimates Similarly, volcano data are anything but precise and certainly are not reliable for determining their competing role in global warming. It is more complex because the number of underwater volcanoes are not known even today, let alone centuries prior (Metz et al., 2016). The NGDC/WDS National Geophysical Data Center/World Data Service (NGDC/WDS, 2018), along with the NOAA (2018), lists the Volcanic Explosivity Index (VEI),2 which gives us a measure of relative explosiveness of volcanic eruptions. These data do not begin to quantify the amount of emission, let alone the accurate composition of the eruption. Today, there are some 1500 active volcanoes, as reported by the USGS, but the number of ocean bed volcanoes are not known. Volcanic eruptions play a dual role. They first and foremost release molten rock, or lava, from deep within the Earth, forming new rock on the Earth’s surface. The impact on the Earth’s surface is immediate. However, these eruptions also impact the atmosphere and this impact is longer-term. The gases and dust particles thrown into the

2

The scale was invented by Chris Newhall of the U.S. Geological Survey and Stephen Self of the University of Hawaii in 1982.

State-of-The-Art of the Climate Change Debate

25

atmosphere during volcanic eruptions have influences on climate. Most of the particles spewed from volcanoes cool the planet by shading incoming solar radiation. The cooling effect can last for months to years depending on the characteristics of the eruption. Finally, the longest-term effect of volcanoes is when intensely high number of eruptions occur, releasing greenhouse gases into the atmosphere. This effect, however, is not likely to be a factor because of the fact that last few centuries there has been no unusual proportion of volcanic activities. With the above-mentioned limitations, Meehl et al., (2004) continue to suggest that the effects of volcanic eruption and solar irradiation has been that of cooling during the period of 1960-onward (Figure 2.2). The real bifurcation between anthropogenic effects and natural effects show after the 1970 s. During this period the effect of anthropogenic greenhouse gas production is so high that the cooling effects of volcanoes are overshadowed. This modeling of Meehl et al., (2004) has become iconic in the debate of global warming. As an evidence of ACC, the following indicators are cited: Rise in: Global surface temperatures Tropospheric temperatures Global Sea Surface Temperatures (SST) Global sea level Water vapor Rainfall intensity Precipitation extratropics Hurricane intensity Drought High temperatures extremes Heat waves Decrease in: Northern hemisphere snow extent Arctic sea ice Glaciers Cold temperatures The most important ‘culprit’ identified in this process is carbon emissions. Global carbon emissions from fossil fuels have significantly increased since 1900, synchronized with the plastic era. As stated earlier, since 1970, CO2 emissions have increased by about 90%, with emissions from fossil fuel combustion and industrial processes contributing about 78% of the total greenhouse gas emissions increase from 1970 to 2011. (Figure 2.4) shows the trends in gas emissions. This growth is in sync with global oil production (Figure 2.3). In this rise of global emission, there is a correlation between economic growth and CO2 emission. For instance, in 2014, the top carbon dioxide (CO2) emitters were China, the United States, the European Union, India, the Russian

26

The Science of Climate Change 11,000 Million metric tons carbon

10,000 9,000 8,000 7,000 6,000 5,000 4,000 3,000 2,000 1,000 0 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010

Figure 2.4 Global CO2 emission during 1900–2010 (from Boden et al., 2017).

Other 30% China 30%

United states 15%

Japan 4% Russian federation 5%

India 7%

EU-28 9%

Figure 2.5 Carbon dioxide emissions far various countries in 2014 (from Boden et al., 2014).

Federation, and Japan. These data include CO2 emissions from fossil fuel combustion, as well as cement manufacturing and gas flaring. Together, these sources represent a large proportion of total global CO2 emissions. Figure  2.5 shows the distribution of CO2 emissions for various countries. Emissions and sinks related to changes in land use are not included in these estimates. As we’ll see in other chapters, changes in land use can be important: estimates indicate that net global greenhouse gas emissions from agriculture, forestry, and other land use were over 8 billion metric tons of CO2 equivalent (FAO, 2014), or about 24% of total global greenhouse gas emissions (IPCC, 2014). In areas such as the United States and Europe, changes in land use associated with human activities have the net effect of absorbing CO2, partially offsetting the emissions from deforestation in other regions. Science behind this analysis will be discussed in latter chapters.

State-of-The-Art of the Climate Change Debate

2.3

27

The Climate Change as a Natural Process

The opponents have dismissed the arguments of the proponents in several steps (Stern et al., 2016). They 1. deny the existence of ACC and related magnitude, rate of progress and risks; (b) question the integrity of scientists that espouse the conclusion that climate change is real; and 2. dismiss the value of any mitigation or remediation efforts. As pointed out by Stern et al., (2016), such a tactic is reminiscent of the now famous ‘silent spring’ outing of the massive usage of pesticide (Whorton, 1974). It is also noted by Stern et al., (2016) that similar arguments were advanced in environmental risk debates concerning arsenical insecticides in the late 1800 s, phosphates in detergents in the 1960s, and the pesticide DDT in the 1960s and 1970 s. Proponents of the status quo first question the scientific evidence that risks exist; then, they question the magnitude of the risks and assert that reducing them has more costs than benefits. As pointed out by Islam et al. (2018a), every debate in favour of the status quo involves economic considerations that themselves are focused on short-term benefits to the corporation. However, this fact is not explicitly mentioned during the policy debate, arguably to avoid using the aphenomenal model that puts decision ahead of data and scientific analysis of a problem. Stern et al., (2016) identified a ‘rhetorical shift away from outright skepticism’, called as “neoskepticism,” that shifted the debate to uncertainties involved during data collection all the way to what exactly a “tipping point” point would look like in an environment that has great resilience and ability to absorb such ‘events’. Neoskeptics do not reject the first premise that ACC is real but denies any need to act with urgency, with a number of arguments in favour of their stance. Figure  2.6 shows the full picture of the various ideological positions in the ACC debate. The so-called Mainstream accepts ACC is real, but immediately designates carbon as the enemy, thus calling for the introduction of so-called ‘renewable’ energy sources. As pointed out by Chhetri and Islam (2008), these ‘renewable’ energy sources (e.g., wind, solar, biofuels) are actually more toxic than fossil fuel as well as less efficient, and certainly more expensive. The skeptic views the ACC process as either part of natural cycle or based on faulty and/or fraudulent science as well as data. The case of faulty/ insufficient data is the one promoted in recent paper by Rancour (n.d.). The work of Chilingar and associates falls under the same category but they do not deny the data that there is global warming, but rather discard it because it is not significant vis a vis the broad geological cycle. In fact, most of Chilingar’s work suggests that the planet earth may very well be within a cooling cycle and what we are experiencing in terms of global warming is miniscule point within the broader cycle. In the historical cases above, dispute resolution rested on both finding new, less-risky practices and applying policy judgment to science. In the DDT case, the administrator of the U.S. Environmental Protection Agency (EPA) stated that he was “convinced

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The Science of Climate Change ACC is unreal Skeptic

ACC is real

Neo-Skeptic

Mainstream Carbon is the enemy

Nature is resilient

Status quo Humans can adapt

Introduce “renewable” Energy sources

Tipping ‘point’ uncertain

Tax fossil fuel

Change is status quo too costly

Subsidize “renewable” energy

Status quo

Maximize profit

Figure 2.6 Modus operandi of various parties of the ACC debate.

by a preponderance of the evidence”. Today, neoskepticism accepts the existence of ACC but advocates against urgent mitigation efforts on various grounds, such as that climate models run “too hot” or are too uncertain to justify anything other than “noregrets” policies as having net benefits. Mainstream climate scientists are well aware of uncertainty in climate projections. But neoskeptics' citing of it to justify policy inaction marks a shift of focus in climate debates from the existence of ACC to its import and to response options. The Intergovernmental Panel on Climate Change stated that there was a “discernible” human influence on climate and that the observed warming trend is “unlikely to be entirely natural in origin” (IPCC 2001). The Third Assessment Report of IPCC stated, “There is new and stronger evidence that most of the warming observed over the last 50 years is attributable to human activities.” Khilyuk and Chilingar (2004) reported that the CO2 concentration in the atmosphere between 1958 and 1978 was proportional to the CO2 emission due to the burning of fossil fuel. In 1978, CO2 emissions into the atmosphere due to fossil fuel burning stopped rising and were stable for nine years. They concluded that if burning fossil fuels was the main cause, then the atmospheric concentration should stop rising, and, thus, fossil fuel burning would not be the cause of the greenhouse effect. However, this assumption is extremely shortsighted and the global climate certainly does not work linearly, as envisioned by Khilyuk and Chilingar (2004). Moreover, the “Greenhouse Effect One-Layer Model,” proposed by Khilyuk and Chilingar (2003, 2004), assumes there are adiabatic conditions in the atmosphere that do not and cannot exist. Figure 2.7 Shows the schematic of the One-Layer Model. As can be seen from this figure, it is the simplest of the models. The following assumptions apply. Atmosphere is a single layer of air at temperature Atmosphere is completely transparent to shortwave solar radiation.

State-of-The-Art of the Climate Change Debate Reflective short waves

Solar input

Radiation to space

29

Space

Atmosphere Radiation up from ground

Radiation down to ground Surface

Solar

Terrestrial

Figure 2.7 One-Layer model of greenhouse effects.

Atmosphere is completely opaque to infrared radiation Both surface and atmosphere emit radiation as blackbodies Atmosphere radiates equally up and down There are no other heat transfer mechanisms By further invoking adiabatic conditions (essentially meaning there is no heat or mass transfer between layers), the authors have concluded that the human-induced emissions of carbon dioxide and other greenhouse gases have a very small effect on global warming. This is due to the limitation of the current linear computer models that cannot predict temperature effects on the atmosphere other than at low levels. Similar arguments were made while promoting dichlorodifluoromethane (CFC-12) in order to relieve environmental problems incurred by ammonia and other refrigerants after decades of use. CFC-12 was banned in USA in 1996 for its impacts on the stratospheric ozone layer depletion and global warming. Khan and Islam (2012) presented detailed lists of technologies that were based on spurious promises. Islam et al., (2018a) complemented this list by providing a detailed list of economic models that are also counterproductive. Khilyuk and Chilingar (2004) explained the potential impact of microbial activities on the mass and content of gaseous mixtures in Earth’s atmosphere on a global scale. However, this study does not distinguish between biological sources of greenhouse gas emissions (microbial activities) and industrial sources (fossil fuel burning) of greenhouse gas emissions. Emissions from industrial sources possess different characteristics because they derive from diverse origins and travel different paths that, obviously, have significant impacts on atmospheric processes. Current climate models have several problems. Scientists have agreed on the likely rise in the global temperature over the next century. However, the current global climatic models can only predict global average temperatures. Projection of climate change in a particular region is considered to be beyond current human ability. Atmospheric Ocean General Circulation Models (AOGCM) are used by the IPCC to model climatic features, but these models are not accurate enough to provide a reliable forecast on how climate may change. They are linear models and cannot forecast complex climatic features. Some climate models are based on CO2

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The Science of Climate Change

doubling and transient scenarios. However, the effect of climate in these models, while doubling the concentration of CO2 in the atmosphere, cannot predict the climate in other scenarios. These models are insensitive to the difference between natural and industrial greenhouse gases3. There are some simple models that use fewer dimensions than complex models and do not predict complex systems. The Earth System Models of Intermediate Complexity (EMIC) are used to bridge the gap between the complex and simple models, but these models are not able to assess the regional aspect of climate change (IPCC 2001). Overall, any level of artificial products in the stratosphere will affect the final and the most important layer of the earth atmosphere. In subsequent chapters, we present how artificial products pollute CO2, rendering them incapable of returning to the ecosystem through participation in photosynthesis activities. The closest layer to the earth surface is troposphere. This layer contains half of the Earth's atmosphere. All transient phenomena related to weather occur in this layer. This layer too contributes to attenuation of sunlight and at the end some 1000 W/m2 falls on the earth when the sky is clear and the Sun is near the zenith. The multiple filtering system of the atmosphere is such that it filters out 70% of solar ultraviolet, especially at the shorter wavelengths. The immediate use of solar energy in terms of sustaining human life is photosynthesis – the process that allows plants to capture the energy (through mass transfer) of sunlight and convert it to ‘live’ chemical form. The energy stored in petroleum and other fossil fuels was originally converted from sunlight by photosynthesis in the distant past. The most significant is the photosynthetic mechanism. There are two classes of the photosynthetic cycle, the Calvin-Benson photosynthetic cycle and the Hatch-Slack photosynthetic cycle. The Calvin-Benson photosynthetic cycle is dominant in hardwoods and conifers. The primary CO2 fixation or carboxylation reaction involves the enzyme ribulose-1,5-diphosphate carboxylase and the first stable product is a 3-carbon compound. This reaction is considered to be “light-independent”. This series of reactions occur in the fluid-filled area of a chloroplast outside of the mytosis membranes. These reactions take the light-dependent reactions and perform further chemical processes on them. Various stages of this process are: carbon fixation, reduction reactions, and ribulose 1,5-bisphosphate (RuBP) regeneration. In describing this cycle of reactions, the role of light energy is marginalized. This process occurs only when light is available. Plants do not carry out the Calvin cycle by night. Instead, they release sucrose into the phloem from their starch reserves. This process happens when light is available independent of the kind of photosynthesis (C3 carbon fixation, C4 carbon fixation, and Crassulacean Acid Metabolism). The exceptions are: Crassulacean acid metabolism, also known as CAM photosynthesis, a carbon fixation pathway that is used by some plants as an adaptation to arid conditions (Zhang et al., 2016a). In a plant using full CAM, the stomata in the leaves remain shut during the day to reduce evapotranspiration, but open at night to collect carbon dioxide (CO2). The CO2 is stored as

3

Islam et al. (2010) first pointed out that this difference exists and because of that difference some CO2’s are not assimilated with the ecosystem.

State-of-The-Art of the Climate Change Debate

31

the four-carbon acid malate, and then used during photosynthesis during the day. The pre-collected CO2 is concentrated around the enzyme RuBisCO, increasing photosynthetic efficiency. On the other hand, the Hatch-Slack photosynthetic cycle is the one used by tropical grasses, corn and sugarcane. Phosphenol-pyruvate carboxylase is responsible for the primary carboxylation reaction. The first stable carbon compound is a C-4 acid, which is subsequently decarboxylated. It is then refixed into a three-carbon compound. These three steps define the canonical C4 photosynthetic pathway. Overall, the photosynthesis process shows how nature converts energy into mass, storing energy for long-term use. This must be understood in order to appreciate the role of natural processing in the context of petroleum usage. The process of energy-to-mass conversion is greatly affected by temperature (Fink, 2013). Sometimes temperatures are used in connection with day length to manipulate the flowering of plants. Chrysanthemums will flower for a longer period of time if daylight temperatures are 50 °F. The Christmas cactus forms flowers as a result of short days and low temperatures. Also, temperatures alone also influence flowering. Daffodils are forced to flower by putting bulbs in cold storage in October at 35 to 40 °F. The cold temperature allows the bulb to mature. The bulbs are transferred to the greenhouse in midwinter where growth begins. The flowers are then ready for cutting in 3 to 4 weeks. Plants produce maximum growth when exposed to a day temperature that is about 10 to 15 °F higher than the night temperature. This allows the plant to photosynthesize (build up) and respire (break down) during an optimum daytime temperature, and to curtail the rate of respiration during a cooler night. High temperatures cause increased respiration, sometimes above the rate of photosynthesis. This means that the products of photosynthesis are being used more rapidly than they are being produced. For growth to occur, photosynthesis must be greater than respiration. Temperature alone can affect this process. Low temperatures can result in poor growth. Photosynthesis is slowed down at low temperatures. Since photosynthesis is slowed, growth is slowed, and this results in lower yields. Each plant has an optimum temperature that allows maximum growth. For example, snapdragons grow best when night time temperatures are 55 °F, while the poinsettia grows best at 62 °F. Florist cyclamen does well under very cool conditions, while many bedding plants grow best at a higher temperature (Evans, 2013). Buds of many plants require exposure to a certain number of days below a critical temperature before they will resume growth in the spring. Peaches are a prime example; most cultivars require 700 to 1,000 hr below 45 °F and above 32 °F before they break their rest period and begin growth. This time period varies for different plants. The flower buds of forsythia require a relatively short rest period and will grow at the first sign of warm weather. During dormancy, buds can withstand very low temperatures, but after the rest period is satisfied, buds become more susceptible to weather conditions, and can be damaged easily by cold temperatures or frost. This series of phenomena have immediate implications to seeds and future of the biomass. Overall, temperature represents a level of subatomic particle activities. Any rise in temperature increases movement of all particles of the system. For certain systems, this would suffice to trigger a chain reaction, while for others this temperature rise would

32

The Science of Climate Change Characteristic speed

Vapor

Liquid Soild

Physical state of material

Figure 2.8 Characteristic speed (or frequency) can act as the unique function that defines the physical state of matter (From Islam, 2014).

simply facilitate dispersion of the mass. In terms of phase change, Figure 2.8 shows how any change in temperature can trigger phase change by altering the characteristic speed of a collection of particles. Similar effects are expected with pressure. Photosynthesis offers an example of natural effect of pressure on organic reactions. Beer and Waisel (1982) studied photosynthetic responses to light and pressure (up to 4 atm) for two seagrass species abundant in the Gulf of Eilat (Red Sea). While one species pressure decreased net photosynthetic rates, in the other (Halophila stipulacea), pressure had no effect on net photosynthetic rates. On the other hand, light saturation was the same for both species. The authors concluded that neither species should be light limited to a depth of about 15 m, and Halophila stipulacea should reach compensation light intensities at about 50 m. The latter depth corresponds well to the natural depth penetration of this species. Overall, it appears that pressure rather than light is one of the factors limiting the depth penetration of this species. The differential pressure response of the two species may be related to aspects of leaf morphology and gas diffusion. The diffusion process itself is extremely sensitive to the presence of heavy metal or other pollutants in the CO2 stream. This aspect is discussed in details in latter chapters. Scientifically, confining pressure is responsible for creating a series of vibrations that are in conflict with natural frequencies of matter. Because of continuity of matter, the external vibrations cause reactions to matter that attempt to escape its confinement. Pressure alone can cause a series of oscillatory events that prompt fundamental changes in the subatomic structure of matter. This aspect is seldom understood in the context of New Science. It’s because New Science depends on characterizing mass and energy separately. In this book, we have used simultaneous characterization of mass and energy by assuming continuity between mass and energy. There is a perception that Neoskpetical claims are driven more by ideology or economic interests than by science (Ferrel, 2016). This attitude in essence dismisses the fact that the opposing view might have scientific merit. For instance, Ferrel (2016), outlines how polarization efforts are influenced by a patterned network of political and financial actors. He correctly identifies that these dynamics are ‘notoriously difficult

State-of-The-Art of the Climate Change Debate

33

to quantify’ play a pivotal role in determining climate change policies. The comprehensive data include all individual and organizational actors in the climate change countermovement (164 organizations), as well as all written and verbal texts produced by this network between 1993–2013 (40,785 texts, more than 39 million words). He reported two major findings: 1) organizations with corporate funding were more likely to have written and disseminated texts meant to polarize the climate change issue; and 2) corporate funding influences the actual thematic content of these polarization efforts, and the discursive prevalence of that thematic content over time. His study, however, doesn’t weigh adequately on corporate pressure on scientific findings on the side of the ACC line. In fact, there is an illusion that undue ethical pressure is entirely on the side of ‘fringe groups’ lobbying for oil companies. This has been a recurring theme that persisted throughout the 8 years of the Clinton era and continued during both Bush 42 and Obama era (Lewandowsky et al., 2015). This attitude has returned during the latest election of Trump to the office of Presidency. Ideological polarization presents increasingly important challenges for sustainability science and solutions for climate change. This is of particular importance in the USA because any scientist stands to gain a great deal by following the path of maximum monetary benefit for research. Much attention has been given to the outcomes of polarization by demonstrating its effect on individual choices about energy-efficient behavior (Gromet et al., 2013). In this process, the segregation has occurred according to alignment with liberalism and conservatism (Gauchat, 2012). More specific to climate change issues, it is the attitude that is set prior to assessing the scientific merit (Hart and Nisbet, 2011), it is overtly mentioned as a conservative problem, but such attitude persists no less dogmatically for liberal elements of the general public, including politicians (Islam et al., 2010). Ironically, the role of politics is common in modern era, in which general public have little patience for objective discovery prior to making up their mind (Oreskes and Conway, 2010; Coll, 2012). However, the arguments of the ‘right’ that question the mainstream view of ACC cannot be discarded as political indoctrination, devoid of scientific merit. While the proponents of ACC mention the two ‘facts’, namely, (a) the Earth is warming and (b) most of that warming has been due to human greenhouse gas emissions (for instance, Anderegg et al., 2010, Doran and Zimmerman, 2009, Oreskes, 2004), they have sealed off any room for criticism as if those two observations are irrefutable facts and more importantly they have made mockery of anyone who do not agree with their mitigation plan. For the ‘right’, opponents of the mainstream ACC group have often emphasized scientific uncertainty in order to forestall mitigative actions (e.g., Kim, 2011, Freudenburg et al., 2008, Nisbet, 2009). In the absence of scientific explanation behind their arguments, they are taken as politically or ideologically motivated. In addition, inaction in the face of any crisis correctly solicits criticism. This is not to say that action plans of the ‘left’ are correct or even scientific. However, an impasse occurs when appeals to uncertainty become so pervasive in political and lobbying circles that scholarly attentions are named “Scientific Certainty Argumentation Methods”, or “SCAM” for short (Freudenburg et al., 2008). SCAMs are widespread and arguably have postponed regulatory action on many environmental problems, including climate change (Freudenburg et al., 2008). These have created a status quo at best and sought out disastrous policy making at

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The Science of Climate Change

worst. However, this hysteria has been used entirely against the opponents of the mainstream views (e.g., Brysse et al., 2013, Freudenburg and Muselli, 2010). As Stern et al., (2016) point out, the questions that the ‘right’ poses cannot be dismissed as political mumbo jumbo or misguided faith material. The legitimate questions raised relate to: i.

the nature and probabilities of crossing climate “tipping points” that would greatly change the profile of the risks; ii. the varied harms climate change may produce (e.g., to businesses, ecosystem integrity, political stability, or human lives); iii. the vulnerability and resilience of potentially affected social and ecological systems; and iv. the benefits and costs of efforts to limit climate change, reduce vulnerability, and increase resilience. Such questions have received scientific and economic analysis before but deserve greater emphasis as attention focuses increasingly on risk management.

These concerns are not political, they are rather serious research questions that should be answered with research without a political agenda. Although the following research steps have been identified as a solution to the impasse (Stern, 2016; NRC, 2011; Stern, 2016), none of them has any hope unless answers to the question posed in this book are sought first. i. ii.

identifies specific technological and institutional options; analyzes the time and resources required for mitigation and adaptation strategies; iii. analyzes the effects of each and of ways to increase effectiveness; iv. identifies and assesses cobenefits and indirect costs of mitigation; and v. evaluates the financial costs and other risks of delay. The science of decision processes is also needed. Much of the needed research must come from the social, behavioral, and economic sciences integrated into a science of human-environment interactions. This line of research started the so-called Adaptation research from 1990s. An entire journal has been dedicated to the science of determining adaptive risk management and prediction of future risks (Editorial, 2016). This research thrust emerged from the 1992 United Nations (UN) Conference on Environment and Development, Rio de Janeiro, Brazil. The UN framework Conventions on climate change, desertification, forests, and loss of biological diversity were in their formative stages. The Montreal Protocol was developing into an effective governing instrument to cope with ozone depleting substances but there was substantial work to be done. The Stockholm Convention on persistent organic pollutants (POPs), and, the Minamata Convention on Mercury were years into the future. While the human footprint on planet Earth was growing, the term Anthropocene was only beginning to become a part of our working vocabulary.

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35

This Clinton era thrust would overwhelm the scientific community that accepted that the ACC was a reality that could only be countered with either adaptation or avoidance of carbon-based energy sources. On the adaptation side, numerous manuscripts have been published in Mitig Adapt Strateg Glob Change (Editorial, 2016) all promoting the need to advance adaptation to what was believed to be an unavoidable addiction to carbon-based energy sources. The most important initiative in terms of Climate change research has been showcased through the Intergovernmental Panel on Climate Change (IPCC) process (Carraroet et al., 2014). However, as we will see in the rest of the book, IPCC panel has failed to answer any of the most pivotal questions about the climate change, instead resorting to promoting the need for more funding need in planning and implementing ‘alternate’ to carbon-based energy sources. Outwardly, the IPCC lacked funding. For instance, despite continued calls from independent reviews for increased support for “human dimensions” research in the US Global Change Research Program, funds devoted to social science declined from 3% to 2% between 1990 and 2007 (NRC, 2012). The program's most recent strategic plan embraces science to inform timely decisions on adaptation and mitigation, but resources commensurate with the needs have not been achieved. In the absence of truly scientific investigation, all focus has been given to various scenarios all involving one side of the climate change debate. Research is being conducted to integrate scientific analysis and social deliberation and to consider trade-offs that might otherwise go unaddressed. In this process, very little is being done to solve the problem of global warming and climate change, instead incorporating issues of equity and value conflict in supporting adaptive risk management (NRC, 2011).

2.4

Conclusions

Two sides of the global warming or climate change debate are deadlocked. Although the vast majority of the mainstream scientific authorities have emerged as the proponent of the ACC hysteria, they have been unable to answer key questions without resorting to dogmatic assertions. The opponent of the ACC debate are often ridiculed as politically or ideologically motivated with little interest in real science. However, policy-making today is vastly done without scientific justification and that occurs before truly scientific investigations into the cause of global warming even begins. Both sides are preoccupied with securing funding for implementing their schemes that would maximize profit for their pet projects.

The Science of Climate Change. M. R. Islam, M. M. Khan. © 2019 Scrivener Publishing LLC. Published 2019 by John Wiley & Sons, Inc.

3 Forest Fires and Anthropogenic CO2

3.1

Introduction

Forest fires may be older than humanity, the link of forest fires to anthropogenic climate change (ACC) is quite new. As late as 2006, correlation between forest fire and global warming trends began to surface. Even though the original work (Sterling et al., 2006) was published in an academic journal, it quickly became a document of public interest and became cornerstone for the proponents of the ACC debate. From that point onward the validity of the original correlation was no longer questioned and numerous publications started to appear confirming the original premise. The debate quickly moved to determining the ecological role of wildland fire, thus automatically assigning correlation between fossil fuel usage and forest fire activities. Even books (not research monographs) started to surface answering this rhetorical question (Struzik, 2017). No sooner than the 2006 article appeared, the debate moved to recounting personal stories, culminating in the book: Firestorm (Struzik, 2017) that talks about people affected by large wildland fires, such as the 566,000-hectare Horse River fire in the Fort McMurray area of Alberta, Canada, in 2016. This work provides a compelling narrative of the firefighters who struggled to understand how they should respond to such a large weatherdriven fire that was far beyond their control, and it describes the experiences of the residents and first responders in Fort McMurray who grappled with the decision of whether and when to evacuate the town. In this chapter, the science of forest fires and its relation to global climate is brought back and discussed with the backdrop of incessant sensualisation of the ACC debate. 37

The Science of Climate Change

38

Picture 3.1 Smoke column rising from prairie fire. (Courtesy of National Park Service, n.d.)

Facts about forest fires and role of various mitigating factors are presented with discussion of the science behind them.

3.2

The Science of Forest Fires

There have been fires since there were plants on the continents. Some of the most spectacular forest fires have been documented in modern era. Throughout history, forest fire had been considered to be natural and beneficial to the ecosystem. Even intervention of humans in creating natural fire in order to clean the environment was recognized until recent times. For instance, DeVoto (1997) writes about the tradition of Native Americans: “The plains are on fire in view of the fort on both sides of the river, it is said to be common for the Indians to burn the plains near their villages every spring for the benefit of the horse and to induce the Buffalow to come near them.”

The magnitude of such a fire is shown in Picture 3.1 in case of a manmade fire, and in Picture 3.2 in the case of a natural fire. Historically, tropical grasslands, savannas and dry tropical forest are the biomes with the highest fire activity; while tundra and deserts had the lowest activity (Pausas and Rebeiro, 2013). Forest fires occur entirely on the continents, as only these lands have environments conducive to burning with open fires. In absence of such environment, such as arid desert, lands with snow, ice, etc. forest fires cannot occur. There is a large variability in fire activity among ecoregions as shown in Figure 3.1. Organic matter is inherently unstable in presence of oxygen and is subject to continuous oxidation, the rate of which can be greatly increased in presence of an open fire. Also important is the presence of humidity which can affect the onset of fire as well as impact the rate and quality of oxidation during a combustion activity. The number of forest fires each year is very high with 100 s of 1000 s occurring each year. In 2017 alone, so far, over six million acres of land has burned in th USA, with 100,000 incidents of forest fires (Pierre-Louis, 2017). There is a trend of reporting that the number of forest fires has skyrocketed in recent years, engulfing even remote places of Siberia (Pierre-Louis, 2017). It is tempting to correlate such rise to climate change.

Forest Fires and Anthropogenic CO2

39

Picture 3.2 Within 3 minutes of lightening strike, fire in Beaumont, British Columbia (July 17, 2018, photo courtesy Fentisha Boswell).

–150

–135

–98

–45

0

45

90

135

45

45

Fire activity 0

–45 –150

Not considered 0.0–0.4 0.4–0.467 0.467–0.533 0.533–0.6 0.6–0.667 0.667–0.733 0.733–0.8 0.8–0.867 0.867–0.933 0.933–1.0

–135

0

–45 –98

–45

0

45

90

135

Figure 3.1 Global map of fire activity (from Pausas and Rebeiro, 2013).

Islam (2014) lists the conditions required for creating an open flame. In fire, the role of carbon and water is pivotal. This discussion needs elaboration.

3.2.1

Role of Water and Carbon

Scientifically, water represents the onset of life, whereas carbon represents the end of life. Together, water and carbon are integral to organic matter. Indeed, water and carbon contain an array of contrasting, yet complimentary properties. Water is polar and is a good solvent due to its polarity. Oily (rich in carbon) materials are known to be hydrophobic. The ability of a substance to dissolve in water is determined by whether or not the substance can match or better the strong attractive forces that water molecules generate between other water molecules. If a substance has properties that do not allow it to overcome these strong intermolecular forces, the molecules are "pushed out" from the water, and do not dissolve. Contrary to the common misconception, water and hydrophobic substances do not "repel", and the hydration of a hydrophobic surface is energetically favorable. The process of hydration can be best described by the process

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The Science of Climate Change

in which water molecules surround the molecule of another compound. Because water molecules are relatively smaller, a number of water molecules typically surround the molecule of the other substance. Carbon in part of the vegetation or oily substances, both representing abundance of carbon embedded in hydrogen atoms. From this point onward, vegetation and petroleum/oil (carbohydrate and hydrocarbon) would be considered equivalent for the purpose of describing the science of fire. Properties of water and oil are different and complementary. For instance, water and oil can form stable emulsions and eventually create soap. Life begins with water but ends with oil in its most stable and stabilized form. In fact, other than honey, oil is the most effective anti-bacterial natural liquid. On a molecular level, oil is hydrophobic but it is not water repellant. In fact, water molecules form very stable bonds around oil molecules. However, on a broader scale, oil deprives whereas water gives life. In microscale, they are opposite in every property but they are essential for life. This entire thing is like Korean Yin Yang symbol that not only bonds together opposites (historically it meant fire, water; life, death; male, female; earth, sky; cold, hot; black, white) and are embedded inside white background, while holding within each another circle that itself has similar Yin Yang structures. The cycle continues all the down to Higgs Boson (as of 2013, when these ‘particles’ were recognized) and beyond (as no doubt smaller ‘particles’ will be discovered in the future), never reaching the same trait as the homogenous, anisotropic, monochrome, boundary-less surrounding. At every stage, there is also another combination of opposite, i.e., intangible (time) and tangible (mass), which essentially is the program that defines the time function. In its fundamental unit, snowflakes represent modules of water, whereas diatoms represent organic units of petroleum (Picture 3.3). In its original form, symmetry exists but only in a broad sense. There is no local symmetry. Picture 3.4 shows various images of snow flakes. If diamonds are from charcoal, petroleum is from diatoms. Table 3.1 shows various sources of water on earth. Water and hydrocarbon are both essential to life, even though they play contrasting roles. Table 3.2. shows some of the unifying and contrasting features of water and petroleum. Water and hydrocarbon are both essential to life, even though they play contrasting roles. Table 3.2 shows some of the unifying and contrasting features of water and petroleum. The above opposites signal to the complimentary nature of water and petroleum. At a molecular level, the following reactions of opposites can be observed.

−→

(3.1)

The result is water vapor, with a standard enthalpy of reaction at 298.15 K and 1 atm of −242 kJ/mol. While this equation is well known, it cannot be stated that original water or natural water is created this way. In fact, all evidence suggest that it is not and the suggestion that oxygen and hydrogen combined to form water as the basis of life bears the same first premise as the one imposed for the Big Bang theory. What we know, however, is if hydrogen burns in oxygen, it produces intense heat (around 2000 C) as compared to heat of a natural flame (e.g., from candle) that is around 1000 C. The above reaction does not take place unless there is a presence of two other components,

Forest Fires and Anthropogenic CO2

889

890

891

892

893

894

895

896

897

898

899

900

41

Picture 3.3 Snow flakes are fundamental units of water (From Islam, 2014).

one tangible (catalyst) and one intangible (spark), that produce a flame. A discussion on what constitutes a flame and its consequences is presented later on in this chapter. This reaction needs a spark that itself has catalysts (tangible) and energy (intangible). However, in nature water does not form by combining oxygen and hydrogen. One theory indicates water is the original matter as contrast to popular theory that puts hydrogen as the original mass (Islam et al., 2014b). Only recently this theory has gained ground as Astrophysicists continue to find evidence of water in outer space (Farihi et al., 2013). Table  3.3. highlights qualities that unite and contrast oxygen and hydrogen. (3.2)

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Picture 3.4 Diatoms as fundamental units of charcoal, petroleum (picture from Colorado State Geological Survey, 2013).

Table 3.1 Various sources of water on earth (From Islam, 2014). Sea water The oceans

97.2%

Inland seas and saline lakes

0.008%

Fresh water Freshwater lakes

0.009

All rivers (average levels)

0.0001

Arctic icecap

1.9

Arctic Icecap and glaciers

0.21

Water in the atmosphere

0.001

Ground water within half a mile from surface

0.31

Deep-lying ground water

0.31

The above reaction takes place at all temperature (e.g., low-temperature oxidation). However, the most natural, yet rapid conversion takes place with fire. Fire itself has tangible (visible part fire) and energy (heat of reaction, intangible). The above contrasting and complementary properties of hydrogen and oxygen and oxygen and carbon give rise to water and fire, respectively, creating a new set of contrasting and complementary components. Together, they form the basic ingredients of life on earth and exemplify natural sustainability.

3.2.2

Combustion and Oxidation

In a complete combustion reaction, a compound reacts with an oxidizing element, such as oxygen, and the products are compounds of each element in the fuel with the oxidizing element. The oxidation with oxygen is the most commonly occurring phenomena

Forest Fires and Anthropogenic CO2

43

Table 3.2 Contrasting features of water and petroleum (From Hutchinson, 1957; Attwood, 1949; Handbook of Chemistry and Physics, 1981). Water

Petroleum

Source of all organic matter

End product of all organic matter

Most abundant fluid on earth

Second most abundant fluid on earth

Oxygen 85.84; Sulfur 0.091 Hydrogen 10.82; Calcium 0.04 Chloride 1.94; Potassium 0.04 Sodium 1.08; Bromine 0.0067 Magnesium 0.1292; Carbon 0.0028

Carbon - 83% to 87% Hydrogen - 10% to 14% Nitrogen - 0.1% to 2% Oxygen - 0.05% to 1.5% Sulfur - 0.05% to 6.0% Metals - < 0.1%

Mostly homogeneous

Hydrocarbon (15%–60%), napthenes (30%–60%), aromatics (3% to 30%), with asphaltics making up the remainder.

Reactivity of water towards metals. Alkali Non-reactive toward metal. metals react with water readily. Contact of cesium metal with water causes immediate explosion, and the reactions become slower for potassium, sodium and lithium. Reaction with barium, strontium, calcium are less well known, but they do react readily. Reaction with non-metals is faster Non-metals like Cl2 and Si react with water Cl2(g)+ H2O(l)→HCl(aq)+HOCl(aq) Si(s)+2H2O(g)→SiO2(s)+ 2H2(g) Some non-metallic oxides react with water to form acids. These oxides are referred to as acid anhydrides. High cohesion

Low cohesion

Unusually high surface tension; susceptible to Unusually low surface tension thin film Adhesive to inorganic

Adhesive to organic

Unusually high specific heat

Unusually low specific heat

Unusually high heat of vaporization

Unusually low heat of vaporization

Has a parabolic relationship between temperature and density

Has monotonous relationship between temperature and density

Unusually high latent heat of vaporization and freezing

Unusually low latent heat of vaporization and freezing (Continued)

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Table 3.2 Cont. Water

Petroleum

Versatile solvent

Very poor solvent

Unusually high dielectric constants

Unusually low dielectric constants

Has the ability to form colloidal sols

Destabilizes colloids

Can form hydrogen bridges with other Poor ability to transport oxygen and carbon molecules, giving it the ability to transport dioxide minerals, carbon dioxide and oxygen Unusually high melting point and boiling point

Unusually low melting point and boiling point

Unusually poor conductor of heat

Unusually good conductor of heat

Unusually high osmotic pressure

Unusually low osmotic pressure

Non-linear viscosity pressure and temperature relationship (extreme nonlinearity at nano-scale, Hussain and Islam, 2010)

Mild non-linearity in viscosity pressure and temperature relationship

Enables carbon dioxide to attach to carbonate Absorbs carbon dioxide from carbonate Allows unusually high sound travel

Allows unusually slow sound travel

Large bandwidth microwave signals propagating in dispersive media can result in pulses decaying according to a nonexponential law (Peraccini et al., 2009)

Faster than usual movement of microwave

Unusually high confinement of X-ray movement (Davis et al., 2005)

Unusually high facilitation of X-ray movement.

in nature. This is because of the abundance of oxygen as well as the ability of oxygen to react all temperatures. In terms of generating energy, most notably heat generation, it is done through the oxidation of hydrogen. Even though it is rarely the case in nature, the oxidation of hydrogen produces the most intense heat in presence of a flame (2000 C) – this is the principle used in rocket engines. The second most intense heat is with carbon (1000 C). This is the principle used in all forms of fossil fuel burning. Unlike hydrogen and oxygen, this reaction is natural and takes place at all temperatures, albeit as a strong function of temperature. The low-temperature oxidation (LTO) is continuous and follows Arrhenius equation, which is an exponential relationship with temperature. However, oxidation of elemental carbon (e.g., graphite and diamond) are both rare because of rarity of those elements, compared to compound form of carbon. For instance, diamond and graphite both burn at 800 C in presence of oxygen, but in absence of oxygen they melt at a very high temperature (3600 C for graphite and 3800

Forest Fires and Anthropogenic CO2

45

Table 3.3 Fundamental properties of oxygen and hydrogen. Oxygen

Hydrogen

Atomic number

8

1

Atomic mass

15.999 g.mol −1

1.007825 g.mol −1

Electronegativity according to 3.5 Pauling

2.1

Density

1.429 kg/m3 at 20 °C

0.0899*10 −3 g.cm −3 at 20 °C

Melting point

−219 °C

- 259.2 °C

Boiling point

−183 °C

- 252.8 °C

Vanderwaals radius

0.074 nm

0.12 nm

Ionic radius

0.14 nm (−2)

0.208 (-1) nm

Isotopes

4

3

Electronic shell

[ He ] 2 s 2 2 p 4

1 s1

Energy of first ionization

1314 kJ.mol −1

1311 kJ.mol −1

Energy of second ionization

3388 kJ.mol −1

Energy of third ionization

5300 kJ.mol −1

Discovered by

Joseph Priestly in 1774

Henry Cavendish in 1766

C for diamond). The next most heat generating combustion is with methane. This reaction is written as follows

 

 

 

 

→



(3.3)

The standard enthalpy of reaction for methane combustion at 298.15 K and 1 atm is −802 kJ/mol. The symbol Σ signifies the time function that stores information regarding intangibles (Islam et al., 2016), such as the history of methane (organic or otherwise), history of oxygen (organic or mechanical, as well as the collection of all elements that are present in non-measurable quantities. The usefulness of Σ is in its ability to track the history in order to chart the future pathway in terms of harm and beneficial quality. For instance, if the oxygen supply is restricted, the following reaction will take place, in stead of Equation 2.2.



 

→

 



(3.4)

This reaction is typical of industry-standard producer gas that is produced by injecting oxygen through hot coke. The resulting gas is a mixture of carbon monoxide (25%), carbon dioxide (4%), nitrogen (70%), and traces of hydrogen (H2), methane (CH4), and oxygen (O2). In addition to this information, Σ will also contain information regarding

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The Science of Climate Change

Table 3.4 Common and contrasting features of oxygen and hydrogen. Oxygen

Hydrogen

Fundamental component of water (89% in mass and 33% in mole), which is ubiquitous on earth (70%).

Fundamental component of water (11% in mass and 67% in mole), which is ubiquitous on earth (70%)

Believed to be 3rd most abundant element in universe

Believed to be most abundant element in universe

If mass-energy discontinuity is removed, most abundant mass in universe

If mass-energy discontinuity is removed, second most abundant in universe

Hydrogen is the most flammable of all It is the essential element for respiratory the known substances. There are three processes for all living cells. hydrogen isotopes: protium, mass 1, found It’s the most abundant element in The Earth’s in more than 99,985% of the natural crust. Nearly one fifth (in volume) of the element; deuterium, mass 2, found in air is oxygen. Non-combined gaseous nature in 0.015% approximately, and oxygen normally exists in form of diatomic tritium, mass 3, which appears in small molecules, O2, but it also exists in triatomic form, O3, ozone. quantities in nature. Oxygen is reactive and will form oxides The dissociation energy of molecular with all other elements except helium, hydrogen is 104 kcal/mole. Molecular neon, argon and krypton. It is moderately hydrogen is not reactive. Atomic hydrogen soluble in water (30 cm3 per 1 liter of water is very reactive. It combines with most dissolve) at 20 Celsius. elements to form hydrides (e.g., sodium Oxygen doesn’t react with acids or bases hydride, NaH), and it reduces metallic under normal conditions. oxides, a reaction that produces the metal in its elemental state. The surfaces of metals that do not combine with hydrogen to form stable hydrides (e.g., platinum) catalyze the recombination of hydrogen atoms to form hydrogen molecules and are thereby heated to incandescence by the energy. Strong bond with hydrogen (110 kcal/mole); slightly stronger bond with oxygen (119 kcal/mole).

Strong bond with oxygen; less strength bond with hydrogen (104 kcal/mole); lesser strength bond with Carbon (98 kcal/mole).

The crust of earth is composed mainly of silicon-oxygen minerals, and many other elements are there as their oxides.

The earth crust has some 45 times less hydrogen than oxygen (Continued)

Forest Fires and Anthropogenic CO2

47

Table 3.4 Cont. Oxygen

Hydrogen

Oxygen gas makes up a fifth of the atmosphere. The oxygen in the Earth's atmosphere comes from the photosyntesis of plants, and has built up in a long time as they utilized the abundant supply of carbon dioxide in the early atmosphere and released oxygen.

Only 0.000055% of earth atmosphere is hydrogen. Sunlight causes photosynthesis that utilizes hydrogen and releases oxygen, forming a closed loop.

Low solubility in water (0.0016 g/kg of water Oxygen is fairly soluble in water (0.045 g/ kg of water at 20 C), which makes life in at 20 C). rivers, lakes and oceans possible. The water in rivers and lakes needs to have a regular supply of oxygen, for when this gets depleted the water will no longer support fish and other aquatic species. At normal temperature hydrogen is a not Nearly every chemical, apart from the very reactive substance, unless it has been inert gasses, bind with oxygen to form activated somehow; for instance, by an compounds. Water, H2O, and silica, SiO2, main component of the sand, are appropriate catalyzer. At high temperatures among the more abundant binary oxygen it’s highly reactive and a powerful compounds. Among the compounds which reducing agent (anti-oxidant). It reacts contain more than two elements, the most with the oxides and chlorides of many abundant are the silicates, that form most metals, like silver, copper, lead, bismuth of the rocks and soils. Other compounds and mercury, to produce free metals. It which are abundant in nature are calcium reduces some salts to their metallic state, carbonate (limestone and marble), calcium like nitrates, nitrites and sodium and potassium cyanide. It reacts with a number sulphate (gypsum), aluminum oxide of elements, metals and non-metals, to (bauxite) and various iron oxides, that are produce hydrides, like NAH, KH, H2S and used as source of the metal. PH3. Atomic hydrogen produces hydrogen peroxide, H2O2, with oxygen. Oxygen is essential for all forms of life since it is a constituent of DNA and almost all other biologically important compounds. Is it even more dramatically essential, in that animals must have minute by minute supply of the gas in order to survive. Oxygen in the lungs is picked up by the iron atom at the center of hemoglobin in the blood and thereby transported to where it is needed.

All compounds and elements produced through hydrogen reduction (see above) are potent toxins for all living organisms. However, organic form of the same toxin is necessary for living organisms. For instance, lack of organic H2S can trigger Alzheimer’s disease.

(Continued)

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The Science of Climate Change

Table 3.4 Cont. Oxygen

Hydrogen

Departure from normal atmospheric composition of oxygen (both too high or too low concentrations) causes lung damage

High concentrations of this gas can cause an oxygen-deficient environment. Individuals breathing such an atmosphere may experience symptoms which include headaches, ringing in ears, dizziness, drowsiness, unconsciousness, nausea, vomiting and depression of all the senses. Under some circumstances, death may occur.

Table 3.5 Fundamental characteristics of carbon. Atomic number

6

Atomic mass

12.011 g.mol −1

Electronegativity according to Pauling

2.5

Density

2.2 g.cm−3 at 20 °C

Melting point

3652 °C

Boiling point

4827 °C

Vanderwaals radius

0.091 nm

Ionic radius

0.26 nm (−4) ; 0.015 nm (+4)

Isotopes

3

Electronic shell

[ He ] 2 s22p2

Energy of first ionization

1086.1 kJ.mol −1

Energy of second ionisation

2351.9 kJ.mol −1

Energy of third ionization

4618.8 kJ.mol −1

Discovered by

The ancients

any other trace elements that can be present due to use of catalyst, heating mechanism, existence of flames, etc. In essence, Σ is the tracker of intangibles. Any combustion reaction is known to be accelerated dramatically in the presence of a flame. A flame is a mixture of reacting gases and solids emitting visible, infrared, and sometimes ultraviolet light, the frequency spectrum of which depends on the chemical composition of the burning material and intermediate reaction products. A standard and beneficial flame is fire, arising from burning wood. This process of heat and light generation is entirely sustainable (Chhetri and Islam, 2008) and produces

Carbon recycled through carbon cycle for sustenance of life Oxygen burns carbon with the second largest heat of reaction for any element (32.8 MJ/kg)

720 38,400

Pool Atmosphere Oceans (total)

16,500 13,500 1.3 0.03

30,000

If mass-energy discontinuity is removed, most abundant mass in universe

Oxygen recycled through water cycle for sustenance of life*

Oxygen burns Hydrogen with the largest heat of reaction for any element (141.8 MJ/kg)

Photosynthesis (land) Photosynthesis (ocean) Photolysis of N2O Photolysis of H2O

Total Gains

Total organic

1,000

(Continued)

If mass-energy discontinuity is removed, third most abundant (after oxygen and hydrogen) in universe.

Believed to be 3rd most abundant element in universe

Losses - Respiration and Decay

Believed to be 4th most abundant element in universe

Most abundant in (65%) of a living body

37,400

Second most abundant (18%) of living body

Fundamental component of water (89% in mass and 33% in mole), which is ubiquitous on earth (70%). The most abundant in mass and numbers.

Total inorganic

Fundamental component of living organisms, second most abundant in mass, and third most abundant in atomic numbers.

Quantity (gigatons)

Carbon

Oxygen

Table 3.6 Contrasting and unifying features of oxygen and carbon (From Islam, 2014).

Forest Fires and Anthropogenic CO2 49

4,130 3,510

Fossil fuels (total Coal

50 12

30,000

Chemical Weathering Surface Reaction of O3

Total Losses

(Continued)

It is the second (second to hydrogen) most important fuel for living organism and sustenance of life. Carbon is the 15th most abundant in earth’s crust.

It is the essential element for respiratory processes for all living cells. It’s the most abundant element in The Earth’s crust. Nearly one fifth (in volume) of the air is oxygen. Non-combined gaseous oxygen normally exists in form of diatomic molecules, O2, but it also exists in triatomic form, O3, ozone.

1,200

Other (peat)

140

Gas

*in units of 1012 kg/year

230

Oil

1–2

Aquatic biosphere

Losses – Weathering

1,200

Dead biomass

600–1000

Living biomass

Oxidation of Volcanic Gases

15,000,000 2,000

Kerogens Terrestrial biosphere (total)

Sedimentary carbonates

>60,000,000

36,730

Deep layer Lithospher

670

Surface layer

Aerobic Respiration Microbial Oxidation Combustion of Fossil Fuel (anthropogenic) Photochemical Oxidation Fixation of N2 by Lightning Fixation of N2 by Industry (anthropogenic) Oxidation of Volcanic Gases 23,000 5,100 1,200 600 12 10 5

Carbon

Oxygen

Table 3.6 Cont.

50 The Science of Climate Change

Carbon is the major component of CO2. After nitrogen, oxygen, and argon, carbon dioxide is the most abundant component of earth’s atmosphere. Very low solubility in water The two most important characteristics of carbon as a basis for the chemistry of life, are that it has four valence bonds and that the energy required to make or break a bond is just at an appropriate level for building molecules which are not only stable, but also reactive. The fact that carbon atoms bond readily to other carbon atoms allows for the building of arbitrarily long complex molecules and polymers. Uniquely suited for metabolism.

The crust of earth is composed mainly of silicon-oxygen minerals, and many other elements are there as their oxides.

Oxygen gas makes up a fifth of the atmosphere. The oxygen in the Earth's atmosphere comes from the photosyntesis of plants, and has built up in a long time as they utilized the abundant supply of carbon dioxide in the early atmosphere and released oxygen.

Oxygen is fairly soluble in water (0.045 g/kg of water at 20 C), which makes life in rivers, lakes and oceans possible.

Nearly every chemical, apart from the inert gasses, bind with oxygen to form compounds. Oxygen is essential for all forms of life since it is a constituent of DNA and almost all other biologically important compounds.

(Continued)

The C–O bond strength is also larger than C–N or C–C. C-C = 83; C-O = 85.5; O-CO = 110;C = O = 192 (CO2); C = O = 177 (aldehyde); C = O (ketone) = 178; C = O(ester)=179; C = O(amide)=179;C O = 258; C C = 200 (all values in kcal/mole)

Strong bond with hydrogen (110 kcal/mole); slightly stronger bond with oxygen (119 kcal/mole).

500,000,000

Carbon’s best reactant is oxygen that produces CO2 – the one needed for synthesis of carbohydrate.

6.1011

2.9.1020

Lithosphere

50

Oxygen is reactive and will form oxides with all other elements except helium, neon, argon and krypton.

3.1014

1.6.1016

Biosphere

4,500

A mass of about 7 × 1011 tons of carbon in the atmosphere as CO2 and about 4.5 × 1011 tons of carbon in vegetation as carbohydrate. The nominal percentage of CO2 in the atmosphere is about 0.034 percent.

3.1014

1.4.1018

Atmosphere

Residence Time (years)

The sun contributes to water mass through photosynthesis and thereby contributes to carbon cycle.

Flux (kg per year)

Capacity (kg O2)

Reservoir

Size (Gt C) 750 610 1580 1020 38,100 4,000 500 500

Carbon major component of all organic matter

Oxygen major component of water that is essential for life. By far the largest reservoir of Earth's oxygen is within the silicate and oxide minerals of the crust and mantle (99.5%). Only a small portion has been released as free oxygen to the biosphere (0.01%) and atmosphere (0.36%). The main source of atmospheric free oxygen is photosynthesis, which produces sugars and free oxygen from carbon dioxide and water. Reservoir Atmosphere Forests Soils Surace ocean Deep ocean Coal Oil Natural gas

Carbon

Oxygen

Table 3.6 Cont.

Forest Fires and Anthropogenic CO2 51

Carbon In its elemental form (graphite and diamond), completely benign and great fuel, only second to hydrogen as an elemental energy generator. Some simple carbon compound can be very toxic, such as carbon monoxide (CO) or cyanide (CN-). Carbon 14 is one of the radionuclides involved in atmospheric testing of nuclear weapons. It is among the long-lived radionuclides that have produced and will continue to produce increased cancers risk for decades and centuries to come. It also can cross the placenta, become organically bound in developing cells and hence endanger fetuses.

Oxygen

Departure from normal atmospheric composition of oxygen (both too high or too low concentrations) causes lung damage.

Table 3.6 Cont.

52 The Science of Climate Change

Forest Fires and Anthropogenic CO2

53

Picture 3.5 Sun picture taken at 9:19 a.m. EST on Nov. 10, 2004, by the SOHO (Solar and Heliospheric Observatory) spacecraft (NASA/European Space Agency, 2004).

Nature

Natural components

Natural light source

Gases

Light

Particles

Figure 3.2 Natural light pathway.

no harmful waste or by-products, therefore, it is waste-free (Khan and Islam, 2016). The fundamental characteristic of this wood flame is that combustion is incomplete, thereby generating incandescent solid particles, called soot. It comes with red-orange glow of fire. This light has continuous spectrum, similar to sunlight spectrum. Even though it is rarely talked about, the orange glow of wood fire is also similar to the glow of sun. See Picture 3.5. The sun that is a natural source of light is an essential element of the ecosystem. One of the benefits of the sun is day light and night light via the moon. The sun does not produce waste since all its resulting particles and effects are used by nature. The sun light service life is infinite. The sun consists of heterogeneous materials and particles. This type of light source is natural, heterogeneous, clean, vital and efficient. Figure 3.2 shows the natural light pathway.

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The Science of Climate Change

Light intensity or energy, efficiency, and quality are functions of the light source composition. The light source is composed of infinite particles with different sizes, di, masses, mi, and temperature, Ti. The light source mass equals:



(3.5)

A particle energy function equals: (3.6) where ai is a constant, and fi is the frequency for the particle i. The light energy of a particle i is also defined as follows: (3.7) where vi is the speed of the particle i. Equation (3) yields: (3.8) Then, the frequency fi for the particle i comes to: (3.9) where bi, pi, qi are the constants defining the particle composition and properties. As a result, the particle speed vi amounts to:





(3.10) The total light energy is the sum of all particle energy values.



(3.11)

The wavelength is the inverse of the frequency: (3.12) where vi is the speed of the particle i: (3.13) li is the distance traveled by the particle i, and ti the travel time. The distance traveled by a particle i is a function of its size, di, mass, mi, and temperature, Ti. The particle mass mi depends on the particle composition. Since this particle i consists of the smallest particle in the universe, its composition is unique and corresponds to one material. The density of the particle i is: (3.14) where Vi is the particle volume: (3.15) αi and βi are the particle size constants. The distance traveled by light particle is described by:

Intensity (counts)

Forest Fires and Anthropogenic CO2 4500 4000 3500 3000 2500 2000 1500 1000 500 0 300

400

500

600

700

800

900

1000

55

1100

Wavelength (nm)

Figure 3.3 Wavelength spectrum of sunlight (From Islam et al., 2015).

Table 3.7 Sun composition (Chaisson and Mcmillan, 1997).

Element

Abundance (percentage of total number of atoms)

Abundance (percentage of total mass)

Hydrogen

91.2

71.0

Helium

8.7

27.1

Oxygen

0.078

0.97

Carbon

0.043

0.40

Nitrogen

0.0088

0.096

Silicon

0.0045

0.099

Magnesium

0.0038

0.076

Neon

0.0035

0.058

Iron

0.0030

0.14

Sulfur

0.0015

0.040

(3.16) which is equivalent to:



 (3.17)

The solar light spectrum is shown in Figure 3.3. Sunlight as the source of energy on earth must be understood in the context of photosynthesis reaction that creates

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The Science of Climate Change

Table 3.8 Wavelengths of various visible colors (From Islam, 2014). Wavelength (nm)

Color

750

Infrared (invisible)

vegetation on earth. Table 3.7 shows the composition of the sun. Considering some 8000 tones of loss of mass per second from the sun, it is reasonable to assume most of the mass loss involves hydrogen. Consequently, this hydrogen must constitute the most active role in photosynthesis. It is indeed the case. Furthermore, this composition is important in terms of overall elemental balance of the ecosystem. It is also important for consideration of beneficial energy. If nature is taken to be perfect and beneficial, solar energy as well as the elements present in the sun must be in beneficial form and should be considered to be the standard of energy. All vegetation on earth starts off with solar energy. If the artificial barrier between energy and mass is removed, the immediate consequence of solar irradiation would be manifested in the light spectrum of sunlight. Interestingly, the most abundant section of the solar light spectrum is the section that produces visible light (wavelength range of 400–750 nm). All wavelengths beyond these wavelengths of visible light are inherently harmful. The premise that nature is perfect leads to the conclusion that other rays are also necessary but their intensity must be very low, in line with the corresponding low intensities. It is important to identify the sources of non-visible rays. While we know all of them are emitted from the sun, the table above shows artificial sources of the same waves. Because artificial sources render these rays inherently unnatural, they make natural materials vulnerable to harm. For every natural ray, there is an artificial version. While each of the natural rays is essential and beneficial, the artificial counterpart is harmful to natural objects. Khan et al., (2008) demonstrated the nature of such artificial mass or energy by eliminating the assumption that transition from mass to energy is discrete and non-reactive.

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Table 3.9 Wavelengths of known waves (From Islam et al., 2015). Type of rays

Wave length

Gamma ray

10−2 – 10−6 nm

X-ray

10 – 10−1 nm

Ultraviolet

10–400 nm

Visible (by humans) light

Violet

400–450 nm

Blue

450–490 nm

Green

490–560 nm

Yellow

560–590 nm

Orange

590–630 nm

Bright red

630–670 nm

Dark red

670–750 nm

Infrared

800–1000 nm

Microwave

0.001–0.3 m

Radio wave

1 m–1 km

3.2.3

From Natural Energy to Natural Mass

In nature, we have the most spectacular example of conversion of energy into mass. The process is called photosynthesis. For most plants, photosynthesis occurs within Chlorophyll bodies. Chlorophyll's are arranged in something called "photosystems" which are in the thylakoid membranes of chloroplasts. The main function of chlorophyll is to absorb light energy and transfer it to the reaction center chlorophyll of the photosystem. Following are various pigments, capable of photosynthesis. Chlorophyll a has an approximate absorption peak of 665 Nm and 465 Nm. Chlorophyll b has an approximate absorption peak of 640 Nm and 450 Nm. In addition, there are accessory pigments that are able to absorb light. Chlorophyll a & b are green and are able to best absorb light in the 450 nm (violet-blue) and 650 nm (red) area of the light spectrum. That leaves the green, yellow and orange parts of the spectrum unusable. This is why plants have extra pigments (colours), in order to take in light from different wavelengths that chlorophyll is not good at absorbing. Carotene is an orange pigment capable of photosynthesis. This pigment transmits light energy to chlorophyll. As well as photosynthesis, these pigments also help protect against too much light, photoinhibition. Phaeophytin a are gray-brown in colour. Phaeophytin b are yellow-brown.

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Table 3.10 Artificial sources of various waves (From Islam et al., 2016). Type of rays

Artificial sources

Gamma ray

Co-60 or Cs-137 isotopes. When an unstable (radioactive) atomic nucleus decays into a more stable nucleus, the “daughter” nucleus is sometimes produced in an excited state. The subsequent relaxation of the daughter nucleus to a lower-energy state results in the emission of a gamma-ray photon.

X-ray

30–150 kV with tungsten, molybdenum or copper. X-rays are produced when electrons strike a metal target. The electrons are liberated from the heated filament and accelerated by a high voltage towards the metal target. The X-rays are produced when the electrons collide with the atoms and nuclei of the metal target.

Ultraviolet

UV rays can be made artificially by passing an electric current through a gas or vapor, such as mercury vapor.

Infrared

Tungsten, Kanthal filaments, Sapphire, Calcium Fluoride, Zinc Selenide, Silicon Nitride, laser, etc.

Microwave

Klystron (high power amplifiers), and reflex klystron (low power oscillators). Magnetron. High power pulsed oscillator. Semiconductors. Specialised transistors and Integrated amplifiers, especially using Gallium Arsenide instead of silicon. Often found in wireless networking devices, gps receivers etc.

Radio wave

When a direct electrical current is applied to a wire the current flow builds an electromagnetic field around the wire. This field sends a wave outward from the wire. When the current is removed, the field collapses which again sends a wave. If the current is applied and removed over and over for a period of time, a series of waves is propagated at a discrete frequency. If the current changes polarity, or direction repeatedly, that could make waves, too. This phenomenon is the basis of electromagnetivity and basically describes how radio waves are created within transmitters.

Xanthophyll are yellow pigments in the carotenoid group. These pigments seem to absorb best at 400–530 nm. These are involved with photosynthesis with chlorophyll. Chlorophyll is often much more abundant than xanthophylls, and this is why the leaves are still a green colour. When fall arrives in many countries and the leaves change colour, the chlorophyll "dies back" and the xanthophylls are more apparent in the yellow colour you see (like a maple tree) The Xanthophyll cycle is a wondeful skill a plant has. In order to protect itself from absorbing too much light, and thus causing photoinhibition,

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Xanthophyll cycle converts pigments that do not quench energy into ones that do. When a plant recieves too much light, the xanthophyll cycle changes violoxanthin to antheraxanthin and zeaxanthin which are photoprotective pigments. Anthocyanin pigments are often red, purple or blue. These pigments have been said to help a plant against light stress and act to help protect a plant from blue-green and UV light. Cacti do not have these, they have Betalain instead. Betalain These pigments are found in Caryophyllales (cacti and beets for example). They are often a red-yellow-purple colour that is often found in flower colour, but it can also be found in leaves, stems, fruits and roots of these plants as well. It is not really known what the exact purpose of these pigments are. Betacyanins are reddish to violet Betalain pigments. They absorb light best at 535 nm. Betaxanthins are yellow to orange Betalain pigments. They absorb light best at 480 nm.

Figure 3.4 Colors and wave lengths of visible light.

Radio waves

Infra red

700 Nm Red

580 Nm Yellow

400 Nm to 700 Nm

Long wavelengths

Visible light spectrum

500 Nm Green

450 Nm Blue

400 NM Violet

100–400NmUltra violet

X rays

Gamma rays

Cosmic rays

Short wavelengths

Given the various pigments, and the areas they are most abundant, that Chlorophyll a and b, and to a lesser extent, the various carotenoids (such as carotene and xanthophyll) would be the most productive in the absoprtion of light for photosynthesis. When applying this to cultivation and artificial lights, it would seem logical to choose lights that peak in the 430–470 nm and 640–680 nm range, to allow the two main chlorophyll types to gather the most energy. Light in the blue spectrum may also be a little stronger to allow the carotenes and xanthophylls to absorb more light as well. Figure 3.4 shows the existence of these wavelengths in visible light. An important note in this regard is that any visible light is either artificial or natural. If it is from the sun or from a natural fire, it would be beneficial. So, the visibility of light itself is not sufficient, one must seek to find the source of the light. A finer point lies within the fact that light that comes from forest fire will have a different overall composition from say domestic fire if the tiniest bits are also included. It is different because domestic fire would have particulates that emerge from oxidation of artificial chemicals whereas forest fire doesn’t contain such particulates. As we’ll see in latter chapters, this aspect becomes prominent in analyzing CO2 emission from crops that have been cultivated with chemical fertilizers and pesticides. Even genetically modified crop will exhibit different compositions but it would not be apparent from conventional mass analysis.

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Green Blue violet

Yellow Orange Bright red

Ultraviolet

Dark red Infra red microwave radio wave

X-ray Gamma ray

1/frequency or characteristic wavelength Green Blue violet Ultraviolet

Yellow Orange Bright red

X-ray Gamma ray

Dark red Infra red microwave radio wave

Degree of harm/vulnerability

Figure 3.5 Artificial and natural lights affect natural material differently.

If the fundamental premise that natural is beneficial and artificial is harmful (Khan and Islam, 2012) is invoked, the picture depicted by Figure 3.5 emerges. Of importance in the above graph is the notion that artificial rays are harmful at all times. As the exposure is increased, the harm is accentuated. For the short-term, artificial light visible light is less harmful than artificial non-visible rays (e.g., gamma ray, X-ray, etc.) on both sides of the spectrum (both long wavelengths and short ones). The reason for such behavior has been discussed by Khan and Islam (2012) and will be discussed later in this section. The above graph follows the same form as the wavelength spectrum of visible sunlight (Figure 3.6). Figure 3.7 recasts visible colors on intensity of solar radiation for the visible light section. This figure confirms that green vegetation should be the most abundant color on earth for which the sun is the only natural source of energy. This figure also shows the area under the intensity-wavelength curve is the greatest for green materials. Red has a longer wavelength but their intensity in sunlight is much smaller than green lights. Figure 3.8 plots radiance values for various wavelengths observed in forest fire as compared to grass and warm ground. For the visible light range, a forest fire follows the same trend as grass very closely. Also, comparable is warm ground. For the invisible range, however, a forest fire produces high radiance values for larger (than infrared) values. For wavelengths larger than 2 mm, both fire and warm ground produce similar radiance, whereas grass doesn’t show any radiation.

Intensity (counts)

Forest Fires and Anthropogenic CO2 4500 4000 3500 3000 2500 2000 1500 1000 500 0 400

450

500

550

600

650

700

61

750

Wavelength (nm)

Intensity (counts)

Figure 3.6 Wavelength spectrum of visible part of sunlight (From Islam et al., 2015).

4500 4000 3500 3000 2500 2000 1500 1000 500 0 400

450

500

600

550

650

700

750

Wavelength (mm)

Figure 3.7 Visible natural colors as a function of various wavelengths and intensity of sunlight. 20000

Radiance

15000 Fire Grass

10000

Warm ground

5000 0 383

837

1292

1790

2280

Wavelength (nm)

Figure 3.8 Wavelength and radiance for forest fire, grass and warm ground (From Li et al., 2005).

Oxidation of butane creates a blue flame. Typically, the separation of one particular component of a natural material skews the balance that a whole natural material would have. The burning of butane is, therefore, a skewed version of forest fire. Figure  3.9 shows how the butane flame produces spikes in the wavelength vs. irradiance graph. This

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SWAN BANDS

CH

Relative irradiance

0.8

0.6

C2

0.4 C2

CN/CH

C2

0.2

C2 C2

0 375

425

475 525 575 Wavelength (nanometers)

625

Figure 3.9 Blue flame radiance for butane (From Islam, 2014). 1.5

Kindle fire HD Nexus 7 new iPad 1.0

0.5

0.0 400

500

Wavelength (nm) 600

700

Figure 3.10 Artificial light spectrum (From Islam, 2014).

light, even though they are from a natural source, lacks balance – the likes of which persisted with sunlight and forest fire. Such imbalance would lead to harm of organic bodies. However, modern engineering typically ignores this fact and manufactures artificial material (energy or matter) that are similar to the natural counterpart only in the external features. For instance, for the case of electronic books, the main feature is to produce writings/pictures on a white background. All colors are artificial but white background is the most toxic because of its deviation from natural light spectrum. Figure 3.10 shows the light spectrum for Kindle Fire HD, Nexus seven and the iPad. Compare these spectra with that of sunlight and further consider irradiation from a white page compared to irradiation from an electronic device. It becomes clear that the artificial device is both imbalanced will create long-term harm to humans as well as the environment. Islam et al., (2015 and 2016) discussed the expected effect of natural and artificial light on humans. Some clinics have

Intensity (counts)

Forest Fires and Anthropogenic CO2 4500 4000 3500 3000 2500 2000 1500 1000 500 0

63

Sun Candle Incandescent Fluorescent Red LED

300 400 500 600 700 800 900 1000 1100 Wavelength (nm)

Figure 3.11 Comparison of various artificial light sources with sunlight (from Islam et al., 2010).

introduced light therapy for remedying various ailments. For instance, Mayo Clinic lists the following ailments that can benefit from light therapy: SAD (Seasonal affective disorder) Types of depression that don't occur seasonally Jet lag Sleep disorders Adjusting to a night time work schedule Dementia Light therapy has also been proposed to treat skin conditions such as psoriasis (for which UV irradiation is used). Unfortunately, no clear clinical studies exist today that would demonstrate the effectiveness of natural light over artificial light. Figure 3.11 shows sunlight along with light produced from a paraffin candle, incandescent light, and other light sources. Note how red LED is the most skewed from sunlight spectrum. The deviation is the most in visible light zone (wavelength of 400–750 nm). With the exception of two spikes at 600 nm and 700 nm, red LED produces very little irradiation in the visible light zone, whereas it produces much higher irradiation in the infrared zone and beyond. Fluorescent light produces similar spikes at 600 nm and 700 nm points but with less intensity than red LED. Overall, candle is the only one among artificial light that produces a broad band of wavelengths. In terms of harm to the environment, red LED is the worst offender, followed by fluorescent, then incandescent, and finally candle light. This vulnerability ranking is done by comparing the area under the curve within the visible light zone (Figure 3.12). If sunlight represents the original and the most beneficial energy source, any natural process emerging from sunlight will become beneficial. Let us consider forest fires. They come from a flame that trees or vegetation as the most important ingredient. All vegetation is indeed a product of natural processing of sunlight, air, water, and carbon components. The following table (Table 3.11) shows the relative amount of various elements in the earth crust as well as the lithosphere. It shows oxygen as the most prevalent in the earth

The Science of Climate Change

Intensity (counts)

64

4500 4000 3500 3000 2500 2000 1500 1000 500 0 400

Sun Candle Incandescent Fluorescent Red LED

450

500

550 600 650 Wavelength (nm)

700

750

Figure 3.12 Comparing within the visible light zone will enable one to rank various artificial light sources (from Islam et al., 2010).

crust, followed by silicon, aluminium, iron and others in lesser quantity. Hydrogen, the component of water, is 10th in the list. The essential cponent of living organism, viz., carbon is a distant 15th. In order to determine the overall mass balance of the ecosystem, one should look into the source of carbon as well as hydrogen. It is known that the atmosphere is composed of approximately 78% nitrogen, 21% oxygen, and less than 1% argon. Theoretically, all other elements in the earth crust should also appear in the atmosphere. This composition remains fairly constant throughout the atmosphere. However, as the altitude goes up, the density is decreased, leading to “thinning” of the air. This thinning leads to the formation of various degrees of ozone within the stratosphere. This ozone layer acts as shield against some of the non-visible emission of the sunlight. The high distribution of visible light, as reported earlier in this chapter, is possible in part due to the presence of this shield. Figure 3.13 shows how such protection is done with a clear and dark lens. This figure shows that how the presence of an even ‘transparent’ lens can alter the wavelength spectrum significantly. Above the mesosphere, the composition changes significantly, both in content and form. The overall composition is still dominated by nitrogen and oxygen, gases are highly ionized and bond between oxygen atoms are broken. Conventional theories cannot explain these phenomena, but it is considered to be essential for earth’s sustainability. In the exosphere, the outer layer of Earth’s atmosphere, air molecules can easily escape the Earth’s gravity and float into space. This process is similar to atomic radiation, which can be captured as long as the artificial boundary between mass and energy is removed (Islam et al., 2014b). In this context, the composition of human body is important. Table 3.12 presents the elemental composition of a typical human body (70 kg). This table does not contain some trace elements. Through continuity, all elements of the earth crust should also be present in a human body. Interestingly, carbon is the 2nd most important component of a human body, followed by hydrogen, nitrogen, and calcium, etc. Obliviously, human needs for various chemicals are met through breathing and consumption of food. The composition of the atmosphere shows that breathing alone

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Table 3.11 Various elements in earth crust and lithosphere (From Islam, 2014). N

Element

Symbol

Lithosphere

Crust

8

oxygen

O

460,000

460,000

14

silicon

Si

277,200

270,000

13

aluminium

Al

81,300

82,000

26

iron

Fe

50,000

63,000

20

calcium

Ca

36,300

50,000

11

sodium

Na

28,300

23,000

19

potassium

K

25,900

15,000

12

magnesium

Mg

20,900

29,000

22

titanium

Ti

4,400

6,600

1

hydrogen

H

1,400

1,500

15

phosphorus

P

1,200

1,000

25

manganese

Mn

1,000

1,100

9

fluorine

F

800

540

56

barium

Ba

6

carbon

C

38

strontium

Sr

16

sulfur

S

40

zirconium

Zr

130

74

tungsten

W

1.1

23

vanadium

V

100

190

17

chlorine

Cl

500

170

24

chromium

Cr

100

140

37

rubidium

Rb

300

60

28

nickel

Ni

90

30

zinc

Zn

79

29

copper

Cu

58

cerium

Ce

60

60

neodymium

Nd

33

340 300

1,800 360

500

100

420

68

(Continued)

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Table 3.11 Cont. N

Element

Symbol

Lithosphere

57

lanthanum

La

34

39

yttrium

Y

29

7

nitrogen

N

27

cobalt

Co

30

3

lithium

Li

17

41

niobium

Nb

17

31

gallium

Ga

19

21

scandium

Sc

26

82

lead

Pb

10

62

samarium

Sm

6

90

thorium

Th

6

59

praseodymium

Pr

8.7

5

boron

B

8.7

64

gadolinium

Gd

5.2

66

dysprosium

Dy

6.2

72

hafnium

Hf

3.3

68

erbium

Er

3.0

70

ytterbium

Yb

2.8

55

caesium

Cs

1.9

4

beryllium

Be

1.9

50

tin

Sn

63

europium

Eu

1.8

92

uranium

U

1.8

73

tantalum

Ta

1.7

32

germanium

Ge

1.4

42

molybdenum

Mo

1.1

33

arsenic

As

2.1

67

holmium

Ho

1.2

65

terbium

Tb

0.94

50

0

Crust

20

2.2

(Continued)

Forest Fires and Anthropogenic CO2

67

Table 3.11 Cont. N

Element

Symbol

Lithosphere

Crust

69

thulium

Tm

0.45

35

bromine

Br

3

81

thallium

Tl

0.530

71

lutetium

Lu

51

antimony

Sb

53

iodine

I

0.490

48

cadmium

Cd

0.15

47

silver

Ag

0.080

80

mercury

Hg

0.067

34

selenium

Se

0.05

49

indium

In

0.160

83

bismuth

Bi

0.025

52

tellurium

Te

0.001

78

platinum

Pt

0.0037

79

gold

Au

0.0031

44

ruthenium

Ru

0.001

46

palladium

Pd

0.0063

75

rhenium

Re

0.0026

77

iridium

Ir

0.0004

45

rhodium

Rh

0.0007

76

osmium

Os

0.0018

0.2

would provide very little carbon, which has to be taken from plants. In this regard, the composition of plant is of utmost importance. The exact chemical composition of plants varies from plant to plant, and within different parts of the same plant. Chemical composition also varies within plants from different geographic locations, ages, climate, and soil conditions (Reimann et al., 2001; Shtangeeva, 1994). However, the most abundant chemical in plants as well as other living bodies is cellulose. The basic component of this chemical is sugar or carbohydrate. This also forms the basis for all petroleum products, irrespective of their physical state. Also, plants are known to show variable compositions in terms of Cd, V, Co, Pb, Ba and Y, while maintain surprisingly similar levels in all plants in some other elements, e.g., Rb, S, Cu, K, Ca, P and Mg (Reimann

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Intensity (counts)

3500 3000 2500 Clear

2000

Lens

1500

Sunglasses

1000 500 0 300

400

500

600

700

800

900

1000 1100

Wavelength (nm)

Figure 3.13 Formation of a shield with dark and clear lenses (From Islam et al., 2010).

et al., 2001). These chemicals, whenever they are derived from natural sources, they are beneficial to human bodies. Whereas they are toxic if they are derived from artificial sources. This is portrayed in Figure 3.14.

3.2.4

Causes of Forest Fires

The above sections clarifies that forest fire can be triggered in presence of drought and concentrated heat, the fuel being available though thick vegetation. In this process, drought plays the most dominant role (Chen et al.,2014; Kitchen, 2016). The next most important aspect is fuel availability (Cai et al., 2014; Donovan and Brown, 2007). As Rancourt (2012) points out, the mechanism whereby drought determines fire occurrence is that flammability of dead or living organic matter is predominantly determined by its water content, which, in turn, is controlled by duration of exposure to dry atmosphere. In chemical terms, both the specific free energy of combustion increases and the free energy barrier for ignition decreases as water-content is lost. Mostly, ecoregion fire occurrences are not ignition limited because there are sufficient ignition events on the spatiotemporal scale of a drought (e.g., lightning, humans). Each of the incidents of forest fires, following factors will play a role (Syphard et al., 2007; Reid et al., 2010; Bowman et al., 2011): water table height and soil humidity attained degree of organic matter dryness fuel structure, including plant ecology history of past disturbances, such as insect attacks (e.g., animal grazing, past fires, controlled burning, harvesting) wind speed during live fire terrain, including slope and aspect (slope orientation relative to the sun’s path) forested-land fragmentation, both natural and anthropogenic frequency and spatial distribution of ignition sources human fire-fighting response

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Table 3.12 Table of elements in the human body by mass (From Emsley, 1998). Element

Mass

oxygen

43 kg (61%, 2700 mol)

carbon

16 kg (23%, 1300 mol)

hydrogen

7 kg (10%, 6900 mol)

nitrogen

1.8 kg (2.5%, 129 mol)

calcium

1.0 kg (1.4%, 25 mol)

phosphorus

780 g (1.1%, 25 mol)

potassium

140 g (0.20%, 3.6 mol)

sulfur

140 g (0.20%, 4.4 mol)

sodium

100 g (0.14%, 4.3 mol)

chlorine

95 g (0.14%, 2.7 mol)

magnesium

19 g (0.03%, 0.78 mol)

Iron

4.2 g

fluorine

2.6 g

Zinc

2.3 g

silicon

1.0 g

rubidium

0.68 g

strontium

0.32 g

bromine

0.26 g

Lead

0.12 g

copper

72 mg

aluminum

60 mg

cadmium

50 mg

cerium

40 mg

barium

22 mg

iodine

20 mg

Tin

20 mg

titanium

20 mg

boron

18 mg (Continued)

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Table 3.12 Cont. Element

Mass

nickel

15 mg

selenium

15 mg

chromium

14 mg

manganese

12 mg

arsenic

7 mg

lithium

7 mg

cesium

6 mg

mercury

6 mg

germanium

5 mg

molybdenum

5 mg

cobalt

3 mg

antimony

2 mg

silver

2 mg

niobium

1.5 mg

zirconium

1 mg

lanthanum

0.8 mg

gallium

0.7 mg

tellurium

0.7 mg

yttrium

0.6 mg

bismuth

0.5 mg

thallium

0.5 mg

indium

0.4 mg

Gold

0.2 mg

scandium

0.2 mg

tantalum

0.2 mg

vanadium

0.11 mg

thorium

0.1 mg

Uranium

0.1 mg

Samarium

50 μg (Continued)

Forest Fires and Anthropogenic CO2

71

Table 3.12 Cont. Element

Mass

Beryllium

36 μg

Tungsten

Benefit

Beneficial

Harmful

Organic

Time

mechanical

Figure 3.14 Natural materials are beneficial whereas unnatural materials are inherently harmful to the environment.

3.3

Climate Change and Forest Fire

An increased number of wildfires is one of the scenarios predicted under climate change in view of the modern day ACC hysteria. It is easily perceived that warmer temperatures lead to more evaporation and drier soils, making it conducive to wildfires. It is also postulated that warmer temperatures mean that snow melt happens earlier, which means soils are drier for longer and more extensive fire seasons. Similarly, there may be a correlation between dead trees and climate change through the resurgence of tree-killing insects. This, however, is also related to the ubiquitous use of pesticide and other unsustainable means of modern agriculture. In presence of such conditions, when a fire breaks out, for instance after a lightning strike, the conditions are such that it can burn hotter and spread further. Similarly, the introduction of invasive species in the United States, most notably cheat grass, has also given actual fuel to the fire. Cheat grass seeds in the fall, grows through the winter, and by June it's lifecycle is more or less done, leaving behind a dry woody plant that is perfect forest fire fodder. While forest management practices in the past, especially those which called for immediately suppressing any fire are now seen as part of the problem, this still does not explain the rise in wildfires in places where forests were not directly managed. The usual target as the ‘culprit’ is the overall climate change. Before a direct correlation between climate change and forest fires can be affirmed with any confidence, one must review such incidents in the historical context. For the last 170,000 years, since the last glaciation (14,000 years), and in the last 1,000 years, on continental and sub-continental scales, droughts are caused by long-cycle

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planetary orbit and inclination changes and by short-cycle planetary oscillations in ocean-coupled atmospheric circulations (Daniau et al., 2013; Wang et al., 2012; Vance et al., 2015). It is generally recognized that the beginning of a drought is difficult to determine. It is because of many reasons (Chin, 1978). Drought is a process that takes often years for even realizing that it is occurring. Similarly, the end of a drought can occur as gradually as it began. Dry periods can last for 10 years or more, often followed by decades of normal period. During the 1930's, most of the United States was much drier than normal (Moreland, 1993). In California, the drought extended from 1928 to 1937. In Missouri, the drought lasted from 1930 to 1941. That extended dry period produced the "Dust Bowl" of the 1930's when dust storms destroyed crops and farms. The first evidence of drought usually is seen in records of rainfall. Within a short period of time, the amount of moisture in soils can begin to decrease. The effects of a drought on flow in streams and reservoirs may not be noticed for several weeks or months. Water levels in wells may not reflect a shortage of rainfall for a year or more after a drought begins. Just like forest fires, floods are not necessarily indicative of climate change, a period of below-normal rainfall does not necessarily result in drought conditions. Some rain returns to the air as water vapor when water evaporates from water surfaces and from moist soil. Plant roots draw some of the moisture from the soil and return it to the air through a process called transpiration. During cool, cloudy weather, evapotranspiration rates may be small enough to offset periods of below-normal precipitation and a drought may be less severe or may not develop at all. Droughts to the overall environment are similar to a good medicine to an ailment (Mooreland, 1993). A single dose of medicine can alleviate symptoms of illness, but it usually takes a sustained program of medication to cure an illness. Similarly, a single rainstorm will not break the drought, but it may provide temporary relief. More importantly, an ailment cannot be fully cured unless the causes of the ailment are removed. In climate research, few if any have focused on determining the scientific causes of climate change. Similarly, a thunderstorm provides some of the same benefits as the shower and related fire triggered by lightening form integral part of the natural process. Thunderstorms often produce large amounts of precipitation in a very short time, and most of the rain will run off into drainage channels and streams rather than soak into the ground. If the rain happens to fall upstream of a reservoir, much of the runoff will be captured by the reservoir and add to the available water supply. No matter where the rain falls, stream levels will rise quickly and flooding may result. Also, because the rainfall and runoff can be intense, the resulting runoff can carry significant loads of sediment, nutrients, and pollutants that are washed from the land surface. Equally important is the groundwater level that is affected by a drought. Droughts, seasonal variations in rainfall, and pumping affect the height of the underground water levels. If a well is pumped at a faster rate than the aquifer around it is recharged by precipitation or other underground flow, then water levels in the well can be lowered. This can happen during drought, due to the extreme deficit of rain. The water level in a well can also be lowered if other wells near it are withdrawing too much water. Droughts are long-term reactions to climates and there is a huge lag time between droughts and overall climate conditions. The time frame of the occurrence of droughts

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is beyond the short-term reactions that are known in the plastic era (e.g., hole in the ozone layer). Not surprisingly, ever since that installation of modern devices of monitoring, water levels and meteorological records have been found to be extremely variables. Matching with the proxy data from tree-rings, ice cores and lake sediments has demonstrated that this variabillty has been going on for the past 10,000 years (Chin, 1978). There is no reason not to expect the same type of variability to continue in the future at least for the next few thousand years. However, the existence or absence of drought cycles is a controversial topic in the scientific community. Since the advent of the electronic computer, meteorologists and hydrologists have increased their efforts in attempting to develop sophisticated procedures for forecasting fluctuations in the climate. Many approaches are being investigated. There are five main types of approaches (Chin, 1978): i. ii. iii. iv. v.

the process-oriented approach; the periodic cycle approach; the sunspot-weather relationships; the extrapolation of existing trends; and the stochastic or statistical approach.

i.

Process-Oriented Approach: Scientists have little understanding of the dynamic interaction between the ocean, atmosphere and land masses and any claim of developing an accurate and sufficiently reliable deterministic mathematical model for forecasting the climate is unwarranted. Because of the immense complexity of the ocean, atmosphere and land mass system, it is practically impossible to factor in all necessary dynamics, let alone solve the resulting mathematical model. Most importantly, today’s science and mathematical tools are grossly insufficient for handling such global phenomena. Periodic Cycles Approach: The assumption that fluctuations in the climate have cycles with fixed periods or phases can be easily discarded, based on historical data. However, diurnal fluctuations, which are caused by the rotation of the earth about its axis, and the monthly and seasonal fluctuations which are caused respectively by the orbital motions of the moon about the earth and the earth about the sun, experience are real and have relatively fixed durations. Scientifically, this indicates that extreme events such as floods and droughts have not occurred at regular or periodic intervals in the past. This is scientifically explained by observing the solar system. Figure  3.15 shows the pattern observed by the solar and galactic system. Note that no object strictly follows the same path as everything is part of a moving galactic system. Islam et al., (2010) related movements of celestial bodies with solar radiation, Earth’s outgassing, and microbial activities operate as the major three forces of nature driving the earth’s climate. They quantify the extent of impacts from natural driving forces. Solar luminosity, solar system geometry, and the gaseous composition of the atmosphere

ii.

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The Science of Climate Change were considered as the first-order climate drivers. Global distribution of continents and oceans on Earth’s surface were considered the second-order climate drivers. Similarly, orbital and solar variability, large scale oceanic tidal cycles, and variation in the structure of oceanic currents were considered the third-order climate drivers. Volcanoes, natural weathering, regional tectonics, El Nino, solar storms and flares, short ocean tidal cycles, meteorite impacts, and human interventions were considered to be the forth-order climate drivers. They consider that global forces of nature are at least 4–5 orders of magnitude greater than results from human activities. iii. Sun-weather Relationships: The assumption that fluctuation in the climate have cycles with flexible amplitude, period and phase. While this approach has been popular among many members of the forecasting community, few attempted to go beyond correlating meteorological and streamflow events with solar activities, such as that measured by sunspot numbers. Not surprisingly, even after a hundred years of study and accumulation of data, there is still no clear indication of a correlation with reasonable confidence, let alone knowledge of the science behind those events. If there is a real relationship, it is a very complicated one, changing its phase relationship from epoch to epoch, which is far beyond the capacity of today’s scientific ability. To date no reliable mathematical relationship has been developed (Slingo and Palmer, 2011). This problem was identified decades ago. It was summarized in a 1975 report of the United States Academy of Science on Understanding Climatic Changes (United States Committee for the Global Atmospheric Research Program, I975). The report stated, "Since the development of modern techniques of time-series analysis, in particular those involving the determination of the variance (or power) spectrum, it has become clear that almost all the alleged climatic cycles are either (1) artifacts of statistical sampling, (2) associated with such small fractions of the

Galactic pathway Sun Moon Earth Figure 3.15 Periodicity occurs in the movement of each natural object.

Forest Fires and Anthropogenic CO2 total variance that they are virtually useless for prediction purposes, or (3) a combination of both." Of course, as Chin (1978) pointed out, even if there were truly a relationship between climatic fluctuations and sunspot cycles, the forecaster will still be faced with an enormous problem of predicting future weather if he were to use sunspot cycles as the deterministic variable. Until today, data on the Sun are miniscule even with decades of monitoring. The so-called 11 year sunspot cycle is merely an average figure and occasionally sunspots may not appear at all for several decades. An interesting hypothesis was advanced by the Soviet era Russians (Smirnov, 1969), relating fluctuations in streamflow and meteorological elements to the long-period tidal variations of the oceans caused by the tide-producing forces of the moon and sun. However, no successful predictive model has yet been developed on the basis of this hypothesis (Beaumont, 1982). iv. Extrapolation of Trends: This approach is the product of decades of reliance on Pragmatism that compels scientists to focus on the outcome rather than the process that produces the outcome. As such, the simplest approach is merely the extrapolation of existing trends. However, for extrapolation to be reliable the trend needs to be accurately known, and its causes sufficiently understood to indicate that the trend will be meaningful. Islam et al., (2010, 2016) have presented the shortcomings of this approach. The principal shortcoming is in the fact that matching data of the past does nothing to validate the predictive model. The introduction of history matching is only a cosmetic approach, devoid of proper science. Statistics has usefulness in the context of social science and epistemology. Statistics works in these cases because these are observable phenomena. On the other hand, if we apply statistics for giving credibility to a theory, it has no scientific meaning. For instance, if there is 0.01% probability that Universe started with a big bang, there is 99.99% probability that it did not. How then one can use the Big Bang narration of universe to be a starting point for prediction of the future? Figure 3.16 shows how weather forecast using initial condition uncertainties lead to a large envelop of forecast uncertainties. The blue lines show the trajectories of the individual forecasts that diverge from each other owing to uncertainties in the initial conditions and in the representation of sub-grid scale processes in the model. The dashed, lighter blue envelope represents the range of possible states that the real atmosphere could encompass and the solid, dark blue envelope represents the range of states sampled by the model predictions. Add to that the fact that initial conditions are numerous, each leading to a different end point. v. The statistical or probability approach: This approach has gained popularity because of its success in various applications. For instance, using long hydrologic records, and on the basis of certain assumptions, it is possible to develop probability statements about the chances of occurrences of a drought of given duration and severity. Such statements, of

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The Science of Climate Change Time Forecast uncertainty Initial condition uncertainty

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Figure 3.16 Forecast uncertaining in weather models (From Slingo and Palmer, 2011).

course, are useful only for planning and design of water related structures. They cannot tell exactly when and where a drought will occur and how severe it will be. Viewed on a broad time scale, the past 10,000 years is but another interglacial period of the Pleistocene Epoch. Very little information can be extracted on that remote past. Based on proxy data, there is no evidence to indicate that the global pattern of climate is undergoing any abrupt and abnormal changes. On the contrary, they appear to confirm that the climate will continue to occur with about the same magnitude, frequency and variability as in recent centuries, Although wet and dry spells tend to occur in groups of years, they do not occur at regular predictable intervals nor for any set predictable duration. During the plastic era all the way to modern time, there has been a dramatic and sustained decrease in forest-fire burnt area on earth (order-of-magnitude decrease in coniferous forests), which is unrelated to patterns of occurrences of drought and which is caused by socio-economic changes in human populations (Figure 3.17). Wallenius (2011) reports that in central Fennoscandia and the Western US, the mean annually burned areas in Pinus-dominated forests diminished between 1850 and 1950 to less than one tenth of what they had been at least since the 16th century. Similarly, a drastic reduction took place in southern Fennoscandia, the end of the 18th century. Also in general the available fire statistics are consistent with the results of the fire-scar-based reconstructions of the burned proportions. Pausas and Ribeiro (2013) observed that fire activity peaked in tropical grasslands and savannas, and significantly decreased towards the extremes of the productivity gradient. Both the sensitivity of fire to high temperatures and above‐ground biomass increased monotonically with productivity. In other words, fire activity in low‐productivity ecosystems is not driven by warm periods and is limited by low biomass; in contrast, in high‐productivity ecosystems fire is more sensitive to

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high temperatures, and in these ecosystems, the available biomass for fires is high. They concluded, however, that climatic warming may affect fire activity differently depending on the productivity of the region. Fire regimes in productive regions are vulnerable to warming (drought‐driven fire regime changes), while in low‐productivity regions fire activity is more vulnerable to fuel changes (fuel‐driven fire regime changes).

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Pausas and Keeley (2014) observed that the stated change is consistent with studies of global human land-use impact on fires, showing supressed fire-burnt areas in association with human population density (Bistinas et al., 2013; Knorr et al., 2014). In this study, Pausas and Keeley reported that climatic changes alone cannot explain many observed abrupt fire regime changes. They acknowledged the need for a wider perspective on global change drivers in making forecasts of future fire regimes. Beyond climatic changes, shifts in fuel structure caused by changes in both domestic and wild grazing animals and by the increasing alien plants can lead to abrupt changes in fuel structure and fire behavior. The role of humans is manifested through various effects, including direct alteration of fuel structure in ways that can lead to fire regime changes. Human activities also affect fire regimes through changes in ignitions, both by diminishing the potential for natural ignitions to play an ecosystem role (fire suppression), and by adding to the natural ignition frequency and altering the seasonal distribution of fires. This latter effect, however, is long-term and cannot be manifested in years or even centuries. In this latter category fall anthropogenic CO2 and N2 fertilization of the atmosphere that can alter fuel levels, as well as fuel moisture. Curiously, no distinction was made between these gases emitted from artificial sources (such as chemical fertilizer and refined petroleum fluids) and from natural sources (such as atmosphere and organic matter). Pausas and Keeley (2014) correlated shear growth in human population fireprone landscapes, leading thereby to future fire regime changes. Furthermore, indirect effects from human activities that can also contribute to fire regime changes were cited. They recognized, however, that increased CO2 enhances water-use efficiency, that is, the amount of carbon gained per unit of water lost, in a wide range of plants and thus it should also favor growth and biomass accumulation in water-limited ecosystems as well as observed previously by Bond and Midgley (2012). A more subtle effect, however, is in the effect on fuel availability for burning. Pausas and Keeley’s (2014) most important conclusion was: “Although global warming is widely interpreted as producing more drought-prone, and thus more fire-prone vegetation, increased water-use efficiency may have the opposite effect. In some Mediterranean climate ecosystems, this increase in water-use efficiency has been predicted to be more than 30% (Cheng 2003), with potential impacts on fuel moisture and subsequent fire activity.”

The importance of climate-independent factors in abrupt fire regime changes can be viewed positively: whereas climate is very difficult to modify in the short term, fuels can potentially be managed to shape fire regimes and to mitigate the effects of global warming (Stephens et al., 2013). However, the success of these actions may be diverse, depending on the historical fire regimes and the adaptive traits of the species in the community. All these analyses continue to miss the crucial point that photosynthesis with gases emerging from an combustion engine cannot be compared with photosynthesis with gases that are emerging from organic systems. This same conclusion is supported by the work of Diaz and Swetnam (2013), who reported evidence in terms of the largest and most severe fires both documented by humans and recorded in tree rings, which were well above 10,000 km2 (1,000,000

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ha). They used two reasonably close analogs to the anomalous spring and summer of 1910 that were noted. One occurred in 1988 and was associated with extreme summer drought in the Midwest United States and extensive fires in the Yellowstone National Park (YNP) region in the northern Rockies (Balling et al., 1992). The 1988 fire was one of the largest wildfire events in the recorded history of YNP. As in most major wild-fire episodes, smaller individual fires quickly grew out of control with increasing winds aided by severe drought and combined into one large conflagration, which burned for several months. A total of 793,880 acres (3,213 km2), or 36% of the park, were affected by the wildfires (Schullery 1989). This led to anomalous anticyclonic conditions prevailing from late spring through summer of 1988. Similarly, the anomalous ridging centered in midcontinent led to extreme drought from the upper Midwest to the northern Rockies and to extreme forest fire conditions in the northern Rockies. In some cases, these record-breaking wildfires have exceeded the previous largest documented wildfires (before 1980) by an order of magnitude. It is likely that increasing areas burned and higher severity fires in some low- and mid elevation drier forest types (such as ponderosa pine forests, dry mixed conifer forests, and pine savannas) are associated with a combination of factors. They observed that the drying (and subsequent combustion) occurs across a broad range of scales, from tree needles and grasses to small branches, whole tree stems (logs and snags), and entire forest canopies and watersheds. Moisture content of dead fuels is particularly important in fire ignition and initial spread rates; however, live fuel moistures (e.g., tree needle moisture content) may be a more important factor in some "crown fire" type conflagrations, where very high-intensity burning occurs as a consequence of increased volatility of these fuels. Reduced live fuel moistures can be important in promoting crown fire behavior and are an optional variable in some models (e.g., Scott and Reinhardt 2001), but the precise (and changing) relationships between live fuel moisture and crown fire behavior are either based on New science theories or based on limited statistical data. The problem with New Science theories, of course, is that they are based on false and illogical premises (Khan and Islam, 2016; Islam et al., 2010; Islam et al., 2018a). These models are simplistic and unrealistic. On the other hand, whenever epistemological analysis has been performed, it relied on very limited data. Such limitations are expected because of the difficulties in measuring live fuel moisture content and related fire intensities (and spread rates, etc.) at the requisite scales and in different forest types. In many cases, spectacular burning of combustible gases emitted from burning forest canopies are commonly visible in intense conflagrations as briefly burning vertical or tilted shafts of flame, or longer-lasting “fire whirls,” reaching heights higher than 100 m above canopies (Forthofer and Goodrick 2011). These observations indicate that combustible gases can be emitted in large quantities and ignited as living tree canopies are heated and burned, thereby extending flaming fronts (especially when wind driven) and contributing to very rapid spread rates. Diaz and Swetnam (2013) hypothesized that the extreme warming and drying conditions over periods of months and seasons (as in 1910 and 2012), which cause lower live fuel moistures at leaf to landscape scales, in turn lead to greater volatility (and hence combustibility) of fuels at all scales. This is not a particularly new idea (e.g., Simard and Donoghue 1987), but Diaz and Swetnam (2013) emphasized the role of

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this factor as being of greater importance than previously recognized (or modeled) in triggering extraordinary wildfire extent. Another factor of common importance in driving large wildfire events, both in 1910 and during many recent very large (>50,000 ha) wildfires, are surface and near-surface winds. The first-person accounts of the 1910 fires include many vivid descriptions of high winds blowing fire and large burning embers far in advance of the burning front. Similarly, winds were a key factor during the largest southwestern wildfires in recent years, with maximum burn rates of more than 20,000 ha in less than 24 hr (e.g., RodeoChediski Fire 2002, Wallow Fire 2011, Las Conchas Fire 2011). These very rapid fire runs resulted in total or near-total tree canopy mortality in long, linear strips, aligned with prevailing winds and extending for 15 km. This factor has some room for associating with synoptic weather patterns (e.g., passage of frontal systems, or “jet” wind currents at the surface or near surface; e.g., Crimmins 2006; Wirth 2011) versus “plume dominated” fires with runs caused by local, down-drafting (and horizontal) winds from collapsing pyro-convection columns (Potter 2011). Both types of wind-related fire behaviors typically occurred during recent large wildfires because they lasted days or weeks, encompassing both kinds of conditions (Diaz and Swetnam, 2013). None of these, however, can be directly correlated with climate change – a phenomenon that can take centuries. Very large wildfire events, like those of 1910 and recent years, are a consequence of many contributing factors operating across a broad range of spatial and temporal scales. The extended multivariate ENSO index (MEI) series available from NOAA’s Earth System Research Laboratory (ESRL; Wolter and Timlin 2011) indicates the occurrence of a strong La Niña during 1910, and it may have contributed to the strong and persistent anomalous anticyclonic pattern over North America in the spring and summer of that year. Weather events (such as regional surface winds) are superimposed upon seasonal and longer climate patterns (such as drought and secular warming), just as forest fuel drying and changing volatility/combustibility conditions are superimposed upon long-term trends of forest fuel growth and accumulation (e.g., the effects of a century of surface fire suppression, or recently induced tree mortality from bark beetle and drought). Improved understanding of the slower, long-term changes and rapid, extreme events we are witnessing today, and potentially predicting them in the future, will depend in large measure upon how thoroughly we can identify, measure, and model these interacting factors. In order to determine natural trends, Beaty and Taylor (2009) examined how the controls of fire episode frequency in the northern Sierra Nevada have varied at different temporal scales through the Holocene. A 5.5 m long sediment core was collected from Lily Pond, a ~ 2.5 ha lake in the General Creek Watershed on the west shore of Lake Tahoe in the northern Sierra Nevada in California, USA. Dendrochronology was used to reconstruct the recent history of fire, and high-resolution charcoal analysis was used to reconstruct fire episodes for the last 14 000 cal. yr BP. They concluded that fire episode frequency was low during the Lateglacial period but increased through the middle Holocene to a maximum frequency around 6500 cal. yr BP. During the late Holocene fire episode frequency generally declined except for noted peaks around 3000 cal. yr BP and 1000—800 cal. yr BP. These variations track major climatic and vegetation changes driven by millennial-timescale variation in the seasonal cycle of

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Number of sites burned

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Figure 3.18 Fire frequency and extent between 1600 and 1900 for 20 sites in the General Creek Watershed, Lake Tahoe Basin, California (from Beaty and Taylor, 2009). Filled circles indicate fire years with a corresponding charcoal peak.

insolation and regional decadal- and centennial-scale variation in effective moisture in the mid and late Holocene in the Sierra Nevada. Fire episode frequency during the Holocene in the Lake Tahoe Basin varied in response to decadal-, centennial-and millennial-scale climatic variability. Their 2009 study concluded that the current fire episode frequency on the west shore of Lake Tahoe is at one of its lowest points in at least the last 14 000 years. A total of 71 fires were recorded between 1616 and 1893 in the 50 fire scar samples from the 20 sample sites (Figure 3.18). The average length of a site fire record was 170 years (range 33–277 years) and all sites last burned in the mid to late nineteenth century. The maximum fire return interval (FRI) recorded at a site during the presuppression period was 47 years and the minimum was two years. The occurrence of intermediate and widespread fires was similar across the entire study period (Figure 3.18). Donovan and Brown (2007) pointed out the need for keeping forest fires at their natural state. They cited the fact that many landowners in these fire‐prone regions recognized that, in some forest types, regular fire was necessary to remove fuel that would otherwise build up and pose a risk of a more destructive fire. This is just in the short term. One can imagine how long-term needs for such natural phenomena would pan out. They quoted GL Hoxie (1910) whose research was from the period before the plastic era: “Why not by practical forestry keep the supply of inflammable matter on the forest cover or carpet so limited by timely burning as to deprive even the lightning fires of sufficient fuel to in any manner put them in the position of master?... Fires to the forests are as necessary as are crematories and cemeteries to our cities and towns; this is Nature's process for removing the dead of the forest family and for bettering conditions for the living.”

This scientific approach is ridiculed by most New Science handlers. Donovan and Brown (2007) pointed out that the bias was introduced by German forest practices, which emphasized a “scientific, ordered approach” (read ‘engineering’) to forest management. Those foresters viewed fires as killing small trees that they believed would otherwise grow to maturity, pejoratively referred to the light burning approach

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advocated by Hoxie and others as “Indian” forestry, a perspective forcefully expressed by FE Olmstead in 1911 (quoted by Carle, 2002): “It is said that we should follow the savage’s example of ‘burning up the woods’ to a small extent in order that they may not be burnt up to a greater extent bye and bye. This is not forestry; not conservation; it is simple destruction…the Government, first of all, must keep its lands producing timber crops indefinitely, and it is wholly impossible to do this without protecting, encouraging, and bringing to maturity every bit of natural young growth.”

Based on a premise that does not have logical basis, the entire practice of forest fire suppression has been introduced. The moral equivalent of such approach can be equated with banning mother’s milk on the basis that it is a savage practice. However, this departure from natural practices is new and has overwhelmingly been supported by the political ‘left’. Only recently has this strictly political stand become synonymous with scientific standards. Contrary to what is perceived as fundamental ‘science’ today, the pioneering forester and conservationist, Aldo Leopold, applauded the explosion of small trees in a ponderosa pine forest in northern Arizona that followed removal of light fires (Leopold, 1920): “It is also a known fact that the prevention of light burning during the past 10 years… has brought in growth on large areas where reproduction was hitherto largely lacking. Actual counts show that the 1919 seedling crop runs as high as 100 000 per acre. It does not require any very elaborate argument to show that these tiny trees, averaging only two inches high, would be completely destroyed by even a light ground fire.”

Although this view was supported by many foresters and some academics, a number of factors impacted an overall shift toward designating forest fire an ‘enemy’ that must be suppressed through managements. The most important factor was noted by Donovan and Brown (2007) as the 1910 fire season, when 2 million ha of Forest Service land burned and 78 firefighters lost their lives. Wildfire exclusion was also consistent with the conservationist ideal of the Progressive Era, which was inclined to view fire as another force of nature to be tamed, not as a potential management tool. It is the same mindset that has prompted New Science engineers to devise schemes after schemes to fight nature. This mindset has driven the current society into developing engineering practices that are inherently unsustainable. All these could have been avoided just by realizing two fundamental time-honoured principles, that is, (1) Nature is perfect; and (2) you cannot fight nature (Islam et al., 2010; 2015; Khan and Islam, 2016). Even after the Forest Service adopted a policy of fire exclusion, some foresters privately admitted that fire could be useful (Carle 2002). The following prescient statement was written in 1920 by SE White (White 1920): “…keep firmly in mind that fires have always been in the forests, centuries and centuries before we began to meddle with them. The only question that remains is whether, after accumulating kindling by twenty years or so of ‘protection’, we can now get rid of it safely… In other words, if we try to burn it out now, will we not get a destructive fire?

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We have caught the bear by the tail – can we let it go? … In this one matter of fire in the forests, the Forest Service has unconsciously veered to the attitude of defense of its theory at all costs. There is no conscious dishonesty, but there is plenty of human nature.”

However, the agency worried that any admission of a positive role for fire would be ‘confusing’; the message that fire was sometimes good and sometimes bad was considered too sophisticated for the general public. Therefore, the Forest Service continued with a policy of aggressive wildfire suppression, which was codified in 1935 by the “10 am policy” (so named because the policy stated that fires were to be under control by 10:00 am the following day), which called for: A century of wildfire suppression in the United States has led to increased fuel loading and large‐scale ecological change across some of the nation's forests. Land management agencies have responded by increasing the use of prescribed fire and thinning (Donovan and Brown, 2007). Ever since, fire suppressing has become a lucrative business, with numerous projects in support of it emerging, many of which are a result of corporate lobbying. The CHAR record for Lily Pond also showed similar results for the last 14000 years (Figure 3.19). As can be seen in Figure 3.19, the fire episode frequency ranged between a low of four fire episodes per 1000 year and a high of 17 fire epidsodes per 1000 year. There was a general trend of increasing fire-episode frequency since 14000 cal. yr BP from a minimum of four fires per 1000 year to a maximum of 17 fires per 1000 year at 6500 cal. yr BP, but there were also pronounced periods of high and low fire episode frequency. Fire episode frequencies declined from c. 17 episodes per 1000 year in 6500 cal. yr BP to 9 episodes per 1000 year around 3650 cal. yr BP. Fire episode frequencies rose again to another peak (11 episodes per 1000 year) that ranged from 3200 to 2900 cal. yr BP. Fire episode frequencies were generally low (mean = 7.5 fires/1000 year) during the period from 2600 to 1500 cal. yr. BP and were high (mean = 9 fires/1000 year) between c. 1000 and 600 cal. yr BP. After this period, there was a steady decline in fire episode frequency that continues to the present time. During this most recent period, there was also an absence of charcoal peaks between c. 500 and 200 cal. yr BP. Discussion The high temporal resolution fire record developed from the Lily Pond core indicates that fire regimes on the west shore of Lake Tahoe varied considerably over time and in response to decadal-, centennial- and millennial-scale climatic changes during the Holocene. The Lily Pond record is the first high-resolution charcoal chronology for the Lake Tahoe Basin and helps bridge our understanding of how variability in fire regimes in the basin were linked to environmental changes during the Holocene. The Forest History Society (Arno, 2014) offers a succulent explanation of how forest fire became an instrument of the political apparatus. The article states: Soon after its inception in the early 1900s the U.S. Forest Service adopted a policy that can be described as “fire exclusion,” based on the view that forest fires were unnecessary and a menace. In the late 1970s, however, the agency was compelled by facts on the ground to begin transitioning to managing fire as an inherent component of the forest. This new direction, “fire management,” is based on realization that fire is inevitable and can be either destructive or beneficial depending largely on how fires and forest fuels are managed. Despite the obvious logic of fire management it continues to be very difficult to implement on a significant scale. To understand why fire management is impeded and perhaps gain insight for advancing its application, we need to look at the history of fire

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Figure 3.19 CHAR record for last 14 000 year at Lily Pond, including CHAR and background CHAR (left), CHAR peaks above background (centre), and running local count of event frequency per 1000 year (right).

policy in tandem with the development of the science of disturbance ecology. It is also important to review changing forest conditions and values at risk to wildfire. Certain aspects of the situation today make it more difficult to live with fire in the forest than was the case a century ago.

Arno (2014) pointed out how the inception in the early 1900s of the policy that can be described as “fire exclusion” was rooted in the premise that forest fires are unnecessary and a menace, thus effectively disconnecting forest fires from the natural cycle of events. It was not until late 1970’s that forest fires are an integral part of natural ecosystem, at which point the term ‘management’ was coined, thus creating a perpetual ‘business’ opportunity to ‘fight nature’. This notion of business profiteering is once again rooted in politics and not science. For instance, soon after President William Howard Taft’s controversial firing of Forest Service Chief Gifford Pinchot, as the “the Big Burn” consumed 3 million forested acres in the Northern Rockies, Forest Service leaders claimed they could have stopped the disaster if they had had enough men and

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Picture 3.6 Scars from individual fires can be seen on the cross-section of a century-old “pitch stump” of ponderosa pine. (US Forest Service, n.d. photo)

money. That mindset took hold of the agency and echoes down through to today in some corridors. Ironically, in 1899 Pinchot had published an article in National Geographic magazine containing many observations on the importance of historic fires in propagating economically important and iconic trees including longleaf pine, giant sequoia, coastal Douglas-fir, and western larch. Pinchot noted that had fires been kept out of the great Douglas-fir forests of western Washington, “the fir which gives them their distinctive character would not be in existence, but would be replaced by the [smaller and less valuable] hemlock . . . with its innumerable seedlings.” (Arno, 2014). Nevertheless, Pinchot clearly advocated control of forest fires. This is not to say that he advocated ‘management’ or suppression of forest fires. In further evidence to favour natural order, in a 1910 Forest Service publication, pioneering ecologist Frederic Clements advocated using controlled fire in the management of high-elevation lodgepole pine forests (Picture and 3.6 and 3.7). On the other hand, Clements and his contemporaries developed widely adopted models of forest succession that fostered a belief that undisturbed “climax” forests, the end-point of succession, were more desirable than forests maintained in a “sub-climax” state by periodic fires even if those disturbances had occurred naturally. The successional models

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appealed to foresters because they implied that keeping fire out and allowing dense forests to develop would lead to greater production of timber. The models appealed to early ecologists as well perhaps because they suggested that the most desirable forest was one protected from “disturbance,” whether by fire, windstorms, or human activities. Despite such knowledge, by the 1910s when federal forestry began focusing on the South, its forests were being indiscriminately logged and grazed by cattle and hogs, and longleaf pine was not regenerating. Biologists speculated that fire might be important in restoring the pinelands, and a professor at Yale’s School of Forestry, H. H. Chapman, began long-term studies of the effects of fire exclusion and controlled burning. Excluding fire allowed low brush, palmetto, and other combustible vegetation, known as the “Southern rough,” to build up rapidly. Chapman found that the rough could out-compete pine seedlings, but also that the practice of annual burning to control the rough killed pine seedlings. However, burning at intervals of a few years controlled the rough and allowed longleaf pine seedlings to attain a larger, fire-resistant size. This periodic burning also controlled brown-spot needle disease that often killed seedlings. Chapman has been recognized as a pioneering scientist, but his philosophy toward forest fire has not been honoured in the new era. Chapman’s publicized findings supported periodic burning and were bolstered by other studies that showed burning the pinelands enhanced their forage value for livestock. Also, the U.S. Biological Survey published studies in 1931 showing that fire was essential for maintaining habitat for the South’s premiere game bird, the bobwhite quail. Moreover, the rapid buildup of Southern rough as a hazard for uncontrollable wildfires compelled many field foresters to stubbornly urge Forest Service administrators to allow controlled burning. By 1934, the Forest Service’s own Southern Research Station was covertly recommending to administrators that controlled burning be allowed if done for specified objectives by skilled technicians. Forest Service headquarters in Washington, D.C., feared that if it admitted fire could be beneficial in Southern forests and granted permission to burn, this would embolden burning advocates in the West. Thus, the agency continued to suppress and censor findings that supported use of fire, as was later revealed in Ashley Schiff’s 1962 book, Fire and Water: Scientific Heresy in the Forest Service. At the same time, the Forest Service covertly allowed controlled burning in many instances in the South, sometimes under the guise of “administrative studies.” Finally in December 1943, the wartime manpower shortage for fighting fires and the swelling tide of evidence and agitation for permission to burn from within and outside of forestry caused Chief Forester Lyle Watts to sanction use of fire, but only in the South. This decision was not motivated by science but by politics. Meanwhile, the January 1943 issue of the Journal of Forestry contained a ‘revolutionary’ article by a government forester, making a case for controlled burning in ponderosa pine forests of the West, based on both practical and ecological considerations. The disturbing light-burning movement that had been snuffed out by 1930 was suddenly reignited, and for the first time promoted in a professional journal by an experienced forester. Its appearance in the Journal of Forestry is remarkable in part because the journal’s publisher, the Society of American Foresters, had since its establishment in 1900 by Gifford Pinchot been closely if informally associated with the Forest Service. Nevertheless, the 1943 article was even more provocative than the Southern research papers that the Forest Service had suppressed.

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Picture 3.7 Prescribed burn in a giant sequoia grove, Sequoia and Kings Canyon National Parks. (National Park Service photo)

Thus, human land-use impact has recently moved the global fire regime outside of the natural long-term drought-fire relationship, and into the current period of fire deficit. Human land-use impact is now a dominant determinant of fires on earth and, in special regional circumstances, can also increase fire-burnt area relative to the newly established deficit value. This occurred in Europe in the mid-20th century, for known socio-economic reasons. (Viedma et al., 2007) gives a recount of forest fires in the Mediterranean countries of southern Europe since the middle of the 20th century. Pictures 3.36 and 3.37 shows some example of forest fires. They reported that forest fires started to increase markedly in the period of study. However, no clear correlation between fire incidents and various hazardous land-use and land-cover (LULC) changes could be established. They determined changes in fire-hazard through time and found that the proportion of hazardous LULC types increased twofold (26–42%) from 1950s to 2000. Until 1986, agriculture abandonment was the dominant LULC change leading to increased fire-hazard. Post-1986, LULC changes were mainly driven by deforestation due to fires and densification caused by natural vegetation dynamics. Models showed that the first abandoned lands were driven by local environmental and socioeconomic constraints (small farms, in distant locations, in municipalities with low population), whereas later abandonments were driven by non-local ones (large farms, in more productive soils, closer to towns, populations with high unemployment, and higher employment in the services sector). Throughout the study period, a high proportion of wildland vegetation, low mechanization level, and large number of land-holders older than 55 years favored abandonment, implying that as the population ages, larger, more accessible and productive areas are abandoned, fire-hazard will increase closer to human settlements, increasing the wild-land urban interface and fire risk. One should recall, it was the 1960’s during which ‘green revolution’ was introduced. This is an era that saw exponential growth in the use of chemical fertilizers, At the same time, farm density was reduced significantly from 1960 onwards (Viedma et al., 2007). It was particularly true for Europe. In 1980, the proportion of municipalities in the first quartile of 1960 increased three times (Figure 3.20a). From 1980 to 1990

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there was certain stability, although the trend to reducing farm density turned more pronounced from 1990 to 2000 (Figure 3.20b–c). Farm density decreased due to the significant increase of large farms (>50 ha) and the loss of very small farms during the entire studied period (Figure 3.20d–f). Veidma et al., (2007) also reported significant changes in relation to farmer’s age. Until 1990, there was a continuous increase of the proportion of land-holders older than 55 years, but from 1990 the trend was inverted (Figure 3.20g–i). For livestock density, from 1960 to 1980 half of the provinces included in the study area reduced their livestock density, whereas the other half increased it (Figure 3.20j). From 1980 to 1990 there was stability, and from 1990 the polarization process became acute (Figure 3.20k–l). Overall, the recent efforts to identify an increasing trend or an abrupt increase in forest fire occurrences (occurring after approximately 1900 when the new anthropogenic fire deficit was established) that can be attributed to anthropogenic CO2 (Syphard et al., 2007, 2012; Lampin-Maillet et al., 2011) is not based on science. There is evidence that many factors play a role including changes in fuels and landscape-level firehazard (Fernandez-Ales et al.,1992; Lepart and Debussche, 1992; Moreira et al., 2001; Kalabokidis et al., 2007; Carmel et al., 2009), socioeconomic factors (Viedma et al., 2007), and others. It is likely that overall lifestyle of the modern era is responsible, but it is not evident from previous studies that one factor is more important than another. When trends in fire activities in various countries are decoupled from changes in

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climate (San-Miguel-Ayanz et al., 2012), it becomes evident that the line about climate change provoking forest fire activities is a political conclusion and not scientific.

3.4

Setting the Stage to Discover a CO2 Effect

Struzik (2017) discusses the potential and probably adverse consequences for many ecosystems—including the threat of range contraction for some high-elevation forest types—due to rising temperatures from climate change, supporting these points with citations of the scientific literature and interviews with climate scientists and field ecologists. Even though this topic has gained popularity the science behind wildfires and their connection to climate change is misunderstood (Hanson and Hansen, 2018). Rancourt (2012) deconstructed the apparent connection between climate change and forest fires. He cited the example of Parry et al., (1996) work that is considered to be pivotal in the climate change debate. This work was published in the middle of Clinton era with the fulfilment of the Al Gore’s vision of global warming (Gore, 1992) and shortly before Kyoto Protocol was signed. After Parry et al.’s work, the premises that they based on were not re-examined by any serious researcher and even the opponents of ACC hysteria didn’t offer a rebuttal. As we have seen in Chapter 2, the Neoskeptics have tacitly accepted the external features of the ACC argument, albeit denying that there should be a course of action to remedy the perceived effects of global warming. Here, the development of “awareness” of negative consequences from anthropogenic CO2 has had a palpable influence on forest fire research, and the history of this influence is recorded in the scientific literature. As Rancourt (2012) pointed out this paper is typical of many such papers and reports intended to guide the perceptions and interpretations of scientists, while thus providing scientists with a path towards increasing perceived importance of their work. The paper introduces a number of fundamental premises, none of which is anchored in any publication in earth science or other disciplines. Embolden with The Framework Convention on Climate Change (UNFCCC), which was signed at the United Nations Conference on Environment and Development in Rio de Janeiro in 1992, Parry et al., (2007) stated an objective of ‘stabilization of greenhouse gas concentrations in the atmosphere at a level that would prevent dangerous anthropogenic interference with the climate system.’ This loaded objective is followed by a dogmatic definition of ‘dangerous’. The word “dangerous” (Parry et al., 1996): “A dangerous action is one that may lead to harm. In the context of Article 2 of the [UN Framework Convention on Climate Change] ‘dangerous interference with the climate system’ may be defined as that leading to climate change within a time frame that is insufficient to allow ecosystems or socioeconomic systems to adapt thus leading to significant damage to those systems.” (p. 1)

This is already of concern because many actions “may” lead to harm. For example, investing in and implementing alternative technology on mass scales may lead to harm. More importantly, in terms of the logic, if “ecosystems or socioeconomic systems” do not “adapt” to increasing CO2 because of slow response times or weak responses, then

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those systems have, by definition, not changed and not suffered harm from changes. Most importantly, this definition has nothing to do with real danger that can be only defined in terms of long-term damage, in line with the definition of true sustainability (Khan and Islam, 2007; Islam et al., 2010). As if it is not illogical enough, Parry et al., (1996) creates further opacity by redefining “dangerous” as “critical”: “Closest in meaning to ‘dangerous’ and having scientific currency is the term ‘critical’: a condition at or relating to a turning-point or transition. Thus (again in terms of Article 2) a critical level of a climate change is that beyond which further change would have a significant effect on ecosystems or socioeconomic systems.” (pp. 1–2)

In this preposterous tactic, the authors now create a hysteria of “turning-point” that can occur anytime as atmospheric CO2 concentration increases, and point scientists towards being on the lookout for such “turning-points” or “transitions”. This has been a classic pattern of disinformation in the realm of New Science. Islam et al., (2015) reminded their authorship of Benjamin Franklin’s famous quote: “We are all born ignorant, but one must work hard to remain stupid.” Margaret Thatcher famously stated, “there is no alternative” (later dubbed the ‘TINA’ doctrine) in reference to having no alternate to market economy, and eventual ‘globalized capitalism’. Zatzman and Islam (2007) popularized the notion as TINA syndrome that obfuscates a conscientious process to move forward. This is also akin to American actress, Kathleen Turner’s statement: “If I am in a room alone and a man enters the room but doesn’t stare at me, he must be gay”1. What this line of cognition leads to is the readership is indoctrinated to seeking solace in their beliefs that are nothing but are cycled version of dogma. This is the unavoidable outcome of linear thinking that goes back to Dogma time but that became secularized after Newton. What we are being told is, we have only two options: False Premise 1; and False Premise 2. Then, the cognitive dissonance kicks in and we debate over which premise would minimize the distance between premise and conclusion, no other option being open to us. Anything else is called radical and everyone that conforms to the system and agrees to disagree is called civilized and worthy of co-existence. In this process the gravest offense is in assuming someone’s intention and the possibility of a different intention. Unfortunately, this has been the most prominent feature of modern-day cognition. In the context of global warming or climate change debate, anyone that took a stand against the mainstream version has been attacked as being the stooge of the oil companies or the political establishment of the accuser’s choice. Then the authors move on to make sure the readership has no option of turning back from the absurd and illogical fundamental premises. It ‘clarifies’ that it’s all about the weather (Parry et al., 1996):

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In the early 1990s, the actress said, “If I amin a room alone and a man enters the room but doesn’t stare at me, he must begay”. Anyone familiar with prophet Muhammad would gasp at this suggestion.Prophet Muhammad, the ideal man in Islamic faith, would be ranked as a ‘gayestman’. In fact, Qur’anic verses (24: 30-31) are clear that we (both male andfemale) are not supposed to stare at anyone, let alone a person one isattracted to

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2. Determine relationship between climate variation and indicator change

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“We may now define a dangerous or critical climate change as that leading to exceedance of threshold values of weather and climate events (again, defined either in terms of their magnitude or frequency).” (p.2)

Presumably, a “climate event” in exceedance is a weather event (or several weather events) that, in magnitude, is (are) outside of the climate norm. We see that scientists are being asked to detect precursor events that announce a dramatic change in climate regime, and that the detection of such precursor events, by its nature, is at the limit of statistical analysis using a needed suitable historic database. In essence, what this paper does is makes sure that the objective is set in such a way that the only conclusion that can emerge is the one that would support the predetermined policy changes. This is depicted in Figure 3.21. This tactic has been called out by Islam et al., (2010) as a modern day scientific fraud that misleads the readership into believing in a false premise. They cited the example of Galileo’s carefully framed test, in which he made a series of increasingly precise measurements of exactly how long it took various masses in free fall to reach the ground from the same height? The greater the precision, the more these incredibly small differences would be magnified. One could hypothesize that air resistance accounted for the very small differences, but how could that assertion then be positively demonstrated? If modern statistical methods had been strictly applied to analyzing the data generated

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Figure 3.22 If the model were true, then the theory would be verified. So, what if the model were false from the outset, betrayed by retention of a first assumption that was not more carefully scrutinized? With more observations and data, this modeling exercise could carry on indefinitely, e.g., a 5-parameter univariate nonlinear.

by such research, magnificent correlations might be demonstrated. None of these correlations, however, would point conclusively to the uniformity of acceleration of the speed at which these freely falling objects descend over any other explanation. As long as the focus remained on increasing the precision of measurement, the necessity to drop Aristotle’s explanation entirely (that object fall freely at speeds proportional to their mass) would never be established unambiguously. The following possible representation of how the data resulting from such a falsified experimental approach reinforces this conclusion (Figure 3.22). The tendency of Parry et al., (2007) and similar ‘activitist’ scientists have been that they make sure that today’s Galileos do not have the faintest possibility to advance a different premise that doesn’t maximize benefit to the Establishment. “function” like y = ax + bx2 + cx3 + px4 + qx5… that continues towards ever higher degrees of “precision.” It is well known in medical research for example, that when threshold detection of harm or benefit relies on statistical analyses using imperfect datasets, in an area of human importance, “most published research findings are false” (Ioannidis, 2005; Goodman and Greenland, 2007; Ioannidis, 2007). As we have seen earlier, forest fire research provides good examples of this phenomenon. The spin that was triggered by Parry et al., (1996) was carried forward by Flannigan et al., (2000). With a presumed relationship between impacts of climate change and forest fires, this paper reports results of general circulation models (GCMs). The opacity added in this line of studies is reflected in the false premises of the mathematical models. We have seen a number of false and misleading premises added by Parry et al., (2007), now Fannigan’s work add false premises of the numerical models then establishes the veracity of previous false premises by showing that mathematical models predict the same outcome. This picture is clarified in the flow chart in Figure  3.23. The entire process becomes an exercise to justify decisions that have been made based on special interests and not science. As we will see below, the introduction of a

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Figure 3.23 Unless premises behind science and logical, science and modeling are but tools for justifying policies.

mathematical model only makes the process more obscure and gives a false sense of accuracy and correctness. Flannigan et al., (2000) conclude, “The two GCMs in this study suggest increases in [Seasonal Severity Rating] SSR of 10–50% across much of the United States by 2060.” The problems with this simplistic conclusion has been highlighted by Rancourt (2016). These are: 1. The SSR is not “a final component of the Canadian forest fire weather index (FWI) system”. Rather, it is a fire-season average of the daily FWIs, each to an exponential power, which weighs “the FWI sharply as it rises, in a manner deemed to reflect the control difficulty” of fires (Van Wagner, 1987). 2. The FWI is entirely based solely on (local) weather measurements, without including fuel structure or soil properties or evolutions of fuel structure and soil properties or any of the known dominant non-weather factors (Van Wagner, 1987). 3. The GCMs do not provide local weather parameters, for correct calculation of FWI. Rather, they provide large-scale (cell-average) weather variables. Flannigan et al., (2000) reported only ratios and percent changes of SSR between 2060 and present, without reporting the actual magnitudes of SSR that are obtained from GCM cell-average weather parameters. Without the magnitudes it is impossible to judge the degree to which the GCMs can provide a realistic FWI. Flannigan et al., are silent on this foundational aspect of their calculation.

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GCMs have their inherent systemic problems. As pointed out by Stone and Risbey (1990), General Circulation Models (GCMs) the meridional transports of heat simulated by GCMs used in climate change experiments differ from observational analyses and from other GCMs by as much as a factor of two. They demonstrate that GCM simulations of the large-scale transports of heat are sensitive to the (uncertain) subgrid scale parameterizations. Of course, other problems inherent to the fundamentals of Newtonian approach (Islam et al., 2010) are not even considered in that work of Stone and Risbey (1990). In addition, Rancour (2016) pointed out the following two fundamental problems with any attempt to use a GCM to predict future fire occurrences. First, fires are known primarily to be controlled by drought (sustained dry weather), from a climate perspective on yearly to millennial timescales, are known primarily to be controlled by planetary oscillations in ocean-coupled atmospheric circulations; whereas GCMs do not and cannot model planetary oscillations in ocean-coupled atmospheric circulations. In terms of realistic planetary oscillations, GCMs are toy models. Secondly, a specific fire regime (frequency, severity, coverage renewal period) results from a convolution of climate-scale drought cycles and local ground-level conditions because ignition and propagation are a local phenomenon that sensitively depends on local conditions (see above); whereas GCMs do not provide local weather conditions, but only cell-average values. However, in absence of real science, the modeling approach caught on and other papers continue to use the approach. In 2004, Fried et al., literally reproduced the scheme outlined in Figure 3.23. They estimated the impact of climatic change on wildland fire and suppression effectiveness in northern California by linking general circulation model output to local weather and fire records and projecting fire outcomes with an initial-attack suppression model. Their computer modeling results showed that when interpolated to most of northern California’s wildlands, these results translate to an average annual increase of 114 escapes (a doubling of the current frequency) and an additional 5,000 hectares (a 50% increase) burned by contained fires. On average, the fire return intervals in grass and brush vegetation types were cut in half. They made the most desired conclusion, that is, in addition to the increased suppression costs and economic damages, changes in fire severity of this magnitude would have widespread impacts on vegetation distribution, forest condition, and carbon storage, and greatly increase the risk to property, natural resources and human life. Rancour (2016) offers the following deconstruction of Fried et al., (2004). Fried et al., (2004) states: “To capture the direct influence of climatically-induced changes in weather, [Changed Climate Fire Modeling System] CCFMS (1) adjusts local, daily, historical weather data according to percentage changes in the relevant climate statistics predicted on a monthly, regional basis by the [Goddard Institute for Space Sciences] GISS GCM.” This means that they fabricated local-weather conditions by scaling present real local weather data following percentage changes in the scenario-generated GCM cellaverage values. There is no prima facie justification for this fabrication. One cannot on the one hand appeal to non-linearity and impending “turning-points” while on the other hand arbitrarily apply linear scaling between dissimilar values, without any expressed and tested reason. This has been a classic display of the aphenomenal (as opposite to knowledge) model that is depicted in Figure 3.24. This figure shows how a

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decision is made without regards to actual data and scientifically processed information. When in Parry’s work we identified a number of false premises, it is equivalent to misrepresenting data that are often objective. This misrepresentation is followed by creating opacity, all designed to justify the desired outcome, which itself is to justify the decision that was made in the first place. The entire process that is passed as ‘evidencebased science’ is actually an exercise in cover-up and obfuscation of due process that would certainly show a different conclusion. In 2004, Gillett et al., (with co-author Flannigan, the author of Flannigan et al., 2000) appear to have been the first to claim an observed forest fire increase that

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unambiguously can be attributed to anthropogenic CO2. Their main graph is shown in Figure 3.25. It shows total area burned, from 1920 to 2000, with a systematic increase starting at approximately 1970, which follows both an “observed” temperature anomaly and a GCM-calculated temperature anomaly, all three curves displayed on the same graph for the temporal range 1920 to 2000. The problem is: None of the data is what it appears to be. On close examination, we find that the plotted variation in area burned is an artefact. The authors themselves admit: “Although an attempt was made to account for fires in provinces and territories with incomplete records, prior to the advent of satellite monitoring in the early 1970 s some fires may be missing from the record due to lack of observations or incomplete recordkeeping. However, the fact that the largest increase in area burned has occurred since 1970 indicates that it is unlikely that the upward trend is purely an artifact of underreporting …”

In fact, despite it being stated also by others in 2002 (Stocks et al., 2004), it is absurd to assume that satellite detection of fires suddenly turned on in 1970 to give reliable archival records of continent-scale fire occurrences. The truth is that satellite detection has a continuous history of improvement, that satellite detection itself has significant limitations, and that fires did not start to be reliably detected by satellite programs until specialized infrared bands came on-line in 1984. Furthermore, paper records kept by government agencies, in the time period of interest since 1900 or so, are notoriously and systematically incomplete (Short, 2015). Thus, a “trend” like the one proposed by Gillett et al., (2004) is likely the result of improving fire detection and record keeping. As the basis for their attribution of the burned area to anthropogenic CO2, Gillett et al., (2004) state: “Although forest fires are influenced by a range of climate parameters, such as temperature, humidity, precipitation, wind speed and lightning occurrence, in long term means, temperature is perhaps the best predictor of area burned.”

Actually, there is no evidence that “long term means” of temperature is a predictor of area burned, and this very notion is contrary to established knowledge about the causes of fire occurrences. Of course, fire-causing droughts (or extended dry periods) are often associated with higher or lower temperatures relative to a longer-term regional average, but this has everything to do with the very nature of a drought and nothing to do with global atmospheric concentration of CO2. A positive or negative correlation between drought and temperature will exist irrespective of CO2. Next, Gillett et al., (2004) apply a creative data manipulation that, by design, artificially creates an enhanced correlation between their area burned values and their mean “temperature” values. In their own words, here is how it works: “In order to give greatest weight to temperature anomalies in fire-prone regions, the temperature in each 5o × 5o grid cell is then weighted by the total area burned in that grid cell over the 1959–1999 period, and a mean is computed over available data, shown by the red line in.” [Emphasis added]

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And the same was done to create GCM “temperatures”: “Five year May–August mean temperature anomalies from an ensemble of three integrations forced with historical greenhouse gas and sulfate aerosol changes were interpolated onto the observational 5o × 5o grid, sampled where observations exist, weighted by total area burned in each grid cell, and averaged. The resulting ensemble-mean anomalies are shown by a green line in.” [Emphasis added]

This means that the average fire-season temperature in a cell where fires were occurring was weighted by the burned area in that cell to calculate the final “average”. This creates an artificially amplified correlation, which only tells the reader that fire-prone dry areas (cell and season specific) were also hot areas (cell and season specific). It does not relate fire to global climate. Global atmospheric CO2 can affect global climate but it cannot affect temperature in specific cells and selected seasons where fires occur. The fatally flawed paper of Gillett et al., (2004) is considered the first finding of a link between forest fires and anthropogenic CO2, and it is cited by several authors as such. But the incorrect notion that forest fires have been shown to be linked to anthropogenic CO2 did not catch on and “go viral” until the research-trend-setting magazine Science got involved (see below). Any public relations body, such as a government agency or the renowned Union of Concerned Scientists NGO, which has an interest in there existing a link between forest fires and anthropogenic CO2 will prominently cite Union of Concerned Scientists (2018), the most influential paper that reports the said link (Westerling et al., 2006). This paper has been positively cited extensively by scientific authors who have an interest in global warming. It is, therefore, important that the article by Westerling et al., (2006) be critically examined. Westerling et al.’s (2006) main result is a stunning graph shown in their Figure 3.26(a), which shows wildfire frequency (bars) for large fires (>400 ha) versus time from 1970 to 2005, compared to the mean March through August temperature for the western United States (line). There is not a correlation with temperature but, more importantly, there is a notable break at 1984–1985 to higher values in frequency of large wildfires. Such a sudden break, with constant low and high values on either side of the break, irrespective of the frequent El Nino episodes known to have occurred both prior to and after the break, is suggestive that something new has occurred. Namely, a CO2-induced “transition”, or at least an increase that should be attributed to increasing anthropogenic CO2, since higher values of CO2 occur after 1984–1985 compared to the values of CO2 prior to 1984–1985. Irrespective of any preferred interpretation, the graph (Figure 3.26), if it contains good data, must give one pause. The whole package was enough to cause palpable and on-going celebration in the global warming scientific literature. The Science Perspectives article emphasized the unprecedented quality of the data (Running, 2006): “Westerling et al., used the most comprehensive data set of wildfire occurrences yet compiled for the western United States to analyze the geographic location, seasonal timing, and regional climatology of the 1166 recorded wildfires with an extent of more than 400 ha.”

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14 15 T (ºC)

wildfire frequency 0 100

Western US Forest wildfires and Spring-summer temperature

Temperature

1970

1975

1980

1985

13

Wildfires 1990

1995

2000

1995

2000

(a) –15 –5 5 15 Days (anomaly)

Days (anomaly) –15 –5 5 15

Timing of spring snowmelt Late

Early 1970

1975

1980

1985

1990

(b)

Day of year 100 300

3 2 1

(c)

1970

1975

1980

2. Last discovery 1985

1990

3. Last control 1995

0

0

1. First discovery

100 300 Day of year

Fire season length

2000

Figure 3.26 (a) Annual frequency of large (>400 ha) western U.S. forest wildfires (bars) and mean March through August temperature for the western United States (line) (26, 30). Spearman's rank correlation between the two series is 0.76 (P90

Ponagamia oil

0.64

Pongamia oil

2.69

Salvadora oil

1.76

Moringa oleifera

2.9

Karanja oil

2.53

Sorghum bug oil

10.5

Mahua oil

21.0

Mahua oil

19.0

Madhuca indica

20.0

Zanthoxylum bungeanum

45.5

Acid oil

59.3

Karanja oil

2.53

Trap grease

50–100%

Finished greases

8.8–25.5%

Crude soybean oil

0.4–0.7% (Continued)

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Table 5.1 Cont. Vegetable oils Restaurant waste grease Waste palm oil Municipal sludge

FFA levels (%) 0.7–41.8% >20% Up to 65%

Animal fat

5–30%

Trap grease

75–100%

Use cooking oil Waste oil

2–7% 46.75%

Table 5.2 Ffas levels in feedstocks (from atadashi et al., 2013). Feedstocks

FFA levels

Trap grease

50–100%

Refined vegetable oils

20% Up to 65%

Animal fat

5–30%

Trap grease

75–100%

Use cooking oil Waste oil

2–7% 46.75%

Transesterification of refined oils with less than 0.5 wt% FFAs via chemical catalysts could lead to high-quality biodiesel fuel with better yield within short time of 30–60 min. Figure 5.10 presents the mechanism of base-catalyzed transesterification reaction. Vicente et al., (2004) compared different basic catalysts (sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide) to produce biodiesel fuel using sunflower oil. The reactions were conducted at temperature of 65 C, methanol to oil molar ratio of 6:1 and basic catalyst by weight of vegetable oil of 1%. They achieved 85.9 and 91.67 wt% yield of esters for NaOH and KOH and 99.33 and 98.46 wt% yields of esters for CH3ONa and CH3OK, respectively. The authors recorded 98 wt% yields of esters for methoxides after separation and purification steps were

Role of Biofuel Processing in Creating Global Warming

201

O C O H- O - H

CH3- O -H

Gly’

K -O- H O C O

Gly’

CH3 - O– –

O C

Gly’

O H

CH3 - O

O - CH3 H- O - H O– C HO - Gly’ CH3 - O

HO - CH3 –OH

Figure 5.10 Mechanism of base-catalyzed transesterification reaction (from Sayed, 2006).

completed. Further, less yields losses and negligible ester dissolution in glycerol were observed with methoxides compared to hydroxides. To evaluate the biodiesel purity, the methyl ester concentration (wt %) in the biodiesel phase was calculated. Conversely, to estimate the biodiesel yield after the reaction and separation stages, the biodiesel weight yield, relative to the initial amount of vegetable oil, was worked out. The results for all the experiments and their repetitions are shown in Table 5.3. The arithmetical averages and standard deviations of the results are also presented in Table 5.3. The standard deviations were very low in all the experiments, indicating a low variation among the repeated experiments. When the four catalysts were used, methyl ester concentrations were nearly 100 wt.%. According to these results, all the transesterification reactions were completed and, therefore, no difference in biodiesel purity was found after 3 hr of reaction. However, if there are no side reactions, the biodiesel weight yields, relative to the initial amount of vegetable oil, should be nearly 100 wt.%. In this sense, the two possible side reactions are triglyceride saponification or neutralisation of the free fatty acid in the vegetable oil. Both of them produce sodium or potassium soaps and, therefore, decrease the biodiesel yield. In this case, however, the free fatty acid neutralisation could not be substantial since the acid index in the sunflower oil was only 0.45 mg KOH/g. Consequently, triglyceride saponification must be the only possible side reaction. As shown in Table 5.3, high biodiesel yields were obtained by using the sodium or potassium methoxides (99.33 and 98.46 wt.%, respectively), because they

Biodiesel yield (wt.%)

Biodiesel purity (wt.%)

91.67 91.33 92.00

87.00

86.71

91.67

86.67

86.71 ± 0.28

99.74

99.65

86.33

99.80

99.72

99.69 99.80

99.71 ± 0.04

91.67 ± 0.27

99.76 ± 0.05

Potassium hydroxide

99.75

99.70

Sodium hydroxide

Catalyst

99.00

99.83

99.33

99.17

99.75

99.72

99.69

99.70

99.33 ± 0.36

99.72 ± 0.03

Sodium methoxide

98.67

98.33

98.50

98.33

99.53

99.65

99.50

99.40

98.46 ± 0.16

99.52 ± 0.10

Potassium methoxide

Table 5.3 Effect of the catalyst on the biodiesel purity and yield (from vincente et al., 2004). Temperature = 65 °C, Methanol:Sunflower oil molar Ratio = 6, Catalyst = 1 Wt%.

202 The Science of Climate Change

Role of Biofuel Processing in Creating Global Warming 100 FAME content (%)

FAME content (%)

100 80 60 40 20 0 50 (a)

C. japonica V. fordll 60 70 80 Reacton temperature (ºC)

60 40 20

(b)

0.5 1 1.5 2 Loading amount of catalyst (g)

100

FAME content (%)

FAME content (%) (c)

80

0 0

90

100 80 60 40 20 0 0

203

5 10 15 Methanol/oil ration

80 60 40 20 0

20 (d)

0

1

2 3 4 Reaction time (h)

5

6

Figure 5.11 FAME content on KOH catalyst with various reaction conditions: (a) FAME content with variation of reaction temperature. (b) FAME content with variation of catalyst loading amount of catalyst. (c) FAME content with different molar ratios of methanol to feedstock. (d) FAME content with reaction time. Other basic reaction conditions were fixed as a 65 °C reaction temperature, a 0.5 g catalyst loading, a 3 hr reaction time, and a 6:1 molar ratio of methanol to feedstock (From Chung, 2010).

only contain the hydroxide group, necessary for saponification, as a low proportion impurity. However, when sodium or potassium hydroxides were utilised as catalysts, biodiesel yields decreased to 86.71 and 91.67 wt.%, respectively. This is due to the presence of the hydroxide group that originated soaps by triglyceride saponification. Owing to their polarity, the soaps dissolved into the glycerol phase during the separation stage after the reaction. In addition, the dissolved soaps increased the methyl ester solubility in the glycerol, an additional cause of yield loss. Chung (2010) transesterified V. fordii and C. japonica seed oils with methanol using alkaline catalysts (KOH, NaOH, and CH3ONa) to produce biodiesel. The fatty acid methyl ester (FAME) contents in the biodiesel produced from the seed oils were above 96% on KOH catalyst in the reaction. The composition and physicochemical properties were investigated in the raw seed oils and the biodiesel products. It was acceptable for the limit of European biodiesel qualities for BD100. Other qualities such as cetane number, acid value, density, and kinematic viscosity, of the produced biodiesels also matched the biodiesel qualities. The optimum reaction conditions used were: 6:1 molar ratio of methanol to the seed oils, 1 wt% loading amount of catalyst, 65 °C reaction temperature, and reaction time of 3 hr. The biodiesel contents of the C. japonica and V. fordii seed oils under these reaction conditions were 97.7% and 96.1% on KOH catalyst. Figure 5.11 shows the FAME contents on KOH catalyst with various reaction conditions. The basic reaction conditions were fixed as a 65 C reaction temperature, 1 wt% loading amount of catalyst to the seed oils, a 3 hr reaction time, and a 6:1 molar ratio

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of methanol to feedstock. The FAME contents of the C. japonica and V. fordii seed oils to the reaction conditions were 97.7% and 96.1% on KOH catalyst, respectively. The high content of FAME was obtained at 65 °C as shown in Figure 5.11(a). The variation of the FAME contents with different loading amounts of KOH catalyst is shown in Figure 5.11(b). The high content of FAME exhibited at 1 wt% KOH catalyst loading to the feedstock. While the loading amount of catalyst exceeded more than 1 wt%, the FAME contents decreased reversely. The effect of methanol addition was evaluated with FAME contents on KOH catalyst (see Figure 5.11(c)). When methanol was added according to the stoichiometry of the reaction as 3:1 molar ratio of methanol to triglyceride, the FAME contents were below 75%. The FAME contents of the biodiesels increased significantly above 96% at 6:1 molar ratio of methanol to feedstock. The FAME contents with reaction time are represented in Figure 5.11(d). The FAME contents reached at equilibrium after 3 hr. The FAME contents exceeded 75% even for 1 hr reaction in the reaction of C. japonica seed oil. Refaat et al., (2008) reported the use of microwave irradiation in order to enhance the reaction rate. The optimum parametric conditions obtained from the conventional technique were applied using microwave irradiation in order to compare both systems. The results showed that application of radio frequency microwave energy offers a fast, easy route to this valuable biofuel with advantages of enhancing the reaction rate and improving the separation process. Using the microwave system, the vegetable oil was preheated to a desired temperature of 65 C. The mixture of alcohol and catalyst then charged into the flask through the condenser. The power output adjusted to 500 W and under reflux the mixture irradiated via different reaction times of 0.5, 1, 1.5, 2, 2.5, 3 and 6 min. Using the microwave irradiation technique, reaction time was reduced by 97% and the separation time reduced by 94%. The study also showed that there is an optimum reaction time for microwave-enhanced biodiesel production that should be respected. Exceeding the optimum reaction time will lead to deterioration of both biodiesel yield and purity. These results are depicted in Figure 5.12. At reaction times more than 2 min., drastic decreases in biodiesel yields were observed. The most accepted interpretation is that the exceeded time favors the equilibrium in the reverse direction. This is typical of catalytic reactions. In this particular application, attributing the decrease in yield after exceeding the optimum time to cracking followed by oxidizing of the formed fatty acid methyl esters to aldehydes, ketones and lower chained Yield (%) 100 80 60 40 20 0 0

50

100

150 Time (sec)

200

250

300

Figure 5.12 Effect of microwave irradiation exposure time on yield (Refaat et al., 2008).

Role of Biofuel Processing in Creating Global Warming

205

organic fractions could be excluded because the GC results do not show peaks of oxygenated compounds. Also, Saifuddin and Chua (2004) optimized transesterification of used frying oil to ethyl ester using microwave irradiation. They used a microwave oven equipped with non-contact infrared continuous feedback temperature system and magnetic stirrer to heat the oil and the alcohol at 60 C. Twenty five percent (25%) of an exit power of 750 W was used to irradiate the reaction mixture. Instead of studying the role of exposure to microwave, they studied the role of exit power and observed an optimum at 50% of exit power. They used different concentrations of sodium methoxide (0.3 wt% to 0.5 wt%) and achieved maximum conversion (87 wt%) at 0.5 wt%. During transesterification process, both sodium ethoxide and potassium hydroxide provided good conversions. However, due simplicity in products phase separation, sodium ethoxide was viewed as most promising catalyst for producing biodiesel. Besides, microwave-assisted transesterification process dramatically reduced the reaction time from 75 min to 4 min at 60 °C, thus saving great time. Additionally, during transesterification, irradiation times must be controlled and the levels of radiation power should not be too high, to avoid destruction of organic molecules. This particular combination of energy catalyst and mass catalyst has been in place without being recognized as such. For instance, the mechanism involved in pre-heating actually is akin to how microwave itself accelerates the reaction. These studies are interesting from a scientific perspective. In this case, an ‘energy’ catalyst is used in place of a ‘mass’ catalyst. The science of catalytic reactions is poorly handled due to the inability of New Science to include intangibles. The use of energy form as a catalyst adds to that difficulty. For instance, anytime the term ‘energy catalyst’ is used, the fact that energy cannot be isolated from mass (there is no energy without mass) is covered up. Along with it, disappears any possibility to connect the product from the source as if energy acted in isolation. Whenever an artificial energy source is used, this is a concern as eventually it leads to conflation of artificial (which is harmful) with natural (which is beneficial). New Science has no way of measuring the effect of such treatment on the pathway followed by the products and that’s why Khan and Islam (2012; 2016) mandated that ‘science of intangibles’ is the only way to determine sustainability of a process. Moreover, to determine optimum operating parameters, such as catalyst concentration, Ferella et al., (2010) studied transesterification reaction of rapeseed oil for biodiesel production using response surface methodology (RSM). They employed a 500 ml jacketed stirred (at 600 rpm) reactor tank. At optimum conditions of temperature of 50 °C, KOH concentration of 0.6% (w/w), reaction time of 90 min, and 60 methanol to KOH ratio by weight, large amount of triglycerides, diglycerides and monoglycerides were converted into biodiesel. Furthermore, the final concentrations were 0.05% triglycerides, 0.09% diglycerides and 0.36% monoglycerides and the triglyceride conversion was 98–99%. The most notable acids commonly employed in transesterification reaction include, among others; sulfuric acid, sulfonic acid, hydrochloric acid, organic sulfonic acid, ferric sulfate, etc. Among these acids, hydrochloric acid, sulfonic acid, and sulfuric acid are usually favored as catalysts for the production of biodiesel. Although the catalysts give high yield of biodiesel, the reaction rates are slow. The alcohol to oil molar ratio is the main factor influencing the reaction. Therefore, the addition of excess alcohol

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speeds up the reaction and favors the formation biodiesel products. The steps involve during acid-catalyzed transesterification are: 1. initial protonation of the acid to give an oxonium ion; 2. the oxonium ion and an alcohol undergo an exchange reaction to give the intermediate; 3. loosening of a proton to produce an ester. Reversibility of each of the above steps is possible but the equilibrium point of the reaction is displaced in the presence of excess large alcohol, by allowing esterification to advance to completion. Additionally, Soriano Jr. et al., (2009) studied transesterification of canola oil to produce biodiesel via homogeneous Lewis acid (AlCl3 and ZnCl2) as catalyst. The reaction occurred in a round bottom flask submerged in an oil bath equipped with a reflux condenser, temperature controller and a magnetic stirrer. The authors reported use of variable parameters such as: reaction time (6, 18, 24 hr), methanol to oil molar ratio (6, 12, 24, 42 and 60), reaction temperature (75, 110 C), with tetrahydrofuran (THF) as co-solvent (1:1 methanol to THF by weight in runs with THF), and a catalyst (AlCl3 or ZnCl2). In all the runs, the catalyst amount was kept at 5% based on the weight of oil. The best conditions with AlCl3 were reported to be 24:1 molar ratio at 110 C and 18 hr reaction time with THF as co-solvent provided a conversion of 98%. AlCl3 was far more active compared to ZnCl2 due to its higher acidity. Regardless of molar ratio and reaction time, conversions using AlCl3 had increased with increase in reaction temperature. It was also a function of molar ration. On the other hand, ZnCl2 was only a function of reaction time, independent of molar ratio. Cardoso et al., (2009) discussed the effects of Lewis acid on the transesterification process in producing biodiesel. The authors have introduced an inexpensive Lewis acid Tin (II) chloride dihydrate (SnCl2·2H2O), and evaluated its potential as catalyst on the ethanolysis of oleic acid of fats and vegetable oils. Tin chloride efficiently promoted the conversion of oleic acid into ethyl oleate in ethanol solution and in soybean oil samples, under mild reaction conditions. The SnCl2 catalyst was shown to be as active as the mineral acid H2SO4. Its use has relevant advantages in comparison to mineral acids catalysts, such as less corrosion of the reactors and as well as avoiding the unnecessary neutralization of products. The effect of the principal parameters of reaction on the yield and rate of ethyl oleate production has been investigated. Kinetic measurements revealed that the esterification of oleic acid catalyzed by SnCl2·2H2O is first-order in relation to both FFAs and catalyst concentration. Experimentally, it was verified that the energy of activation of the esterification reaction of oleic acid catalyzed by SnCl2 was very close those reported for H2SO4. The catalytic tests were carried out in triplicate with a molar ratio fatty acid: catalyst (100:1), reaction time of 2 hr. Using these conditions, the process provided more than 90% biodiesel yield with a high selectivity of more than 93%. The two acidic catalysts have different structures and acid character and certainly, different mechanisms of action. In spite of that, they displayed quite similar activities, as can be confirmed by the attainment of comparable ethyl oleate yields at a given reaction time, as shown in Figure 5.13. Note that reaction yields have increased steadily to a maximum value of 90 %, in approximately 120 min after setting

Role of Biofuel Processing in Creating Global Warming Conversion (%) 100

207

SnCl2

80 60

H2SO4

40 20 0 0

20

40

60 80 Time (min)

100

120

Figure 5.13 Ethanolysis of oleic catalyzed by Brønsted (H2SO4) and Lewis acids (SnCl2) (from Cardoso et al., 2009).

up the reaction. The monitoring of reaction for periods higher than 120 min reveals that the yields of both remained invariable after this time. Table 5.4 presents reaction yield as function of the homogeneous catalyst weight. The data obtained shows that production of biodiesel via homogeneous catalyst could yield more than 99%.

5.2.2.2

Effect of Heterogeneous Catalysts

Recent research on alcoholysis has focused on heterogeneous catalysts (Suppes et al., 2001; Ebiura et al., 2005; Corma et al., 1998; Xie et al., 2006; Suppes et al., 2004). The number of researches in the area of heterogeneous catalysts has increased recently. A great variety of catalysts in catalytic transesterification of vegetable oils have been used. These include zeolites, hydrotalcites, oxides, γ-alumina, etc. Recently, several researches were conducted on heterogeneous catalysts with the aim of finding solutions to problems caused by using homogeneous catalysts in producing biodiesel. As a result, a good number of heterogeneous catalysts were explored and many of the catalysts have displayed very good catalytic performances (Wang and Yang, 2007). Heterogeneous catalysts could improve the synthesis methods by eliminating the additional processing costs associated with homogeneous catalysts. However, heterogeneous catalysts have a different appeal: the fact that natural catalysts are the most heterogeneous ones. This aspect has not been considered in conventional analysis, although the key to developing sustainable technologies reside within the use of natural catalysts (Helwani et al., 2009). Helwani et al., (2009) reviewed biodiesel production by transesterification of triglycerides from a catalytic standpoint with the aim of using heterogeneous catalysts and to replace or complement the current homogeneous catalysts with the heterogeneous ones, to incorporate catalysts that are effective for a broader spectrum of reactants that can tolerate higher levels of impurities. Even though

1.25

H2SO4

H2SO4

KOH

Sodium methoxide

KOH

KOH

KOH

Sodium hydroxide

Potassium hydroxide

NaOH

NaOH

H2SO4/KOH

Waste tallow (chicken)

Palm fatty acid

Sunflower oil

Jojoba oil-wax

Brassica carinata

Canola oil

Jatropha curcas

Cottonseed oils

Roselle oil

Rubber seed oil (Hevea brasiliensis)

Mahua oil (Madhuca indica)

Mahua oil

1/0.7

1

1

1.5

0.5

0.5

–

1

0.55

–

Conc. (wt/v/v)

Catalyst

Feedstock

1

2

1

1

1

1

0.33

–

4

–

2

24

Reaction time (h)

60

60

60

60

55

30

25

–

60

70

70

50

Reaction temp (°C)

Table 5.4 Reaction yield as function of the homogeneous catalyst weight (from cardoso et al., 2009).

98

92

84.46

99.4

77

92

86.1

98.27

55

96

99.6

99.01 ± 0.71

Yield/conv. (w/w%)

(Continued)

6:1

6:1

6:1

8:1

–

–

6:1

–

7.5:1

–

7.2:1

1:30

Molar ratios

208 The Science of Climate Change

Sulfuric acid

KOH

KOH

H2SO4/KOH

KOH

Rice bran oil

Used frying oil

Waste cooking oils

Jatropha oil

Karanja oil

1

0.25–1.5/0.5

0.75

1

2

1.5

NaOH

Tobacco seed oil

Conc. (wt/v/v) 1

Catalyst

Sunflower frying oil KOH

Feedstock

Table 5.4 Cont.

3

2

0.33–2

2

8

1.5

0.5

Reaction time (h)

65

60

30–50

60

100

55

25

Reaction temp (°C)

97–98

90–95

88–90%

72.5

98

max

max

Yield/conv. (w/w%)

6:1

6:1/9:1

7:1–8:1

12:1

–

3:1

6:1

Molar ratios

Role of Biofuel Processing in Creating Global Warming 209

210

The Science of Climate Change Methyl ester yield (%) 100 90 80

5% 1% 2%

70 60 0.5% nano 50 MgO Non-catalyst 40 0 3 6 9 12 15 18 21 24 27 30 33 Reaction time, min

Figure 5.14 Effect of nano-MgO content on methyl ester yield of the transesterification of soybean oil. Reaction temperature 523 K; reaction pressure 24.0 MPa; soybean oil 100 ml; methanol 150 ml; molar ratio of methyl to soybean oil: 36:1; stirring 1000 rpm. (From Wang and Yang, 2007).

they are called impurities, if they are natural they in fact add synergy to the reaction, adding benefits that are not tractable with conventional analysis. They review biodiesel production using heterogeneous solid catalysts, such as metals, anchored metal complexes, solid bases and solid acids. Some of these catalysts include, among others; oxides, hydrotalcides, zeolites, etc. Currently, majority of heterogeneous catalysts used in producing biodiesel are either oxides of alkali or oxides of alkaline earth metals supported over large surface area (Helwani et al., 2009). Wang and Yang (2007) investigated the possibility of using nano-MgO to improve the transesterification reaction of soybean oil with supercritical/subcritical methanol. The variables affecting the yield of methyl ester during the transesterification reaction, such as the catalyst content, reaction temperature and the molar ratio of methanol to soybean oil were investigated and compared with those of non-catalyst. When nanoMgO was added from 0.5 wt% to 3 wt%, the transesterification rate increased evidently, while the catalyst content was further enhanced to 5 wt%, little increased in yield. It was observed that increasing the reaction temperature had a favorable influence on methyl ester yield. In addition, for molar ratios of methanol to soybean oil ranging from 6 to 36, the higher molar ratios of methanol to oil was charged, the faster transesterification rate was obtained. When the temperature was increased to 533 K, the transesterification reaction was essentially completed within 10 min with 3 wt% nanoMgO and the methanol/oil molar rate 36:1. Such high reaction rate with nano-MgO was mainly owing to the lower activation energy (75.94 kJ/mol) and the higher stirring. Figure 5.14 shows the relationship between the reaction time and the catalyst content. It can be affirmed that nano-MgO can evidently accelerate the methyl ester conversion from soybean oil in 523 K and 24.0 MPa even if a little catalyst (0.5 wt%) was added. The transesterification rate was improved obviously as the content of nanoMgO increased from 0.5 to 3 wt%. However, when the catalyst content was further enhanced to 5 wt%, methyl ester yield increased a little. Such phenomena can also be

Role of Biofuel Processing in Creating Global Warming

211

confirmed in their velocity coefficients. The coefficients are almost identical when the nano-MgO content increased from 3 to 5 wt%. Furthermore, the maximal yield fell down slightly if an excess of nano-MgO was put in, it may be because that nano-MgO not only exhibits the higher catalytic activity for the transesterification of triolein with methanol, but also is effective for the glycerolysis of triolein with glycerol. Therefore, 3% nano-MgO is more suitable. Table  5.5 lists different heterogenous catalysts for transesterification of vegetable oils reported in the literature. Most of these catalysts are alkali or alkaline oxides supported over large surface area supports. Similar to their homogeneous counterparts, solid basic catalysts are more active than solid acid catalysts. CaO, used as a solid basic catalyst, possesses many advantages such as long catalyst lifetimes, higher activity and requirement of only mild reaction conditions. The reaction rate, however, was slow in producing biodiesel. Lee and Saka (2010) reported simultaneous esterification and transesterification of waste cooking oil using solid catalyst ZnO–La2O3, which combines acid (ZnO) and base sites (La2O3). Although the process provided high conversion of 96% in 3 hr, but like zirconia, lanthanum is a rare and expensive metal, therefore cost of the catalyst would prohibit it high use in the production of biodiesel. More importantly, these metals are far more toxic to the environment than others in use. Solid alkaline catalysts such as CaO provide many advantages for instance higher activity, long catalyst life times, and could run under only moderate reaction conditions (Kouzu et al., 2008). Kouzu et al., (2008) carried out transesterification of edible soybean oil with refluxing methanol in the presence of calcium oxide (CaO) – hydroxide (Ca(OH)2), or – carbonate (CaCO3). At 1 hr of reaction time, yield of FAME was 93% for CaO, 12% for Ca(OH)2, and 0% for CaCO3. Under the same reacting condition, sodium hydroxide with the homogeneous catalysis brought about the complete conversion into FAME. Also, CaO was used for the further tests transesterifying waste cooking oil with acid value of 5.1 mg-KOH/g. The yield of FAME was above 99% at 2 hr of reaction time, but a portion of catalyst changed into calcium soap by reacting with free fatty acids included in the oil at initial stage of the transesterification. Owing to the neutralizing reaction of the catalyst, concentration of calcium in FAME increased from 187 ppm to 3065 ppm. By processing waste cooking oil at reflux of methanol in the presence of cation-exchange resin, only the free fatty acids could be converted into FAME. The transesterification of the processed waste cooking oil with acid value of 0.3 mg-KOH/g resulted in the production of FAME including calcium of 565 ppm. Also, Liu et al., (2008) have produced biodiesel fuel from soybean oil using CaO as a solid base catalyst. The authors reported that use of CaO as a catalyst could provide a numbers of advantages such as: high activity, lengthen catalyst life and moderate condition of reaction. In this study, transesterification of soybean oil to biodiesel using CaO as a solid base catalyst was studied. The reaction mechanism was proposed and the separate effects of the molar ratio of methanol to oil, reaction temperature, mass ratio of catalyst to oil and water content were investigated. The experimental results showed that a 12:1 molar ratio of methanol to oil, addition of 8% CaO catalyst, 65 C reaction temperature and 2.03% water content in methanol gave the best results, and the biodiesel yield exceeded 95% at 3 hr. The catalyst lifetime was longer than that of calcined K2CO3/γ-Al2O3 and KF/γ-Al2O3 catalysts. CaO maintained sustained activity

15 30

WO3/ZrO2, zirconia–alumina and sulfated tin oxide

Calcined LDH (Li–Al)

Mg–Al–CO3 (hydrotalcite)

La/zeolite beta

MgO MgAl2O4

NaOH/alumina

MgO, ZnO, Al2O3

Cu and Co

CaO/SBA-14

CaO

Cs-heteropoly acid, SO42−/ZrO2, SO42−/Al2O3, SO4 2−/SiO2, WO3/ZrO2

Mg–Al HT

CaO, SrO

Soybean oil

Soybean oil

Palm oil

Soybean oil

Soybean oil

Sunflower oil

Soybean oil

Soybean oil

Sunflower oil

Jathropa Curcas oil

VO

Rape oil

Soybean oil

12

6

19.4

9

12

5

55

6–48

3

14.5

40

8

Mesoporous silica loaded with MgO

Blended vegetable oil

Ratio MeOH/oil

Catalyst

Vegetable oil

Table 5.5 Different heterogeneous catalysts used for transesterification of vegetable oils.

0.5–3

4

1

2.5

5

3

7

1

10

4

6

1–6

20

5

Reaction time, h

65

65

75

70

160

70

70,100,130

50

65

160

100

65

200–300

220

Temperature, C

(Continued)

95

90.5

70

93

95

–

82

99

57

48.9

86.6

71.9

90

96

Conversion %

212 The Science of Climate Change

Catalyst

ETS-10

Mg–Al–CO3 HT

Soybean oil

Cotton seed oil

Cont.

Vegetable oil

Table 5.5

6

6

Ratio MeOH/oil

12

24

Reaction time, h

180–220

120

Temperature, C

87

94.6

Conversion %

Role of Biofuel Processing in Creating Global Warming 213

214

The Science of Climate Change Biodiesel yield, (%) 100 80

12% 8% 4% 2%

60

1% 40 20 0 0.0

0.5

1.0 1.5 2.0 Time, hour

2.5

3.0

Figure 5.15 Effect of mass ratio of CaO to oil on biodiesel yield. Methanol/oil molar ratio: 6:1; reaction temperature: 65 °C; water content: 2.03% (from Liu et al., 2008).

even after being repeatedly used for 20 cycles and the biodiesel yield at 1.5 hr was not affected much in the repeated experiments. Figure 5.15 shows the effects of the mass ratio of catalyst to oil. The results indicate that the biodiesel yield was significantly improved with the increase of CaO. The biodiesel yield reached 90% after 3 hr when the CaO/oil mass ratio was 8%. However, only 55% yield was obtained at a 2% CaO/oil mass ratio. It was also recognized that the catalytic activity was influenced by alkalinity, but the effect of CaO amount on biodiesel yield was slight when the mass ratio of CaO to oil was above 8%. In these conditions, the intensification of mass transfer becomes more important than increasing the amount of catalyst. Even though, this series of tests do not clearly show the existence of an optimum concentration, the function of yield vs time reaches saturation after 8% concentration. Lim et al., (2009) noted that transesterification reaction involving CaO needs longer reaction time. But the benefits gained from the process such as elimination of neutralization process, less waste generation and prospect of catalyst reusability compensates the delay. They conducted parametric study found the optimal conditions to be: methanol/oil mass ratio 0.5:1; catalyst amount 6 wt.%, and reaction temperature of 65 C. The highest purity of 98.6 ± 0.8% was achieved within 2.5 hr. Biodiesel yield under the solid catalyst was quantified as 90.4% as compared to 45.5% and 61.0%, respectively for classical NaOH, and KOH homogeneous catalysts. Zabeti et al., (2009) talked about environmental impacts due to its low solubility in methanol and can be synthesized from cheap sources like limestone and calcium hydroxide. They discussed one of the ways to minimize the mass transfer limitation for heterogeneous catalysts in liquid phase reactions by using catalyst supports. Supports can provide higher surface area through the existence of pores where metal particles can be anchored. Supports such as: alumina, silica, zinc oxide and zirconium oxide have been used in biodiesel production. They identified the following features of the naturally occurring chemicals. Alumina: Aluminum oxide exists in forms of porous γ-alumina and ή-alumina and nonporous crystalline α-alumina has been widely used as a support in catalysis processes, such as polymerization, reforming, steam reforming, dehydration and hydrogenation owing to its extremely thermal and mechanical stability, high specific surface

Role of Biofuel Processing in Creating Global Warming

215

area, large pore size and pore volume and. This also includes in the synthesis of biodiesel. Catalytic activity of titanium oxide–zinc oxide supported by alumina (ATZ) and titanium oxide–bismuth oxide supported by alumina (ATB) for transesterification of colza oil with methanol was studied (Belfort et al., 2006). Al2O3/ZrO2/WO3 solid acid catalyst was prepared by co-precipitating method and was investigated in the methanolysis of soybean oil (Furuta et al., 2006). The catalyst was compatible for both esterification and transesterification reaction and under reaction conditions of temperature of 250 C and alcohol/oil molar ratio of 40:1 methyl ester yields of 90% were obtained. This catalyst was also compared to Al2O3/ZrO2; however, the yields were 80%. Xie et al., (2006) evaluated the catalytic efficiency of potassium supported by alumina as a solid base catalyst in the transesterification of soybean oil to biodiesel. The catalyst was prepared by an impregnation method of aqueous solution of potassium nitrate alumina. The results demonstrated that the catalyst calcined at 500 C and loaded by 35 wt.% of KNO3 was the most active. From Hammett indicator method, the basicity was 6.75 mmol/g and a correlation between catalyst performance and basic sites on the surface of catalyst, probably K2O and Al–O–K, was detected. The highest conversion of oil reached 87%, after the reaction time of 8 hr with molar ratio of methanol to soybean oil of 15:1 and 6.5 wt.% of catalyst. Zinc oxide: Yang and Xie (2007) compared the catalyst performance of alkali earth metals loaded on different catalyst supports for soybean oil conversion to biodiesel and discovered a correlation between loading amount of catalyst precursor on support and the conversion of oil. They also found that the catalyst performance depends upon concentration of basic sites on the surface of the catalyst. Different catalysts were prepared by impregnation method of water solution of an alkali earth metal nitrate with specified concentration and calcined at 600 °C for 5 hr and among them ZnO/Sr (NO3)2 showed the best catalytic activity. In this case the most active catalyst was obtained by loading 2.5 mmol of strontium nitrate on zinc oxide which resulted in basicity of 10.8 mmol/g. After 5 hr of reaction time, at 65 °C, with 12:1 molar ratio of alcohol/oil and 5 wt.% of catalyst content, the maximum conversion achieved was 93.7%. Xie and Huang (2006) also applied potassium supported by zinc oxide as a solid base catalyst and the catalyst was prepared by an impregnation method of aqueous solution of potassium fluoride followed by calcination at 600 °C for 5 hr. Based on Hammett titration method the concentration of basic sites reached 1.47 mmol/g when 15 wt.% of KF was loaded on ZnO. The reaction was performed with alcohol/oil molar ratio of 10:1 and catalyst content of 3 wt.% and after 9 hr of the reaction time 87% of soybean oil was converted. The result is quite similar to that of Al2O3/KNO3 which was previously described (Xie et al., 2006). A mixture of Zn/I2 was used as a heterogeneous catalyst for transesterification of soybean oil with methanol. The metal was treated with distilled water and diluted HCL, and iodine was treated by sublimation. A mixture of 5 wt.% Zn and 2.5 wt.% I2 was applied in the reaction. After 26 hr, by using alcohol/oil molar ratio of 42:1, the conversion of oil reached 86%. The influence of co-solvent on the reaction rate was also investigated by introducing co-solvents such as THF and DMSO into the reaction and a 10% increase in conversion of soybean oil was observed after adding a certain amount of DMSO into the reaction mixture. A mixture of Zn/I2 was used as a heterogeneous catalyst for transesterification of soybean oil with methanol (Li and Xie, 2006). The metal was treated with distilled

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water and diluted HCL, and iodine was treated by sublimation. A mixture of 5 wt.% Zn and 2.5 wt.% I2 was applied in the reaction. After 26 hr, by using alcohol/oil molar ratio of 42:1, the conversion of oil reached 86%. The influence of co-solvent on the reaction rate was also investigated by introducing co-solvents such as THF and DMSO into the reaction and a 10% increase in conversion of soybean oil was observed after adding a certain amount of DMSO into the reaction mixture. Silicate: Catalyst properties of CaO supported on different types of mesoporous silica were studied and results from XRD characterization showed that after impregnation of CaO, the hexagonal structure of SBA-15 remained stable while this structure of MCM-41 and fumed silica was collapsed indicated that only SBA-15 can stabilize calcium oxide species on its surface (Albuquerque et al., 2008). The optimum catalyst was obtained by loading 15 wt.% of calcium oxide on SBA-15 followed by calcination at 900 °C and using this catalyst the maximum conversion of sunflower oil achieved 95% within 5 hr. Transesterification reaction was carried out at 60 C, with 1 wt.% catalyst and methanol to sunflower oil molar ratio of 12. Lin and Radu (2006) patented the application of sulfonic acid supported by mesoporous silica as a strong solid acid for transesterification reaction. The method of catalyst synthesis was relatively complicated, whereby Tetraethoxysilane (TEOS) was used as a precursor of silica. Mesoporous silica was synthesized by cetthyldimethylammonium bromide functionalized group denoted as CDAB, while those prepared by using tri-block Pluronic L64 and Pluronic P123 copolymers denoted as SBA-15. Zirconium oxide: Zirconia-supported heteropoly and isopoly tungsten acids were applied in biodiesel synthesis from sunflower oil and the result indicated that isopoly tungsten was more active than heteropoly tungsten since it possesses more Bronsted acid sites (Sunita et al., 2007). Oil conversion of 97% was reached after 5 hr of reaction time under reaction conditions of temperature of 200 C with catalyst content of 15 wt.% and alcohol/oil molar ratio 15:1. The catalyst activity of some metal oxides and catalyst supports for the biodiesel production is summarized in Table 5.6. From this table it can be concluded that, generally solid catalysts need a longer reaction time than homogeneous catalysts. Solid acid catalysts either supported or unsupported require higher temperature to give more methyl esters yields, even though solid acid catalysts are active for both transesterification and esterification reactions are able to convert oils with high amount of FFA. All alkali earth metal oxides except MgO produced high concentration of methyl esters at lower temperature of 65 C at a moderate reaction time. Furthermore, from the table it can be observed that alumina was more preferred as a support than other supports for transesterification reaction. Helwani et al., (2009) reviewed various technological methods to produce biodiesel being used in industries and academia. Their focus was catalytic transesterification, the most common method in the production of biofuel. They reviewed both homogeneous and heterogeneous types of catalysts used in batch and continuous processes. Although batch production of biodiesel is favored over continuous process in many laboratory and larger scale efforts, the latter is expected to gain wider acceptance in the near future, considering its added advantages associated with higher production capacity and lower operating costs to ensure long term supply of biodiesel. Table 5.7 lists different heterogenous catalysts for transesterification of vegetable oils reported in the literature, as collected by Helwani et al., (2009). Most of these catalysts are alkali

CaO powder was calcined at 1000 C.

Not reported.

SSAa =32 m2 /g, MPSb = 25–30 nm

SSA = 56 m2 /g

Nano MgO solid base

CaO solid base

CaO solid base

Calcium methoxide was Soybean oil synthesized by a direct reaction of calcium and methanol at 65 C for 4 hr.

Ca(OCH3)two solid base SSA = 19 m2 /g, pore size = 40 nm

Sunflower oil

The catalyst was prepared by an impregnation method of aqueous solution of calcium acetate on the support followed by calcination at 900 C for 4 hr.

Soybean oil

Sunflower oil

Soybean oil

Feedstock

Ca(C2H3O2)2/SBA-15 SSA = 7.4 m2 /g, pore volume = 0.019 solid base T = 60 °C, t cm3 /g = 5 hr,

Not reported.

Particle size = 60 nm

Catalyst

Catalyst preparation

Catalyst characterizations

(Continued)

T = 65 °C, t = 2 hr, 98% alcohol/oil = 1:1, catalyst content = 2%

methanol/oil = 12:1, 95% catalyst content = 1%

T = 65 °C, t = 3 hr, 95% alcohol/oil = 12:1, catalyst content = 8%

T = 60 °C, t = 100 min, 94% alcohol/oil = 13:1, catalyst content = 3%

P=24 MPa, T = 250 °C, 99% t = 10 min, alcohol/ oil = 36:1, catalyst content = 3%

Operation conditions

Result conversion or yield

Table 5.6 Summarization of the activity of metal oxides and supported catalysts as heterogeneous catalysts for biodiesel production (from sunita et al., 2007).

Role of Biofuel Processing in Creating Global Warming 217

Catalyst characterizations

SSA = 1.05 m2 /g

Basicity = 10.8 mmol/g

Basicity = 14.54 mmol/g.

Basicity = 1.62 mmol/g

Basicit y = 1.57 mmol/g

Catalyst

SrO solid base

ZnO/Sr(NO3)two solid base

ZnO/Ba solid base

ZnO/KF solid base

Al2O3/KI solid base

Table 5.6 Cont.

Feedstock

The catalyst was prepared by an impregnation method from aqueous solution of potassium iodide, dried at 120 °C and activated at 500 C for 3 hr.

The supported catalyst was prepared by impregnation method with an aqueous solution of KF. Afterward was dried at 393 K and calcined at 600 C in air for 5 hr.

The catalyst was prepared by an impregnation method using barium nitrate as precursor on ZnO. Dried overnight and calcined at 600 C in air for 5 hr.

The aqueous solution of Sr (NO3) two was loaded on ZnO by impregnation method and calcined at 600 C for 5 hr.

Soybean oil

Soybean oil

Soybean oil

Soybean oil

SrO was prepared from calcination Soybean oil of strontium carbonate in a muffle furnace at 1200 C for 5 hr.

Catalyst preparation

(Continued)

Methanol/oil = 15:1, yields = 96% catalyst content = 2.5%, t = 8 hr Methyl ester

T = 65 °C, t = 9 hr, 87% methanol/oil = 10:1, catalyst content = 3%

T = 65 °C, t = 1 hr, 95% methanol/oil = 12:1, catalyst content = 6%

T = 65 °C, t = 5 hr, 93% methanol/oil = 12:1, catalyst content = 5%

T = 65 °C, t = 30 min, 95% alcohol/oil = 12:1, catalyst content = 3%

Operation conditions

Result conversion or yield

218 The Science of Climate Change

Vanadyl phosphate was obtained from the suspension of V2O5 in diluted phosphoric acid. Then activated at 500 C.

SSA = 2–4 m2 /g

Not reported

Not reported

VOPO4·2H2O solid acid T

ZnO solid acid

ZnO/I2 solid acid

Soybean oil

Soybean oil

Soybean oil

Feedstock

The metal was prepared just by Soybean oil some treatment with distilled water and dilute HCl. Iodine was treated by sublimation.

Pure metal oxide was used. 1-palm coconut oil kernel oil 2-.

The catalyst was prepared by mixing of γAl2O3, NaOH and metal sodium in a stainless steel reactor at 320 C.

SSA = 83.2 m2 /g

Al2O3/Na/NaOH solid base

Catalyst preparation KNO3 was loaded on alumina by an impregnation method from aqueous solution, dried at 393 K for 16 hr and finally calcined at 500 C for 5 hr.

Catalyst characterizations

Basicity = 6.67 mmol/g

Cont.

Al2O3/KNO3 solid base

Catalyst

Table 5.6

(Continued)

T = 65 °C, t = 26 hr, 96% methanol/oil = 42:1, catalyst content = 5% Zn and 2.5% I2

T = 300 °C, t = 1 hr, 77.5% alcohol/oil = 6:1, catalyst content = 3% 1-methyl ester yields = 86.1% 2- methyl ester

=150 °C, t = 1 hr, 80% alcohol/oil = 1:1, catalyst content = 2% Methyl ester

T = 60 °C, t = 2 hr, 83% methanol/oil = 9:1, catalyst content = 1 g Methyl ester

Methanol/oil = 15:1, 87%. catalyst content = 6.5%, t = 7 hr Methyl ester

Operation conditions

Result conversion or yield

Role of Biofuel Processing in Creating Global Warming 219

(Continued)

Cottonseed oil T = 230 90%. °C, t = 8 hr, alcohol/ oil = 12:1, catalyst content = 2% Methyl ester

TiO2·nH2O was prepared from precipitation of TiCl4 using aqueous ammonia. Then immersed to sulfuric acid and finally calcined at 550 °C for 3 hr to give TiO2–SO4 2−.

SSA = 99.5 m2 /g

TiO2/SO4 2− solid acid

T = 200 °C, t = 1 hr, 1-methyl alcohol/oil = 6:1, ester yields catalyst content = 1% = 90.3% 1-methyl ester 2- methyl ester yields = 86.3%

97%

coconut oil Zirconia powder were immersed in sulfuric acid solution, filtered, dried and calcined at 500 °C for 2 hr. 1-palm kernel oil 2-.

Operation conditions

Not reported

ZrO2/SO4 2− solid acid

Feedstock T = 200 °C, t = 5 hr, alcohol/oil = 20:1, catalyst content = 15%

Catalyst preparation

Result conversion or yield

The isopoly tungstated zirconia Sunflower oil was prepared by suspending a known amount of zirconium oxyhydroxide powder in an aqueous solution of ammonium metatungstate, finally calcined at 750 C.

Catalyst characterizations

Not reported

Cont.

ZrO2/WO3 2− solid acid

Catalyst

Table 5.6

220 The Science of Climate Change

The catalyst was prepared from Soybean oil mixture of hydrated zirconia, hydrated alumina and ammonium metatungstate and deionized water. Calcined at 900 C for 1 hr.

The catalyst was prepared by coColza oil mixing of boehmite, titanium gel and zinc oxide in the presence of nitric acid and water. Calcined at 600 C for 3 hr.

SSA = 62 m2 /g

Al2O3/ZrO2/WO3 solid Not reported acid

Operation conditions

Methyl ester yields = 94%

Methyl ester yields = 69%.

Result conversion or yield

(Continued)

T = 250 °C, t = 20 hr, Methyl ester methanol/oil = 40:1, yields = 90% catalyst content = 4 g

T = 200 °C, t = 8 hr, alcohol/oil = 1:1, atalyst content = 6%

Palm kernel oil T = 200 °C, t = 5 hr, methanol/oil = 5:1, catalyst content = 10 g

Feedstock

Al2O3/TiO2/ZnO solid acid

Catalyst preparation Aluminum nitrate hydrated with nine moles of water dissolved in water and 85% orthophosphoric acid was added. The PH was controlled at seven by aqueous solution of ammonia. The final precipitation was filtered out, washed, and dried at 383 K for 12 hr. finally calcined at 400 °C for 3 hr.

Catalyst characterizations

Not reported

Cont.

Al2O3/PO4 3− solid acid.

Catalyst

Table 5.6

Role of Biofuel Processing in Creating Global Warming 221

Cont.

SBA-15-SO3H-P123 solphonic acid supported on mesoporous silica. Solid acid

Catalyst

Table 5.6

Catalyst preparation

SSA = 735 m2 /g, pore Tetraethoxysilane (TEOS) volume = 0.67 cm3 was used as silica source. /g 3-(mercaptopropyl)trimethoxysilane was used as mesoporous silica modifier. Pluronic P123 (tri-block copolymer) used as surfactant. A cocondensation method was applied.

Catalyst characterizations Soybean oil

Feedstock

T = 75 °C, t = 20 hr, methanol/oil = 20:1, catalyst content = 10%

Operation conditions

Methyl ester yields = 85%

Result conversion or yield

222 The Science of Climate Change

15 30

Mesoporous silica loaded with MgO

WO3/ZrO2, zirconia–alumina and sulfated tin oxide

Calcined LDH (Li–Al)

Mg–Al–CO3 (hydrotalcite)

La/zeolite beta

MgO MgAl2O4

NaOH/alumina

MgO, ZnO, Al2O3

Cu and Co

CaO/SBA-14

CaO

Cs-heteropoly acid, SO42−/ZrO2, SO42−/Al2O3, SO42−/SiO2, WO3/ ZrO2

Mg–Al HT

CaO, SrO

Blended vegetable oil

Soybean oil

Soybean oil

Palm oil

Soybean oil

Soybean oil

Sunflower oil

Soybean oil

Soybean oil

Sunflower oil

Jatropha Curcas oil

VO

Rape oil

Soybean oil

12

6

19.4

9

12

5

55

6–48

3

14.5

40

8

Catalysts

Vegetable oil

Ratio MeOH/ Oil

0.5–3

4

1

2.5

5

3

7

1

10

4

6

1–6

20

5

Reaction time, h

65

65

75

70

160

70

70, 100, 130

50

65

160

100

65

200–300

220

Temperature, °C

Table 5.7 Different heterogeneous catalysts used for transesterification of vegetable oils (from helwani et al., 2009).

(Continued)

95

90.5

70

93

95

82

99

57

48.9

86.6

71.9

90

96

Conversion, %

Role of Biofuel Processing in Creating Global Warming 223

Catalysts

ETS-10

Mg–Al–CO3 HT

Vegetable oil

Soybean oil

Cotton Seed oil

Table 5.7 Cont.

6

6

Ratio MeOH/ Oil

12

24

Reaction time, h

180–210

120

Temperature, °C

87

94.6

Conversion, %

224 The Science of Climate Change

Role of Biofuel Processing in Creating Global Warming

225

or alkaline oxides supported over large surface area supports. Similar to their homogeneous counterparts, solid basic catalysts are more active than solid acid catalysts. CaO, used as a solid basic catalyst, possesses many advantages such as long catalyst lifetimes, higher activity and requirement of only mild reaction conditions. The reaction rate, however, was slow in producing biodiesel (Liu et al., 2009).

5.2.2.3

Future Trends and the Impact on the Environment

Biodiesel has been popularized due to its reputation in emitting less carbon monoxide and other pollutants to the atmosphere. The main process of biodiesel manufacturing is transesterification in the presence of triglycerides and alcohol. If these chemicals are not produced with sustainable technologies, the product would not become sustainable. More importantly, it is the choice of catalyst that would dictate the fate of the product. Both catalyst and raw material selection play a significant role in the cost of biodiesel production. Because it is the economics that governs the selection, it is important to note the future developments in light of economic appeal. The heterogeneous catalyst offers a wide option for the catalytic selection because of its high selectivity and reusability characteristics. If they are selected from natural materials and used before value addition through refining is made, the price can come down significantly (Chhetri and Islam, 2009). In reducing costs, waste vegetable oil has become popular (Chhetri et al., 2008). Many studies have investigated for the use of waste cooking oil, greases, animal fats, tallow and spent bleaching for the biodiesel production. Next, The barrier in commercialization of biodiesel production is the cost of feedstock. The use non-edible oils has become popular due to several advantages such that, they are inexpensive and does not possess any threat to the environment, and most importantly do not compete with the food supply. Table  5.8 lists the major feedstocks for biodiesel. In this table, the sustainability requirements are pointed out, along with shortcomings. As can be seen from this table, very few sources are sustainable and inexpensive. The role of microwaves was also presented. Recently, ultrasonic treatment has been popularized as a concept. Ultrasound during transesterification creates cavitation between oil and alcohol phases and makes the mixing is efficient. This process uses less energy consumption when compared to other conventional mechanical stirring process. It is reported that the cavitation of bubbles due to ultrasonication enhances the mass transfer rates with the record of high yield (Fan et al., 2010). The ultrasonic wave provides high temperature and pressure such that it increases the catalytic surface area with low frequency modes (Yu et al., 2010). Solid catalyst was reported to be efficient for ultrasonic assisted transesterification, as the wave energy breaks the catalyst into fine small particles (Georgogianni et al., 2008). The literature supports the use of ultrasound assisted transesterification using sunflower as major feedstock. The 95% biodiesel yield was reported at 60 °C in 20 min. The frequency maintained throughout the process was 24 kHz with molar ratio of 7:1 (Georgogianni et al., 2008). The ultrasound assisted transesterification was reported to be highly suitable as stability of the catalyst were expected to have a longer lifetime.

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Table 5.8 Biodiesel feedstocks and economic feasibility. Oil content % Requirement for sustainability/ (w/w) shortcoming

Type of oil

Feedstock

Edible

Soybean

15–20

Orgnic source/expensive

Rapeseed

38–46

Organic source/ expensive

Sunflower

25–35

Organic source/ expensive

Peanut oil

45–55

Organic s source/ expensive

Coconut

63–65

Organic s source/ expensive

Palm

30–60

Organic s source/ expensive

Jatrropha seed

35–40

Naturally grown/not common

Pongamia pinnata

27–39

Naturally grown

Neem oil

20–30

Expensive

53

Expensive

Rubber seed

40–50

Expensive

Sea mango

54

Cotton seed

18–25

Organic source/Expensive,

Microalagae

30–70

Organic source

Non-Edible

Castor Other sources

inexpensive

Table 5.9 List of homogeneous catalyst used for transesterification reaction. Catalyst

Source

Yield % (wt/wt)

Comment

NaOH

Waste cooking oil

86

Unsustainable

CH3ONa

Soybean

94

Unsustainable

KOH

Pongamia pinnata

92

Likely sustainable

H2SO4

Jatropha

99

Likely sustainable

The presence of catalyst increases the rate of the reaction consequently yield of the product also increases. The catalysts used for the transesterification reaction are grouped into three categories as homogeneous, heterogeneous and enzymes as catalyst. Transesterification can also be carried by non-catalytic mechanism under super critical conditions. The overview of various catalysts for the production of biodiesel have been discussed the following chapters in detail and summarized their merits and demerits as listed in Table 5.9. In this table, the last columns refers to

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227

sustainability. The sustainability criterion of Khan and Islam (2007) was applied1. Only natural (but not cooking oil) sources are deemed potentially sustainable. It is assumed that these sources are organic and no chemical fertilizer or pesticide has been used. Also, the catalyst used must be organically produced. For the waste cooking oil, the only way it can be sustainable if it is organic – an unlikely occurrence. Soybean even if organic isn’t considered to be sustainable because it is a food and should not used as a fuel for energy production. Acid catalyzed transesterification reaction requires high of amounts of alcohol for high yield of esters. The advantage of acid catalyst is that they are performed at low temperature and pressure. Bronsted acids such sulfuric and sulfonic acids are used for transesterification reaction yielding high biodiesel. On protonation of ion the methyl/ ethyl ester are obtained with the displacement of alcohol. The use of sulfuric acid for the completion of a transesterification reaction was achieved in single step acid catalysis reaction with high FFA content (Palligarnai and Briggs, 2008). The effect of canola oil conversion to biodiesel under various operating conditions was studied. The AlCl3 and ZnCl2 were used as catalyst and compared. The catalytic activity of AlCl3 is higher than that of ZnCl2 (Soriano et al., 2009). Water content seems to great challenge for the acid catalyzed reaction as the presence of water content deactivates the catalyst. This issue arises due to polar carboxylic group present in the feedstock. The other noted disadvantage with acid catalysis is that they lead to corrosion and decreasing the yield of the product. Homogeneous catalysts frequently used for the production of biodiesel are NaOH, KOH, H2SO4 and CH3Na. Table 5.10 shows optimal conditions for operations of various catalysts. Note that Khan and Islam (2007) criterion is used to determine sustainability. Also, see the logic used in describing Table 5.9. The most notable progress in catalyst technology has been in using nanosized catalyst because of high stability over the repeated use. Nanocatalyst solves various bottleneck problems associated in the production of biodiesel (Baskar and Aiswarya, 2016). Nanocatalyst plays a crucial role in the field of energy and environment. Increased stability, activity and reusability are important characteristics of nanocatalyst. Nanocatalyst has high selectivity due to nano-dimensional pores on the surface (Baskar and Aiswarya, 2015). The nanoparticle tends to reduce the diffusion limitations and provides an efficient surface to volume ratio for enzyme loading. Nanocomposites has gained attention as they possess a large surface area with enhanced interaction between the reactant and catalyst. Sodium titanate nanotubes was used as catalyst for the production of biodiesel. The surface area of the catalyst was found to have 200 m2 /g with a pore volume of 0.61 cm3 /g. The yield was around 98% with 1% catalyst loading and 20:1 of methanol to oil ratio (Hernandez-Hipolito et al., 2014). Shahraki et al., (2015). Reported 95% yield when they used nono-solid based catalyst, KF/γAl2O3 for production of biodiesel. The reaction was performed in the sonication mode of 45 W. This is a significant improvement, which can be explained by the fact that

1

This criterion is described in a latter section of this chapter

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Table 5.10 List of heterogeneous catalyst commonly used for biodiesel production. Catalyst

Source

Yield % (wt/wt)

Comment

KI/Mg-Al-mixed metal oxides

Soybean

>90

Sustainable

CaO/Al2O3

Palm oil

98.6

Sustainable

CaO

Sunflower oil

Mg-Al hydrotalcite

80

Likely sustainable

Jatropha

95.2

Likely sustainable

K2CO3 supported MgO

Soybean

99.5

Likely sustainable

Mg/Zr

Sunflower

98

Fe-Zn Double metal cyanide (DMC) complex

Sunflower

98.3

Unsustainable

Na/BaO

Canola oil

97.5

Unsustainable

SO4 2-/TiO2

Jatropha

97

Unsustainable

WO3/ZrO2

Sunflower oil

97

Unsustainable

ZS/Si

Waste cooking oil

98

Unsustainable

Vanadium

Soybean

80

Unsustainable

Al2O3/ ZrO2/WO3

Soybean

90

Unsustainable

Sustainable

sonification increases the surface area of the reactants thus increasing the reaction rate. Besides, surface modification of the nanoparticles through immobilization provides bifunctional characteristics for the production of biodiesel. The reaction was found to be efficient because of the stability of the nanobiocatalyst (Macario et al., 2013). Lipasecoated magnetic nanoparticle was reported for the production of FAME from soybean and olive oil. The enzyme from species Candida rugosa on magnetic nanoparticle was reported with maximum yield of 94% (Xie et al., 2009). Immobilization of enzyme over the support is not sufficient for the high yield of methyl esters. Selection of a reactor is also important in applying to industrial level. Scale-up of the transesterification reaction was achieved by using the packed bed reactors for the efficient synthesis of biodiesel using nanobiocomposite (Wang et al., 2011). Magnetic nanocarriers were found to be efficient. But the availability of enzyme and binding capacity in terms of stabilization creates termination at industrial scale (Ngo et al., 2013). Supercritical technology/Non-catalytic transesterification reaction Supercritical processes do not require a catalyst for the reaction to initiate. Supercritical method has a greater advantage than transesterification reaction using the catalysts. The final purification of the product is not required because the supercritical process does not involve the use of catalyst. This method can be used for the feedstock which has high-water content, as the presence of water does not influence the reactions at supercritical condition. The reaction time for

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the supercritical process is 2–4 min (Saka and Kusdiana, 2001). Production of biodiesel from palm oil under supercritical method along with monitoring of different variables was reported. The major drawback in using supercritical process for commercial biodiesel production is the high operating temperature and pressure with a high ratio of oil to methanol (Tan et al., 2010). The most preferred technique for the quantification of the components in biodiesel is GC–MS due to its increased accuracy. HPLC has an advantage that it can be used for different feedstocks. Spectroscopic techniques used for characterization are NMR and IR. NMR is most commonly applied for the determination of blend level. Particularly 1 H-NMR was reported to monitor the yield of transesterification where the conversion is calculated from the peaks corresponding to the different ppm range. The other analytical method is IR spectroscopic techniques, which gives details about the estimation of both FAME and triglycerides simultaneously. The quality of the biodiesel is assessed from the physio-chemical data analysis, such as kinematic viscosity, density, cloud point and pour point in accordance with ASTM.

5.2.3

Greening of the Biodiesel Process

The connection between greening and climate change (or CO2 concentration in the atmosphere) is in the fact that a sustainable process produces CO2 that are readily absorbed by the environment. The difficulty arises from the lack of a comprehensive sustainability criterion that indeed can identify the process, which renders CO2 non-absorbable in the environment. Before true greening can be discussed, one should consider this scientific sustainability criterion. In this chapter, we gave reference to the sustainable criterion that characterizes most of the biofuel technologies as unsustainable. This criterion was developed by Khan and Islam (2007), which was used to test sustainability of the green biodiesel (Khan et al., 2007). According to this criterion, to consider any technology sustainable in the long term, it should be environmentally appealing, economically attractive, and socially responsible. The technology should continue for infinite time, maintaining that the indicators function for all time horizons. For a green bio-diesel, the total environmental benefits, social benefits, and economics benefits are higher than the input for all time horizons. For example, in the case of environmental benefits, burning green bio-diesel produces “natural” CO2 that can be readily synthesized by plants. The products generated during bio-diesel burning are also not harmful because there are no toxic additives involved in the bio-diesel production process. The plants and vegetables for bio-diesel feedstock production also have positive environmental impacts. Thus, switching from petrodiesel to bio-diesel fulfils the condition:

≥

(5.1)

where Cn is the total environmental capital of the life cycle process of bio-diesel production. Similarly, the total social benefit, where Cn is the total environmental capital of the life cycle process of bio-diesel production. Similarly, the total social benefit,

 

and economic benefit,

≥

(5.2)

230

The Science of Climate Change Agriculture, 13%

Transport, 2%

Crushing, 13%

Conversion, 7%

Use, 65%

Figure 5.16 Share of energy at different stages of biodiesel production (From Chhetri and Islam, 2008).





≥

(5.3)

become positive by switching from mineral diesel to bio-diesel. Bio-diesel can be used in practically all areas Chhetri and Islam (2006) presented the recipe for the truly green biodiesel model. They pointed out that existing bio-diesel production process is neither completely “green” nor renewable. In addition to using fossil fuel as a feedstock to producing methanol, it uses catalytic agents that taint the process. Each of the artificial chemicals used will lead to the emission of oxides and other products that will not be absorbed by the ecosystem. The current biodiesel production uses fossil fuel at various stages such as agriculture, crushing, transportation, and the process itself (Carraretto et al., 2004). Figure  5.16 shows the share of energy use at different stages from farming to biodiesel production. Approximately 35% of the primary energy is consumed during the life cycle from agriculture farming to biodiesel production. This energy basically comes from fossil fuels. To make the biodiesel completely green, this portion of energy also has to be derived from renewable sources. For energy conversion and crushing, direct solar energy can be effectively used while renewable biofuels can be used for transportation and agriculture. Table 5.11 shows that biodiesel has all kinds of emissions as does petrodiesel, but the emission level is significantly reduced when biodiesel is replaced by petrodiesel. Islam et al., (2010) reported that the CO2 produced from fossil fuel burning may be heavier than CO2 produced from fresh biological sources. Biological sources produce new CO2, which is easily taken up by plants. Plants discriminate heavier CO2 during photosynthesis (NOAA, 2005). The use of toxic chemicals and catalysts during the biodiesel production process increases the possibility of generating heavier CO2, which are less likely acceptable for plants (Islam et al., 2010). Similarly, methanol synthesized from natural gas is also different from methanol produced from starch or grains fermentation because of their isotopic difference. Fresh biomass-based renewable alcohol is less toxic and more easily degradable compared to petroleum-based methanol. The pathway for conventional bio-diesel production and petrodiesel production follows a similar path (Figure 5.1). Both fuels have similar pollutants in their emissions, such as benzene, acetaldehyde, toluene, formaldehyde, acrolein, PAHs, and xylene.

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Table 5.11 Difference in average toxic effects at two biodiesel blend levels (from chhetri and Islam, 2008). Average % change compared to base fuel Toxins

20% biodiesel

100% biodiesel

Acetaldehyde

−7.10

−14.40

Acrolein

−1.50

−8.50

Benzene

16.50

−0.80

1,3-Butadiene

39.00

−12.30

Ethylbenzene

−44.90

−61.00

Formaldehyde

−7.80

−15.10

n-Hexane

−48.70

−12.10

Naphthalene

−13.80

−26.70

Styrene

−3.70

39.30

Toluene

19..90

13.30

Xylene

−12.30

−39.50

MeOH NaOH Refined vegetable oil

Water washing or H3PO4

Catalyst preparation

Aqueous Phosphates phase

Catalyst neutralization

Transesterification at 60ºC 1.4-4.0 bar Glycerin/alcohol phase

Vacuum distillation 28ºC, 0.2 bar

H3PO4

Fatty phase Phosphates

Filtration and

Methanol recycle

Catalyst neutralization

Separator

Separator

Vacuum distillation Oil waste

Vacuum distillation Aqueous phase

MeOH and water Glycerin (92%) Biodiesel (99.6%)

Figure 5.17 A simplified block flow diagram for a typical base-catalyzed process for the production of biodiesel (from Helwani et al., 2009).

Figure 5.17 depicts a simplified block flow diagram for a typical biodiesel production process using base catalysis. A simplified block flow diagram of the acid process is shown in Figure 5.18.

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The Science of Climate Change H2SO4

Oil

MeOH Biodiesel (99.6%)

H2SO4/MeOH

Yellow grease

Methanol and water

Simultaneous esterification and transesterification reaction (main reactor)

Distillation

Vacuum distillation

Glycerin (92%) and water Vacuum distillation

Water washing

H2SO4+CaO Ca SO4+H2O

Gravity separation

CaO

CaSO4

Figure 5.18 A simplified block flow diagram of the acid-catalyzed process for the production of biodiesel (from Helwani et al., 2009). Organic waste/sludge

Anaerobic digestion

Methane

Slurry

Agri-use

Methanotroph Methanol bacteria

Figure 5.19 Production of methanol from methane by microbial conversion.

The key to greening is introducing all natural sources of mass as well as energy at each stage. 100% greening appears to be a remote goal because it would mean the use of organically grown vegetable oil (or fully free-range animal fat) along with heating with solar or wood burning in a clay stove with all containers made of natural products, such as naturally processed metals, clay, and ceramics. In the interim, Chhetri and Islam (2008) developed a process that renders the biodiesel production process truly “green,” using waste vegetable oil as bio-diesel feedstock. The catalysts and chemicals used in the were non-toxic, inexpensive, and natural. The catalysts used were sodium hydroxide, obtained from the electrolysis of natural sea salt, and potassium hydroxide, obtained from wood ash. The new process substituted the fossil fuel-based methanol with ethanol produced by grain-based, renewable products. The use of natural catalysts and non-toxic chemicals overcame the limitation of the existing process. Fossil fuels were replaced by direct solar energy for heating, making the bio-diesel production process independent of fossil fuel consumption. Chhetri and Islam (2008) proposed a new approach, based on the use of alcohol produced from renewable sources. Methanol is produced by utilizing microbes to convert methane to methanol (Figure 5.19). Methane produced from anaerobic digestion is acted upon by methanotrops that convert methane into methanol. Hanson and Hanson (1996) and Murrell (1994) reported that methanotrophs are aerobic bacteria which utilize methane as their sole carbon and energy source. Methanotrophs are physically versatile and can be effectively utilized to produce methanol from a wide variety of wastes. Use of

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233

ethyl alcohol fermented from grain-based biomass such as corn or sweet sorghum and molasses from sugar for alcoholysis of vegetable oils or fats is also a sustainable option (Figure 5.20). Both of these alternatives eliminate the consumption of huge amount of natural gas to make methanol. No expensive or toxic chemicals are involved in these processes. Figure 5.21 is the schematic diagram of proposed new concept of biodiesel production. In this process, potassium hydroxide derived from wood ash or sodium hydroxide derived from sea salt is used as the catalyst along with bio-based methanol or ethyl alcohol. Waste cooking oil is preheated up to 50 °C before mixing the methanol and potassium hydroxide mixture in it. After mixing, the mixture is heated to 60 °C at which the reaction takes place to form biodiesel and glycerin. The glycerin is separated by gravity separation. The crude biodiesel is heated to 65 °C to evaporate and recover methanol to reuse in the process. In case ethyl alcohol is used as medium for alcoholysis, it should be heated to 80 °C to evaporate the ethyl alcohol. The biodiesel is then washed with either mist or bubbles and then dried to evaporate all water vapor before sending to storage or usage. The biodiesel produced from this process is a nontoxic product because all the chemicals and catalysts are nontoxic. The CO2 produced is “new” CO2, with lighter isotopes, and it is not contaminated by any chemicals because the biological sources produce new CO2 (Islam, 2004). Plants will synthesize this “fresh” CO2 and complete the carbon cycle. Similarly, the NOx and CO produced during combustion of nontoxic biodiesel is not harmful compared to the petrodiesel and conventional biodiesel. Formaldehyde and other emissions from biodiesel combustion are different from those emitted from petrodiesel or conventional biodiesel.

Plants

Sugars from strach and grains

Fermentation

Ethyl alcohol

Carbon dioxide

Figure 5.20 Flow process for production of ethyl alcohol (from Helwani et al., 2009).

Condenser KOH from ash + bio-based methanool/ethyl alcohol (50 C) Waste cooking oil (60 C) Oil preheating 67 C

Methanol distillate (67 C)

Biodiesel (distillation)

Wash water

Biodiesel washing

Water vapour

Ester drying (Sunlight) Biodiesel

Glycerol

Distillation 67 C

Waste water (treatment)

Fresh CO2, NOX, CO no toxic emission

Figure 5.21 Schematic diagram of a green biodiesel production process (from Helwani et al., 2009).

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Conclusions

Conventionally, biofuels are considered to be renewable and hence inherently sustainable. This conclusion is reached only because New Science fails to include all salient features of biofuel production. This chapter uses biodiesel as an example and shows biofuels are not renewable. Such unsustainability comes from the source material of biofuels. Previous chapters have shown that the use of chemical fertilizers and pesticides causes organic materials to become inherently toxic to the environment. This chapter shows that further toxicity arises from the current methods of material processing, which is highly toxic. This toxicity comes from the highly toxic chemicals and catalysts used in the process. As new types of catalysts are introduced, the level of toxicity increases. This is because the focus has been economic benefit, while it is taken for granted that longterm sustainability is assured. Because New Science does not include the role of trace components, such as catalysts that are used in a small quantiity, conventional analyses fail to evaluate the role of these catalysts in altering long-term qualities of the products. In this chapter, a new process for biodiesel production is presented and its impact discussed. This process makes the biodiesel production independent of fossil fuels as well as toxic chemicals, relying instead on natural sources of both mass and energy. This new process proposes bio-based methanol/ethyl alcohol for alcoholysis of waste cooking oil/animal fat. The catalysts proposed in this process are completely natural. Potassium hydroxide derived from wood ash and sodium hydroxide derived from sea salt are proposed to replace the synthetic sodium or potassium hydroxide as catalysts. Ash is a very cheap source and a by-product of biomass burning. Naturally occurring potash, sodium carbonates, titanium oxide, and other heterogeneous catalysts are considered for the transesterification process. Since this process follows a completely natural path, the biodiesel is inherently nontoxic and environmentally friendly. The direct application of solar energy to convert vegetable oil into biodiesel is the cost effective and environmentally friendly option. This concept makes the biodiesel production truly green.

The Science of Climate Change. M. R. Islam, M. M. Khan. © 2019 Scrivener Publishing LLC. Published 2019 by John Wiley & Sons, Inc.

6 Role of Refining on Climate Change

6.1

Introduction

Refining is crude oil is synonymous with value addition, which itself is synonymous with the plastic era that marks the beginning of the golden petroleum era. Today’s main energy fuels are a derivative of the crude oil, which is the cheapest and arguably most abundant source of energy for today’s industrialized society. Plastics, which are finer derivative of the crude oil, are polymers, and we are known to be living in the polymer (or plastic) age. With just over 100 years of synthetic plastic production, plastic today is ubiquitous. Plastics, fibers, elastomers, adhesives, coating, rubber, and nylon are all polymers. They are common in our modern life and the world is unimaginable without them. Both crude oil and natural polymers have been used for thousands of years, and natural rubber, silk and other proteins, cellulose (found in wood and cotton), and starch are a few examples of the most useful natural materials. Yet, today the derivatives of the crude oil and plastics are considered to be the driver of global toxicity. As the New scientists focus on eliminating the entire crude oil and other fossil fuels, in this chapter we present the science behind refining and demonstrate the source of toxicity that rendered crude oil – the most abundant energy source on earth to the driver of global warming and climate change.

235

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The Science of Climate Change Refining process

Crude oil

Ethane Propane Butane

Naptha

Benzene Toluene Xylene

Butadiene

Propelene

Natural gas

Ethylene

Methanol

Figure 6.1 The pathway followed by the refining process.

6.2

The Refining Process

Crude oil is a mixture of hydrocarbons. These hydrocarbon mixtures are separated into commercial products by numerous refining processes. They have very similar compositions as vegetable oils. As a result, many properties of the two sets of fluids are similar, including biodegradability, flashpoint, dead oil viscosity, density, bactericidal properties, etc. However, petroleum fluids are almost never used in their original form, even though it is known that petroleum fluids have been used in various cultures from ancient times. One exception is the use of crude oil as mosquito repellant in the former Soviet Union. It was a logical option because it has been well known that the oil of organic origin is a natural mosquito repellant (Maia and Moore, 2011). Even though it eradicated malaria from much of the Soviet Union, they joined in the production of DDT after the Nobel-Prize winning synthesis of this toxic chemical, but most likely for commercial reasons. After DDT was banned in 1972, the use of crude oil as a pesticide did not return into practice. Today, petroleum fluids are transported to refineries prior to any usage. Oil refineries are enormous complex processes. Figure 6.1 shows major components involved in a refining process. The fundamental process of refining involves the breakdown of crude oil into its various components and the separation of them to sell as a value added product. Because each component loses its natural properties during the denaturing process, chemicals are added to restore original qualities. This is a typical chemical decomposition and re-synthesis process that has been in practice in practically all sectors of the modern age, ranging from the plastic industry to pharmaceutical industries. Figure 6.2 shows the major steps of a conventional refining process. The first step is transportation and storage. In the crude oil refining process, fractional distillation is the main process that separates oil and gas. For this process, the distillation tower is used, which operates at atmospheric pressure and leaves a residue of hydrocarbons with boiling points above 400C and more than 70 carbon atoms in their chains. Small molecules of hydrocarbons have low boiling points, while larger molecules have higher boiling points. The fractionating column is cooler at the top than at the bottom, so the vapors cool as they rise. Figure 6.3 shows the pictorial view of a fractional column. It also shows the ranges of hydrocarbons in each fraction. Each fraction is a mix of hydrocarbons and each fraction has its own range of boiling points and comes off at a different level in the tower. Petroleum refining has evolved

Role of Refining on Climate Change

237

Transportation and storage of crude oil Vacuum distillation Hydrocarbon separation Atmospheric distillation Cracking, Coking etc. Hydrocarbon creation Alkylation, reforming etc. Hydrocarbon blending Removal of sulfur other chemicals Cleaning impurities Solvent dewaxing, caustic washing Figure 6.2 Major steps involved in a refining process.

Gases 490ºC

Fuel oil

>580ºC Bitumen

Figure 6.3 Pictorial view of fractional column.

continuously in response to changing consumer demands for better and different products, such as from aviation gasoline to jet fuel. Each requires various degrees of “refinement” to conform to specific needs of machineries that are designed according to certain “ideal” fluid behavior.

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Petroleum refining has evolved continuously in response to changing consumer demands for better and different products, such as from aviation gasoline to jet fuel. Each requires various degrees of “refinement” to conform to specific needs of machineries that are designed according to certain “ideal” fluid behavior. A summary of a detailed process flow chart for oil refining steps is presented in Table 6.1. The table also describes the different treatment methods for each of the refining phases. The third column in the above table shows how the refining process can render natural petroleum fluids into toxic chemicals. If the heat source and catalysts used are products of unsustainable practices, their contact with petroleum fluids will result in unsustainable products. Unless this is recognized, further refinement of the process, e.g., optimization of catalysts, automation of heating elements, blending of various additives, and corrosion protection, will not solve the sustainability problem. Catalysts used in processes that remove sulfur are impregnated with cobalt, nickel, or molybdenum, each of which is a toxic element, with far more impact on the environment than the sulfur in crude oil. During the separation process, sulfur from crude oil is removed only in exchange for traces of these catalysts. As discussed by Khan and Islam (2016), trace elements are not negligible and must be accounted for in determining long-term impacts. These trace elements will accompany the refined oil and will end up in combustion chambers, eventually polluting the CO2 emitted from a combustion engine. The inability of current detection techniques to identify these trace elements will not ensure that the pollution of CO2 does not take place. We will see in follow up chapters that contaminated CO2 is not acceptable by plants or trees, which reject this strand of CO2. This process ends up contributing to the overall concentration of CO2 in the atmosphere, delaying natural consumption and utilization of CO2 in the ecosystem. If the removal of sulfur is the objective, the use of zeolite can solve this problem. It is well known that naturally occurring zeolite has the composition to act as a powerful agent that would adsorb unwanted matters with high levels of adsorption, ion exchange, and catalytic actions (Primo and Garcia, 2014). However, numerous forms of synthetic catalysts have been developed each claiming to be optimized for a specific application. Conventionally, synthetic catalysts are used for enhancing the petroleum cracking process. Even when naturally occurring chemicals are used, they are acid-treated. With the acid being synthetically produced, the process becomes irreversibly contaminated. More recently, microwave treatment of natural materials is being proposed in order to enhance the reactivity of natural materials (Henda et al. 2006). With microwave heating not being a natural process, this treatment will also render the process unsustainable. However, such treatment is not necessary because natural materials, such as zeolite, clay, and others, do contain properties that would help the cracking process (Lupina and Aliev 1991). Acid enhancing, if at all needed, can be performed with organic acid or acid derived from natural sources. Acid-function catalysts impregnated with platinum or other noble metals are used in isomerization and reforming. Research on this topic has focused on the use of refined heavy metal elements and synthetic materials (Baird, Jr. 1990). These materials are known carcinogens and have numerous long-term negative effects on the environment. In addition, the resulting products are aromatic oils, carcinogenic polycyclic aromatic compounds, or other hazardous materials, and they may also be pyrophoric. This becomes a difficult short-term problem. When such a problem is addressed, solutions that are

Role of Refining on Climate Change

239

Table 6.1 Details of oil refining process and various types of catalyst used.

Catalyst/Heat/ pressure used

Process

Description

Distillation Processes

It basically relies on the difference of the Heat boiling point of various fluids. Density also has an important role to play in distillation. The lightest hydrocarbon at the top and the heaviest residue at the bottom are separated.

Coking and Thermal process

Coking unit converts heavy feedstocks into solid coke and lower boiling hydrocarbon products that are suitable to offer refinery units to convert to higher value transportation fuel. This is a severe thermal cracking process to form coke. Coke contains high boiling point hydrocarbons and some volatiles that are removed by calcining at a temperature of 1095–1260°C. Coke is allowed sufficient time to remain in high temperature heaters in insulated singe drums, hence, it is called delayed coking.

Heat

Thermal Cracking

The crude oil is subjected to Excessive heat pressure, and large molecules and pressure are broken into small ones to produce additional gasoline. The naphtha fraction is useful for making many petrochemicals. Heating naphtha in the absence of air makes the molecules split into shorter ones.

Excessive heat and pressure

Catalytic Cracking

Catalytic cracking converts heavy oils into Nickels, zeolites, high gasoline, less heavy oils, and lighter acid treated gases. Paraffins are converted into C3 and natural C4 hydrocarbons. The benzene rings of alumina aromatic hydrocarbons are broken. Rather silicates, than distilling more crude oil, an alternative amorphous is to crack crude oil fractions with longer and crystalline hydrocarbons. Larger hydrocarbons split synthetic into shorter ones at low temperatures if silica alumina a catalyst is used. This process is called catalyst. catalytic cracking. The products include useful short chain hydrocarbons. (Continued)

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Table 6.1 Cont.

Catalyst/Heat/ pressure used

Process

Description

Hydroprocessing

Hydroprocessing (325 °C and 50 atm) includes Platinum, both hydrocracking (350 °C and 200 atm) tungsten, palladium, and hydrotreating. Hydrotreating involves the addition of hydrogen atoms to molecules nickel, and without actually breaking the molecule into crystalline mixture of smaller pieces and improves the quality of various products (e.g., by removing sulfur, silica alumina; cobalt and nitrogen, oxygen, metals, and waxes and by converting olefins to saturated compounds). molybdenum oxide on Hydrocracking breaks longer molecules into alumina nickel smaller ones. This is a more severe operation oxide, nickel using higher heat and longer contact time. thiomolybdate Hydrocracking reactors contain fixed, tungsten, multiple catalyst beds. nickel sulfide, vanadium oxides, and nickel thiomolybdate are used for sulfur removal, and nickel molybdenum catalyst is used for nitrogen removal.

Alkylation

Alkylation or "polymerization" is the process of forming longer molecules from smaller ones. Another process is isomerization, in which straight chain molecules are made into higher octane branched molecules. The reaction requires an acid catalyst at low temperatures and low pressures. The acid composition is usually kept at about 50%, making the mixture very corrosive.

Sulfuric acid, or hydrofluoric acid, HF (1–40 °C, 1–10 atm). Platinum onAlCl3/ Al203 catalyst is used as a new alkylation catalyst. (Continued)

Role of Refining on Climate Change

241

Table 6.1 Cont.

Process

Description

Catalytic Reforming

This uses heat, moderate pressure, and fixed bed catalysts to turn naphtha, short carbon chain molecule fraction, into high-octane gasoline components — mainly aromatics.

Catalyst/Heat/ pressure used Catalyst used is a platinum (Pt) metal on an alumina (AL03) base.

Treating NonTreating can involve chemical reactions and/ hydrocarbons or physical separation. Typical examples of treating are chemical sweetening, acid treating, clay contacting, caustic washing, hydrotreating, drying, solvent extraction, and solvent dewaxing. Sweetening compounds and acids desulfurizes crude oil before processing and treats products during and after processing. no more sustainable are usually offered. For instance, in order to combat pyrophoricy, a patented technology uses aromatic hydrocarbons such as alkyl-substituted benzenes including toluene, xylene, and heavy aromatic naphtha. Heavy aromatic naphtha comprises xylene and higher aromatic homologs (Roling and Sintim 2000). The entire process spirals further down the path of unsustainability. Table 6.2 shows the various processes and products used during the refining process. Each of the above functions can also be performed with natural substitutes that are cheaper and benign to the environment. This list includes the following: zeolites, alumina, silica, various biocatalysts, and enzymes in their natural state. The use of bacteria to decompose large hydrocarbon molecules offers an attractive alternative because the process is entirely sustainable (as per the Khan and Islam (2007) criterion. Khan and Islam (2007a) also suggest the use of gravity segregation from distillate lighter components to heavier ones. The use of solar heating, in conjunction with heating from flares that are available in the oil field, will bring down the heating cost and make the process sustainable. Table 6.3 (compiled from the Environmental Defense 2005) enumerate the primary emissions at each activity level. There are seven primary air release emissions and 23 primary hazardous/solid wastes. The primary hazardous/solid wastes include the following: 1,2,4-trimethylbenzene, 1,3-butadiene, ammonia, anthracene, benzene, copper, cumene, cyclohexane, diethanolamine, ethylbenzene, ethylene, hydrofluoric acid, mercury, metals, methanol, naphthalene, nickel, PAHs, phenol, propylene, sulfuric acid aerosols or toluene, vanadium (fumes and dust), and xylene. The most important resource in the refinery process is energy. The refining process uses a lot of energy. Typically, approximately 2% of the energy contained in crude oil is used for distillation. The efficiency of the heating process can be increased drastically by combining

Combining

Polymerize

Grease compounding

Polymerizing

Catalytic

Thermal

Catalytic

Unite 2 or more olefins

Combine soap and oils

Unit olefins and isoparaffins

Cracker olefins

Lube oil, fatty acid, alky metal

Rearrange

Treatment

I > ol-,,drat on

Solvent

Isomerization

Amine treating

Desalting

Furfural extraction

extraction

Alteration/ dehydration

Catalytic reforming Straight chain to branch

Upgrade low octane naphtha

Absorption

Absorption

Upgrade mid distillate & lubes

Remove contaminants

Remove acidic contaminants

TREATMENT PROCESSES Absorption

Catalytic

Catalytic

Cycle oils & lube feedstocks

Crude oil

w/CO, & H„.5

Sour gas, HCs

pentane, hexane

Butane,

Coker/ hydro-cracker naphtha

(Continued)

High quality diesel & lube oil

Desalted crude oil

Acid free gases & liquid HCs

Isobutane/ pentane/ hexane

High oct. Reformate/ aromatic

High-octane naphtha, petrochemical stocks

Lubricating grease

Tower isobutane/ cracker Iso-octane (alkylate) olefin

CONVERSION PROCESSES—ALTERATION OR REARRANGEMENT

Combining

Alkylation

Conversion processes — UNIFICATION

Table 6.2 Various processes and products in oil refining process.

242 The Science of Climate Change

Hydrogenation

Solvent

Hydrotreating

Phenol extraction

Treatment

Solvent extr.

Treatment

Action

Separation

Solvent dewaxing

Solvent extraction

Sweetening

Process name

Atmospheric

distillation

Treatment

Solvent deasphalting

extraction

Treatment

Hyfrodesulfarization

Table 6.2 Cont.

Thermal

Residuals, cracked HC's

High-sulfur residual/ gas oil

Separate fractions

oil

Desalted crude

Feeds tock(s)

Untreated distilate/ gasoline

Remove H2S, convert mercaptan Purpose

Gas oil, reformate, distillate

Vac. tower lube oils

Vac. tower residual, propane

Separate unsat. oils

Remove wax from lube stocks

Remove asphalt

Improve vise, index, color Lube oil base stocks

Remove impurities, saturate HC's

Remove sulfur, contaminants

FRACTIONATION PROCESSES

Method

Catalytic

Abspt/precip.

Cool/filter

Absorption

Abspt/therm

Catalytic

Catalytic

Conversion processes — UNIFICATION

residual

distillate,

(Continued)

Gas, gas oil,

Product(s)

High-quality distilate/ gasoline

gasoline

High-octane

Dewaxed lube basestock

Heavy lube oil, asphalt

High quality lube oils

Cracker feed, distillate, lube

olefins

Desulfurized

Role of Refining on Climate Change 243

Separation

Alteration

Polymerize

Hydrogenate

Decompose

Decompose

Decompose

Catalytic cracking

Coking

Hydrocracking

Hydrogen steam reforming

Steam cracking

Visbreaking

Cont.

Vacuum distillation

Table 6.2

Separate w/o cracking

Atmospheric tower residual

Thermal

Thermal

Gas oil coke, distillate

HCs

Convert to lighter

Reduce viscosity

Crack large molecules

hydrogen

Atm tower residual

Atm tower, heavy fuel/ distillate

Desulfurized gas, O,, steam

Gas oil, cracked oil residual

Convert vacuum residuals Gas oil coke, distillate

Upgrade gasoline

Catalytic/ thermal Produce

Catalytic

Thermal

Catalytic

CONVERSION PROCESSES - DECOMPOSITION

Thermal

Conversion processes — UNIFICATION

Distillate tar

Cracked naphtha, coke, residual

co2

Hydrogen, CO,

Lighter higher quality products

feedstock

petrochemical

Gasoline,

feedstock

petrochemical

Gasoline,

Gas, gas oil, lube, residual

244 The Science of Climate Change

Role of Refining on Climate Change

245

Table 6.3 Emissions from refinery. Materials transfer and storage Source

Emissions

Air releases

Carbon monoxide, nitrogen oxides, particulate matter, sulfur dioxide, VOCs (polluted with catalysts and other toxic additives)

Hazardous/solid waste

Ammonia, anthracene, benzene, 1–3-butadiene, cumene, cychlohexane, ethylbenzene, ethylene, methanol, naphthalene, phenol, PAHs, propylene, toluene, 1,2,4-trimethylbenzene, xylene (polluted with catalysts and other toxic additives) Separating hydrocarbons

Source

Emissions

Air releases

Carbon monoxide, nitrogen oxides, particulate matter, sulfur dioxide

Hazardous/solid waste

Ammonia, anthracene, benzene, 1–3-butadiene, cumene, cychlohexane, ethylbenzene, ethylene, methanol, naphthalene, phenol, PAHs, propylene, toluene, 1,2,4-trimethylbenzene, xylene (polluted with catalysts and other toxic additives)

direct solar heating (with non-engineered thermal fluid) with direct fossil fuel burning. The advantage of this process is a gain in global efficiency as well as environmental benefit. It is estimated that the total energy requirement for petroleum refining can be reduced to less than 0.5% of the energy contained in crude oil by designing the heating systems with a zero-waste scheme, as outlined by Khan and Islam (2016). A number of procedures are used to turn heavier components of crude oil into lighter and more useful hydrocarbons. These processes use catalysts or materials that help chemical reactions without being used up themselves. Table 6.4 shows different toxic catalysts and base metals. Refinery catalysts are generally toxic and must be replaced or regenerated after repeated use, turning used catalysts into a waste source. The refining process uses either sulfuric acid or hydrofluoric acid as catalysts to transform propylene, butylene, and/or isobutane into alkylation products, or alkylate. Vast quantities of sulfuric acid are required for the process. Hydrofluoric acid (HF), also known as hydrogen fluoride, is extremely toxic and can be lethal. Using catalysts with fewer toxic materials significantly reduces pollution. Eventually, organic acids and enzymes, instead of catalysts, must be considered. Thermal degradation and slow reaction rates are often considered to be biggest problems of using organic acid and catalysts. However, recent discoveries have shown that this perception is not justified. There are numerous organic products and enzymes that can withstand high temperatures, and many of them induce fast reactions. More importantly, as discussed in Chapter 5 in the

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Table 6.4 Primary wasters from oil refinery. Alkylation and reforming

Sulfur removal

Air releases: carbon monoxide, nitrogen oxides, particulate matter, sulfur dioxide, VOCs

Air releases: carbon monoxide, nitrogen oxides, particulate matter, sulfur dioxide, VOCs

Air releases: carbon monoxide, nitrogen oxides, particulate matter, sulfur dioxide, VOCs

Hazardous/solid wastes, wastewater: ammonia, anthracene, benzene, 1, 3-butadiene, copper, cumene, cyclohexane, ethylbenzene, ethylene, methanol, naphthalene, nickel, phenol, PAHs, propylene, toluene, 1, 2, 4-trimethylbenzene, vanadium (fumes and dust), xylene

Hazardous/solid wastes: ammonia, benzene, phenol, propylene, sulfuric acid aerosols or hydrofluoric acid, toluene, xylene Wastewater

Hazardous/solid wastes: ammonia, diethanolamine, phenol, metals Wastewater

Cracking/coking

context of biodiesel, the process can be modified in order to eliminate the use of toxic substances (see Table 6.5). The same principle applies to other materials, e.g., corrosion inhibitors, bactericides, etc. Often, toxic chemicals lead to very high corrosion vulnerability, and even more toxic corrosion inhibitors are required. The whole process spirals down to a very unstable process, which can be eliminated with the new approach (Al-Darbi et al. 2002).

6.3

Additives and Their Functions

Oil refining and natural gas processing are very expensive processes in terms of operation and management. These operations involve the use of several chemicals and catalysts that are very expensive. Moreover, these catalysts and chemicals pose a great threat to the natural environment including air and water quality. Air and water pollution ultimately have impacts on the health of humans, animals and plants. For instance, the use of catalysts, such as lead, during crude oil refining to produce gasoline has been a serious environmental problem. Burning gasoline emits toxic gases containing lead particles, and the oxidation of lead in the air forms lead oxide, which is a poisonous compound affecting the lives of every living thing. Heavy metals such as mercury and chromium and the use of these metals in oil refining are major causes of water pollution that eventually permeates to the entire ecosystem. Consider the consequences of some of these chemicals.

6.3.1 Platinum It is well known that platinum salts can induce numerous irreversible changes in human bodies, such as DNA alterations (Jung and Lippard 2007). In fact, an entire branch of

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Table 6.5 Chemicals used in refining. Chemicals used in refining

Purpose

Ammonia

Control corrosion by HCL

Tetraethyl lead (TEL) and tetramethyl lead (TML)

Additives to increase the octane rating

Ethyl tertiary butyl ether (ETBE), methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME)

To increase gasoline octane rating and reduce carbon monoxide

Sulfuric Acid and Hydrofluoric Acid

Alkylation processes, some treatment processes.

Ethylene glycol

Dewatering

Toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone, methylene chloride, ethylene dichloride, sulfur dioxide

Dewaxing

Zeolite, aluminum hydrosilicate, treated bentonite clay, fuller's earth, bauxite, and silica-alumina

Catalytic cracking

Nickel

Catalytic cracking

Granular phosphoric acid

Polymerization

Aluminum chloride, hydrogen chloride

Isomerization

Imidazolines and Surfactants Amino Ethyl Imidazoline Hydroxy-Ethyl Imidazoline Imidazoline/ Amides Amine/Amide/DTA

Oil soluble corrosion inhibitors

Complex Amines Benzyl Pyridine

Water soluble corrosion inhibitors

Diamine Amine Morpholine

Neutralizers

Imidazolines

Emulsifiers

Sulfonates Alkylphenolformaldehyde, polypropeline glycol

Desalting and emulsifier

Cobalt Molybdate, platinum, chromium alumina AlClj-HCl, Copper pyrophosphate

medical science evolves around exploiting this deadly property of platinum compounds in order to manufacture pharmaceutical drugs that are used to attack the DNA of cancer cells (Farrell 2004a, 2004b, 2004 c, 2005). It is also known that platinum compounds cause many forms of cancer. Once again, this property of platinum is used to develop pharmaceutical drugs that could possibly destroy cancer cells (Volckova et al. 2003). Also, it is well known that platinum compounds can cause liver damage (Stewart et al.

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Table 6.6 Pollution prevention options for different activities in material transfer and storages.

Cracking/coking

Alkylation and reforming

Using catalysts Using catalysts with fewer toxic with fewer toxic materials reduces materials reduces the pollution from the pollution from "spent" catalysts "spent" catalysts and catalyst and catalyst manufacturing.

Sulfur removal

Cooling

Use "cleaner" crude oil," containing less sulfur and fewer metals. Using oxygen rather than air in the Claus plant reduces the amount of hydrogen sulfide and nitrogen compounds produced.

Ozone or bleach should replace chlorine to control biological growth in cooling systems Switching from water cooling to air cooling could reduce the use of cooling water by 85%.

1985). Similar damage to bone marrow is also observed (Evans et al. 1984). Platinum is also related to hearing loss (Rybak 1981). Finally, potentiation of the toxicity of other dangerous chemicals in the human body, such as selenium, can lead to many other problems. The above are immediate concerns to human health and safety. Consider the damage to the environment that might be incurred through vegetation and animals (Kalbitz et al. 2008). It is already known that platinum salts accumulate at the root of plants, from which it can easily enter the food chain, perpetually insulting the environment. In addition, microorganisms can play a role to broaden the impact of platinum. This aspect of ecological study has not been performed as of now. In the mean time, platinum is touted as a tool for remedying air pollution. Since 1976 in the United States, Canada, and Japan, and later in other countries, the exhaust system of gasoline powered cars has been equipped with catalytic converters containing Pt and/or Pd and/or Rh. This has resulted in a very significant decrease in urban air pollution for various chemical species such as NOx, CO, and hydrocarbons. While this ‘success’ is celebrated, New Science cannot fathom what toll this ‘success’. There has, however, been concern that their ever-increasing use might lead to Platinum Group Metals (PGMs) becoming widely dispersed in the environment. From the analysis of Pt, Pd, and Rh in central Greenland recent snow and ancient ice using the ultrasensitive inductively coupled plasma sector field mass spectrometry technique, Barbante et al. (2001) showed that the concentrations of these metals in snow dated from the mid 1990 s are indeed 40–120 times higher than in ice dated from 7000 years ago. The fact that such an increase is observed far away from populated areas at a high-altitude location indicates there is now a large-scale contamination of the troposphere of the Northern Hemisphere for PGMs. Pt/Rh mass ratio in the most recent snow samples is close to the same ratio documented for catalytic converter exhausts in a recent study,

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Table 6.7 Catalysts and materials used to produce catalysts base metals and compounds. Names of catalysts

Name of metals base

Activated alumina, Amine, Ammonia, Anhydrous hydrofl uoric acid Anti-foam agents – for example, oleyl alcohol or Vanol, Bauxite, Calcium chloride, Catalytic cracking catalyst, Catalytic reforming catalyst, Caustic soda, Cobalt molybdenum, Concentrated sulphuric acid, Demulsifi ers – for example, Vishem 1688, Dewaxing compounds (catalytic) – for example, P4 Red, wax solvents Diethylene glycol, Glycol –Corrosion inhibitors), Hydrogen gas, Litharge, Na MBT (sodium 2-mercaptobenzothiazole) – glycol corrosion inhibitor (also see the taxable list for Oil Refi ning – Corrosion inhibitors), Na Cap – glycol corrosion inhibitor (also see the taxable list for Oil Refi ning – Corrosion inhibitors), Nalcolyte 8103, Natural catalysts – being compounds of aluminum, silicon, nickel, manganese, iron and other metals, Oleyl alcohol – anti-foam agent, Triethylene glycol, Wax solvents – dewaxing compounds

Aluminum (Al), Aluminum Alkyls, Bismuth (Bi), Chromium (Cr), Cobalt (Co), Copper (Cu), Hafnium (Hf), Iron (Fe), Lithium (Li), Magnesium (Mg), Manganese (Mn), Mercury (Hg), Molybdenum (Mo), Nickel (Ni), Raney Nickel, Phosphorus (P), Potassium (K), Rhenium (Re), Tin (Sn), Titanium (Ti), Tungsten (W), Vanadium (V), Zinc (Zn), Zirconium (Zr), and More.

which suggests that a large fraction of the recent increase for Pt and Rh might originate from automobile catalytic converters. At the same time, other publications indicate that even the use of platinum in catalytic converters has created a massive problem. In as early as 2001, Barbante et al., discussed the long-term impact of platinum and other precious metals on the air pollution. They reported that the planet has been covered with a fine layer of osmium due largely to efforts to clean up car exhausts, according to a global survey of rainwater. Externally, these are not considered to be harmful, mainly because they fall under the realm of ‘intangibles’ the science of which is beyond the current expertise of New Science (Jones, 2009). These pollutants come from cars that have been fitted with catalytic converters to keep nitrogen oxides and carbon monoxide out of the air. This cuts down on smog and has huge health benefits. But catalytic converters created a demand for platinum, which has its own environmental impact. The smelting of platinum can release metals into the air, for example — particularly osmium tetroxide, the impact of which is likely to be more significant than other pollutants that are featured prominently. Typically, it is the tangible aspect that alerts scientists and regulatory agencies to issue new measures. However, we make the point that focusing on tangibles will not

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resolve the crisis as the most important aspect of pollution takes place in intangible forms1 and by the time scientists can detect these forms (e.g., with new detection tools), the problem has already gone out of control. One such example is offered by recent work of Chen et al. (2009). Chen et al. (2009) reported that the osmium concentration in surface ocean water has risen unexpectedly. Osmium is one of the rarer elements in seawater, with a typical concentration of ≈10 × 10−15g g−1 (5.3 × 10−14 mol kg−1). The osmium isotope composition (187Os/188Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈1.3) and mantle/cosmic dust (≈0.13). Chen et al. (2009) showed that the 187Os/188Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (≈0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower 187 Os/188Os ratio (≈0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts. This outcome was not certainly expected from platinum use.

6.3.2

Cadmium

Cadmium is considered to be a non-essential and highly toxic element to a wide variety of living organisms, including man, and it is one of the widespread pollutants with a long biological half-life (Plunket 1987; Klaassen 2001; Rahman et al. 2004). A provisional, maximum, tolerable daily intake of cadmium from all sources is 1–1.2 g/kg body mass (Bortoleto et al. 2004) and is recommended by FAO-WHO jointly. This metal enters the environment mainly from industrial processes and phosphate fertilizers and is transferred to animals and humans through the food chain (Wagner 1993; Taylor 1997; Sattar et al. 2004). Cadmium is very hazardous because humans retain it strongly (Friberg et al., 1974), particularly in the liver (half-life of 5 to 10 years) and kidney (half-life of 10 to 40 years). The symptoms of cadmium toxicity produced by enzymatic inhibition include hypertension, respiratory disorders, damage of kidney and liver, osteoporosis, formation of kidney stones, and others (Vivoli et al. 1983; Dinesh et al., 2002; Davis, 2006). Environmental, occupational, or dietary exposure to Cd(II) may lead to renal toxicity, pancreatic cancer (Schwartz 2002), or enhanced tumor growth (Schwartz et al. 2000). The safety level of cadmium in drinking water in many countries is 0.01ppm, but many surface waters show higher cadmium levels. Cadmium can kill fish in one day at a concentration of 10 ppm in water, whereas it can kill fish in 10 days at a concentration of 2 ppm. Studies with cadmium have shown harmful effects on some fish at concentrations of 0.2ppm (Landes et al. 2004). Plants

1 Itmeans that the main players in creating pollution are below thedetection level and behave like undetected cancer cells, whosemanifestation in tangible form comes too late for intervention, letalone mitigation.

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can accumulate cadmium up to a level as high as 5 to 30 mg/kg, whereas the normal range is 0.005 to 0.02 mg/kg (Cameron 1992). Taken up in excess by plants, Cd directly or indirectly inhibits physiological processes, such as respiration, photosynthesis, cell elongation, plant–water relationships, nitrogen metabolism, and mineral nutrition, all of which result in poor growth and low biomass. It was also reported that cadmium is more toxic than lead in plants (Pahlsson 1989; Sanita di Toppi and Gabbrielli 1999). In particular, Sanitå di Toppi and Gabbrielli (1999) summarized the state of the art of higher plant responses to cadmium. The principal mechanisms reviewed included phytochelatin-based sequestration and compartmentalization processes, as well as additional defense mechanisms, based on cell wall immobilization, plasma membrane exclusion, stress proteins, stress ethylene, peroxidases, metallothioneins, etc. An analysis of data taken from the international literature has been carried out, in order to highlight possible ‘qualitative’ and ‘quantitative’ differences in the response of wildtype (non-tolerant) plants to chronic and acute cadmium stress. The dose-response relationships indicate that plant response to low and high cadmium level exposures is a very complex phenomenon, in which cadmium evokes a number of parallel and/or consecutive events at molecular, physiological and morphological levels. They postulated that above all in response to acute cadmium stress, various mechanisms might operate both in an additive and in a potentiating way. Thus, they called for a holistic and integrated approach to study of the response of higher plants to cadmium. While cadmium detoxification is a complex phenomenon, authors found tolerance to cadmium in mine plants or in plant systems artificially grown under long-term selection pressure, exposed to high levels of cadmium to be a linear process, possibly involving only monogenic/oligogenic control. They concluded that, following a ‘pyramidal’ model, (adaptive) tolerance is supported by (constitutive) detoxification mechanisms, which in turn rely on (constitutive) homeostatic processes. The presence of Cd leads to long-term adaptation mode and found to affect long-term selection pressure, which may increase the frequency of one or a few tolerance gene(s). It is to be noted that the cadmium that was used by these researchers was that of refined kind, meaning they are not in their natural form, in which case it would cause little harm in low concentration and more importantly could be expelled from the organic system in case the concentration is too high for absorbance. In engineering terms, this behaviour can be explained by metal-organic framework (MOF) materials, which are related to organic chemistry, inorganic chemistry, polymeric materials, physics, crystal engineering and topology, and other scientific fields. In the context of Climate change, MOF plays an important role in gas storage, gas purification, and as such as can offer an explanation why a small amount of cadmium can render a huge volume of CO2 unacceptable to the plants and trees, thus releasing them in the atmosphere as ‘tainted’. This tainted CO2 is the main cause of global increase in the CO2. It is known that carboxylic acid ligands can form multi-functional complexes with many kinds of metals. Zhang et al. (2016) synthesized nine new tetranuclear centrosymmetric linear complexes that are called tetranuclear complexes. Magnetic studies reveal that both DyIII-based complexes (3 and 8) exhibit single-molecule magnet (SMM) behavior under a zero dc field. Furthermore, complex 3 presents one relaxation process under a zero dc field, while application of an external dc field (1500 Oe) induces multi-relaxation signals of the ac magnetic susceptibility. This study showed strong

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The Science of Climate Change O9C

O7C c

b a

O3

Cd1

O4A O12 O5A O8D

O5B O2

O1

O11 O6

Cd2

O8

O10E O10

O4 O5

(a)

O7

O9

O C Cd

c a

O C Cd

(b) b a

c

O C Cd

(c)

Figure 6.4 (a) Coordination environment of Cd in complex 1; Symmetry code: A: x, 1 + y, z; B: 1 − x, 1 − y, 2 − z; C: x, y, 1 + z; D: −1 + x, y, z; E: −x, 2 − y, 1 − z; (b) Rod-shaped secondary building unit of complex; (c) Three-dimensional network structure; Hydrogens are omitted for clarity.

link between Cd (of artificial origin) and distortion of the magnetic field, which can have fundamental impact on the way these molecules interact with carboxyl groups. Zhao et al. (2018) used a new cadmium complex, [Cd2(dcpa)·2H2O]n·H2O (1), which was synthesized by hydrothermal reaction based on the multiple acid ligand 4-(2,5-dicarboxyphenoxy)phthalic acid (H4-dcpa). Single crystal X-ray diffraction analysis reveals that 1 is a three-dimensional structure with pores. The result of X-ray diffraction analysis revealed that the complex, with a formula of Cd2 C16H12O12, crystallizes in the triclinic system, space group P-1. The asymmetric unit consists of two Cd ions, one dcpa ligand and three water molecules (O3, O11, and O12) in the lattice. As depicted in Figure 6.4(a), Cd1 is surrounded by five O atoms (O1, O2, O5B, O7C, and O9C) from a dcpa ligand and one O atom (O3) from water; Cd2 is surrounded by five O atoms (O4A, O5A, O8D, O10, and O10E) from a dcpa ligand and one O atom (O11) from water. The coordination geometry can be described as a distorted octahedron. The O-Cd-O angles are in the range of 53.06(14) to 159.75(17)°. The Cd–O bond lengths are in the range of 2.244(4)–2.474(4) Å; the bond lengths are within the

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COOH COOH

COOH

O COOH

Figure 6.5 Structure of H4 dcpa.

Intensity (a.u.)/106 7 6 5 4

[Cd2(dcpa) 3H20]n

3 2 1 0 (a)

H4dcpa 200

300 400 450 Wavelength (nm)

500 (b)

Figure 6.6 (a) Emission spectra H4 dpca and 1; (b) CIE chromaticity diagram of H4 dpca (A) and 1 (B) (From Zhao et al., 2018).

normal range. The neighboring Cd ions were linked by the carboxylate groups along the a-axis to form a rod-shaped secondary building unit (SBU) (Figure  6.4(b)). The adjacent SBUs were further linked by the dcpa ligand to form a three-dimensional network structure (Figure 6.4(c)). The fluorescence test results show that the complex has excellent blue fluorescence. The adsorption of nitrogen and carbon dioxide gas test results show that the complex has adsorption effects on carbon dioxide. This is of significance vis-à-vis greenhouse gases. N2 and CO2 adsorption measurements (up to 1 bar) were performed on an Autosorb-3.0 (Quantachrome) volumetric analyzer (Figure 6.5). The solid-state fluorescence spectra of H4-dpca and 1 were recorded at room temperature on a FLS980 spectrophotometer under an excitation of 320 and 260 nm, respectively. Figure  6.6 (a) shows that H4dpca itself has a weak emission at around 468 nm. Complex 1 shows a strong emission peak at 350 nm; the complex formed has a large anti-stock’s shift of about 118 nm. This phenomenon is attributed to the intramolecular charge-transfer effect caused by Cd coordination. In other words, the blue shift of the complex should be attributed to formation of the dpca–Cd coordination complex that brings about the change of the electronics of dpca. The coordination interaction between Cd and dcpa will reduce the electron-withdrawing ability of the oxygen atoms, lower the electron density of dcpa, shift the frontier orbital level, and

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N2 desorption 0.2

0.4

0.6

N2 adsorption 0.8 1.0

Relative pressure (P/PO)

Figure 6.7 (a) The N2 adsorption/desorption isotherms of 1 at 273 K (Zhao et al., 2018).

thus result in the blue shift of absorption as well as fluorescence emission. At the same time, the fluorescence intensity of the complex is eight times that of the ligand. The CIE chromaticity indicates that the position of the ligand H4dpca is (0.02, 0.23), but that of the complex is (0.15, 0.05), and from the CIE chromaticity diagram the great blue shift of the complex can be directly seen. The enhancement of luminescence in the complex are attributed to several factors. First, the conjugation effect of the new system was enhanced after the coordination reaction, which effectively increases the rigidity of the ligand and reduces the loss of energy by radiationless decay. At the very minimum, this means a change in the natural frequency of ligand. Secondly, organic ligands have a high UV absorption coefficient; after the complex was formed, energy absorbed by the dpca will efficiently transfer to the Cd ion and the results lead to a high fluorescence efficiency of the complex. Due to its porous structure and structural rigidity, a N2 adsorption experiment at 77 K and CO2 adsorption at 273 K in an ice-water bath were performed to evaluate the porosity of 1. The pore diameter of the complex is 3.814 nm as measured by Autosorb-3.0 (Quantachrome) volumetric analyzer, and the total accessible volume of the fully desolvated complex 1 is ca. 15.1% (863.2 Å3 per unit cell vol), calculated using the PLATON program. As shown in Figure 6.7(a), the complex has a weak adsorption effect on nitrogen. The experimental results show that the isotherm presented a typical type I curve, which is characteristic of microporous materials. As is seen in Figure 6.7(b), the CO2 adsorption experimental results show that the adsorption amounts of CO2 increase abruptly over the low-pressure range, up to 14 cm3/g (STP) at 0.2 atm and finally up to 18 cm3/g at 1 atm. It can be seen from the adsorption curve that the carbon dioxide and the complex have a strong interaction. Also, it can be seen from the desorption curve that desorption of carbon dioxide has some hysteresis. It means that the organic body will retain part of the chemical but will release enough to the CO2 that will remain ‘tainted’ and thus unabsorbable by the organic system.

6.3.3 Lead Lead (II) is a highly toxic element to humans and most other forms of life. Children, infants, and fetuses are at particularly high risk of neurotoxic and developmental

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Volume STP cc/g

16

CO2 desorption

14 12 10

CO2 adsorption

8 6 4 2 0.0 (b)

0.2 0.4 0.6 0.8 Relative pressure (P/PO)

1.0

Figure 6.7 (b) CO2 adsorption isotherms of 1 at 273 K. (Zhao et al., 2018).

effects of lead. Lead can cause accumulative poisoning, cancer, and brain damage, and it can cause mental retardation and semi-permanent brain damage in young children (Friberg et al. 1979; Sultana et al. 2000). At higher levels, lead can cause coma, convulsion, or even death. Even low levels of lead are harmful and associated with a decrease in intelligence, stature, and growth. Lead enters the body through drinking water or food and can accumulate in the bones. Lead has the ability to replace calcium in the bone to form sites for long-term release (King et al. 2006). The Royal Society of Canada (1986) reported that human exposure to lead has harmful effects on the kidney, the central nervous system, and the production of blood cells. In children, irritability, appetite loss, vomiting, abdominal pain, and constipation can occur (Yule and Lansdown 1981). Pregnant women are at high risk because lead can cross the placenta and damage the developing fetal nervous system; lead can also induce miscarriage (Wilson 1966). Animals ingest lead via crops and grasses grown in contaminated soil. Levels in plants usually range from 0.5 to 3 mg/kg, while lichens have been shown to contain up to 2,400 mg/kg of lead (Cameron 1992). Lead ingestion by women of childbearing age may impact both the woman’s health (Lustberg and Silbergeld, 2002) and that of her fetus, for ingested lead is stored in the bone and released during gestation (Angle et al. 1984; Gomaa et al. 2002). Conventional analysis does not reveal how lead can affect the nature of carbon dioxide or pollute the air. However, it is known that metal electrodes such as Cu, Pb and Zn have been extensively employed in the electrochemical reduction of CO2. Depending on the metal used as cathode the final reaction products can vary considerably. This wide range of end products extends from hydrocarbons (methane, propane, ethylene, etc.) to oxygenated molecules, the most important of which are methanol, ethanol, and formic and oxalic acids. The reaction product distribution is very sensitive to various parameters such as applied potential, buffer strength and local pH, local CO2 concentration, CO2 pressure and the surface crystal structure of the electrode. The metals which have been found to most effectively catalyse CO2 reduction are those with a small number of electrons in the sp orbital and/or full d-orbitals. Examples of these include In, Pb, Cu and Pd. They all reduce CO2 into carbon monoxide. Any of these reactions can poison the CO2 in the atmosphere.

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Carbon dioxide can be reduced to a wide range of end products. Each of these paths from CO2 to a particular product can be described as one of many competing ‘overall’ reactions. The extent to which each progresses will depend on the metal catalyst, the electrolyte and the cathode potential. Overall reactions are, however, a series of intermediate steps with competing reactions at each of these steps. Depending on the nature of the metal catalyst (natural state or artificial state), it is possible therefore that an overall reaction with a very positive open circuit potential, may not occur to a significant extent within a particular system. This will be the case if one of the intermediate steps does not occur to a significant extent, there being a more favoured alternative reaction at that point. Chaplin and Wragg (2003) conducted electroreduction of carbon dioxide in aqueous and alkaline medium having hydrogenocarbonate ions as the predominant species in solution (pH = 8.6 after bubbling CO2 in a 0.1 M NaOH solution). Taking into account the bands of species present in various spectra obtained with in situ IR reflectance spectroscopy, they proposed a reaction mechanism of selective hydrogenation of HCO3− to HCOO−. The disappearance of the band ascribed to CO2 when applying a cathodic electrode potential gives evidence that CO2 is not absorbed nor is it the electroreducible species on the lead electrode surface. Accordingly, formate was the exclusive organic species identified from HCO3− reduction during chronoamperometry/FTIRS experiments at −1.6 V vs. SCE in aqueous medium. This study was significant because it related cathode properties in terms of the electron configuration of the metal catalysts present within the cathode, the adsorption/desorption properties of which can be predicted from these electron configurations. This allows predictions to be made as to which metal groups are likely to produce the longest lasting impact on the environment. There has long been an interest in the electroreduction of CO2 in order to make carbon based compounds, and there have been parallels drawn between this and photosynthesis, albeit being the unnatural version of it. In their review of the topic, Jitaru et al. (1997) refer to papers which review over 100 years of work on the subject. The review concludes that CO2 represents an infinite source of carbon that can be generated into methanol, ethanol, aldehydes, methane, ethylene, formic and oxalic acids. An alternative option is to develop a process that will produce a useful ratio of CO to H2 (i.e., Syngas). The growing promise of electrochemical methods is leading to many papers and patents. Much work is also ongoing on photocatalytic reduction. Carbon dioxide can be reduced to a wide range of end products. Each of these paths from CO2 to a particular product can be described as one of many competing ‘overall’ reactions. The extent to which each progresses will depend on the metal catalyst, the electrolyte and the cathode potential. Each overall reaction has its own open circuit potential and, for any given system, its own ‘overpotential against current density’ profile. Overall reactions are, however, a series of intermediate steps with competing reactions at each of these steps. It is possible therefore that an overall reaction with a very positive open circuit potential, may not occur to a significant extent within a particular system. This will be the case if one of the intermediate steps does not occur to a significant extent, there being a more favoured alternative reaction at that point. Some of the common reduction products are shown in Table 6.8. The competing intermediate reactions and resulting products can be most easily shown in a branching form. At each point, competing reactions create different

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Table 6.8 Equilibrium potentials for various co2 electroreduction reactions (from jitaru et al., 1997). E/V − −

→

−0.475

→

−0.199

−

→

−0.109

−

→

−0.071

−

→

+0.030

−

→

+0.169

CO2(g) + CO(g)

A CO2(ad)

C

CO+

+ e–

+ CO2(g) +e–

+e–

J

+2H+ + 3e–

+CO32–

+ 2H+ D

K –

–

CO2(ad)

CO2(aq)

C

+H–

G

Oxalate

+ H+ B

+ H+ H

C1

COOH(ad)

COOH(aq)

C2

F CO2(g)

+ H+

CO(g)

+ e–

I COH

+ e–

E

+ H2O

–

COOH (aq) HCOOH (aq) + OH (aq)

Figure 6.8 CO2 reduction routes commonly proposed for an acid system (From Chaplin and Wragg, 2003).

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branches. Eventually, end products can be grouped together according to what intermediate species they have in common. In Figure 6.8, each competing reaction is given a reference letter. Many of the reaction paths are described in differing ways by different workers, for example, path –B is frequently described as being a reaction between CO2ad and either Had or H2Oad. Innocent et al. (2010) formulated the reduction mechanism of the synthesis of formate from hydrogenocarbonate on lead electrode in alkaline solution. Taking into account the bands observed in spectra the various analyses focused on a selectivity of the reaction towards formate. The following hydrogenocarbonate reduction formulation was assumed. The first step is the reduction of the solvent, as shown by Chaplin and Wragg (2003): − − → (6.1) Then the adsorption of hydrogenocarbonate at the lead sites could be written: O–

–

O

Pb +

C

–

O +e

HO

HO

C

O–

Pb

(6.2)

Hydrogenation then occurs by the interaction between two adsorbed species: O

O– HO

O–

C

C

Pb

O– + HO–

(6.3)

Pb O

Pb

Hads

+

C Pb

O–

2Pb + HCOO–

(6.4)

This assumed mechanism is almost analogous to that reported by Jitaru et al. (2003) for the “sp” group metal cathodes that we discussed. Additional evidences were provided herein, with the adsorbed species obtained by in situ FTIR spectroscopy. Actually, potential-dependent shifts of HCO3−ads (30 cm−1/V) and HCOO−ads (26 cm−1/V) were found in Figure 6.9, Figure 6.10, which denotes weak adsorptions on lead electrode in comparison with those obtained with COL on Pt (45 cm−1/V).

6.4

Science of Nanoscale

Unlike commonly held belief, the use of nanoparticles has a long history. Nanoparticles were used by artisans as far back as the 9th century in Mesopotamia for generating a glittering effect on the surface of pots. This was denoted as “luster art,” which refers to a metallic film applied to the transparent surface of a glazing, consisting of Cu or Ag nanoparticles. In this way, beautiful iridescent reflections of different colours (in particular gold and ruby-red) are obtained (Padeletti, and Fermo, 2003). During the Islamic golden era (8th-13th centuries), this technology was taken to another high as non-gold decoration materials are sought after in Islamic culture (Khan and Islam, 2016). Michael

Role of Refining on Climate Change 1397 cm–1

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–1.5 V vs. SCE

0.05%

–1.6 V vs. SCE –1.0 V vs. SCE

–1.7 V vs. SCE

1639 cm–1

1388 cm–1

–1.2 V vs. SCE

ΔR/R

ΔR/R

–1.1 V vs. SCE

0.5% 1631 cm–1

–1.3 V vs. SCE 1104 cm–1

1383 cm–1

–1.4 V vs. SCE –1.45 V vs. SCE 1635 cm–1

1000 1250 1500 1750 2000 2250 2500

(a)

Wavenumber (cm–1)

–1.8 V vs. SCE

1000 1250 1500 1750 2000 2250 2500

(b)

Wavenumber (cm–1)

Figure 6.9 SPAIR spectra on a Pb electrode after bubbling CO2 in 0.1 M NaOH until pH = 8.6; ΔR/R = (RE2 − RE1)/RE1, where the “reference” spectrum, RE1, was taken at E = −1.8 V vs.SCE. (a) Electrode potential from −1.0 V to −1.45 V vs. SCE. (b) Electrode potential from −1.5 V to −1.8 V vs. SCE (From Chaplin and Wragg, 2003).

Faraday was the first one among New scientists to study the size-dependent optical properties of gold and silver colloids or nanoparticles (Wilcoxon, 2009). However, only recently renewed interest in nanoparticles has emerged, mainly because of the possibility of revolutionizing novel materials production (Zaman et al, 2012; Islam and Mokhatab, 2018; Morris, 2011). In the modern era, and in the last decade in particular, insights and discoveries in the field of nanostructures are booming (Morris, 2011). The combination of reduced size and special properties make nanoscience intriguing. Nearly 3 decades of worldwide revolutionary developments in nanoscience, combining physics, chemistry, material science, theory and even biosciences, have brought us to another level of understanding. The public interest and popularization of nanotechnology has made the importance of this science synonymous with the Information Age. With it has come the ‘science fiction’ version of New Science. New Science has morphed into quantum science, with the promise to fabricate, characterize, and manipulate any natural tendencies of nature into artificial structures, whose features are controlled at the nanometer level. Such properties can be, for instance, strength, electrical and thermal conductivity, optical response, elasticity, or wear resistance. Research is also evolving toward materials that are designed to perform more complex and efficient tasks. Examples include materials that bring about a higher rate of decomposition of pollutants, a selective and sensitive response toward a given biomolecule, an improved conversion of light into current, or more efficient energy storage. For such and more complex tasks to be realized, novel materials have to be based on several components whose spatial organization is engineered at the molecular level. The problem is, nanotechnology has encouraged development of technologies that are excellent in producing results that conform to the market demand rather than addressing the problem of

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1%

ΔR/R

1632 cm–1

1629 cm–1

–1.8 V vs. SCE –1.0 V vs. SCE 1000 1250 1500 1750 2000 2250 2500 Wavenumber (cm–1) Figure 6.10 SPAIR spectra on a Pb electrode after bubbling CO2 in 0.1 M NaOH until pH = 8.6; ΔR/R = (RE2 − RE1)/RE1, where the “reference” spectrum, RE1, was taken at E = −1.0 V vs.SCE (From Chaplin and Wragg, 2003).

original unsustainability of a technique. For instance, the microelectronics industry is fabricating integrated circuits and storage media whose basic units are approaching the size of few tens of nanometers. For computers, ‘‘smaller’’ means higher computational power at lower cost and with higher portability. Unfortunately, the advent of new methods for the controlled production of nanoscale materials has provided new tools that can be adapted for this purpose, all maximizing speed of producing results for the smallest amount of investment costs. New terms such as nanotubes, nanowires, and quantum dots are now common jargon of scientific publications. These objects are among the smallest man-made units that display physical and chemical properties which make them promising candidates as fundamental building blocks for novel transistors. The advantages envisaged here are higher device versatility, faster switching speed, lower power dissipation, and the possibility of packing many more transistors on a single chip. However, this race toward higher performance assumes that original versions are actually accurate and sustainable. In reality, the opposite is the truth, as outlined by Islam et al. (2016). This trend in nanotechnology has virtually guaranteed new technologies are more unsustainable than the older ones. As intervention takes place in locations involving smaller ‘particles’, the departure from natural order takes place at a more fundamental level. This is very similar to what has happened in the agricultural section that has seen the use of toxic pesticide with even more harmful genetic modification schemes, as discussed in Chapter 5.

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Similarly, the pharmaceutical and biomedical industries are rushing to synthesize large supramolecular assemblies and artificial devices that mimicking the superficial aspects of the complex mechanisms of nature or that can be potentially used for more efficient diagnoses and better cures for diseases. Examples in this direction are nanocapsules such as liposomes, embodying drugs that can be selectively released in living organs, or bioconjugate assemblies of biomolecules and magnetic (or fluorescent) nanoparticles that may provide faster and more selective analysis of biotissues. The entire exercise hovers around developing more and more unnatural means to study nature. Of course, whenever a contradiction arises, it is countered with dogmatic fervor and yet another new term is coined to explain away paradoxical ‘science’ (Islam et al., 2015). ISO’s working definition of Nanotechnology is: the application of scientific knowledge to the control and use of matter at the nanoscale, where size related phenomena and processes may occur (ISO, n.d.). The type of properties that could not be perceived in the past, such as, ultralightweight, superstrong, rust-proof materials, could be developed based on nanoscale technology. Laboratory measurements have made it clear that one can take a multiwall carbon nanotube and get what amounts to 100-gigapascal tensile strength, which is 20 times stronger than the strongest carbon fiber made today. The intrigue in this technology is, unlike common perception, there needs to be no genetic-engineering like manipulation involved. Carbon nanotubes are essentially continuous Buckyballs, allotropes of carbon with a cylindrical nanostructure. Nanotubes can be single- or multiple-walled, and can be constructed with a length-todiameter ratio of up to 132 million-to-1, significantly larger than any other material. It is well known that the carbon-to-carbon bond is the strongest of all possible elemental bonds, with nanotubes exhibiting tensile strengths 100 times that of steel. In addition to their extraordinary strength, nanotubes have novel electrical and thermal conductive properties that give them potential value in a range of applications but that are extremely difficult to characterize with new science. This difficulty stems from the fact that the atomic theory has been hopeless in addressing these problems because none of the conventional theory applies in nanoscale. Nanotechnology deals with the small construction at the atomic and molecular levels about the length occupied by five to ten atoms stacked together or equivalently, 1/50000th the diameter of human hair. At least one characteristic length of the constructional and functional unit of nanostructure should be in nanometer range. At this dimension, amazing manifestation of the nano-materials –such as, 10 times lighter but 250 times stronger than steel – creates the potential for a new horizon in different areas of science and technology. The petroleum industry is not an exception. This industry too needs technological breakthrough to meet the tremendous increase in demand. At present, the fascination for understanding nano-scale phenomenon is entirely driven by economics. The economic and societal promise of nanotechnology has led to involvement and investments by governments and companies around the world. The type of involvement US government had in terms of internet technology that has onset the Information age is repeated in nanotechnology. As early as 2000, the United States became the first nation to establish a formal, national initiative to advance nanoscale science, engineering, and technology—the National Nanotechnology Initiative. This initiative has generated significant domestic and international investment opportunities

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Billions of dollars

3000

Lux 2006

2500 2000

Cientifica 2008

1500

NSF 2001

1000 500 0 2000

2005

2010 Year

2015

Figure 6.11 Estimates of revenues from nanotechnology applications in USA (updated from Tiague, 2007).

in nanoscale research. In 2014, Lux Research, an emerging technologies consulting firm, estimated total (public and private) global nanotechnology funding for 2012 to be approximately $18.5 billion (Report 1). Previously, Lux Research had estimated that in 2010 corporate R&D had surpassed publicly funded R&D for the first time (Report 2). Another company, Cientifica, a privately held nanotechnology business analysis and consulting firm, estimated global public investments in nanotechnology in 2010 to be approximately $10 billion per year, with cumulative global public investments through 2011 reaching approximately $67.5 billion. In 2011, Cientifica also concluded that the United States had fallen behind both Russia and China in nanotechnology R&D funding on a purchasing power parity (PPP) basis (which takes into account the price of goods and services in each nation), but still led the world in real dollar terms (adjusted on a currency exchange rate basis) (Cientifica, 2011). Global investments in nanotechnology have begun to yield economic benefits as products incorporating nanotechnology enter the marketplace. Nano-enabled products are estimated to have produced $731 billion in revenues in 2012 (Lux, 2014). These offer great potentials for future applications of nanotechnology. The current market includes nanotechnology products—such as faster computer processors, higher density memory devices, lighterweight auto parts, more energy-efficient computer and television displays, stain-resistant clothing, antibiotic bandages, cosmetics, and clear sunscreen—are evolutionary in nature, offering incremental improvements in characteristics such as performance, aesthetics, cost, size, and weight. Figure 6.11 shows how various organizations predicted revenues from nanotechnology activities. Some pessimistic sides of these predictions vastly ignore the applications in the oil and gas industry. Magnetic Sensing, although known throughout history, has taken a new meaning under the auspices of nanotechnology revolution. Today, such particles can be manufactured. These nanoparticles that can be manipulated using magnetic field gradients. Such particles commonly consist of magnetic elements such as iron, nickel and cobalt and their chemical compounds. They might involve particle size ranging from 0.5 nm to 500 nm. While nanoparticles are smaller than 1 micrometer in diameter (typically 5–500 nanometers), the larger microbeads are 0.5–500 micrometer

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in diameter. The magnetic nanoparticles are attractive for many applications, ranging chemical engineering to medicine. Specific applications are in developing catalysts (Tadic et al., 2014; Lu et al., 2004), biomedicine (Gupta and Gupta, 2005), magnetically activated photonic crystals (He et al., 2014), microfluidics (Kavre et al., 2014), magnetic resonance imaging (MRI) (Mornet et al., 2006), magnetic particle imaging (Gleich and Weizenecker, 2005), data storage (Frey et al., 2009), environmental remediation Hoel et al., 2004; Azain Abdul Kadhar et al., 2014), nanofluids (Philip et al., 2006), optical filters (Philip et al., 2003), defect sensor (Mahendran, 2012), and cation sensors (Philip et al., 2013). The physical and chemical properties of magnetic nanoparticles can be greatly affected by slight changes in synthesis method and chemical structure. Only recently, techniques are emerging that would allow one to invoke changes without altering natural properties of matter (Kalia and Averous, 2011). Islam and Mokhatab (2018) recently identified major research thrusts in nanotechnology as follows: a. Characterization of nanomaterials b. Pathway analysis of natural and engineered nanomaterials c. Synthesis and manipulation of nanomaterials and the long-term impact on the environment d. Modeling of nanoscale phenomena e. Novel methods of microscopy and spectroscopy f. Natural nanoparticles as nanosensors g. Novel methods for describing forces prevalent in nanoscale h. Comprehensive modeling of subatomic particles i. Novel nanosensors j. Nanomagnetics k. Nanobiotechnology and health impact l. Coprehensive theories of nano-optics, nano-photonics m. Nanoscaled modeling and simulation n. Scaling up of nanoscale phenomena o. EOR and Improved Waterflood with nanofluid p. New generation of 4D mappin The previous line of research has been strictly on the path of developing engineered materials. It has been almost forgotten what the purpose of the research actally was. Picture 6.1 shows how far this obsession with artificial has gone. This picture shows how nanomaterials are being ‘branded’. If the premise that unnatural cannot be sustained (Khan and Islam, 2012), one must have concern for the long-term impact of the engineered chemicals. This concern has been in the forefront of US strategy. For instance, Mihelson (2013) writes: However, upon further review of this particular set of “top 10” priorities, the third entry on the list might seem somewhat out of place. Titled “Small Comfort”—and illustrated with a circular image encompassing a series of hexagonal shapes that, perhaps, are meant to indicate the structure of atoms and molecules—the ensuing description notes that “long touted as the next ‘big thing,’ nanotechnology is already moving from research

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Picture 6.1 Laboratory name is branded on nanomaterials with focused ion beam.

to market…. But safety concerns continue to dog the emerging field” to the extent that “the next president must decide if the country needs to revise its nano safety strategy to strengthen protections for the public” (Michelson, 2013).

Whereas natural water-borne nanoparticles are ubiquitous, their very small size, ranging from 1 to 100 nanometers means they are both highly mobile and chemically reactive. Nanoparticles are central in buffering environmental systems, serving the dual role of limiting potentially toxic metal concentrations, while at the same time providing a supply of metals at levels that enables biochemical reactions to take place. Recent analysis of Islam et al. (2015) indicates that natural nanomaterials are both sustainable and necessary for the ecosystem, whereas engineered materials are bound to show negative impact on the environment.

6.4.1

Connection Between Subatomic and Bulk Properties

One of the biggest problems in describing material properties is the fact that the theories are based on atomic theory whereas validated with bulk properties, while bulk properties are observable and measurable, atomic and subatomic properties are not (Khan and Islam, 2016). In fact, it is clear today that at no space solid, rigid, uniform, and spherical particles that was once thought to be atom do not exist. Instead, subatomic particles are more akin to clouds – a phenomenon that has been described by Islam with his ‘galaxy

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model’ (Islam, 2014). This galaxy model is capable of explaining both nano- and bulkscale properties. It is important to have a correct description of fundamental building ‘blocks’ because if they are described improperly, the description of the macro-system will be meaningless irrespective of what parameters are introduced in order to match bulk properties with governing equations. Take, for instance, an example of an atom. If this atom is considered to be a collection of single nucleus and electrons, with nucleus being a collection of rigid particles and electrons are much smaller rigid particles, there is no room left to consider some 69 smaller particles that we know exist. This description is not any improvement over the original atomic theory that considered the entire atom to be a solid spherical particle. However, New Science takes the pragmatic approach and forces analytical solutions based on hydrogen atom (Atkins, 1986; Karplus and Porter, 1970). It is assumed that one electron orbits around one proton with the following properties remain constant: 1. size of the proton (comes from the assumption that it’s a rigid, uniform sphere. 2. uniform spinning rate and angle 3. uniform orbital path The above assumptions collapse, of course, as soon as there is more than one electron, in which case nuclear-electron force has to be adjusted for accommodating electron-electron forces. This complexity is addressed by invoking approximations, because of the presence of a non-linear terms make it impossible to determine an analytical solution. In order to justify such assumptions, the notion of atomic orbital (AO), with an associated discrete energy level is introduced. No justification for such discrete nature of energy level is given. In addition, various angular moments are ascribed, once again without justification. Different types of orbital shapes are introduced, such as, spherical (s-orbital), club-like (p-orbital) or a more complicated (d-, f -orbitals) shape. The eight valence electrons of a neon atom, for example, occupy one s- and three p-orbitals around the nucleus, one spin up and one spin down per orbit (Karplus and Porter, 1970), where the energy level of the s-orbital is lower than that of the p-orbitals. The reason there is no explanation is provided is that quantum mechanics is invoked. The rules of quantum mechanics dictate that the energy levels are discrete. In layman’s terms, this illogical assertion means there is this dogma that A can be A and B at the same time. As pointed out by Islam et al. (2015; 2016) and Khan and Islam (2016), this is simply the polished and disguised version of Dogma. The next level of dogma ‘science’ moves to a bigger structure, that is the molecule that obtained from the combination of several atoms. It is thus asserted that electrons orbit collectively around more than one nucleus. In a molecule, electrons that are responsible for the covalent bonds between individual atoms can no longer be ascribed to one individual atom, but they are ‘‘shared’’. For instance, in methane (CH4), each of the four sp3 atomic orbitals of the central carbon atom is linearly combined with the s orbital of a hydrogen atom to form a bonding (σ) and an anti-bonding (σ*) orbital, respectively. Since these orbitals are ‘‘shared’’ between the atoms, they are called molecular orbitals (MO, see Figure  6.12). The straw man argument that the lowest energy (bonding) orbitals are occupied, therefore the stability of methane is assured is

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sp3

s atom

Conduction band

σ*

p

Quantum dot σ

Energy gap Valence band

molecule

Bulk solid-state body Number of connected atoms

Figure 6.12 Electronic energy levels depending on the number of bound atoms. By binding more and more atoms together, the discrete energy levels of the atomic orbitals merge into energy bands (here shown for a semiconducting material). Therefore semiconducting nanocrystals (quantum dots) can be regarded as a hybrid between small molecules and bulk material.

made (Karplus and Porter, 1970). Based on this aphenomenal model, which is a refined version of the original Atomic theory, is then used to derive the electronic structure of more complex systems such as large molecules or atomic clusters. While combining atoms to form a molecule, discrete energy levels of the atomic orbitals are added to obtain similarly discrete levels of molecular orbitals (Atkins, 1986). When the size of a polyatomic system becomes progressively larger, the calculation of its electronic structure in terms of combinations of atomic orbitals becomes unfeasible (Harrison, 1989) and another level of absurdity is introduced. Simplifications arise if the system under study is deemed to be periodic, thus reaching the level of an infinite series. This assumption is invoked for, for instance, crystals. In this model, perfect translational symmetry of the crystal structure is assumed, and contributions from the surface of the crystal are neglected by assuming an infinite solid (periodic boundary conditions). Electrons are described as a superposition of plane waves extended throughout the solid. With these fantastically unnatural traits, the new model emerges as being able to eliminate the assumption of discrete energy and the description of Figure 6.12 emerges. In reality, this model is not any less absurd than the original discrete model, albeit with the newly added complexity giving it a cosmetic of a real model that captures reality. Of course, the assumption of ‘infinity’ does not apply to smaller crystals of nanometer dimensions (called nanocrystals). Therefore, for nanocrystals, a new set of absurd definitions needed to be introduced. Following assumptions are added: 1. energy levels of a nanocrystal are discrete; 2. their density is much larger than similar atomic clusters; 3. their spacing is smaller than for the corresponding levels of one atom or a small atomic cluster. These logical absurdities are called quantum dots. These dots mark the connection between bulk and nano-scale properties. Highest occupied atomic levels of the atomic (or ionic) species interact with each other to form the valence band of the nanocrystal.

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Similarly, lowest unoccupied levels combine to form the conduction band of the nanocrystal. The energy gap between the valence and conduction bands results in the band gap of the nanocrystal. As an example, consider a metallic quantum dot. Its level spacing at the Fermi level is roughly proportional to EF = N, where N is the number of electrons in the quantum dot. In very small crystals of nanometer dimensions, so called nanocrystals, the assumptions of translational symmetry and infinite size of the crystal are no longer valid, and thus these systems cannot be described with the same model used for a bulk solid. We can imagine indeed that the electronic structure of a nanocrystal should be something intermediate between the discrete levels of an atomic system and the band structure of a bulk solid. This can be evidenced from Figure 6.12, the energy levels of a nanocrystal are discrete, their density is much larger, and their spacing is smaller than for the corresponding levels of one atom or a small atomic cluster. Because of their discrete energy levels, such structures are called also quantum dots. The concept of energy bands and band gap can still be used. Highest occupied atomic levels of the atomic (or ionic) species interact with each other to form the valence band of the nanocrystal. Similarly, lowest unoccupied levels combine to form the conduction band of the nanocrystal. The energy gap between the valence and conduction bands results in the band gap of the nanocrystal. As an example, consider a metallic quantum dot. Its level spacing at the Fermi level is roughly proportional to EF = N, where N is the number of electrons in the quantum dot. Given that EF is a few eV and that N is close to 1 per atom, the band gap of a metallic quantum dot becomes observable only at very low temperatures. Conversely, in the case of semiconductor quantum dots, the band gap is larger and its effects can be observed at room temperature. The size-tunable fluorescence emission of CdSe quantum dots in the visible region of the spectrum is for instance a very explanatory illustration of the presence of a size-dependent band gap. At the outset, there is no harm in characterizing material in this fashion other than the fact that it is not logical. However, the real harm is in disconnecting metal components from the rest of the environment. In addition, such characterization of both mass and energy disconnects the mass from the energy component and makes no distinction between natural chemical and artificial ones. Crystals in nature, however, are processed very differently from the artificial processing that we are used to. Before this atomic model is confidently extended to a bulk system, three-dimensional scaling is performed and to do so the concept of ‘free’ electron is introduced. A ‘‘free’’ electron means that it is delocalized and thus not bound to individual atoms. In scientific term, it means electrons are assigned the ability to exist in multiple positions in space simultaneously. It does not stop there; furthermore assumptions are invoked. For instance, it is assumed that the interactions between the electrons, as well as the interactions between the electrons and the crystal potential, can be neglected. This amounts to neglecting mass of a snow flake while calculating the impact of an avalanche or nature (natural or artificial) of a photon while determining the role of light in an organic system. Yet, this model system, called ‘‘free-electron gas’’ has become foundation of the study of material properties (Ashcroft and Mermin, 1976). Unsurprisingly, scientists then marvel at how well this model captures many physical aspects of a real system, which is expected because all measuring tools are also based on the same principle (Islam, 2019). It means, scientists are busy falsely measuring properties of real materials to justify theories that are based on false premises. Even

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then, whenever divergence occurs between measured and theoretic observations, it is explained away based on another set of false assumptions. When it becomes unbearable to maintain such theories, new parameters and yet another set of dogmatic assertions are invoked. In this particular application, it is deemed sufficient to replace the free-electron mass m by an ‘‘effective’’ mass m*, which implicitly contains the corrections for the interactions, although the ‘correction’ remains entirely arbitrary and the original ‘free-electron’ picture becomes the new norm. With this premise, velocity of electron, its mass and energy are connected through the following equation



→



(6.5)

where, velocity, v is considered to be strictly orthogonal with components vx, vy, vz in three dimensions. According to Pauli’s exclusion principle, each electron must be in a unique quantum state. This stunning principle assigns unique properties to otherwise homogenous, spherical, rigid, particles – called electron, without explaining why such uniform bodies will have unique properties. It is also asserted that electrons can have two spin orientations (ms = 1/2 and ms = - 1/2). It then follows that two electrons with opposite spins can have the same velocity, v. This case is analogous to the old Bohr model of atoms, in which each orbital can be occupied by two electrons at maximum. In essence, the new description is nothing different from the long-discredited Atomic model. In connecting the transition between energy and mass, solid-state physics introduces another layer of obscurity. The velocity term, v is replaced by wave vector, k (expressed as kx, ky, and kz) in order to describe a particle’s state. Its absolute value is called the wave number (akin to speed). The wavevector is stated to be directly proportional to the linear momentum, p and thus also to the velocity, v of the electron: →

→

→

(6.6)

In the above equation, which asserts a linear relationship between p and k obscure any role of real radiation by invoking the scaling constant, h, the Planck constant. In essence, Planck's constant relates the energy in one ‘quantum’ of electromagnetic radiation to the frequency of that radiation. In the International System of units (SI), the constant is equal to approximately 6.626176 × 10-34 joule-seconds. All of a sudden, the entire transition from mass to energy is fabricated as this ‘quantum’ subsequently called photon or any other unit of energy, typically characterized as devoid of mass, yet having a definite pattern in electromagnetic wave. This absurd notion forms the basis of today’s Quantum Physics. The science is further obscured by the introduction of the De Broglie relation (Ashcroft and Mermin, 1976) that relates wave length to Planck’s constant through the following relationship.

±

→

±

(6.7)

In this equation, wave number is related to wave length, λ. This assumption (known as matter-wave duality) implies that matter behaves like waves, the latter being a feature of energy that has no mass attached to it. In essence, it disconnects mass from

Role of Refining on Climate Change (kx, ky, kz)

269

Δky

kz kz

z x (a)

kx

dx y (b)

kx

E(kx, y, z)

(c)

Δkx, y, z

ky

ky D3d(E)

0

kx, y, z

E (d)

Figure 6.13 Electrons in a three-dimensional bulk solid (From Ashcroft and Mermin, 1976).

energy, implying that energy can emerge from nothing. After all this molestation of mass energy transition comes the manipulation of the boundary condition. It is assumed that periodic boundary conditions exist for every particle. This is the opaque version of the real boundary condition that is being imposed, the real meaning the infinite boundary condition that was the one that gave analytical solutions in the past. The scientific meaning of imposition of such an absurd boundary condition is to assert that an electron does not ‘feel’ the border, therefore it ‘behaves’ as though it is in a bulk. Now that this depiction of bulk material has nothing to do with reality, scientists solve the resulting equations with a great deal of zeal and draw a 3-D picture of electrons and resulting energy (Figure 6.13). The debate now becomes that of cosmetics of this visualization and how to make the predictions close to real observations – observations that are made with the tools that have the same depiction imbedded in it. In this figure, (a) shows how a solid entity can be modeled as an infinite crystal along all three dimensions x; y; z. The picture (b) shows how periodic boundary conditions yield standing waves solutions for free electrons. Each of the dots shown in the figure represents a possible electronic state kx; ky; kz. Each state in k-space can be only occupied by two electrons. In Figure (c) the dispersion relation for free electrons in a three-dimensional solid is shown. The energy of free electrons varies with the square of the wavenumber, and its dependence on k is described by a parabola. For a bulk solid the allowed states are quasi-continuously distributed and the distance between two adjacent states (here shown as points) in k-space is very small. In figure (d), Density of states of D3d for free electrons in a three-dimensional system are shown. The allowed energies are quasi-continuous and their density varies with the square root of the energy E1/2.

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Eg(d) [eV]

4

3 Bulk 2

Experiment Theory

1 4

6 d [nm]

8

10

Figure 6.14 Size dependence of the energy gap for colloidal CdSe quantum dots with diameter d. (From Trindade et al., 2001).

Figure 6.14 shows how the theoretical curve based on the above formulation ends up predicting experimental values within the margin of error. As stated earlier, the entire exercise of developing equations that have nothing to do with the actual material properties and everything to do with formulating an equation that will yield desired results have indeed borne fruit.

6.4.2 The Correct Formulation The term nanoparticle describes a subset of the colloidal range between 1 and 100 nm (Hochella 2002). The distinction is justified partly on their very high specific surface area (Lead & Wilkinson 2006) and partly on their potentially different behavior at this small scale, due to the spatial constraint of electronic properties (in an analogous manner to engineered nanoparticles: Madden et al. 2006). As particles transition to smaller and smaller sizes, they become effectively all surface with minimal internal volume, giving rise to their enhanced reactivity. Figure  6.15 includes results from Islam and Mokhatab (2018) that corrects the conventional graph to account for the continuity in subatomic level. This figure shows the difficulties in both describing phenomena and handling of such materials. Engineered materials behave similarly but with unpredictable results of reactivity. For instance, natural materials will form biomaterials and become an integral part of the life cycle, whereas engineered materials will form toxins to the living objects. This forms the core of the question that should be asked in any future research. The unique feature of this technology is that the behaviour of the matter is very different from what is well-known, commonly accepted and generally understood. Laws related to physics are different than on macro-scale. Even though it is commonly perceived that the laws of quantum mechanics are applicable, recent research findings show that nanomaterials are beyond the scope of quantum mechanics, from both a scientific (Islam, 2014; Islam and Mokhatab, 2018) and philosophical perspective (Martin, 1981). At the nanoscale conventional forces like, gravity, or inertia do not play much role; instead, other forces, not apparent in macroscale, such as, van der Waal’s forces, electrostatic, magnetism, etc., are more important. The problem is none of these

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Particle number Specific surface area

Change in reactivity/arb. units

Atomic clustes

Nanoparticles

Macroscopic particles

Conventional Islam (2015)

10–10

10–9

10–8

10–7

10–6

10–5

Particle size/m

Figure 6.15 Generalized trend for size-dependent reactivity change of a material as the particle transitions from macroscopic (bulk-like) to subatomic. Reactivity can increase or decrease depending on the material and the chemical reaction involved (modified from Islam and Mokhatab, 2018).

forces are amenable to measurements and even their mere existence remains tentative. It is, however, understood that alteration of nano-properties can make metals harder, ceramics softer, alloys malleable as per design could be engineered to become harder or softer and mixtures with specifically designed properties could be achieved (Wang et al., 2015). New devices based on nanotechnology will be different from the conventional one as the governing laws and other properties are different. The main problem with nano devices is whether this kind of machines will operate at any hostile environment or not, as the shearing-off or melting of a single layer of atoms may alter the characteristics of the nanomachine. While this has been known for over a decade (Krim, 2005), little is done as to how to describe the real problem, or which theory would explain it. For static devices, the results are much promising than the devices with moving parts. For example, nano-electronics will open a new horizon for smaller but faster computing that will go beyond the theoretical limits of current technology. New forms of memory and storage device with increased capacity and reliability will be achieved using single electron/molecular design. However, for moving nano machines as friction plays a vital role it may pose a big hurdle to overcome. However, manifestation of ‘superlubricity’ or very low friction (Socoliuc et al, 2004, Dienwiebel et al, 2004) in some nanostructure shades some light too. Liu et al. (2012) identified the process, in which shearing a microscale lithographically defined graphite mesa led to the sheared section retract spontaneously to minimize interface energy. They showed that the frictional forces involved are due to superlubricity, where ultralow friction occurs between incommensurate surfaces. The effect is remarkable because it occurs reproducibly under ambient conditions and over a contact area of up to 10 × 10 μm2, more than seven orders of magnitude larger than previous scanning-probe-based studies of superlubricity in

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graphite. It shows frictions and lubrication at atomic and meso-scale are ill-understood with today’s science. A new generation of sensors and imaging technology as a result of nanotechnology will help to deploy those at different places that are now inaccessible and/or infeasible with the current technology due to size and performance. Nanoscience is based on the fact that properties of materials change as a function of the physical dimension of that material, and nanotechnology takes advantage of this by applying selected property modifications of this nature to some beneficial endeavour. Small et al. (2005) showed how nanotechnology is and will affect geosciences. In a similar fashion we can predict the impact on petroleum industry. The magnetic, electrical, mechanical and chemical properties may be surprisingly different than the host material, apart from the physics of the material. Our macroscopic common-sense may not apply to the nano-scale phenomenon. For example, water can pass through the hydrophobic carbon nano tubes (Sansom et al, 2001, Hummer et al, 2001). Many fluids behave abnormally when confined in a space of nanometre dimensions. For example, simple organic liquids become solid-like when squeezed between two smooth surfaces into a film that is less than about five molecular layers thick. In contrast, if water is squeezed between two mica surfaces, only small changes in viscosity occur. The nature of the confining surfaces also has an effect. Depending on the nanotube dimension, nano-ice may be formed as well. Not to mention, nanophase behaviour depends on the preparation process apart from the particle size (Roy et al, 2006). Yin et al (2006) showed that adding nano-materials changes the rheology of the fluid. The dimension affects the behaviour significantly. For example, the electrorheology (ER, change in viscosity due to applied electric field) effect of the raw material of TiO2 nanoparticles is very weak, while the ER fluid containing titanate nano-whiskers shows high yield stress. So, it is possible to change some of the material properties using nano particles or creating a new kind of catalyst, suspension etc. It is also true that nanomaterials are ubiquitous and any colloidal liquid would show viscosity variation in nanoscale. This is demonstrated in Figure 6.16 that shows how viscosity in nano scale increases drastically as the sample size is reduced. This variation is beyond the Log (nano viscosity/macro viscosity) 16 14 12 10 8 6 4 2 0 0

5

10

15

20

25 30 Length ratio

Figure 6.16 Variation in nano viscosity as a function of length ratio (probe size/particle size) (From Chiu et al., 2013).

η/mPa.s

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8900 8700 8500 8300 8100 7900 7700 7500 7300 0

0.2

0.4

w/%

0.6

0.8

1

Figure 6.17 Effect of particles type on sample viscosity at a fixed temperature (25 C) and particles size: top line, micron – sized iron; , bottom-line, micron – sized copper; midline- micron – sized iron oxide (III) (figure from Shokrlu, 2013). Characteristic speed

Photon

Galaxy

Higgs boson Sun

Quark Electron

Earth

Proton Nucleus

Moon

Dust speck

Particle size

Figure 6.18 Orbital speed vs size (not to scale) (from Islam 2014).

effect of high pressure that is insensitive to the size of particles (Forst et al., 2000). With that, small addition of nanoparticles would alter the rheology of the liquid drastically. Such process unlocks great potentials for heavy oil upgrading or even downhole refining of petroleum products. Figure 6.17 shows how viscosity of heavy oil is affected with different types of nanomaterials. The same facts can be used to understand how rock/ fluid interaction would take place (Chiu et al., 2013). Recent developments in subatomic physics highlight the presence of optimum in terms of characteristic speed. Figure 6.18 shows characteristic speed as a function of particle size. This is in harmony with universal order, in which the graph is continuous in both sides of the size spectrum. Both sides approach the speed of light (Brown et al., 2015).

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Natural direction

Artifical direction

Figure 6.19 Natural artificial both act the same way, except for the time function.

In Figure 6.18, a dust speck represents reversal of speed vs. size trend. For so-called subatomic particles, speed increases as the size decreases. Higgs boson is assigned a smaller value than quark but larger value than photon. This is done deliberately in order to float the notion that fundamental particle and finality in determining such particle is a spurious concept and the actual size of it is arbitrary. Note that these characteristic speeds are all a function of time. This also follows that reactivity is greater as size is decreased. Any chemical reaction is similar to any other irreversible mass/ energy transfer, in which there is a quantum change. Such change is a characteristic feature of phase transfer, chemical reaction, or when a life begins (from non-organic to organic) or ceases for an individual (from organic to non-organic). In this process, life and death are triggers or bifurcation points as associated time functions change drastically. It should be noted that such transition is subjective and death of one entity only means death for that particular object. The time function, f(t) defines the pathway of any entity within the universal order. In Figure 6.18, dust specks represent the most objects closest to stable and steady state. The pathway followed by dust specks is the one that is organic and beneficial to the ecosystem. In nano scale reactivity increases and therefore the divergence between natural and artificial particles gains momentum. This divergence is similar to organic and non-organic or living or dead object. Figure 6.19 shows how the direction of a natural particle and its ‘orbit’ is opposite to that of artificial particle. Unless long-term analysis is done, it is not possible to observe the difference between these two types. Such observation is necessary in order to determine the true impact of a new material. To-date, research topics are more concerned about the short-term impacts that are little more than safety analysis. In this research, Khan and Islam’s (2007) criterion will be used to determine applicability of various nanomaterials and nanofluids and the long-term impacts thereof.

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Natural

Benefit

The approach of obliquity

Time The myopic approach

Artificial Harmful

Figure 6.20 Historically, natural objects were synonymous with sustainability (from Khan and Islam, 2012).

History supports the notion that harmfulness of artificial was well-known or previous civilizations did not attempt to produce artificial products. Figure 6.20 shows how important it is to distinguish between artificial process and natural process. As pointed out by Islam et al. (2010), every artitifical chemical has created irreversible damage to the environment whereas every natural chemical led to global sustainability (Khan and Islam, 2016). The superflux of artificial started with Democritus’ model that was first accepted by Aristotle and later glamourized by scholars affiliated with the Roman Catholic church. While New Science claims that it has broken out of dogmatic cognition, in reality, every theory in New Science emerges from aphenomenal premises, much like Atomism or dogma (Islam et al., 2012). A correct material property model should include all rheological properties as function of particle size that include memory effects (Hossain et al., 2007) in order to capture the time function in its entirety. Experimental results with artificial nanomaterials suggest that a wide range of variation is expected. The key is to make best use of the variability. Figure 6.21 shows how friction coefficient can vary with viscosity. It becomes more complex when viscosity is a function of time. Viscosity itself highlights the level of interactions with the environment. For instance, for the same viscosity, natural material will improve the environmental health while artificial material will degrade it. The pores in mud-rocks are in nanoscale. For petroleum reservoirs, the pore size distribution contains most, if not all, nanoscale pores. Therefore, the flow of the reservoir fluids is surely somehow affected by the nano-structure, as the fluid flow behaviour through nanopores are surprisingly different than that of through macro scale. For example, Majumder et al (2005) showed that fluid flow through carbon nanotubes (CNTs) is four to five orders of magnitude faster than predicted by conventional fluid flow theory. Therefore, to fully understand the reservoir mechanism we need to know

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Coefficient of friction

10

10–2

10–3

10–4 101

102

103 104 105 Speed X viscosity

106

Figure 6.21 Lubricity of various artificial fluids as a function of viscosity (From Islam and Mokhatab, 2018).

the behaviour of reservoir rock-fluid properties in nano-scale too. This knowledge will help to recover more from the reservoirs. Even, at least modification to the existing theories, if not new theories, is required to incorporate knowledge acquired from nanoscience. Hochelle (2002) pointed out the remarkable impact of particle size on particle behaviour and tried to explain it in terms of property-size dependence on electronic structure of matter. The interest of using nanoparticles in membrane structures mainly focuses on their assumed beneficial effect on fluxes and fouling resistance. Kim and Van der Bruggen (2010) reviewed potential applications of nanoparticles-enhanced membranes in general. They conclude that the use of nanoparticles in the development of low-fouling membranes allows for a high degree of control over membrane characteristics as well as the ability to produce ceramic membranes in the nanofiltration membrane range. A wide range of nanoparticle types are used, such as TiO2 (Sotto et al., 2011; Soroko and Livingston, 2009; Li et al., 2009; Yang et al., 2007). Nanomaterials such as ZnO (Balta et al., 2012), Al2O3 (Yan et al., 2009; Yu et al., 2012), Au (Vanherck et al., 2011), zero-valent iron (ZVI) (Xu and Bhattacharyya, 2005), Pd (Tanaka et al., 2006) have been looked at. It would be interesting to use some of these materials in their natural state – the state that offers unconditional sustainability and environmental integrity. These membranes can be used for water treatment, oil-water separation and gas-gas separation. The gas-gas separation can be enhanced by impregnating with nanoliquids. According to Pendergast and Hoek (2011), the most promising functionalities in water treatment applications include zeolitic and catalytic nanoparticle-coated ceramic membranes, hybrid inorganic-organic nanocomposite membranes, and bioinspired membranes such as hybrid protein-polymer biomimetic membranes, aligned nanotube membranes, and isoporous block copolymer membranes. Surface diffusion is a ubiquitous phenomenon playing a highly important role both in natural and technological processes (Naumovets, 2005). Current refining processes use lots of toxic materials that create environmental havoc. Nanostructure may provide better insight of filtering. That, in turn, will provide us a way to use filters (natural

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or nano-engineered) in refining without or minimal use of toxic material. This knowledge will benefit other industrial process as well. New kind of catalysts will open new horizon too. For example, although gold does not behave as a catalyst in bulk form, nanoparticles of gold or other transition metals may be used as a substitute for platinum, where platinum is one of the most used catalyst in hydrocarbon reaction (Guczi, 2005). More recently, Shiju and Guliants (2009) reviewed progresses made in catalysts that use nanostructures. Noble metal nanoparticles such as Pt, Pd, Rh, Au and their alloys with other metals have been extensively employed to catalyze a wide range of dehydrogenation, hydrogenation, and selective oxidation reactions of organic molecules. Novel approaches are still required to synthesize and characterize stable gold and other metal nanoparticles with tightly controlled sizes to further advance the knowledge of their unique size-dependent catalytic behavior. The bulk mixed metal oxides of vanadium, molybdenum, and other transition metals, such as the M1 phase for propane ammoxidation to acrylonitrile, have shown great promise as highly active and selective oxidation catalysts. However, fundamental understanding of surface molecular structure–reactivity relationships of these systems remains highly limited.

6.5

Zeolite as a Refining Catalyst

Even before the detailed composition of naturally occurring zeolite is known, the natural state of such a powerful agent should confirm that its usage is not harmful to the environment. Similar properties have been identified in limestone as well as in vegetable oils, which can be used as a solvent for removing sulfur compounds. The use of zeolite or similar naturally occurring separation materials would be benign to the environment and would also eliminate the additional cost of cobalt, nickel, and molybdenum processing, bringing in double dividend to the petroleum processing industry. Zeolites can be defined as crystalline, porous aluminosilicates in which the primary building blocks are TO4 tetrahedra having a Si4+ or Al3+ cation (T atoms) at the center and four oxygen atoms at the corners (Primo and Garcia, 2014). Each corner is shared by two TO4 units forming a tridimensional framework defining cavities, channels and empty spaces generally denoted as ‘‘micropores’’. This porosity defined by the rigid crystal lattice is open to the exterior of the solid crystallite allowing the mass transfer from the exterior to the interior of the zeolite particle and the intracrystalline diffusion of molecules smaller than the micropore dimensions. Zeolite has long been known for its very high internal surface area that contributes to water absorption. The microstructure of zeolite is such that it acts like a molecular sieve, providing the site for perfect ion exchange (Breck, 1973). Zeolites have a porous structure that can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+ and others. These positive ions are rather loosely held and can readily be exchanged for others in a contact solution. The advantage of this structure is these chemicals can be released easily thereby activating their role as a catalyst. As these cations are natural, they do not pose any negative impact on the refining process. Some of the more common mineral zeolites are analcime (NaAlSi2O6·H2O), chabazite ((Ca,K2,Na2)2[Al2Si4O12]2·12H2O), clinoptilolite ((Na,K,Ca)2-3Al3(Al,Si)2Si13O36·12H2O), heulandite ((Ca,Na)2-3Al3(Al,Si)2Si13O36·12 H2),

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Control: During synthesis after synthesis

Organic or inorganic exchangeable AcidZeolite H+

Variable thermally reversible

Mx/nx+ [AIxSiyO2(x+y)]x– zH20

y/x between 1 and infinite number of countercations hydrophilicity

Figure 6.22 Chemical composition of zeolites and possibilities for its control. Key parameters are the nature of charge-balancing cations and the Si/Al ratio.

natrolite (Na2Al2Si3O10·2H2O), phillipsite ((Ca,Na2,K2)3Al6Si10O32·12H2O), and stilbite (NaCa4(Si27Al9)O72·28(H2O)). An example of the mineral formula of a zeolite is: Na2Al2Si3O10·2H2O, the formula for natrolite. These cation-exchanged zeolites possess different acidity – a quality that dictates its effectiveness and applicability as a catalyst. The key parameter that controls many properties of the zeolites having a large influence on their catalytic activity is their aluminum content – as measured by the number of aluminum atom for each silica atom. Zeolites can be classified depending on the pore size as small, medium and large pore size zeolites when the openings of the micropores are constituted by rings of eight, ten or twelve oxygen atoms. Figure 6.22 summarizes the chemical composition of a zeolite and the properties that derive from it. Due to the different charge of Al3+ and Si4+, the TO4 tetrahedra can have a net negative charge (AlO4) or can be neutral (SiO4). The consequence of the presence of Al3+ in framework positions is the appearance of an equivalent number of negative charges in the framework that require the presence of charge-balancing cations to ensure the electroneutrality of the solid. These chargebalancing cations occupy the micropore space and because they are not grafted into the framework and are bonded to the lattice by Coulombic forces, they can be totally or partially exchanged by different cations. In fact, one of the main applications of zeolites is in detergent formulations as water softener to remove Ca2+ ions from hard waters by ion exchange with Na+. These compensating cations can exist naturally or can be introduced during the synthesis of zeolites and can be either inorganic or organic. One particular case that is of considerable importance for the use of zeolites as catalysts in refining is the case in which the charge compensating cation is formally a proton. In this case, zeolites are called ‘‘solid acids’’ and due to the microporosity these internal protons can act as Brönsted centers in heterogeneous catalysis. Although Si4+ and Al3+ ions have very similar ionic radius and fit nicely in the center of TO4 tetrahedra, the presence of Al3+ introduces a relative lattice instability due to the somewhat larger ionic radius of Al3+ with respect to Si4+, the charge unbalance and low coordination number around Al3+. Thus, there is a tendency of Al3+ to migrate outside the lattice forming octahedrally coordinated Al species that are generally denoted as extra framework aluminium (EFAL). High Al3+ content makes the zeolites very prone to

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AIO+ H+ δ–

O

O

–

O

Si

δ

O–

O

O AI O

Figure 6.23 Synergy between Lewis acid sites (AlO+) and Brönsted OH site leading to an increase in acid strength.

develop EFAL, generating Lewis acid sites. The Brönsted acidity of a zeolite is also influenced by the presence of Lewis acidity. This synergy between EFAL and Brönsted acid sites resulting in an increase of the acid strength is similar to that found in liquid acids in which the combination of Brönsted and Lewis acids can render superacids with remarkably enhanced strength. Besides the composition, the acidity of the zeolites also depends on their structure. It has been found that for similar chemical composition, the strength of acid sites in medium pore size zeolites is higher than that found in large pore size zeolites (Corma et al., 1994; Huang et al., 2009). Acidity is an extremely important property in catalysis by zeolites for refining since many of the processes are proteolytic C–C bond cleavages or involve the generation of carbocations. The most widely accepted mechanism for hydrocarbon cracking involves protonation of single C–C or C–H bonds of alkanes and the generation of carbocations that subsequently undergo b-scission forming a smaller carbocation and an alkene. One point that has been controversial and of wide interest is to determine whether or not the acid sites of zeolites can be considered as superacidic and what is the maximum acid strength that can be achieved in zeolites. However, the most important point in this regard is the fact that if the zeolite is naturally occurring, it will make the subsequent reactions sustainable and if it is synthetic, the opposite would take place. As stated earlier, zeolite microstructure acts as a sieve. One of the main problems in porous solids in which the reaction takes place predominantly inside the pores is intracrystalline diffusion. The pores defined by the framework are open to the external surface allowing the mass transfer from the exterior toward the interior of the particle, provided that the size of the molecule is smaller than the dimensions of the pores. Zeolites are microporous materials (pore size of 2 nm). Zeolites can be classified according to the pore size. In ‘‘small pore’’ zeolites, having apertures defined by eight oxygen atoms, only small gas molecules can access the interior. In the case of ‘‘medium pore’’ zeolites (10-membered ring apertures), benzene, toluene and para-substituted aromatics can enter through the pores. The range of molecules that can diffuse in ‘‘large pore’’ zeolites having 12 membered rings is much larger, since the dimensions of these pores are typically around 0.7 nm. Besides pore dimension, the geometry of the pore system is crucial to determine the intracrystalline diffusion coefficient of molecules. Diffusion in monodirectional zeolites, which is typically a synthetic product, having parallel channels, such as mordenite, is generally more difficult than in bi- and tridirectional zeolites. In the case of monodirectional pores, molecules diffusing in the

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No diffusion

Diffusion Acid site

Figure 6.24 Schematic of the shape selectivity for the formation of p-xylene in toluene disproportionation.

channel have to move one after the other following the same direction and can be easily blocked by a single molecule. In contrast, diffusion in open tridirectional zeolites, such as faujasites X and Y, is easier, since the cavities can be accessed through four independent windows. Furthermore, monodirectional zeolites are prone to becoming deactivated by a small percentage of poisons blocking the entrance of the channels, while bi- and tri-directional zeolites can tolerate a larger percentage of poisons before undergoing deactivation. In this process natural zeolites have a distinct superiority over synthetic ones. In external features, both natural and synthetic zeolitic crystalline aluminosilicates are useful as catalysts and adsorbents. These aluminosilicates have distinct crystal structures which are demonstrated by X-ray diffraction. The crystal structure defines cavities and pores which are characteristic of the different species. The adsorptive and catalytic properties of each crystalline aluminosilicate are determined in part by the dimensions of its pores and cavities. Thus, the utility of a particular zeolite in a particular application depends at least partly on its crystal structure. Because of their unique molecular sieving characteristics, as well as their catalytic properties, crystalline aluminosilicates are especially useful in such applications as gas drying and separation and hydrocarbon conversion. Although many different crystalline aluminosilicates and silicates have been disclosed, there is a continuing need for “new” zeolites and silicates with desirable properties for gas separation and drying, hydrocarbon and chemical conversions, and other applications. The tendency in the industry has been to produce synthetic form, custom designed for particular applications. Crystalline aluminosilicates are usually prepared from aqueous reaction mixtures containing alkali or alkaline earth metal oxides, silica, and alumina. On the other hand, "nitrogenous zeolites" have been prepared from reaction mixtures containing an organic templating agent, usually a nitrogen-containing organic cation. By varying the synthesis conditions and the composition of the reaction mixture, different zeolites can be formed using the same templating agent. Use of N,N,N-trimethyl cyclopentylammonium iodide in the preparation of Zeolite SSZ-15 molecular sieve is invented through a series of patents. These patents rely on very toxic processes that retain the external features of Zeolites while replacing naturally occurring chemicals with artificially produced ones. Often other chemicals are blended in so that the resulting zeolite can have specialized qualities. For instance, the use of aluminum oxide, gallium oxide, iron oxide, boron oxide, silicon,

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Isobutone +butenes Alkylate CH3OR

Reformate

Gasoline pool

Light straight run

Isomerization Hydrocracking FCC unit RESIDS Vacuum gasoil

Figure 6.25 Streams contributing to gasoline pools.

germanium and mixtures thereof has gained widespread applications in the manufacturing industry. Concerning reactivity, the pore size can be responsible for the control of the product distribution. The term ‘‘shape selectivity’’ has been coined to denote those cases using zeolites or other microporous solids as catalysts in which the reason why a product is predominantly formed is exclusively the molecular shape and dimensions. For naturally occurring zeolite, this is not an option and one cannot custom design to fit a particular application. As can be seen from Figure 6.24, when carrying out the reaction inside the medium pore zeolite ZSM-5 in which the pore dimension only allows diffusion of p-xylene, m- or p-xylene formed in the crossings of the channel system cannot diffuse out of the crystals and become entrapped until they rearrange to the p-xylene that is the only one that can go out of the pores.

6.5.1

Gasoline Pool

The automotive industry has been using the light naphtha fraction of the crude oil marketing it as gasoline (‘‘light straight run’’ gasoline). The quality of the gasoline is quantitatively measured by the octane number, the higher the octane number, the higher the ability of the gasoline to stand high pressure and temperature. In this scale the performance of n-heptane and 2,4,4- trimethylpentane has been arbitrarily assigned 0 and 100. In general, the octane number of a pure hydrocarbon increases with the degree of branching, presence of cycles or for aromatic compounds. As the demand for gasoline increased as well as the need for octane numbers higher than those characteristic of light straight run gasoline (about 70), it was necessary to blend various streams of the refinery in a pool to meet the requirements of gasoline production and quality. Figure 6.25 presents the composition of a representative gasoline pool indicating the origin of the individual components.

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6.5.2 Linear Paraffin Isomerization One of the components of the gasoline pool is the naphtha fraction. Light straight run naphtha is constituted, mainly, by linear alkanes accompanied by a small percentage of aromatics, and has typically an octane number about 74 or below, insufficient to be added directly to the gasoline pool. This light straight run naphtha should be, therefore, submitted to isomerization, a process that is based on the use of acid zeolites as catalysts. The octane number of linear alkanes decreases as the number of carbons increases, and therefore, these long-chain linear compounds present in this fraction (mainly C7 and C8) should be preferentially isomerized in the process. At a given temperature the equilibrium distribution among isomers limits the extent in which linear paraffins are converted into branched isomers. The general tendency is that isomerization is disfavored as the temperature increases in the range from 0 to 600 C. Therefore, from the thermodynamic point of view, it is convenient to work at the lowest possible temperature. Thus, the role of the catalyst is to increase the reaction rate allowing the reaction to reach equilibrium at the lowest possible temperature. Isomerization of linear alkanes requires acidity combined with dehydrogenation/hydrogenation capability. In this particular application, both the natural state of zeolite as well as the form of energy related to the heating will dictate if the products will be environmentally benign or not.

6.5.3 Isobutane–Butene Alkylation About 12% of the blend in the gasoline pool may come from butene alkylation. The acid catalyzed mechanism for isobutane–butene alkylation is shown in Figure 6.26. This stream has a high octane number, ideally 100, and is much valued since it does not contribute to the gasoline sulfur content, because isobutane and butene are free from this contaminant. Classical alkylation processes are based on the use of homogeneous liquid acids and particularly HF and H2SO4. From the catalytic point of view, the two main relevant properties of the liquid acids are their decay and isobutane solubility in the acid phase. Isobutane solubility is much higher in HF than in H2SO4. This allows reaching a higher concentration of isoalkane favoring hydrogen transfer steps to carbenium ions, reducing the carbocation lifetime and minimizing secondary reactions. These advantages exhibited by HF allow shorter contact times and operation at higher temperatures where the reaction rate is higher. In contrast, although the acid strength of H2SO4 is much higher, this acid presents also high viscosity and density unfavorable for the mixing with hydrocarbons, complicating significantly reactor design to ensure sufficient contact between the two phases. An additional problem with the use of H2SO4 is that the amount of acid lost in the products is much higher, requiring larger catalyst make up. Make up and regeneration are about 30% of the total operation cost in the case of H2SO4, while they represent only 5% for HF. The main problem of HF is, however, its large negative environmental impact that requires strict safety measures due to the high risk of accidental leakages and the fact that HF aerosol can stand as highly corrosive, persistent clouds over long periods of time. For this reason, there is no clear advantage in the use of HF as opposed to H2SO4 as an alkylation catalyst. One alternative to the use of liquid acids is the use of solid acids. Amorphous silica–alumina has been used as solid catalyst, but zeolites have the advantage of a higher activity,

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COKE

i-C16+ i-C5+, i-C6+, i-C7+ HT

i-C12+

C5–C7 Isomer.

Alkylat. t-C4+ + 2-C4=

HT TMP+

[2,2,3-TMP]+

TMP+t-C4+

sec-C4+ DIMER HT (i-C4)

+ n-C4= OLIGOMERS

DMH+

DMH + t-C4+

COKE

OLIGOMER.

Octenes

Figure 6.26 Simplified mechanism for isobutane–butene alkylation and competing unwanted processes. t-C4+: tert-butyl cation; 2-C4Q: isobutene; TMP: trimethylpentanes; sec-C4+ : sec-butyl cation; DMH: dimethylhexanes; HT: hydride transfer.

higher durability and lower deactivation. The activity of zeolites depends on the Si/Al ratio and on the crystal structure.

6.5.4

Fluid Catalytic Cracking (FCC)

FCC provides a surplus of high octane number gasoline by converting vacuum distillates, particularly vacuum gasoil, into gasoline. From the chemical point of view, several molecular transformations are concurrently taking place during FCC, including shortening of linear long alkanes, isomerization of linear into branched alkanes and dehydrogenation of cyclic olefins into aromatic naphthenes. Figure  6.27 shows the schematic of the process involved. Figure 6.28 shows the major reactions that take place during FCC (from Islam et al., 2010). The FCC catalyst contains an active component (10 to 50 wt%) dispersed on a solid matrix (between 50% and 90% of the total) providing physical and mechanical resistance and embedding the active component, and some additives that increase the tolerance of the catalyst against deactivation by poisoning (Figure 6.29). The active phase is generally a large pore zeolite, often accompanied with rare earth metals. In general, an increase in the percentage of rare earth metals leads in an increase in feed conversion accompanied by an undesirable decrease in the octane number of

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Longer paraffins

Shorter paraffins + Olefins Cracking

Shorter olefins

Cyclization Isomerization Olefins

Naphthenes Branched olefins

H transfer

H transfer

Branched paraffins

Paraffins

Cyclization

Coke

Condensation dehydrogenation Cracking Naphthenes

Olefins

Dehydrogenation

Cyclo-olefins

Isomerization

Dehydragenation

Aromatics

Naphthenes with different rings

Figure 6.27 Elementary processes taking place in FCC.

Rearrangement n-alkane

Strong acid site

Secondary carbocation

Tertiary carbocation β-scission

Olefin

Hydrogenation

Hydride transfer Different Rearrangement carbocation Methyl/alkyl hydride

Shorter chain isoalkane

β-scission Tertiary carbocation

Figure 6.28 Elementary steps assumed to take place in catalytic cracking on zeolites.

Acid zeolite

Binder

Additives

10–50 wt% Large pore Responsible for Activity

50–90 wt% Responsible for mechanical strength Typically Al2O3 or SiO2

Avoid negative effect of metals Aimed at increasing octane number

Figure 6.29 Components present in general formulations of a FCC catalyst.

the resulting gasoline. Also, framework dealumination results in an increase in the activity of the zeolite, particularly considering that zeolite Y has high Al content. Steam treatment is a convenient procedure to reduce framework Al, and that also increases mesoporosity of the crystallites due to the partial damage of the zeolite particles leading to the creation of mesopores above 6 nm, highly beneficial for the activity and stability of the zeolite by favoring intracrystalline diffusion of substrates and products reducing poisoning derived from long contact times of substrates and products with the acid sites.

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Parameters controlling catalytic activity of zeolites

Si/Al ratio Population and strength of acid sites

Steaming Creating EFAL controlling selectivity

Crystallite size Controlling diffusion increasing external surface area

Figure 6.30 Main parameters that influence the catalytic activity of zeolites in FCC formulations.

In addition, the composition (Si/Al ratio) is an important parameter that controls the activity and selectivity, which in general increase as the average crystal size decreases. Figure 6.30 summarizes the parameters that control the activity of zeolites as cracking catalysts. One problem of FCC catalysts is the tolerance to the presence of metals and particularly Ni and V. These and other metals can be present in high molecular weight organic compounds present in the FCC feed. Deposition of Ni on the catalyst favors the generation of coke on the catalyst due to its dehydrogenating capability. To minimize the influence of Ni, FCC catalysts contain additives, such as Sb that acts as a poison of Ni by forming Ni–Sb alloys, inactive to promote dehydrogenation. These catalysts can render the entire fluid stream toxic, thereby making the resulting oxides unacceptable by the ecosystem. Also, the effect of Ni can be neutralized by alumina present abundantly in the catalyst matrix by forming Ni aluminates that have much lower dehydrogenation activity. V also has some activity for hydrogen evolution and coke formation during the FCC process. However, the main problem caused by V is the formation of strong acids during regeneration of FCC catalyst that produce deterioration of the zeolite crystal structure reducing its service life. To minimize this effect of V, the use of more robust zeolites, generally those having low Na and Al content, as well as the presence of vanadium trapping compounds in the additives, generally basic solids such as CaO, Al2O3 or MgO, is recommended. However, this should not lead to the use of synthetic zeolite. The fraction of additives of FCC catalysts may also contain some components to effect NOx decomposition. Nitrogen is present in the FCC feed and about 50% of the N in the FCC feed becomes deposited on the catalyst as coke. During FCC catalyst regeneration by combustion of coke, part of the nitrogen evolves as N2, but the other part forms NOx that have to be decomposed to avoid their emission to the atmosphere. Another problem of the FCC stream is that this fraction contributes to a large extent to the total sulfur content present in gasoline and diesel. About 90% of the total sulfur content of the gasoline is due to the FCC contribution, coming mainly from the heaviest fractions. Typical sulfur-containing compounds in FCC gasoline are mercaptans, dialkylsulfides, thiophenes, alkylthiophenes and benzothiophene, while heavier aromatic sulfur components particularly dibenzothiophene and its alkyl derivatives are present in diesel. Legal regulations are constantly reducing the sulfur content of fuels

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R

S

R

60–80 ºC/ catalyst

O

Oxidant

S

Sulfur substrate

R

+ R

Sulfoxide

O R

S

O R

Sulfone

Higher boiling point Increased hydrophilicity

Figure 6.31 Desulfuration based on catalytic oxidation of sulfur compounds present in heavy gasoil fractions.

Alkanes

Shorter Alkanes

Alkanes

Cycloalkanes + H2

Cycloalkanes

Cyclohexanes

Cyclohexanes

Aromatics

Figure 6.32 Elementary reactions occurring simultaneously in the reforming of naphtha.

and achievement of such low S contents currently requires the combination of several technologies. The overall strategy to control the sulfur content in fuels includes the selection of crude oil and adequate fractionation of FCC gasoline to reduce the sulfur in the feed, but also post-treatment of FCC gasoline and diesel. Among FCC desulfuration post-treatments, one of the emerging technologies is the selective liquid-phase oxidation of thiophene and aromatic S compounds under mild conditions, using tert-butyl hydroperoxide or H2O2 as the oxidizing reagent. In this way, the sulfur atom becomes oxidized to sulfoxide or sulfone, increasing considerably water solubility and boiling point of the sulfur compounds, allowing their easier separation from the fuel, as shown in Figure 6.31. This catalytic oxidative desulfuration could lead to fuels with sulfur content below 10 ppm that will be the legal specification in the very near future. One promising catalyst for oxidative desulfuration is Beta zeolite containing Ti atoms, which can exist in natural state in certain zeolites.

6.5.5

Reforming

One of the most important processes in refining is the reforming of the heavy naphtha fraction into mixtures in which aromatic compounds and particularly benzene, toluene and xylenes are the predominant compounds. Chemically, the reforming corresponds to the chemical transformation of saturated acyclic and cyclic hydrocarbons into aromatic compounds by dehydrogenation without reducing substantially the number of carbons of the products with respect to the substrates. Figure 6.32 presents the elementary transformations that take place in reforming. These transformations include cyclization of acyclic compounds, isomerization of cyclic compounds into cyclohexene and dehydrogenation and aromatization. The main purpose of reforming is to obtain aromatics because these compounds exhibit octane numbers over 100 and following their addition into the gasoline pool they lead to a notable increase in the octane number of the resulting blend. A minor percentage

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Isomerisation

+

287

+

Isoalkanes

Figure 6.33 Co-processing of benzene in naphtha isomerization.

of reformate is used by the chemical industry to obtain pure benzene, toluene and xylenes and from them bulk chemicals, monomers and commodities, but this use represents around 10% of the total reforming capacity. Two processes related to the industrial use of reformate are toluene disproportionation and xylene isomerization. The composition of gasoline and transportation fuels have been evolving to comply with legal regulations, and one common trend in developed countries, together with providing gasoline with high octane number and the use of the three way catalysts to avoid the presence of unburned hydrocarbons in the flue emissions, has been to limit and reduce the percentage of benzene in gasoline. The regulations have targeted crude oil instead of targeting artificial chemicals that are used during the refining process. Among all the aromatic compounds, it is considered that benzene is the most toxic one and has a well proven carcinogenic effect. The source of this toxicity, however, is not aromatic compound itself, but rather the artificial heavy metal components that are used (Islam et al., 2015). Consequently, the tendency in the refinery to reduce the percentage of benzene in reformate by adjusting the operation conditions has missed the mark by targeting benzene from reformate to reprocess this chemical mainly with linear alkenes in the isomerization process. Figure 6.33 illustrates the use of reformate and the connection between reformate and linear isomerization of alkanes. Since according to the chemical transformation dehydrogenation with hydrogen evolution is the major individual process taking place in the reforming, acidity is not a requirement for the catalyst, which, in contrast, should have noble metals with high hydrogenation/dehydrogenation activity as the main active component. Thus, most of the commercial reforming catalysts are based on Pt supported on large surface area solids such as non-acidic zeolites or metal oxides. As we will see in latter sections, this Pt is a major source of carcinogenicity of the petroleum products.

6.5.6

Hydrocracking

One constant feature in refining is the need to convert efficiently less valuable, heavier fractions into mixtures of hydrocarbons of lesser number of carbons for their consumption as transportation fuels. For the conversion of heavier into lighter fractions, one of the processes that is performed on a large scale is the hydrocracking of heavy gasoil, vacuum gasoil and gasoil from coke into lighter compounds. To carry out this process hydrogen is required to minimize the formation of coke and carbonaceous residues on the catalyst and for this reason is termed ‘‘hydrocracking’’. Several elementary chemical transformations take place in the hydrocracking process, which are similar to those that

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Alkanes n-Alkanes

Hydrocracking

Isoalkanes + branched alkanes

Alkanes

Olefins + H2

Alkanes

Cycloalkanes + H2

Cycloalkanes

Aromatics + H2

Figure 6.34 Elementary steps occurring simultaneously during hydrocracking.

have been already commented for the cracking. These classes of individual reactions include shortening of the chain length of the paraffins in the feed, isomerization of the linear into branched alkanes, ring closure and hydrogenation/dehydrogenation of the C–C bond (Figure 6.34). There are two main general types of hydrocracking processes although each of them can be subjected to modifications depending on the needs of each refinery. One of these types is the single-stage hydrocracking in which the fractionating unit is located after the hydrocracker (Figure 6.35). In this type, it can be more than one hydrocracker in series and it could be also recycling or not of the unconverted feed. In the other case, the process is known as oncethrough, single-stage hydrocracking. The two-stage hydrocracking is characterized by having the main fractionating unit located between two hydrocrackers (Figure 6.35). Generally the first reactor is used to perform hydrotreatment of the feed to eliminate sulfur, nitrogen, oxygen and metals that could be present in the heavy gasoil fractions. In this first reactor, it could also be a light hydrocracking of the alkanes with formation of a certain percentage of lighter alkanes. Hydrocracking producing effective shortening of the average number of chain carbons takes place predominantly in the second hydrocracker. Hydrocracking requires bifunctional catalysts that are able to promote hydrogenation of olefins and cracking of alkanes. At the metal sites of the catalyst dehydrogenation of the n-paraffin gives rise to the formation of n-olefins that subsequently are protonated by the acid sites to form secondary carbenium ions that undergo spontaneous rearrangement to more stable tertiary carbenium ions. These tertiary carbenium ions can form cracked products through b-scission at the carbocation center or can give rise to an isoolefin that upon hydrogenation will form finally isomerized alkanes. Conventional catalysts for hydrocracking contain a metal that has as the capability to perform hydrogenation/dehydrogenation of unsaturated/saturated hydrocarbons. This metal component can be noble metals such as Pt, Pd or their alloys or can be even metal sulfides such as combinations of Ni, Mo, Ni–W and Co–Mo. Each of these metals is highly carcinogenic, when refined using conventional techniques. The hydrogenating capability is the highest for Pt and noble metals and is lower for metal sulfides that require higher percentages and higher temperatures in order to exhibit the desired activity, but are less prone to deactivation by sulfur. The order of hydrogenating performance of sulfides is Ni/W 4 Ni/Mo 4 Co/Mo. This metallic component is supported on an acid solid such as amorphous silica–alumina or preferably

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Fractionator Product gas

Single-stage reactor

Light naphtha

Single stage product

Fresh feed

Heavy naphtha Jet Fuel/ Kerosene Diesel

Fractionator

First-stage reactor Fresh feed

Product gas

Second-stage reactor

Light naphtha Heavy naphtha Jet Fuel/ Kerosene Diesel

First stage product

Second stage product

Figure 6.35 Diagram of a single-stage (top) and a two-stage (bottom) hydrocracking process.

zeolites. The acid strength of zeolites is higher than that of amorphous silica–alumina and, for this reason, zeolites require lower temperature to act as hydrocracking catalysts, typically, between 300 and 330 C. In contrast, amorphous silica–aluminas operate at temperatures between 340 and 390 C. This feature of zeolite is appealing from both economic and environmental perspectives, considering the fact that extra heating with conventional technique also adds to the accumulation of artificial chemicals in the final product. In addition, zeolites also exhibit a lower tendency to deactivate. Generally, amorphous silica–aluminas undergo a quick deactivation at short time on stream leaving a residual acidity that then decreases in activity more gradually for longer times on stream. Concerning the performance of zeolites in hydrocracking, it has been found that high acid strength leads to an increase in the percentage of naphtha formation in hydrocracking at the expense of middle distillates. Increasing the catalyst zeolite content and using strong acid zeolites increases feed conversion and naphtha selectivity. One problem of zeolites as catalysts is the impeded diffusion of large molecules

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through the internal pores. It has been found that the catalytic activity of Ni-containing Y zeolite decreases drastically along the alkane chain length, a parameter that correlates with the boiling point of the gasoil. If this Ni is made available from a natural source, e.g., ore, the sustainability of the process is assured. In contrast, amorphous silica–aluminas lacking porosity exhibit higher activity as the boiling point of the feed increases. This increase of feed conversion with the average chain length of the paraffin is a reflection of the intrinsic higher reactivity of long alkanes towards cracking and should also be observed for zeolites. In order to increase the activity of zeolites for high boiling point gasoil fractions, it is necessary to increase accessibility of the reactants to the acid sites. One way to enhance the population of accessible sites is to increase the zeolite external surface area. This increase of the external area can be achieved by reducing the average particle size of the zeolite crystallites from the micro to the nanometer length. This particular requirement has been exploited in order to custom design synthetic zeolites. However, synthetic zeolites are necessarily toxic to the environment and thereby pollute the petroleum products, generating oxidants that are no longer absorbed by the ecosystem. One example of how the dimensions and geometry of the pore system can control the product distribution that has considerable implications in refining is the cracking of heavy gas oil to gasoline with minimum amounts of gases using a bidirectional zeolite ITQ-36 zeolite. In this case, there are two intersecting channels with different dimensions. Gas oil molecules can diffuse through the larger channels accessing the acid sites, but not through the smaller channels. In the acid sites, gas oil molecules undergo cracking forming smaller molecules in the range of the gasoline fraction that diffuse away preferentially through the smaller channels without undergoing undesirable consecutive cracking. Figure 6.35 illustrates the process. An alternative to the use of microporous zeolites for hydrocracking of long-chain, high-boiling point hydrocarbons is the use of acidic mesoporous aluminosilicates. The synthesis in the 80 s of MCM-41 and related mesoporous silicas by Mobil researchers constituted a breakthrough in materials science, since these porous materials overcome the pore size limitation found for conventional large pore zeolites below 1 nm and constitute a logical expansion of porous aluminosilicates into the mesopore range. Each of these technologies, however, introduce yet another set of toxic material to the petroleum products. For instance, Ni–Mo support is common. It is true that if the time spent by a hydrocarbon inside the micropores of a zeolite increases, then the

Gasoil Acid site

Gasoline

Figure 6.36 Molecular traffic of gas oil through the 18 membered ring channels reaching acid sites and diffusion of gasoline through the smaller channels.

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probability to reduce the size of this hydrocarbon to C1–C4 products by consecutive cracking increases. A careful selection of the type of zeolites can make the process more efficient and the need to use synthetic catalysts is eliminated. It appears that the use of large pore zeolites favors the formation of preferred trimethylpentanes and that stronger acidity leads to 2,2,4-trimethylpentane that is the standard isoalkane with an octane number of 100. Large pore acid zeolites are preferred to minimize the loss of activity along the time on stream. Besides deactivation, it appears that the presence of some coke causing a partial decrease of the catalytic activity also affects the product distribution, reducing the percentage of C5–C7 with respect to C8–C9+, while dimerization of butenes may become the predominant process vs. isobutane alkylation. In isobutane alkylation, as in most of the refining processes using microporous solids, catalyst reactivation is the key issue.

6.6

Conclusions

Petroleum fluids are natural and there is no reason for them to emit toxic chemicals that are not absorbed by the ecosystem. This chapter reveals that the refining process itself introduces toxic chemicals. They are toxic because they are artificial or artificially refined. The result is the introduction of toxic components that pollute the air. By preference, these additives are attracted to CO2 and therefore the most damage is done to CO2 that become unabsorbable by the ecosystem. The emergence of nanotechnology has made the sustainability picture more dismal as now types of catalysts are more toxic than their previous counterparts. However, the quantum physics version of New Science fails to characterize these materials properly and therefore their long-term sustainability remains shrouded in mystery. The conventional theory of new science cannot track this form of environmental degradation, leading to largely ignoring the role of refining in producing greenhouse gases that are not assimilated by the ecosystem.

The Science of Climate Change. M. R. Islam, M. M. Khan. © 2019 Scrivener Publishing LLC. Published 2019 by John Wiley & Sons, Inc.

7 Scientific Characterization of Petroleum Fluids

7.1

Introduction

Scientific characterization involves ranking in terms of energy contents as well as environmental impact. Energy is known to be the cause of actions that are ubiquitous. Environmental impact is measured by the end result of the actions. Scientifically, every action and movement has a driver. Because every object is in motion, that driver is ubiquitous. New science has identified the sun as the ultimate energy source for the Earth. While this conclusion is true, the premise that defines energy in New science is false (Islam et al., 2014). Also false is the conclusion that states that environment degrades continuously, meaning at the end of every energy usage we end up having an environment that is worse off than what it was prior to the use. In this section, some of the scientific aspects of energy will be discussed, along with a discussion on the fate of this energy usage. The conventional notion of energy and the conservation of energy emerges from a discrete description of mass and energy. It assumes that mass exists independent of energy. In addition, the ‘ability to work’ is considered to be energy. The term ‘work’ refers to displacement of an object. Therefore, if an object is moved around and brought back to the original place, no work has been performed on it. By definition, the pathway or the time function being mooted from the description of the process, one has lost track of actual work performed. 293

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In addition, any ‘work’ is also related to ‘heat’ as a outcome. This notion dates back to Lord Kelvin’s notion of the universe that in his view was constantly degrading to the point of being “heat dead” eventually. This tactic removes any dissimilarity between sunlight and solar heat from electric light and electrical heating, for instance. It also conflates energy from food with energy from, say, gasoline. Finally, it removes the ability to identify true impact of an energy source. The problem is further confounded due to the fact that the environmental impact as a marker of the type of energy source is no longer applicable. For instance, at present Carbon footprint calculation is the standard way of measuring and reporting the environmental impact of a particular energy usage. Such measurement of environmental impact is disconnected from the notion that solar energy is not carbon intensive. Furthermore, carbon is the essence of life whereas environmental impact is a measure of ‘loss of life’, thus creating a paradox in terms of energy usage and environmental impact. This is often noticed when scientists struggle to make sense of the environmental impact of nuclear energy, electric energy or solar energy. The core of this cognition has been in measuring blocks. For instance, Btu (British thermal unit) is defined as the amount of heat energy required to increase the temperature of one pound of water by one degree Fahrenheit, at sea level. This definition assumes and imposes a strictly linear property of water. It also conceals the chemical property of water. The hyperbolic extension doesn’t stop here. This “Btu” is then transformed into energy from food in a strictly organic setting. Conventionally, electricity does the same as the sunlight and New science provides no basis for distinguishing electric energy from solar energy. This is one of numerous disconnections between organic (or natural) and mechanical (or artificial) systems. Interestingly, electricity and electromagnetism is based on the same Atomic principle as the one used for describing mass and conservation of mass. Along with the assumption of spherical rigid balls, it is also assumed that each atom as well as subatomic particles are identical. After the discovery of some 69 subatomic particles, it is now commonly known that none of these particles are symmetrical, uniform, spherical, or rigid. However, the assumption of uniformity and identical form still holds, even when it comes to the “fundamental particle”, most recently asserted as Higgs boson. While this notion won the Nobel prize in 2013, scientists still do not have an answer to the questions, “If all Higgs bosons are identical and if there is nothing smaller than Higgs boson, how are these particles moving? Does it mean then, there is certain space that is empty and devoid of anything?” This leads to the placement of Higgs boson as a static object. Static matters cannot impart energy transfer, thereby creating disconnection between mass and energy. Higgs bosons are also considered to be ‘uniformly distributed’ as well as ‘highly unstable’. They are contradictory properties by themselves. In essence, this narration is not anything different from the age old atomic theory that has long been discredited. Also spurious is the energy model of Maxwell that simply assumes unit of electricity as being rigid spherical objects that are also uniform. We have seen in Chapter 6 how quantum physics has introduced more opacity in name of science, while evaluating energy level of electrons. This treatment of electrons is not any different from the treatment of atoms centuries ago. However, New Science has managed to make even more outlandish assertions. One dogmatic assertion involves the notion that photons from a radioactive substance ‘feel’ the electromagnetic force

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as well as the weak force, but neutrinos only ‘feel’ the weak force. This assertion makes neutrinos less reactive while more mobile within a material system. In order to remedy such an obvious logical gaffe more assertions are made that are equally aphenomenal. As such, it is stated that when a photon is emitted, it is attracted by the electromagnetic force that is generated by the atoms around it. While photons are attracted, neutrinos are considered to be deflected by the same atomic body. The aphenomenal assumption there is that the nucleus and electron are all ubiquitous to the extent that photons would ‘hit’ them, whereas neutrinos wouldn’t, even though both types of particles are ‘mass-less’. Other anomalies and contradictions also exist in terms of energy description. For instance, light is considered to be a collection of photons with finite speed (speed of light being the maximum possible speed by virtue of the assumption of zero mass of photons). This assertion disconnects light from its source, thereby removing the possibility of light pollution or the ability to distinguish between sunlight and artificial light. It is also inferred that Higgs boson can travel through opaque objects at a speed close to the speed of light (some actually postulated it to be faster than light) whereas light can only travel through “transparent” bodies. This assertion doesn’t appear as an anomaly in conventional analysis because of the pre-existing assumption that light and mass are discrete from each other. The atomic model is used to describe mass and chemical reaction. This centuries-old model used to assume that atoms are the elemental particles and are solid, spherical, and rigid. At a later stage, such properties were invoked to neutron, proton and electrons. It was hypothesized that certain atoms have loosely attached electrons. An atom that loses electrons has more protons than electrons and is positively charged. An atom that gains electrons has more negative particles and is negatively charge. A “charged”atom is called an “ion.” Depending on the number of missing electrons, an ion would be more prone to ‘bonding’ with another element. This line of reasoning helped explain chemical reactions. However, the only way such reaction could be linked to energy is through ‘heat of reaction’. Typically, this analysis satisfied the need of engineers, whose principal focus was heat. However, this disconnected ‘light’ in general and artificial light in particular from being connected to chemical change. This remains a source of inconsistency in New science. In terms, energy generation through radiation, the concept of ‘unstable isotope’ was introduced. The word ‘isotope’ is defined as an atom that has an unusual number of neutrons. It is called stable isotope when the nucleon is not prone to breaking down. There are only a few stable isotopes recognized today. When an isotope is prone to breaking down spontaneously, it is called ‘unstable isotope’. It is hypothesized that when unstable isotopes break down into new isotopes, they usually emit alpha, beta, or gamma radiation. The term ‘radioactivity’ is synonymous with the emission of this radiation. This notion has been in existence since the early work of French physicist Henri Becquerel, who observed potassium-uranyl sulfate crystals on a film and concluded that the sun emits X-rays. Becquerel also found that all compounds of uranium and pure uranium behaved the same way. They all emitted what seemed to be X-rays, yet they did not need to be excited first with light or an electron beam. The uranium and its compounds could ionize gases, which permitted the gases to conduct an electric current.

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The early work of Becquerel was further advanced by physicists Marie SklodowskaCurie of Poland and Pierre Curie of France who conducted a series of experiments to determine which other elements and compounds emitted this mysterious radiation. They found that the element thorium behaved much like uranium. But the radiation from pitchblende, a uranium ore, was far greater than it should have been, considering the known percentage of its uranium content. They therefore suspected that the pitchblende contained some other previously undiscovered element. Beginning with a large sample of pitchblende, they employed a series of chemical separation techniques, always discarding the separated fraction, which did not emit the disproportionately high radiation. Eventually, they isolated a new radioactive element, which they called polonium in honor of Marie's home country. This was the beginning of ‘purification for nuclear energy’. Four years later, starting with 100 kg of pitchblende, and using similar techniques, they were able to isolate 0.1 g of an even more intensely radioactive substance, which they called radium. After Pierre's accidental traffic death in 1906, Marie was appointed in his place as a professor of physics at the Sorbonne in Paris. She was awarded the Nobel Prize in 1911 for her discovery of polonium and radium. She died in 1934 of leukemia, which was probably caused by overexposure to the radiation involved in her research. However, this connection was not made and until now, the failure to change the premise that separated mass from energy has made it impossible for scientists to find the root of energy pollution as well as cancer. In the meantime, Ernest Rutherford, 1st Baron Rutherford of Nelson, a New Zealand-born British physicist became prominent for his work on radiation, which eventually earned him the title “father of nuclear physics”. His research focus was to measure the "penetrating power" of uranium's mysterious radiation. He discovered that the radiation was made up of three different types of “rays” with very different powers of penetration. The intensity of what he called alpha (α) rays, could be reduced to one-half as much by a very thin (0.005 mm) piece of aluminum foil. A similarly thin piece would cut the intensity by half again as much, to a total intensity of one-fourth; and a third piece would cut the total to one-eighth, etc. Beta (β) ray intensity could be reduced to one-half as much by a 0.5 mm aluminum sheet; and again, each additional 0.5 mm sheet would cut the prevailing amount by one-half. In general, the thickness of a specific material required to reduce a certain type of radiation by one-half is called a half-thickness. The half-thickness for gamma (γ) the third type of uranium radiation was found to be 80 mm of aluminum. Rutherford sealed a thin-walled vial of alpha-emitting radon gas inside a second glass tube. All the air was pumped out of the second outer tube before sealing. Rutherford attempted to ionize any possible remaining gas in the outer tube, and at first he was unsuccessful. However, as time passed, gas accumulated in the second outer tube. This was the beginning of light emission through excitation of ions. Today, this technique is promoted as the most effective lighting of buildings. They are dubbed as ‘energy savers’ and many countries are considering making them mandatory. This ‘discovery’ of Rutherford became useful in explaining artificial electricity generation. It was postulated that electrons can be made to move from one atom to another, as long as they were kept in a state of instability. When those electrons move

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between the atoms, a current of electricity is created. The electrons move from one atom to another in a “flow.” One electron is attached and another electron is lost. Subsequent research in ‘creating’ energy involves various ways to move electrons off of atoms. In another word, creating instability or imbalance became the only means to generate energy. The principal task becomes that of creating a system that generates large numbers of positive atoms and free negative electrons. Since positive atoms have affinity toward negative electrons so they can be balanced, they have a strong attraction for the electrons. The electrons also has an affinity toward the positive atom so there is an overall balance. This principle is the basis for electricity generation. Even the briefest examination of the narrowness in the focus of the approach taken by New science to the phenomenon of radiation—whether artificially induced or naturally occurring—uncovers interesting phenomena. Consider carbon. Carbon is one of the most persistent elements to be found in the atmosphere and soils of the Earth. Over time—especially geological periods of time—ordinary C-C bonds and especially C-C double bonds seem to have proven particularly resistant to the effects of radiation. This is not the case for most other elements connected chemically to such carbon bonds. Most elements apart from the noble gases seem vulnerable to radiation effects at the molecular level. This particular feature of carbon bonding seems rife with many actual and potential consequences. Nevertheless, partly because there seems to be no consistent explanation afforded by the conventional treatment by New Science applied to sorting out this question, many geological transformations in the Earth remain incompletely or incorrectly accounted for. The most important ‘victim’ of this tradition has been the impact assessment, which is done in terms of carbon footprint. Yet, in the waste stream the most important natural element happens to be carbon. Instead of looking into what makes these carbon elements unacceptable by the ecosystem, the focus has been to ‘blame’ carbon. Before one can examine the science of energy that includes light and heat, one must review the existing theories and analyze their shortcomings. This will follow with proper characterization of energy with fundamentally sound premises.

7.2

Organic and Mechanical Frequencies

Considered in its most general aspect, the universe comprising all phenomena can be comprehended as comprising two broad categories: the mechanical and the organic. Many mechanical phenomena can be found within the organic category. Certain aspects of many organically based phenomena can be defined or accounted for entirely within the category that comprises all forms of mechanism. Frequency, and its measurement, often appears to bridge this mechanical-organic divide. Organically-based frequencies have an operating range which itself varies, e.g., the length of the lunar year. On the one hand, purely mechanical frequencies also have an operating range, and this range can be set or otherwise manipulated up to a point, e.g., the resonant frequency at which a bridge structure may collapse in a sustained high wind. On the other hand, although organically based frequencies can be detected and measured, there is usually little or

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nothing, beyond a very definite window, that must be determined by trial-and-error, that can be done to manipulate such frequencies. Since Galileo’s brilliant and successful deployment of an elaborate water-clock as an organic-frequency device for measuring with some precision the differential rates of descent to earth of freely falling masses of different weights, all kinds of apparently natural clocks have been deployed to calibrate many things. This includes even universal standards of the metric system, e.g., the cesium atom clock at a Paris laboratory used for setting the standard length of the meter. Problems arise when such frequency-based devices are treated as the generator of values for a variable that is treated as being independent in the sense that we take Newton’s fictional time-variable t to be varying “independently” of whatever phenomenon it is supposed to measuring/calibrating/counting. Outside of a tiny instantaneous range, e.g., the period in which Δt approaches 0, naturally sourced frequencies cannot be assumed to be independent in that way. This is a false assumption whose uncritical acceptance vitiates much of the eventual output of the measuring/calibration effort. Such a problem arises the moment one makes the phenomenal assumption that frequency is fixed. This is the idea behind the unit of 'second' for time (solar orbit to cesium radiation frequency). New science fixed the frequency (it's like fixing speed of light), then back calculated time. No wonder, later on, time was made into a function of perception (relativity) thereby making the unique functionality schizophrenic. Not only is it the case that “such a problem arises the moment you make the phenomenal assumption that frequency is fixed.” Even if you allow that it is not fixed and undergoes changes in value, i.e., that its frequency is not necessarily fixed, this problem persists if the subtler but still toxic assumption is accepted that the rate at which the variable t changes — Δt — is constant in some “continuous” interval over which the derivative df(t)/dt may be taken. Here is where we uncover the truly toxic power of Newton’s Laws of Motion over conscience-based consciousness. That is when they invoke 'known' function, which itself is aphenomenal. The only function that is valid is with infinite order of periodicity (this is beyond chaotic).

7.3

Redefining Radiation and Energy

All currently available fundamental definitions in New science emerge from Newton’s laws. We will now review the conventional definitions and present thereafter the scientific definition that emerges from the above section.

7.3.1

Radiation

New Science considers radiation as emission of energy from a mass. It can be considered as electromagnetic waves or as moving subatomic particles, especially high-energy particles that cause ionization. A non-scientific statement involves characterizing radiation related to alpha particles (α) that are stopped by a sheet of paper, while beta particles (β) are stopped by an aluminum plate. It considers Gamma radiation (γ) which is damped when it penetrates lead.

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In the modern age, the word ‘radiation’ is synonymous with safety issues and rarely people see it as a necessarily ubiquitous and natural phenomenon. As such, the international symbol for types and levels of radiation that are unsafe for unshielded humans (Podgorsak, 2010). However, radiation in general exists throughout nature and is integral component of any matter. New Science characterizes radiation in following categories: – electromagnetic radiation, such as radio waves, microwaves, infrared, visible light, ultraviolet, x-rays, and gamma radiation (γ); – particle radiation, such as alpha radiation (α); – beta radiation (β); – and neutron radiation (particles of non-zero rest energy); – acoustic radiation, such as ultrasound, sound, and seismic waves; – gravitational radiation, radiation that takes the form of gravitational waves, or ripples in the curvature of spacetime. Until now, radiation is often categorized as either ionizing or non-ionizing depending on the energy of the radiated particles. The ionization phenomenon itself is not well defined and depends on the long-discredited Atomic theory. In practical terms, this characterization has helped define safety limits because beyond ionization energy, any radiation becomes harmful to living organisms. A popular source of ionizing radiation is radioactive materials that emit α, β, or γ radiation, consisting of helium nuclei, electrons or positrons, and photons, respectively. The hypothesis here is that only certain electrons will radiate and that the radiation is limited to electron movements. A different level of radiation alert is triggered when sources that emit X-rays are present. Finally, cosmic rays are recognized as high-speed particles, namely electrons or atomic nuclei. Gamma rays, X-rays and the higher energy range of ultraviolet light constitute the ‘ionizing’ part of the electromagnetic spectrum. The word "ionize" refers to the breaking of one or more electrons away from an atom, an action that requires the relatively high energies that these electromagnetic waves supply. It is assumed that the non-ionizing lower energies of the lower ultraviolet spectrum cannot ionize atoms, but can disrupt the inter-atomic bonds which form molecules, thereby breaking down molecules rather than atoms. These descriptions conform with the Big Bang theory and the assumption of Dark matter and Dark energy (Figure 7.1). Although it has been repeated assured that knowledge has continuously evolved from suspicion to actualization, none of these theories have scientific or even logical basis behind them. These numbers, including the radiation percentage of 0.01 is random and without logical basis. The above characterization of radiation is not scientific. An accurate description of radiation is the movement of subatomic particles caused by friction. It emerges from the fact that every particle is in motion and there is continuity everywhere. Any object is continuously emitting subatomic particles and consequently mixing with the environment. As a result, there is no isolation in nature and no matter how small an insult to environment is, its impact will be propagated.

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The Science of Climate Change Visible matter (stars 0.4%, gas 3.6%) 4% Dark matter (suspected since 1930s known since 1971s)

26%

70% Dark energy (suspected since 1980s known since 1998)

Also: radiation (0.01%)

Dark matter 25%

Dark energy 69%

Neutrinos (0.1%) Photons (0.01%) Black holes (0.005%)

Figure 7.1 New Science description of the ‘known universe’.(data from Spergel, 2015).

Figure 7.2 Depiction of matter with the galaxy model.

Islam (2014) introduced the so-called galaxy model in which subatomic particles are presumed to move in a fashion similar movement of the entire galaxy. Figure 7.2 shows this depiction. The phenomenon of radiation is best explained through the movement of a galactic system (top right inset picture) that has an axial velocity (in direction of x) as well as an angular velocity (in direction of θ). This depiction explains the transition from energy to mass and vice versa, as it does not distinguish between light particles and subatomic particles. This theory considers that radiation is continuous as evident

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from the inset picture. As long as the entire system is moving, there would be continuous exchange of locations for particles. Recall that there is no empty space in nature, subsequently, particle exchange is the only means of keeping all particles moving is through exchange in which smaller particles constantly navigate through larger particles. The word ‘particle’ here applies to smallest particle possible going all the way to photons – the so called ‘mass-less’ unit of light. The important feature of this narration of subatomic particles is that natural and artificial materials have different natural frequencies. So, whenever artificial matter comes in contact with natural materials, collision pathways evolve, instead of synergistic pathways. This increases the rate of mixing or what can be properly described as pollution. This is the mechanism that can explain why anytime unnatural chemicals are used, it results in pollution of a vast amount of natural media. If sunlight represents the original and the most beneficial energy source, any natural process emerging from sunlight will become beneficial. Let us consider a forest fire. It comes from a flame that trees or vegetation as the most important ingredient. All vegetation are indeed a product of natural processing of sunlight, air, water, and carbon components. When a flame is visible, oxidation of wood is rapid. As oxidation takes place, movement of each particle within the system is greatly enhanced, creating a sharp increase in natural frequencies of every particle. For instance, a solid can burn into gases unleashing natural frequency change for each particle. In practical term, it means if an unnatural heating source is used, the rate of pollution will skyrocket. Yet, New science considers heating as just heating without considering the source of heating. For instance, water boiled in a microwave is deemed the same as water boiled with open wood fire. Scientifically, they should be different in terms of follow up reactions with the media, but New Science is completely incapable of making any distinction. figure 7.9 shows how any natural flame will have a smooth spectrum as shown in the spectrum of the sunlight. This spectrum, in essence, sets the standard for useful/beneficial light/energy. Figure 7.3 also indicates that photon emission is similar to any other radiation from a body of mass. This emission within the visible wavelengths is related to the existence of a flame. Even though a flame is typical of visible light emission, most recent theories indicate the presence of continuous emission throughout the entire spectrum. As a flame burns, the characteristic features of each particle changes drastically. Figure 7.3 shows how dust specks (similar to pulverized graphite) present an optimum case in terms of stability. This state is typical of a solid state. This state represents the most stable as well as most non-reactive or conservative state of matter. At subatomic level, a reversal in characteristic vs. particle size trend line takes place and the speed increases as the particle size becomes smaller. Such transition from matter to energy (light) can explain the existence of a flame. In addition, this treatment of matter and energy enables one to track the source of light pollution. The onset of flame is invariably associated with a temperature rise, which in turn triggers vigorous changes in particles, leading to the formation of different structures that are similar to the galaxy in mega scale. Because of the change in characteristic speed due to the onset of a flame that invariably follow changes in temperature, heat being the result of particle motion that triggers radiation. Such connection of radiation with particle movement and heat of reaction is new (Islam et al., 2014a). The rate of emission is a strong function of

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The Science of Climate Change Number of particles

Proton Higgs Boson quark electron proton dust specks boulders moons

planets Sun

Galaxy

Particle size

Figure 7.3 Number of particles vs. particle size (not to scale, modified from Khan and Islam, 2012).

Characteristics speed

Vapor

Liquid Solid Physical state of material

Figure 7.4 Characteristic speed (or frequency) can act as the unique function that defines the physical state of matter.

temperature and is responsible for changing color of the flame. As stated earlier, radiation takes place in all values of spectrum. Overall, temperature represents level of subatomic particle activities. Any rise in temperature increases movement of all particles of the system. For certain systems, this would suffice to trigger a chain reaction, while for others this temperature rise would simply facilitate dispersion of the mass. In terms of phase change, Figure 7.4 shows how any change in temperature can trigger phase change by altering the characteristic speed of a collection of particles. At this point, it is worth revising characteristic orbital speed for various ‘particle’ sizes. In Figure 7.5, a dust speck represents reversal of speed vs. size trend. For so-called subatomic particles, speed increases as the size decreases. The Higgs-boson is assigned a smaller value than quark but larger value than photon. This is done deliberately in order to float the notion that fundamental particle and finality in determining such

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Characteristics speed

Photon Galaxy Higgs boson Sun

Quark Electron

Earth

Proton Nucleus

Moon

Dust speck

Particle size

Figure 7.5 Orbital speed vs size (not to scale) (From Islam, 2014).

particle is a spurious concept. Note that the actual speed in absolute sense is infinity for smallest particle. It is because each element has a speed in every dimension. This dimensionality is not restricted to Cartesian coordinate. As the number of dimension goes up, so does the absolute speed, approaching infinity while projected in absolute scale. The characteristic speed also increases as the size of the entity goes down. For infinitely small entity, the speed would approach infinity. This analysis shows how both small and large scales are in harmony with infinitude, associated with ‘void’. Similar effects are expected with pressure. Photosynthesis offers an example of a natural effect of pressure on organic reactions. Beer and Waisel (1982) studied photosynthetic responses to light and pressure (up to 4 atm) for two seagrass species abundant in the Gulf of Eilat (Red Sea). In Halodule uninervis (Forssk.) Aschers. pressure decreased net photosynthetic rates, while in Halophila stipulacea (Forssk.) Aschers. pressure had no effect on net photosynthetic rates. In both species, light saturation was reached at 300 μE (400–700 nm) m−2 s−1 and the compensation point was at 20–40 μE (400–700 nm) m−2 s−1. Comparing these results to in situ light measurements, neither species should be light limited to a depth of about 15 m, and Halophila stipulacea should reach compensation light intensities at about 50 m. The latter depth corresponds well to the natural depth penetration of this species. Halodule uninervis is never found deeper than 5 m in the Gulf of Eilat, and it appears that pressure rather than light is one of the factors limiting the depth penetration of this species. The differential pressure response of the two species may be related to aspects of leaf morphology and gas diffusion. Scientifically, confining pressure is responsible for creating a series of vibrations that are in conflict with natural frequencies of matter. Because of the continuity of matter, the external vibrations cause reactions to matter that attempt to escape its

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Table 7.1 Various colors vs. Temperature for an organic flame (from islam, 2014). Color

Temperature (C)

Red Just visible:

525

Dull:

700

Cherry, dull

800

Cherry, full

900

Cherry, clear

1000

Orange Deep

1100

Clear

1200

White Whitish

1300

Bright

1400

Dazzling

1500

confinement. Pressure alone can cause a series of oscillatory events that prompt fundamental changes in the subatomic structure of matter.

7.3.2

Flames and Natural Frequencies of Flames

We will now review the colors of a flame (with carbon particles emitting light) for various temperatures. Table 7.1 shows the temperature for various colors of flame. With these colors, one can analyze the above forest fire. Near the ground, where most burning is occurring, the fire is white, the hottest color possible for organic material in general, or yellow. Above the yellow region, the color changes to orange, which is cooler, then red, which is cooler still. Above the red region, the flame is no longer visible. The black smoke that is visible is essentially pulverized carbon particles. These particles form the soot. The common distribution of a flame under normal gravity conditions depends on convection, as soot tends to rise to the top of a general flame, as in a candle in normal gravity conditions, making it yellow. In micro gravity, such as an environment in outer space, convection slows down significantly, leading to a more symmetric shape of the black smoke. While the presence of blue indicates perfect combustion, such flame cannot be sustained as the produced CO2 tend to smother the flame, especially around the connection between carbon matter and the flame. There are several possible explanations for this difference, of which the most likely is that the temperature is sufficiently evenly distributed that soot is not

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Picture 7.1 Burning vehicles are examples of artificial flame.

formed and complete combustion occurs. Experiments by NASA reveal that diffusion flames in micro gravity allow more soot to be completely oxidized after they are produced than diffusion flames on Earth, because of a series of mechanisms that behave differently in micro gravity when compared to normal gravity conditions. Existing theories cannot account for such dependence of gravity on color of a region within the flame. This is because zero mass is assigned for both photon and Higgs boson. If that spurious assumption is removed, flames in any location can be explained with the emerges of a flame as the trigger event. Picture 7.1 shows the color of burning cars. They essentially represent burning of artificial carbon material (e.g., plastic, refined oil, etc.) The color yellow and red are dispersed throughout the flame body and there is no segregation between red and yellow colors. This is not unlike the existence of a trigger that onsets life within inorganic bodies. The following figure shows a depiction of the onset of fire as well as of life. Consider what happens with life; a living plant and a dead plant have little tangible difference for some time period. The reason the exact time of death cannot be identified is it is an intangible. Similar to what was discussed in terms of yin-yang duality, both life and death have tangible and intangible components to them. When a seed becomes alive, no tangible change occurs in the seed or the surrounding. Similarly, when death

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Picture 7.2 Depiction of a flame.

occurs in a plant, there is no tangible change. It is not until a few cycles have passed that one notices tangible changes. This cycle is characteristic of a living object. Similarly, extinction or onset of a flame involves an intangible. When a flame is onset there is no tangible change, for instance, in terms of temperature, ingredient. When a flame is extinguished, the only change that is visible is the disappearance of the flame’s glow. (Picture 7.2). While it is true, heat alone can act as spark for a flame, the fact that a spark triggers a flame cannot be explained with conventional science. This is because New science is grossly deficient in details of factors that aren’t amenable to linearization (Zatzman et al., 2007b). Following are some of the typical temperatures for various types of flames and fires. 1. 2. 3. 4. 5.

Oxyhydrogen flame: 2,000 C Bunsen burner flame: 1,300 to 1,600 C Blowtorch flame: 1,300 C Candle flame: 1,000 C Smoldering cigarette: Always hotter in the middle. a. Temperature without drawing: side of the lit portion; 400 C; middleof the lit portion: 585 C b. Temperature during drawing: middle of the lit portion: 700 C

This confirms that the minimum temperature associated with a flame is 1,000 C. Thehighest temperature is recorded for the case of oxyhydrogen flame. However, this flameis not natural because no such reaction takes place on Earth under natural conditions.Bunsen burner flame, on the other hand, represents natural gas burning. Natural gas issuch that it does not oxidize in any substantial amount if there is no flame. However,if there is a flame, ambient conditions offer the best condition. When the exposureto air is reduced, the completeness of oxidation reaction is affected. Less air yields anincomplete and thus cooler reaction, while a gas stream well mixed with air providesoxygen in an equimolar amount and thus a complete and hotter reaction. The hottestflame emerges with a blue color when air is mixed freely with the fuel. If the

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Brightness Dazzling Bright Whitish White 1300 Clear Deep Orange 1100 Cherry, clear Cherry, full Cherry, dull Dull: Just visible: Red 0

200

400

600

800

1000

1200

1400

1600

Temperature, ºC

Figure 7.6 Natural flame colors and temperature.

mixing is reduced by choking the inlet of air, the flame will be less hot; however, the brightness of the flame will be increased. The yellow flame is called "luminous flame". Incontrast, when the burner is regulated to produce a hot, blue flame it can be nearlyinvisible against some backgrounds. The hottest part of the flame is the tip of the innerflame, while the coolest is the whole inner flame. Increasing the amount of fuel gasflow through the tube by opening the needle valve will increase the size of the flame. Inbrief, the Bunsen burner offers a contradictory behavior between heat and light generation, higher light leading to less efficient burning. This is in sharp contrast to the trendobserved in natural flame (Figure 7.6) Bunsen burner produces luminosity by decreasing air supply. In other words, there is a reverse relationship between yield (or efficiency) and luminosity. In the simplest case, the yellow flame is luminous due to small soot particles in the flame which are heated to incandescence. The flame is yellow because of its temperature. To produce enough soot to be luminous, the flame is operated at a lower temperature than its efficient heating flame. The color of simple incandescence is due to black-body radiation. This phenomenon is captured with Planck's law that models black body radiation as an inverse function of temperature, going from blue to yellow. Luminosity is similarly affected by pressure. These factors are captured in designing artificial lights. Such behavior is typical of artificial light that employs chemical alteration. Such is typical of a pyrotechnic colorant that triggers chemical reaction to ‘burn’ into a certain color. These colorants are used to create the colors in pyrotechnic compositions like fireworks and colored fires. The color-producing species are usually created from other chemicals during the reaction. Metal salts are commonly used; elemental metals are used rarely (e.g., copper for blue flames). The color of the flame is dependent on the metal cation; the anion of the salt has very little direct influence. The anions, however, influence the flame temperature, both by increasing it (e.g., nitrates, chlorates) and decreasing it (e.g., carbonates, oxalates), indirectly influencing the flame brightness and brilliancy. For temperature-decreasing

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additives, the limit of colorant may be about 10–20 wt.% of the composition. Table 7.2 shows how various colors can be produced with artificial flames. The visible particulate matter in such smokes is most commonly composed of carbon (soot). This is the most tangible part. Other particulates may be composed of drops of condensed tar, or solid particles of ash. The presence of metals in the fuel yields particles of metal oxides. Particles of inorganic salts may also be formed, e.g., ammonium sulfate, ammonium nitrate, or sodium chloride. Inorganic salts present on the surface of the soot particles may make them hydrophilic. Many organic compounds, typically the aromatic hydrocarbons, may be also adsorbed on the surface of the solid particles. Metal oxides can be present when metal-containing fuels are burned, e.g., solid rocket fuels containing aluminium. Depleted uranium projectiles after impacting the target ignite, producing particles of uranium oxides. Magnetic particles, spherules of magnetite-like ferrous ferric oxide, are present in coal smoke. New science does not have any means of characterizing these emissions based on artificiality, thereby failing to distinguish between organic and non-organic emissions (Islam et al., 2010a; 2012a; Khan and Islam, 2012).

7.3.3

Energy

Conventionally, a force is defined to be an influence which tends to change the motion of an object. The inherent assumption is that this ‘force’ is external to the object. This is a false premise because the entire creation is internal and connected to each other, as presented by recent works of Islam et al. (2010a, 2012) and Khan and Islam (2012). Currently it is believed there are four fundamental forces in the universe, the gravity force, the nuclear weak force, the electromagnetic force, and the nuclear strong force in ascending order of strength. In mechanics, forces are seen as the causes of linear motion, whereas the causes of rotational motion are called torques. The action of forces in causing motion is described by Newton's Laws under ordinary conditions. Subsequently, forces are inherently vector quantities, requiring vector addition to combine them. This further characterization is yet another tactic to cover up for the false first premise. Khan and Islam (2012, 2016) provide detailed deconstruction of Newton’s laws. With the scientific theory of the previous section, one can redefine force as something that drives the universal movement. It is Constant, Absolute, and immutable. With this definition, there is no need to further characterize force in the above-mentioned categories. This replaces the notion of gravity in conventional sense. The source of this force is the Absolute light that is omnipresent. This description answers the questions regarding what forces make the entire galactic system move – a question that has perplexed modern scientists (Cowen, 2012). Energy is commonly defined as the capacity for doing work. One must have energy to accomplish work – it is like the "currency" for performing work. To do 100 joules of work, one must expend 100 joules of energy. New science postulates the purest form of energy is light that is comprised of photons. These photons are thought to have zero mass. As stated earlier in this chapter, this assertion disconnects mass from energy but invokes Einstein’s formula, E=mc2, which itself is based on Maxwell’s formula that considers energy a collection of solid,

Compound name

Strontium nitrate

Strontium carbonate

Strontium oxalate

Strontium sulfate

Strontium chloride

Calcium carbonate

Calcium chloride

Calcium sulfate

Hydrated calcium sulfate

Color

Red

Red

Red

Red

Red

Orange

Orange

Orange

Orange

CaSO4(H2O)x*

CaSO4

CaCl2

CaCO3

SrCl2

(Continued)

High-temperature oxidizer. Excellent orange source in strobe compositions.

Produces orange flame. Yields carbon dioxide on decomposition. Often used in toy fireworks as a substitute for strontium.

Common. Produces bright red flame.

Common. High-temperature oxidizer. Used in strobe mixtures and some metal-based red compositions.

Decomposes yielding carbon dioxide and carbon monoxide. In presence of magnesium fuel, carbon monoxide reduces particles of magnesium oxide, yielding gaseous magnesium and eliminating the black body radiation of the MgO particles, resulting in clearer color.

SrC2O4

SrSO4

Common. Produces good red. Slows burning of compositions, decomposes yielding carbon dioxide. Fire retardant in gunpowders. Inexpensive, non-hygroscopic, neutralizes acids. Superior over strontium oxalate in absence of magnesium.

Common. Bright red, especially with metal fuels. Used in many compositions including road flares.

Occurrence and other traits

SrCO3

Sr(NO3)2

Chemical formula

Table 7.2 Colors and sources of artificial flames.

Scientific Characterization of Petroleum Fluids 309

Compound name

Charcoal powder

Iron powder with oxygen based carbon OC12

Sodium bicarbonate

Sodium carbonate

Sodium chloride

Sodium oxalate

Sodium nitrate

Cryolite

Barium chloride

Barium chlorate

Gold/Yellow

Gold/Yellow

Yellow

Yellow

Yellow

Yellow

Yellow

Yellow

Green

Green

Cont.

Color

Table 7.2

Ba(ClO3)2

BaCl2

Na3AlF6

NaNO3

Na2C2O4

(Continued)

Classic exhibition green with shellac fuel. Sensitive to shock and friction. Oxidizer.

One of the few sodium salts that is nonhygroscopic and insoluble in water.

Also acts as oxidizer. Bright flame, used for illumination.

Non-hygroscopic. Slightly reacts with magnesium, no reaction with aluminium.

Loses hygroscopicity on heating. Corrodes metals.

Hygroscopic. Significantly decreases burning rate, decomposes evolving carbon dioxide. Strongly alkaline. Very effective colorant, can be used in small amounts. Corrodes magnesium and aluminium, incompatible with them.

Na2CO3

NaCl

Compatible with potassium chlorate. Less burning rate decrease than sodium carbonate. Incompatible with magnesium and aluminium, reacts evolving hydrogen gas.

Occurrence and other traits

NaHCO3

Fe + C

C

Chemical formula

310 The Science of Climate Change

Compound name

Barium carbonate

Barium nitrate

Barium oxalate

Copper(I) chloride

Copper(I) oxide

Copper(II) oxide

Copper carbonate

Basic copper carbonate

Copper oxychloride

Paris Green

Green

Green

Green

Blue

Blue

Blue

Blue

Blue

Blue

Blue

Cont.

Color

Table 7.2

Cu(CH3COO)2.3Cu(AsO2)2

3CuO·CuCl2

CuCO3·Cu(OH)2, 2 CuCO3·Cu(OH)2

CuCO3

(Continued)

Copper acetoarsenite, Emerald Green. Toxic. With potassium perchlorate produces the best blue colors. Non-hygroscopic. Fine powder readily becomes airborne; toxic inhalation hazard. Used in majority of Japanese blue compositions as it gives very pretty color.

Good blue colorant with suitable chlorine donor.

Occurs naturally as malachite and azurite. Good with ammonium perchlorate and for high-temperature flames with presence of hydrogen chloride. Not easily airborne, less poisonous than Paris Green.

Best when used with ammonium perchlorate.

Used with chlorine donors. Excellent in composite stars.

Lowest cost blue colorant.

Cu2O CuO

Richest blue flame. Almost insoluble in water.

Not too strong effect. With chlorine donors yields green color, without chlorine burns white. In green compositions usually used with perchlorates.

Pretty color when ammonium perchlorate is used as oxidizer.

Occurrence and other traits

CuCl

BaC2O4

Ba(NO3)2

BaCO3

Chemical formula

Scientific Characterization of Petroleum Fluids 311

Compound name

Copper arsenite

Copper sulfate

Copper metal

Combination of red and blue compounds

Rubidium compounds

Aluminium powder

Magnesium powder

Titanium powder

Blue

Blue

Blue

Purple

Purple

Silver/White

Silver/White

Silver/White

Cont.

Color

Table 7.2

Ti

Mg

Al

Rb

Sr + Cu

rarely used

(Continued)

Rarely used, other compounds are easier to work with. Yields pretty blue color in ammonium perchlorate based compositions; but reacts with ammonium perchlorate and liberates ammonia in presence of moisture. The composition must be kept dry.

Can be used with nitrates and perchlorates. Acidic, incompatible with chlorates. With red phosphorus in presence of moisture liberates heat, may spontaneously ignite. Less expensive than copper acetoarsenite. Anhydrous copper sulfate is hygroscopic, can be used as a desiccant. With ammonium perchlorate produces almost as pretty blue color as achievable with copper acetoarsenite.

CuSO4·5 H2O

Cu

Almost non-hygroscopic. Almost as good colorant as copper acetoarsenite. Toxic. Can be used with chlorate oxidizers.

Occurrence and other traits

CuHAsO3

Chemical formula

312 The Science of Climate Change

Compound name

Antimony (III) sulfide

Caesium nitrate

Rubidium nitrate

Color

Silver/White

Infrared

Infrared

Table 7.2 Cont.

RbNO3

CsNO3

Sb2S3

Chemical formula

two powerful spectral linesat 852.113 nm and 894.347 nm

Occurrence and other traits

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spherical, rigid balls (similar to atoms). The assertion of zero mass also invokes infinite speed (a notion that was promoted by Aristotle but was discarded by Ibn Hatham, some 900 years ago). This obvious gaffe is ‘remedied’ by forcing speed of light, ‘c’ to be constant and maximum attainable speed by any particle. Apart from the fact that a zero mass would not qualify to be called a ‘particle’, this also poses the obvious spurious solution to the equation, E=mc2 and renders it an absurd concept. This mathematical fallacy is ‘solved’ with the dogmatic assertion of Quantum physics. As such, the product of 0 times infinity gives a value that is a function of the frequency of the photon. Furthermore, it is asserted that a photon can be converted to a particle and its antiparticle (a process called pair creation), so it does convert energy into mass. All equations, therefore, give an answer but are completely devoid of any physical significance. Similar illogical attributes are assigned to Higgs boson, neutrino, and a number of other particles, some of which have zero mass. In addition, it is asserted that certain particles, such as neutrino, can travel through opaque material, albeit with a speed lower than that of light (photons). In order to compensate for the concept of gravitational force that is conventionally non-existent in zero-mass conditions, it is asserted that the Higgs particle is a carrier of a force. This force mediated by the Higgs boson is considered to be universal as the Higgs boson interacts with all kinds of massive particles, no matter whether they are quarks, leptons, or even massive bosons (the electroweak bosons). Only photons and gluons do not interact with the Higgs boson. Neutrinos, the lightest particles with almost zero mass, barely interact with a Higgs boson. This description and assignment of special ‘power’ to certain particles is characteristic of the pragmatic approach (Khan and Islam, 2012). In simple terms, they are stop-gap tactics for covering up the fundamental flaws in basic premises. Neutrinos are considered to be similar to electrons, with one crucial difference: neutrinos do not carry electric charge. Because neutrinos are electrically neutral, they are not affected by the electromagnetic forces which act on electrons. Neutrinos are affected only by a “weak” sub-atomic force of much shorter range than electromagnetism, and are therefore able to pass through great distances in matter without being affected by it. If neutrinos have mass, they also interact gravitationally with other massive particles, but gravity is by far the weakest of the four known forces. Such repeated characterization of matter and energy with contradicting traits has been the most prominent feature of New science. The characterization offered by Islam et al. (2012) and Khan and Islam (2012) eliminates such needs. When it comes to ‘heat energy’, New science is full of gaffes as well. The entire ‘heat engineering is based on Lord Kelvin’s work. Lord Kelvin, whose ‘laws’ are a must for modern-day engineering design, believed that the Earth is progressively moving to a worse status which would eventually lead to the ‘heat death’. So, if Kelvin were to be correct, and we are progressively moving to greater energy crisis, indeed we need to worry about how to fight this ‘natural’ death of our planet. Kelvin also believed flying an airplane was an absurd idea, so absurd that he did not care to be a member of the aeronautical club. Anyone would agree that it is not unreasonable to question this assertion of Lord Kelvin, but the moment one talks about nature progressively improving, if left alone (by humans, of course), many scientists break out in utter contempt and invoke all kinds of arguments of doctrinal fervor. How do these scientists explain, then, if the Earth is progressively dying, how it happened that life evolved from the

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non-biological materials and eventually very sophisticated creature, called homo sapiens (thinking group) came to exist? Their only argument becomes the one that has worked for all religions, ‘you have to believe’. All of a sudden, it becomes a matter of faith and all the contradictions that arise from that assertion of Lord Kelvin become paradoxes and we mere humans are not supposed to understand them. Today, the Internet is filled with claims that Kelvin is actually a god and there is even a society that worships him. This line of argument cannot be scientific (Islam et al., 2010). Modern scientists claim to have moved away from doctrinal claims of Kelvin. However, no theory has challenged the original premise of Kelvin. Even NobelLaureate-winning works (review, for instance the work of Roy J. Glauber, John L. Hall, and Theodor W. Hänsch, along with their Nobel-prize-winnng work on light theory), consider Kelvin’s concept of Absolute temperature a fact. Theoretically, at that point, there is zero energy, hence matter would not exist either. A matter is being rendered non-existence because it does not move – an absurd state. In reality, shows how everything in creation is in a state of motion, including time itself. However, instead of realizing this obviously spurious premise, New science offers the following explanation (Bayer et al., 2000): If you take away energy from an atom, you do so by lowering the energy level of its electrons, which emits a photon corresponding to the energy gab between the electron bands. Keep doing that until the electron is absorbed by the nucleus, and converts a proton to a neutron. Now you need to extract energy from the nucleus. How are you going to do that? How are you going to shield the resulting neutron from the influence of the rest of the universe, including radio waves, that penetrate everything? Another explanation attempts to justify discontinuity between mass and energy, by saying, “All matter has energy, unless it is at absolute zero temperature, true. But that amount of energy is tiny compared to the energy you could get if the matter were totally converted to energy via Einstein's famous equation, E = mc². But there is no way for that to happen unless you are dealing with antimatter. Even the sun converts only a tiny percentage of the matter to energy, but that tiny percentage (because of the c² term) produces a lot of energy.” In this, the notion of “anti-matter”1 is invoked. Natural light or heat is a measure of radiation from a system (called “material” in the above section). This radiation is continuous and accounts for change in mass within a system. In this, there is no difference between heat generation and light generation, nor there is any difference in radiation of different types of “radiation” (such as X-ray, gamma-ray, visual light, infrared, etc.) other than they are of various frequencies. This can be reconciled with New science for the limiting cases that say that there is an exponential relationship between reactants and products (Arrhenius equation) through the time function. Such a relationship is continuous in time and space. For instance, as long as the assumption of continuity is valid, any substance is going to react with the media. The term ‘reaction’ here implies formation of a new system that will have components of the reactants. This

1 In modern physics, antimatter is introduced as a fudge factor that emulates the yin yang trait of nature. It is defined as a material composed of the antiparticle (or "partners") to the corresponding particles of ordinary matter. Antimatter particles bind with one another to form antimatter, just as ordinary particles bind to form normal matter.

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Picture 7.3 Fire from wood (top left) is part of the organic cycle whereas smoke from a tungsten bulb (bottom right) is that of the mechanical (hence implosive and non-sustainable) cycle. While these extremes are well known, confusion arises as to how to characterize plastic fire (top right) and smoke from a cigarette (bottom left) that have very similar CO2 emission as in natural wood burning.

reaction has been explained by Khan et al. (2008) as a collection of snowflakes to form an avalanche. Islam et al. (2014) developed a similar theory that also accounts for energy interactions and eliminates separate balance equations for mass and energy. This theory considers energy or mass transfer (chemical reaction or phase change) as merger of two galaxies. Before merger, the two galaxies have different sets of characteristic frequencies. However, after merger, a new galaxy is formed with an entirely new set of characteristic frequencies. Such phenomena are well understood in the context of cosmic physics. Picture 7.3 shows how various sources of light or heat can be characterized scientifically knowing the source of the Carbon dioxide. Picture 7.4 shows a NASA picture of two galaxies that are in a collision course. Cowan (2012) reports the following: Four billion years from now, the Milky Way, as seen from Earth in this illustration, would be warped by a collision with the Andromeda galaxy. It’s a definite hit. The Andromeda galaxy will collide with the Milky Way about 4 billion years from now, astronomers announced today. Although the Sun and other stars will remain intact,

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Picture 7.4 It is reported that two galaxies are on a collision course (Cowan, 2012).

the titanic tumult is likely to shove the Solar System to the outskirts of the merged galaxies. Such a collision doesn not involve the merger of two suns or any planets or moons. It simply refers to the reorientation of the stars and planets within a new family. Note how conservation of mass is strictly maintained as long as an artificial boundary is not imposed. In new science, such artificial boundary is imposed by confining a system within a boundary and imposing ‘no-leak’ boundary conditions. Similarly, adiabatic conditions are imposed after creating artificial heat barriers. With the galaxy model, physical or chemical changes can both be adequately described as change in overall characteristic frequency. So, how does heat or mass get released or absorbed? As stated above, “the titanic tumult” would cause the stars to be “shoved” toward the outskirts of the newly formed galaxy. In case they are indeed placed around the outskirts, this would translate into excess heat near the boundary. However, if those stars are “shoved” inside the new giant galaxy, for an outsider, it would appear to be a cooling process, hence, endothermic reaction. In this context, the “titanic tumult” is equivalent to the “spark” that lights up a flame or starts a chain reaction. It is also the equivalent of the onset of life or death as well as the “Big Bang” in the universal sense. Even though these terms have been naturalized in New science vocabulary, they do not bear scientific meaning. Islam et al. (2012; 2014) recognized them to be unknown and unexplainable phenomena that cause the onset of a phase change. They can be affected by heat, light, and pressure that are direct results of changes within the confines of a certain system. The source of heat is associated with “collisions” as represented above in the context of galaxies, be it in subatomic level (known as chemical reactions), in combustion within a flame, or in giant scale (such as solar radiation). For our system of interest, i.e., the Earth, our primary source of heat is the sun that radiates mass in various wavelengths. New science recognizes “the solar constant” as the amount of power that the sun deposits per unit area that is directly exposed to sunlight. The solar constant is equal to approximately 1368 W/m2 at a distance of one astronomical unit (AU) from the sun (that is, on or near Earth). Sunlight at the top of Earth's atmosphere is

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composed (by total energy) of about 50% infrared light, 40% visible light, and 10% ultraviolet light. In other words, the heat source is inherently linked to the light source. As discussed in previous sections, this transition between different forms of energy is continuous and should be considered to be part of the same phenomenon characterized here as ‘dynamic nature of everything in creation’. These are not ‘mass-less’ photons or ‘energy-less’ waves, they are actually part of mass transfer that originates from radiation of the sun. Before solar emissions enter the atmosphere of the Earth, nearly one-third of the irradiative material are deflected through filtering actions of the atmospheric particles. How does it occur? It is similar to the process described above as galactic collision. During this process, the composition of the atmospheric layer changes continuously and “new galaxies” form continuously in the “tumult” mode, while some of the material are deflected outside the atmosphere and the rest penetrate the atmosphere to trigger similar ‘tumult” events through various layers of the atmosphere. These atmospheric layers are such that all the layers act similar to a stacked-up filtering system. Following is a brief description of different layers of the atmosphere. 1. The exosphere is the thinnest (in terms of material concentration) layer. This is the upper limit of the Earth’s atmosphere. 2. The thermosphere is a layer with auroras. This layer sees intensive ionic activities. 3. The next layer is mesosphere. This is the layer that burns up meteors or solid fragments. The word “solid” implies most passive levels of activities of the constitutive material. See Figure 7.4 with reference to “solid” representing a collection of ‘dust specks’ that exhibit the slowest characteristic speed. Meteors or rock fragments burn up in the mesosphere. Another way to characterize matter in terms of solid liquid and vapor state. Within Earth, the following configuration applies. It is possible that such configuration of various states will apply to other celestial entities, but that is not the subject of interest in the current context. Figure 7.4 shows how the relationship between characteristic speed and physical state of matter is a continuous function. Note that natural state of matter is an important consideration, particularly in relation to human species and life. For instance, the most abundant matter on Earth is water, which is most useful for the human species in its liquid state. It turns out that water is also the most abundant in liquid state. Amongst solids, clayey matter (Si02, see the position of “dust speck” in Figure  7.5) is the most abundant, and scientists are beginning to find out humans are also made out of such matter. Here is a quote from the Daily Mail (2013): The latest theory is that clay - which is at its most basic, a combination of minerals in the ground - acts as a breeding laboratory for tiny molecules and chemicals which it 'absorbs like a sponge'. The process takes billions of years, during which the chemicals react to each other to form proteins, DNA and, eventually, living cells, scientists told the journal Scientific Reports.

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Biological Engineers from Cornell University’s department for Nanoscale Science in New York state believe clay 'might have been the birthplace of life on Earth'. It is a theory dating back thousands of years in many cultures, though perhaps not using the same scientific explanation.

Clay also retains the most amount of water – the most essential ingredient of life and organic material. As would be seen in other chapters as well as later in this section, similar optima exist in terms of visible light being the most abundant of sunlight rays and Earth being the densest of all the planets in the solar system. Overall, all characteristic features for the Earth make it the most suitable as a ‘habitat for mankind’ (Khan and Islam, 2012). 1. The next layer of the atmosphere, called the stratosphere, is the most stable layer of the atmosphere. Many jet aircraft fly in the stratosphere because it is very stable. Also, the ozone layer absorbs harmful rays from the sun. By the time sunrays enter the final and fifth layer, almost 30% of the total irradiation have been removed. This is the energy (in the form of light and heat) that is ideal for rendering the Earth system totally sustainable and ideal for human habitation. This layer is the most vulnerable to human intervention and is the cause of global warming (Islam et al., 2012). Overall, any level of artificial products in the stratosphere will affect the final and the most important layer of the Earth’s atmosphere. 2. The closest layer to the Earth’s surface is troposphere. This layer contains half of the Earth's atmosphere. All transient phenomena related to weather occur in this layer. This layer too contributes to attenuation of sunlight and at the end some 1000 W/m2 falls on the Earth when the sky is clear and the sun is near the zenith. The multiple filtering system of the atmosphere is such that it filters out 70% of solar ultraviolet, especially at the shorter wavelengths. The immediate use of solar energy in terms of sustaining human life is photosynthesis – the process that allows plants to capture the energy (through mass transfer) of sunlight and convert it to ‘live’ chemical form. The energy stored in petroleum and other fossil fuels was originally converted from sunlight by photosynthesis in the distant past.

7.3.4

Conversion of Energy Into Mass

The most significant of this conversion process is the photosynthetic mechanism. There are two classes of the photosynthetic cycle, the Calvin-Benson photosynthetic cycle and the Hatch-Slack photosynthetic cycle. The Calvin-Benson photosynthetic cycle is dominant in hard- woods and conifers. The primary CO2 fixation or carboxylation reaction involves the enzyme ribulose-1,5-diphosphate carboxylase and the first stable product is a 3-carbon compound. This reaction is considered to be “light-independent”. This series of reactions occur in the fluid-filled area of a chloroplast outside of the mytosis membranes. These reactions take the light-dependent reactions and perform further

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chemical processes on them. Various stages of this process are: carbon fixation, reduction reactions, and ribulose 1,5-bisphosphate (RuBP) regeneration. In describing this cycle of reactions, the role of light energy is marginalized. This process occurs only when light is available. Plants do not carry out the Calvin cycle by night. They, instead, release sucrose into the phloem from their starch reserves. This process happens when light is available independent of the kind of photosynthesis (C3 carbon fixation, C4 carbon fixation, and Crassulacean Acid Metabolism. The exceptions are: Crassulacean acid metabolism, also known as CAM photosynthesis, a carbon fixation pathway that is used by some plants as an adaptation to arid conditions. In a plant using full CAM, the stomata in the leaves remain shut during the day to reduce evapotranspiration, but open at night to collect carbon dioxide (CO2). The CO2 is stored as the four-carbon acid malate, and then used during photosynthesis during the day. The pre-collected CO2 is concentrated around the enzyme RuBisCO, increasing photosynthetic efficiency. On the other hand, the Hatch-Slack photosynthetic cycle is the one used by tropical grasses, corn and sugarcane. Phosphenol-pyruvate carboxylase is responsible for the primary carboxylation reaction. The first stable carbon compound is a C-4 acid, which is subsequently decarboxylated. It is then refixed into a three-carbon compound. These three steps define the canonical C4 photosynthetic pathway. Overall, the photosynthesis process shows how nature converts energy into mass, storing energy for long-term use. This must be understood in order to appreciate the role of natural processing in the context of petroleum usage. The process of energy-to-mass conversion is greatly affected by temperature (Fink, 2013). Sometimes temperatures are used in connection with day length to manipulate the flowering of plants. Chrysanthemums will flower for a longer period of time if daylight temperatures are 50 F. The Christmas cactus forms flowers as a result of short days and low temperatures. Also, temperatures alone also influence flowering. Daffodils are forced to flower by putting bulbs in cold storage in October at 35 to 40 °F. The cold temperature allows the bulb to mature. The bulbs are transferred to the greenhouse in midwinter where growth begins. The flowers are then ready for cutting in 3 to 4 weeks. Plants produce maximum growth when exposed to a day temperature that is about 10 to 15 F higher than the night temperature. This allows the plant to photosynthesize (build up) and respire (break down) during an optimum daytime temperature, and to curtail the rate of respiration during a cooler night. High temperatures cause increased respiration, sometimes above the rate of photosynthesis. This means that the products of photosynthesis are being used more rapidly than they are being produced. For growth to occur, photosynthesis must be greater than respiration. Temperature alone can affect this process. Low temperatures can result in poor growth. Photosynthesis is slowed down at low temperatures. Since photosynthesis is slowed, growth is slowed, and this results in lower yields. Each plant has an optimum temperature that allows maximum growth. For example, snapdragons grow best when night time temperatures are 55 °F, while the poinsettia grows best at 62 °F. Florist cyclamen does well under very cool conditions, while many bedding plants grow best at a higher temperature. Buds of many plants require exposure to a certain number of days below a critical temperature before they will resume growth in the spring. Peaches are a prime example; most cultivars require 700 to 1,000 hr below 45 °F and above 32 °F before they

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Oxygen cycle reservoirs & Flux Photolysis Atmosphere (0.5%)

Wealthering

Photosynthesis

Respiration & Decay

Biosphere (0.01%)

Weathering

Burial

Lithosphere (99.5%)

Figure 7.7 Oxygen cycle in nature involving the Earth.

break their rest period and begin growth. This time period varies for different plants. The flower buds of forsythia require a relatively short rest period and will grow at the first sign of warm weather. During dormancy, buds can withstand very low temperatures, but after the rest period is satisfied, buds become more susceptible to weather conditions, and can be damaged easily by cold temperatures or frost. This series of phenomena have immediate implications to seeds and future of the biomass. Even though no evidence exists in nature that hydrogen combined with oxygen in their elemental form to produce water, it is commonly accepted that elemental balance in oxygen and hydrogen exists independently. This connection comes from the Big Bang theory that assumes that the original mass was hydrogen. This new version of Atomism has been challenged by several researchers and remains a subject of ongoing debate (Islam et al., 2015). In every cycle, however, there are components that cannot be accounted for with conventional scientific analysis. Figure 7.7 shows how the oxygen cycle is complete within the echo system. In every step, there is involvement of living organism. That itself is a matter of intangible as “life” cannot be quantified or even qualified and is inherently intangible. The first reaction identified in the following figure is photolysis. This is a term coined to include the role of sunlight in sustaining the terrestrial ecosystem. Photolysis is part of the light-dependent reactions of photosynthesis. The general reaction of photosynthetic photolysis can be given as





→

−



(7.1)

The chemical nature of "A" depends on the type of organism. For instance, in purple sulfur bacteria, hydrogen sulfide (H2S) is oxidized to sulfur (S). In oxygenic photosynthesis, water (H2O) serves as a substrate for photolysis resulting in the generation of diatomic oxygen (O2). The Σ symbol includes information about the pathway, f(t), for the photons. For instance, for sunlight it would be something intangible that is beneficial in the long term and for artificial light, it would be something intangible that is harmful in the long term. This is the process which returns oxygen to Earth's

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atmosphere. Photolysis of water occurs in the thylakoids of cyanobacteria and the chloroplasts of green algae and plants. Photosynthesis is the next process that involves the sunlight. Similar to photolysis, photosynthesis also involves living organisms. Photosynthetic organisms are photoautotrophs, which means that they are able to synthesize food directly from carbon dioxide and water using energy from light. However, not all organisms that use light as a source of energy carry out photosynthesis, since photoheterotrophs use organic compounds, rather than carbon dioxide, as a source of carbon. In plants, algae and cyanobacteria, photosynthesis releases oxygen. This is called oxygenic photosynthesis. However, there are some types of bacteria that carry out anoxygenic photosynthesis, which consumes carbon dioxide but does not release oxygen. In that case, they act as an oxygen sink. Carbon dioxide is converted into “sugars” in a process called carbon fixation. Carbon fixation is an endothermic redox reaction, so photosynthesis needs to supply both a source of energy to drive this process, and the electrons needed to convert carbon dioxide into a carbohydrate. This addition of the electrons is a reduction reaction. In general outline and in effect, photosynthesis is the opposite of cellular respiration, in which “glucose” and other compounds are oxidized to produce carbon dioxide and water, and to release exothermic chemical energy to drive the organism's metabolism. In this process, the intan. This symbol contains two sets of information, gibles are captured by another set of one regarding the source of carbon dioxide and the other regarding the source of light. The general equation for photosynthesis is:

 or,

→



→ 2





2

(7.2)

In oxygenic photosynthesis water is the electron donor and, since its hydrolysis releases oxygen, the equation for this process is:

 Or,

→





→ 2



2

(7.3)

Figure 7.8 shows the cycle involving hydrogen balance. It is customary to look into hydrogen balance. This notion comes from the Big Bang theory that presumes the existence of hydrogen at the birth of the Universe. However, Islam (2014) pointed out that this starting point is illogical. A consistent and scientifically sound starting point is water as the first matter that embedded the rest of the creation. Figure 7.9 shows the overall water balance. Scientifically, water balance is the only natural balance. This has been a focus of latest research regarding solar system (Hammond et al., 2016) as well as outer galaxy (Coghlan, 2018; Sokol, 2017).

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O2 Photoelectrolysis

Fuel cell Energy + H 2O

H2

H2 Storage

Figure 7.8 Hydrogen cycle in nature involving the Earth.

Figure 7.9 (Continued)

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Precipitation

Condensation Solar energy

Water-vapor transport

le

Infiltration

ff no Ru

ab ter t Wa

Evapotranspiration

Evaporation Evaporation Ocean Groundwater flow

Sunlight Auto and factory emissions

CO2 cycle

Photosynthesis Plant respiration Animal respiration Organic carbon

Decay organisms

Dead organisms and waste products

Fossils and fossil fuels

Root respiration

Ocean uptake

Figure 7.9 Water cycle, involving energy and mass.

7.4

Role of Petroleum Sources

Not long ago, organic sources were the only ones considered for defining petroleum fluids. Even though igneous rocks posed an interesting dilemma in terms of how organic matters accumulated there, there was no shortage of dogmatic interpretation of geologic

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Mixed volcaniclastic

Granite Kimberlite Basalt Serpentenite Peridotite Syenite/Trachyte

Rhyolite (tuffs & lavas)

Andesite

Figure 7.10 The distribution of hydrocarbons in and around igneous rocks according to lithology (from Schutter 2003).

history. However, many questions arise than answers exist concerning hydrocarbons in and around igneous rocks. Figure 7.10 shows the distribution of hydrocarbons in and around igneous rocks. This figure shows that the highest reported occurrences are in basalts, followed by andesite and rhyolite tufts and lavas. Although volcanic rocks in this survey constitute close to three-quarters of all hydrocarbon-bearing lithotypes, the majority of production and global reserves appears to be confined predominantly to fractured and weathered granitic rocks (Petford & McCafrey, 2003). In order to make non-controversial conclusion regarding the source of this hydrocarbon, one would need to have more data on magma composition as well as the process of hydrocarbon generation in an inorganic setting. Islam et al. (2018) established a systematic framework for the study of the sources of basement hydrocarbons practical applications that arise. This should include consideration of the relationship to possible source rocks, the maturation history, the possible migration pathways, the possible reservoir characteristics and the type of traps likely to be present. They provided logical explanations for each aspect of the theories presented. Finally, the framework of scientific investigation of the origin of hydrocarbons is laid out in order to facilitate the study of sustainability and the true nature of hydrocarbons.

7.4.1 Organic Origin of Petroleum The most notable groups of chemicals used in the processes of living organisms include: Proteins, which are the building blocks from which the structures of living organisms are constructed (this includes almost all enzymes, which catalyse organic chemical reactions) Nucleic acids, which carry genetic information Carbohydrates, which store energy in a form that can be used by living cells Lipids, which also store energy, but in a more concentrated form, and which may be stored for extended periods in the bodies of animals.

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Silicon has been a theme of non-carbon-based-life since it also has four bonding sites and is just below carbon on the periodic table of the elements. This means silicon is very similar to carbon in its chemical characteristics. In cinematic and literary science fiction, when man-made machines cross from nonliving to living, this new form would be an example of non-carbon-based life. Since the advent of the microprocessor in the late 1960 s, these machines are often classed as "silicon-based life". Another example of silicon-based life is the episode "The Devil in the Dark" from Star Trek: The Original Series, where a living rock creature's biochemistry is based on silicon. Scientifically, natural processing of organic materials into petroleum products is entirely environment-friendly as each stage of processing is well balanced through proper use of characteristic frequencies (Islam et al., 2014). It is commonly agreed that petroleum has an organic origin. Organic materials are transformed by heat and pressure into a complex mixture, known as kerogen. Depending on the initial ingredients and the geologic conditions, kerogen can produce either coal (a solid carbon-rich fuel derived mostly from woody plants) or hydrocarbons (a relatively hydrogen-rich substance that comes from algae and various lipid-containing plant parts). Oil forms from kerogen, a mixture of organic compounds in sedimentary rocks. It is most abundant in shales. Shales are analyzed and characterized as potential “source rocks” for oil based largely on their TOC (total organic content). For kerogen to be transformed into oil, it must be buried to a depth where the temperature and pressure are sufficiently high to convert the kerogen into oil. The place where the depth is sufficient to achieve this is called the “oil window”. Oil shale which contains only kerogen was never buried deeply enough to generate oil. Therefore, humans must artificially convert the kerogen in oil shale into oil at high temperatures. The processing time of petroleum is longer than a million years. Such a long processing time makes petroleum fluids the most stabilized and environmentally benign fluid other than water. Petroleum is equivalent to natural batteries that pack solar energy in the most efficient and environment-friendly way known to mankind. In contrast, pyrolysis is inherently artificial as it uses artificial sources of energy (heat and pressure) and often contains catalysts (artificial chemicals). As a consequence, pyrolysis leaves behind a trail of heavy footprints and sets off negative impact on the environment, even though the final products of pyrolysis and natural processing are similar (e.g., methane, ethane, propane, and others). In terms of environmental impact, naturally processed petroleum products are completely benign to the environment. History tells us that the usage of petroleum products in their natural state does not endanger the environment. At the onset of the modern age, starting with the mechanization of natural science and engineering, a bifurcation between economic index (driver of the modern civilization) and environmental index has taken place. Using 2000 as the reference point, Vassilis et al. (2013) presented the following graph (Figure 7.11) that shows the nature of this bifurcation. It is, therefore, unfathomable that such modus operandi had been in place in previous civilizations that were no less glamorous than the modern age. The most remarkable distinction is in the use of petroleum as a fuel. Today, 85% of petroleum use in the United States is as a fuel. Non-fuel applications include lubricants for cars, asphalt for roads, tars for roofing, waxes for food wrapping, as well as solvents for paints, cosmetics, and dry-cleaning products. Petrochemicals also provide the building blocks for a

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160

140 Economic index 120

100 Environmental index 80

60 2000

2005

2010

2015

Figure 7.11 Even in the short term, the modern age is synonymous with decoupling of economic index from environmental index (from Vassili et al., 2013).

vast panoply of plastics and foams. The pharmaceutical industry also uses petroleum plastics as well as chemicals derived from petroleum. In each application, however, numerous stages of refinement and processing are involved. Originally, petroleum played an entirely different role. There were oil pits near Ardericca (near Babylon). The Chinese drilled for “rock oil” to provide heating and lighting, and the Byzantines sprayed "Greek fire" as an incendiary weapon. Many cultures have also employed petroleum as a medicinal cure, giving it names such as “St. Quirinus oil,” “Barbados tar” and “Seneca oil.” Our modern society continues to use petroleum jelly as a skin ointment. Petroleum became a significantly valuable commodity in the mid-19th century, when modern techniques of chemical distillation were developed to separate kerosene from crude oil. The refined kerosene could be used in lamps, replacing the more expensive whale oil.

7.4.2 Implication of the Abiogenic Theory of Hydrocarbon As stated earlier, maturation of organic-rich sediments was considered to be the only source of hydrocarbons in all types of petroleum reservoirs. As early as 1988, Abrajano et al. (1988) discussed an alternate origin in conjunction with natural gas seeps in an ophiolite in the Philippines. Under some circumstances, the serpentinization of ultramafic rocks may produce hydrogen from the reaction of olivine with water; if carbon is also present, methane may be the product. The reaction resembles the Fischer-Tropsch reaction for generating synthetic hydrocarbons (Szatmari 1989). Even though this knowledge existed among scientists of the former Soviet Union for many decades, the notion of non-organic origin of oil was dismissed in the west as marginal, ‘conspiracy theory’ like notions (Gold and Soter, 1980). Abiotic hydrocarbons from serpentinization or from the mantle may be identified by the anomalous distributions of carbon

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2 Continent 1

2

Transition zone Lower mantle

4 5

Ocean Water-rich zone

3

Outer core

Water-rich zone

Inner core

Figure 7.12 Water plays a more significant role in material production than previously anticipated (from the Guardian, March 12, 2014).

isotopes and helium isotope ratios (Abrajano et al. 1988). Giardini & Melton (1981) stated that hydrocarbons with a δ13C value more depleted than −18% may be abiogenic in origin. This rediscovery of abiogenic hydrocarbons led a series of studies. Sherwood et al. (1988) discussed the origin of CH4 found in the Precambrian crystalline rocks of the Canadian Shield. They noted that the CH4 lacked the characteristic isotopic signature of either organic matter or a mantle source. Some of the CH4 was strongly depleted in deuterium, and some was accompanied by H2, leading the way to theorize about serpentinization. Then came the discoveries of the presence of huge amount of water in the mantle (Guardian, 2014) leading Islam (2014) to theorize the formation of hydrocarbon under numerous conditions, virtually making it a continuous process. Islam (2014) argued that the notion of ‘clean’ energy has to be revised in view of natural processing time for various energy sources. Scientists are still grappling with the origin of earth or universe, some discovering only recently that water was and remains the matrix component for all matter (Pearson et al, 2014). Figure 7.12 shows this depiction. As pointed out by Islam (2014), natural evolution on earth involved a distinctly different departure point not previously recognized. Pearson et al. (2014) observed a ‘rough diamond’ found along a shallow riverbed in Brazil that unlocked the evidence that a vast "wet zone" deep inside the Earth that could hold as much water as all the world's oceans put together. This discovery is important for two reasons. Water and carbon are both essential for living organisms. They also mark the beginning and end of a life cycle. All natural energy sources have carbon or require carbon to transform energy in usable form (e.g., photosynthesis). World petroleum reserve takes a different meaning if the possibility of abiogenic hydrocarbon is added to the equation. The resource picture becomes even more interesting Added to that is the recent discovery of cyanobacteria that may have been active in all known epochs of life on earth (Sarsekeyeva et al., 2015). All these considerations and discoveries has to be integrated in a logical discussion (Islam et al., 2018). In general, the processing time for various energy sources is not a well understood science. Scientists are still grappling with the origin of the Earth or the universe, some

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discovering only recently that water was and remains the matrix component for all matter (Pearson et al., 2014). We see in Figure 7.12, how natural evolution on Earth involved a distinctly different departure point not previously recognized (Islam et al., 2018). Pearson et al. (2014) observed a ‘rough diamond’ found along a shallow riverbed in Brazil that unlocked the evidence of a vast "wet zone" deep inside the Earth that could hold as much water as all the world's oceans put together. This discovery is important for two reasons. Water and carbon are both essential for living organisms. They also mark the beginning and end of a life cycle. All natural energy sources have carbon or require carbon to transform energy in usable form (e.g., photosynthesis). The origin of oil and gas has been a long-debated theoretical issue. There are two opposing points of view: 1) the organic origin theory and 2) the inorganic origin theory. Organic origin theory considers oil and gas to come from biological processes. Inorganic origin theory explains the origin of oil and gas through inorganic synthesis and mantle degassing. The earliest organic origin theory was proposed by Lomonosov in 1763 (Dott, 1969). He hypothesized that fertile substances underground, such as oil shale, carbon, asphalt, petroleum and amber, originated in plants. The hydrocarbon formation theory of kerogen thermal degradation proposed by Tissot and Welte (1984) and Hunt (1975) are the representatives of the organic hydrocarbon generation theory. The hydrocarbon formation theory of kerogen thermal degradation is based on the diagenesis of organic matter resulting from biopolymers into geopolymers, then kerogen. Kerogen is the main precursor material of oil compounds during the process of hydrocarbon generation, when thermal degradation plays a major role. For sufficient hydrocarbon class and commercial oil gathering, sedimentary rocks must experience the hydrocarbon generation and temperature threshold. Mass hydrocarbons are formed at temperatures from 60 °C to 150 °C by heated organic matter (Hunt, 1975). According to this theoretical model, the sedimentary organic matter maturity, especially for kerogen, becomes the key factor for evaluating hydrocarbon potential. When the threshold burial depth is reached, kerogen will be changed from immature to mature. The theory has been accepted gradually by the majority of petroleum geologists and plays a major role in oil and gas exploration. By contrast, non-organic origin of petroleum is considered to be controversial. However, a significant number of basement reservoir fluids cannot be explained with the conventional organic origin concept. Over the last 30 years, geochemical research has demonstrated that abiotic methane (CH4), formed by chemical reactions which do not directly involve organic matter, occurs on Earth in several specific geologic environments. Methane as well as higher chain molecules of hydrocarbon can be produced by either high-temperature magmatic processes in volcanic and geothermal areas, or via low-temperature ( Unconventional--> Conventional-->Biofuel

ProCambrian

Paleozoic

Mesozoic

Cenozoic

Figure 7.18 Natural processing time differs for different types of oils (From Islam et al., 2018).

The same rule applies to essential oils. These natural plant extracts have been used for centuries in almost every culture and have been recognized for their benefits outside of being food and fuel. Not only does the long and rich history of essential oils usage validate their efficacy specifically, it also highlights the fact that pristine essential oils are a powerfully effective resource with many uses and benefits—from beauty care, to health and wellness care, fast effective pain relief, and emotional healing, and others. In another word, the benefits of oils are diverse and it is the overall benefit that increases with longer processing time. Figure 7.19 is based on the analysis originally performed by Chhetri and Islam (2008) that stated that natural processing is beneficial in both efficiency and environmental impact. However, as Khan and Islam (2012, However, 2016) have pointed out, such efficiency cannot be reflected in the short-term calculations that focus on the shortest possible duration. The efficiency must be global, meaning it must include long-term effects, in which case natural processing stands out clearly. Figure 7.19 shows how longer processing time makes a natural product more suitable for diverse applications.

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Intrinsic value of natural products

Fuel Food

Medicinal, environmental

Natural processing time

Figure 7.19 Natural processing enhances intrinsic values of natural products (From Islam et al., 2018).

This graph is valid even for smaller scales. For instance, when milk is processed as yogurt, its applicability broadens, so does its ‘shelf life’. Similarly, when alcohol is preserved in its natural state, its value increases. Of course, the most useful example is that of honey, which becomes a medicinal marvel after centuries of storage in natural settings (Islam et al., 2015). In terms of fuel, biomass, which represents minimally processed natural fuel, produces readily absorbable CO2 that can be recycled within days to the state of food products. However, the efficiency of using biomass to generate energy is not comparable to that which can be obtained with crude oil or natural gas. Overall, energy per mass is much higher in naturally processed fuel. Let us review examples from both oil and natural gas. Historically it has been believed that conventional gas and oil is miniscule compared to unconventional. With it comes the notion that it is more challenging to produce unconventional petroleum resources. In addition, at least for petroleum oil, the notion that unconventional resources are more challenging to process is prevalent. This notion is false. With the renewed awareness of the environmental sustainability it is becoming clear unconventional resources offer more opportunities to produce environment-friendly products than conventional resources. Figure 7.20 shows the pyramid of both oil and gas resources. On the oil side, the quality of oil is considered to be declining as the API gravity declines. This correlation is related to the processing required for crude oil to be ready for conversion into usable energy, which is related to heating value. Heating value is typically increased by refining crude oil upon addition of artificial chemicals are principally responsible for global warming (Chhetri and Islam, 2008; Islam et al.,, 2010). In addition, the process is inefficient and results in products that are harmful to the environment. Figure 7.21 shows the trend in efficiency, environmental benefit and real value with the production cost of refined crude. This figure shows clearly there is great advantage to using petroleum products in their natural state. This is the case for unconventional oil. For instance, shale oil burns naturally. The color of flames (left image of Picture 7.5) indicates that crude oil produced from shale oil doesn’t need further processing. The right image of Picture 7.5 emerges from burning gasoline and has similar colors to those of the left. In addition, crude oil from shale oil is ‘cleaner’ than other forms of crude oil because of the fact that it is relatively low in tar content as well sand particles. Another crucial aspect is the fact that sulfur content or other toxic elements of crude oil have no

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Conv. Oil

Heavy oil Y3>Y2>Y1>Y0. If profit margin is used as a criterion, practices that give the most crop yield would be preferred. Of

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course a t a time (t= “right now”'), this is equivalent to promoting “'crops are crops”'. Aside from any considerations of product quality, which might suffer great setback at a time other than 't= “right now”', their higher yield directly relates to higher profit. Historically, a portion of the marketing budget is allocated to obscure the real quality of a product in order to linearize the relationship between yields and profit margins. The role of advertisement in this is to alter peoples’ perception, which is really a euphemism for forcing people to exclusively focus on the short-term. In this technology development, if natural rankings are used, Cases D through G would be considered to be progressively worse in terms of sustainability. If this is the ranking, how then can one proceed with that characterization of a crop that must have some sort of quantification attached to it? For this, an sustainability index is introduced in the form of a Dirac δ function, δ (s), such that: δ(s) = 1, if the technology is sustainable; and δ(s) = −1, if the technology is not sustainable. Here, sustainability criterion of Khan and Islam (2007) was used. A process is aphenomenal if it doesn’t meet the sustainability criterion and it assumes a δ value of −1. Therefore, the adjustment we propose in revising the crop yield is as follows:



−

 

(10.6)

Here Y stands for the actual crop yield, something recorded at present time. Note that Yreal has a meaning only if future considerations are made. This inclusion of the reality index forces decision makers to include long-term considerations. The contribution of a new technique is evaluated through the parameter that quantifies quality as, Qreal (stands for real quantity), given as:



(10.7)

For unsustainable techniques, the actual quantity, Y will always be stheory is dependent on a series of assumptions whichmaller than Y0. The higher the apparent crop yield for this case, the more diminished the actual quality. In addition to this, there might be added quality degradation that is a function of time. Because an unsustainable technology continues to play havoc on nature for many years to come, it is reasonable to levy this cost when calculations are made. This is done through the function, L (t). If the technique is not sustainable, the quality of product will continue to decline as a function of time. Because quality should be reflected in pricing, this technique provides a basis for a positive correlation between price and quality. This is a sought-after goal that has not yet been realized in the post-industrial revolution era (Zatzman and Islam, 2007b). At present, price vs. quality has a negative slope, at least during the early phase of a new technology. Also, the profit margin is always inversely proportional to the product quality. Nuclear energy may be the cheapest, but the profit margin of the nuclear energy is the highest. Herbal medicines might be the only ones that truly emulate nature which has all the solutions, but the profit margins are the lowest in herbal medicines. Today, organic honey (say from the natural forest) is over 10 times more expensive than farm honey when it is sold in the stores. However, people living close to natural habitats do have access to natural honey free of cost, but the profit margin in farm honey is still the highest. In fact, pasteurized honey from Australia is still one expensive locally available unadulterated honeys (from a local source, but not fully organic) in the Middle East.

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The aim of this approach is to establish in stepwise manner a new criterion that can be used to rank product quality, depending on how real (natural) the source and the pathways are. This will distinguish between organic flower honey and chemical flower honey, use of antibiotics on bees, electromagnetic zones, farming practices, sugar for bees, as well as numerous intangibles. This model can be used to characterize any food product that makes the value real. In this context, the notion of mass balance needs to be rethought, so that infinite dimensions (using t as a continuous function) can be handled. What we have to establish is the dynamism of the mass-energy-momentum balance at all scales, and the necessity for non-linear methods of computing just where the balance is headed at any arbitrarily-chosen point. Non-linear needs to be taken and understood to mean that there is no absolute boundary. There is only the relative limit between one state of computation and other computational states. Differences between states of computation are not necessarily isomorphic (in 1:1 correspondence) with actual differences between states of nature. Knowledge gathered about the former is only valuable as one of a number of tools for determining more comprehensively what is actually going on with the latter. What does it mean to capture intangibles and make sense of them without throwing away tangibles? The climate change conundrum suggests that problems of this type require considering all energy sources and all masses, still using the mass balance equation, for example, but in this redefined form. Consider in particular, what is involved in the producing CO2. Every living organism emits certain amount of CO2 after utilizing naturally available oxygen from the atmosphere. During that process, every molecule of CO2 will never be by itself and invariably be accompanied with every type of molecules, including artificial ones that will act as a ‘cancer’ to the organism. When the produces CO2 encounters vegetation, photosynthesis will be attempted and immediately the photosynthesis will be affected by every molecule that accompanied the CO2 molecule in question. How can we then expect a natural system (such as plant) to not consider all the accompanying molecules and ‘look’ at the CO2 as independent of the other molecules? It is indeed an absurd concept. Modeling nature as it is, nevertheless, would still involve collecting and collating a large amount of data that takes at least initially the form of apparently discrete events. The temptation is to go with statistical methods, as has been the case for the ‘97% consensus’ group. This, however, is also one of those points of bifurcation where the actual content of the data of nature has to be taken into account. The fact that events recorded from some processes in nature may be observed as discrete and distinct, does not mean or necessarily prove that these events are stochastically independent. According to the prevailing theories of mathematical probability, it is legitimate to treat a sufficiently very large number of similar events, e.g., tossing dice, as though these discrete events approximated some continuous process. There is a “Strong Law of Large Numbers” [SLLN] and a more relaxed, less bounded version known as the “Weak Law of Large Numbers” [WLLN], which propose a mathematical justification for just such a procedure (Kolmogorov, 1930). When we are examining moments in nature, however, which are defined to some extent by some actual passage of time, apart from continuous fluid flow or other motion that is similarly continuous in time, how legitimate or justifiable can it be to

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approximate discrete events using “nice”, i.e., tractable, exponential functions that are continuous and defined everywhere between negative and positive infinity? If the event of interest, although in itself discrete, cycles in a continuum, it would seem that there should arise no particular problem (Of course, there is also no problem for any phenomenon that has been human-engineered and whose data output is to that extent based on human artifice rather than nature). However, the fact that some recorded data of any large number of such discrete events, exists cannot be taken as sufficient. It is also necessary to be able to establish that the observations in question were recorded in the same time continuum, not in different continua attended by a different set or sets of external surrounding [boundary] conditions. To group and manipulate such data with the tools of mathematical statistics, however, as though the conditions in which the phenomena actually occurred were a matter of indifference, and cannot be justified on the basis of invoking the logic of either the SLLN or WLLN. The continuity of the number and of the characteristics of the abstract construct known as “the real numbers”, which form the basis of the SLLN and WLLN, has nothing inherently to do with whether natural phenomena being studied or measured are themselves, actually continuous or occurring within a continuum possessing cyclical features. Some definite yet indeterminate number of such data measurements of the same event — recorded, however, in unrelated and distinct times and places — would likely be so truly “discrete” as not to form part of any actual time-continuum in nature. Mathematically, working purely with numbers, it may not matter whether there was any physical continuum within which discrete data points were being recorded. In such cases, the strictures of the SLLN and WLLN are adequate, and the approximation of the discrete by the continuous generates no problem. But what we can “get away with” dealing in pure numbers is one thing. Interpreting the results in terms of physical realities is another matter. When it comes to interpreting the results in terms of physical realities in the natural environment in which the phenomena of interest were observed and recorded, the absence of a physical continuum means that any conclusions as to the physics or nature-science that may underlie or may also be taking place will, and indeed must necessarily, be aphenomenal. Correlations discovered in such data may very well be aphenomenal. Any inferences as to possible “cause-effect” relationships will also be aphenomenal. Assuming abstract numerical continuity on the real-number line for an extremely large number of discrete data points generated for the same abstract event, lets us overlay another level of information atop the actual discrete data because the tendency of the numerical data purely as numbers is isomorphic to the envelope generated by joining the discrete data points. This isomorphism, however, is precisely what cannot be assumed in advance regarding the underlying phenomenon, or phenomena, generating whatever observations are being recorded from some actual process taking place in nature. What does this mean? When it comes to the science of nature, the mere fact of some event’s occurrence is necessary information, but in itself this information is also insufficient without other additional “meta”-data about the pathway(s) of the event’s occurrence, etc. There are strong grounds here for treating with the greatest skepticism a wide range of quantitative projections generated by all the current models of global warming and climate changes.

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491

Removable Discontinuities: Phases and Renewability of Materials

By introducing time spans of examination unrelated to anything characteristic of the phenomenon itself being observed in nature, discontinuities appear. These are entirely removable, but they appear to the observer as finite limits of the phenomenon itself, and as a result, the possibility that these discontinuities are removable is not even considered. This is particularly problematic when it comes to the matter of phase transitions of matter and the renewability or non-renewability of energy. The transition between the states of solid, liquid and gas in reality is continuous, but the analytical tools formulated in classical physics are anything but; each P-V-T model applies to only one phase and one composition, and there is no single P-V-T model applicable to all phases (Cismondi and Mollerup, 2005). Is this an accident? Microscopic and intangible features of phase-transitions have not been taken into account. As a result, this limits the field of analysis to macroscopic, entirely tangible features and modeling therefore becomes limited to one phase and one composition at a time. When it comes to energy, everyone has learned that it comes in two forms—renewable and nonrenewable. If a natural process is being employed, however, everything must be “renewable” by definition in the sense that, according to the Law of Conservation of Energy, energy can be neither created nor destroyed. Only the selection of the time frame misleads the observer into confounding what is accessible in that finite span with the idea that energy is therefore running out. The dead plant material that becomes petroleum and gas trapped underground in a reservoir is being added to continually, but the rate at which it is being extracted has become set according to an intention that has nothing to do with what the optimal timeframe in which the organic source material could be renewed. Thus, “non-renewability” is not any kind of absolute fact of nature. On the contrary, it amounts to a declaration that the pathway on which the natural source has been harnessed is anti-Nature.

10.5.2 Rebalancing Mass and Energy Mass and energy balances inspected in depth disclose intention as the most important parameter, as the sole feature that renders the individual accountable to, and within, nature. This is rife with serious consequences for the black-box approach of conventional engineering, because a key assumption of the black-box approach stands in stark and howling contradiction to one of the key corollaries of that most fundamental principle of all: the Law of Conservation of Matter. In fact, this is only possible if there is no leak anywhere and no mass can flow into the system from any other point. However, mass can flow into the system from any other point – thereby rendering the entire analysis a function of tangible measurable quantities; i.e., a “science” of tangibles-only Figure 10.27. The mass conservation theory indicates that the total mass is constant. It can be expressed as follows:



(10.8)

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Known accumulation

Known mass out

Figure 10.27 Conventional Mass Balanceequation incorporating only tangibles. Unknown mass in

Known accumulation Known mass out

Known mass in

Unknown accumulation

Unknown mass out

Figure 10.28 Mass-balance equationincorporating tangibles and intangibles.

where m = mass and i is the number from 0 to ∞. In the true sense, this mass balance encompasses mass from macroscopic to microscopic and detectable to undetectable; i.e., from tangible to intangible. Therefore, the true statement should be as illustrated in Figure 10.28:

” ” ”

− ” ” −

” ”

− ” − ” ”

(10.9)

”

The unknown masses and accumulations are neglected, which means they are considered to be equal to zero. Every object has two masses: 1. Tangible mass. 2. Intangible mass, usually neglected. Then, equation [3.5] becomes:











 (10.10)

The unknowns can be considered intangible, yet essential to include in the analysis as they incorporate long-term and other elements of the current timeframe. In nature, the deepening and broadening of order is continually observed, with many pathways, circuits and parts of networks being partly or even completely repeated and the overall balance being further enhanced. Does this actually happen as arbitrarily as conventionally assumed? A little thought suggests this must take place principly as a result and/or

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as a response to human activities and the response of the environment to these activities and their consequences. Nature itself has long established its immediate and unbreachable dominion over every activity and process of everything in its environment, and there is no other species that can drive nature into such modes of response. In the absence of the human presence, nature would not be provoked into having to increase its order and balance, and everything would function in the “zero net waste” mode. An important corollary of the Law of Conservation of Mass, that mass can be neither created nor destroyed, is that there is no mass that can be considered in isolation from the rest of the universe. Yet, the black-box model clearly requires just such an impossibility. Since, however, human ingenuity can select the time frame in which such a falsified “reality” will be exactly what the observer perceives, the model of the black box can be substituted for reality and the messy business of having to take intangibles into account is foreclosed once and for all.

10.5.3

Energy: Toward Scientific Modeling

There have been a number of theories developed in the past centuries to define energy and its characteristics. However, none of the theories is enough to describe energy properly. All of the theories are based on much idealized assumptions which have never existed practically. Consequently, the existing model of energy and its relation to others cannot be accepted confidently. For instance, the second law of thermodynamics depends on Carnot cycle in the classical thermodynamics where none of the assumptions of Carnot’s cycle exists in reality. Definitions of ideal gases, reversible processes and adiabatic processes used in describing the Carnot’s cycle are imaginary. In 1905, Einstein came up with his famous equation, E=mc2 which states an equivalence between energy (E) and relativistic mass (m), in direct proportion to the square of the speed of light in a vacuum (c2). However, the assumptions of constant mass and the concept of vacuum do not exist in reality. Moreover, this theory was developed on the basis of Planck’s constant which was derived from black body radiation. Perfectly black bodies don’t even exist in reality. So it is found that the development of every theory is dependent on a series of assumptions which do not exist in reality. The scientific approach must include restating the mass balance. For whatever else remains unaccounted for, the mass balance equation, which in its conventional form necessarily falls short of explaining the functionality of nature coherently as a closed system, is supplemented by the energy balance equation. For any time, the energy balance equation can be written as:

(10.11) Where a is the activity equivalent to potential energy. In the above equation, only potential energy is taken into account. Total potential energy, however, must include all forms of activity, and here once again, a large number of intangible forms of activity, e.g., the activity of molecular and smaller forms of matter, cannot be “seen” and accounted for in this energy balance. The presence of human activity

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introduces the possibility of other potentials that continually upset the energy balance in nature. There is overall balance but some energy forms, e.g., electricity (either from combustion or nuclear sources), would not exist as a source of useful work except for human intervention which continually threaten to push this into a state of imbalance. In the definition of activity, both time and space are included. The long term is defined by time being taken to infinity. The “zero waste” condition is represented by space going to infinity. There is an intention behind each action and each action is playing an important role in creating overall mass and energy balance. The role of intention is not to create a basis for prosecution or enforcement of certain regulations. It is rather to provide the individual with a guideline. If the product or the process is not making things better with time, it is fighting nature – a fight that cannot be won and is not sustainable. Intention is a quick test that will eliminate the rigorous process of testing feasibility, long-term impact, etc. Only with “good” intention can things improve with time. After that, other calculations can be made to see how fast the improvements will take place. In clarifying the intangibility of an action or a process, the equation has some constant which is actually an infinite series:



(10.12)

If each term of Equation (3.8) converges, it will have a positive sign, indicating intangibility; hence the effect of each term thus becomes important for measuring the intangibility overall. On this path, it should also become possible to analyze the effect of any one action and its implications for sustainability overall as well. It can be inferred that man-made activities are not enough to change the overall course of nature. Failure up until now, however, to include an accounting for the intangible sources of mass and energy, has brought about a state of affairs in which, depending on the intention attached to such interventions, the mass-energy balance can either be restored and maintained over the long-term, or increasingly threatened and compromised in the short- term. In the authors’ view, it would be far better to develop the habit of investigating Nature and the prospects and possibilities it offers Humanity’s present and future, by considering time t at all scales, going to infinity, and giving up once and for all the habit of resorting to time scales that appear to serve some immediate ulterior interest in the short-term but which in fact have nothing to do with natural phenomena, must therefore lead to something that will be anti-Nature in the long-term and the short-term., The main obstacle to discussing and positioning the matter of human intentions within the overall approach to the Laws of Conservation of Mass, Energy and Momentum stems from notions of the so-called “heat death” of the universe, predicted in the 19th century by Lord Kelvin and enshrined in his Second Law of Thermodynamics. In fact, however, this idea that the natural order must “run down” due to entropy, eliminating all sources of “useful work,” naively attempts to assign what amounts to a permanent and decisive role for negative intentions in particular without formally fixing or defining any role whatsoever for human intentions in general. Whether they arise out of the black-box approach of the mass-balance equation or the unaccounted missing potential energy sources in the energy balance equation, failures in the shortterm become especially highly consequential when they are used by those defending

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the status quo to justify anti-Nature “responses” of the kind well-described elsewhere as typical examples of “the roller coaster of the Information Age” (Islam et al., 2003).

10.5.4

The Law of Conservation of Mass and Energy

Lavoisier’s first premise was “mass cannot be created or destroyed”. This assumption does not violate any of the features of Nature. However, his famous experiment had some assumptions embedded in it. When he conducted his experiments, he assumed that the container was sealed perfectly — something that would violate the fundamental tenet of Nature that an isolated chamber can be created. Rather than recognizing the aphenomenality of the assumption that a perfect seal can be created, he “verified” his first premise (law of conservation of mass) “within experimental error”. Einstein’s famous theory is more directly involved with mass conservation. He derived E = mc2 using the first premise of Planck (1901). However, in addition to the aphenomenal premises of Planck, this famous equation has its own premises that are aphenomenal. However, this equation remains popular and is considered to be useful (in the pragmatic sense) for a range of applications, including nuclear energy. For instance, it is quickly deduced from this equation that 100 kJ is equal to approximately 10-9 gram. Because no attention is given to the source of the matter nor of the pathway, the information regarding these two important intangibles is wiped out from the conventional scientific analysis. The fact that a great amount of energy is released from a nuclear bomb is then taken as evidence that the theory is correct. By accepting this at face value (heat as a one-dimensional criterion), heat from nuclear energy, electrical energy, electromagnetic irradiation, fossil fuel burning, wood burning or solar energy, becomes identical. In terms of the well-known laws of conservation of mass (m), energy (E) and momentum (p), the overall balance, B, within Nature may be defined as some function of all of them: (10.13) The perfection without stasis that is Nature means that everything that remains in balance within it is constantly improving with time. That is: (10.14) If the proposed process has all concerned elements so that each element is following this pathway, none of the remaining elements of the mass balance discussed later will present any difficulties. Because the final product is being considered as time extends to infinity, the positive (“>0”) direction is assured.

10.5.5 Avalanche Theory A problem posed by Newton’s Laws of Motion, however, is the challenge they represent of relying upon and using the principle of energy-mass-momentum conservation. This principle is the sole necessity and the sufficient condition for analyzing and modeling natural phenomena in situ, so to speak — as opposed to analyzing and generalizing from fragments captured or reproduced under controlled laboratory conditions.

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The underlying problem is embedded in Newton’s very notion of motion as the absence of rest, coupled with his conception of time as the duration of motion between periods of rest. The historical background and other contradictions of the Newtonian system arising from this viewpoint are examined at greater length in Abou-Kassem et al. (2008), an article that was generated as part of an extended discussion of, and research into, the requisites of a mathematics that can handle natural phenomena unadorned by linearizing or simplifying assumptions. Here the aim is to bring forward those aspects that are particularly consequential for approaching the problems of modeling phenomena of Nature, where “rest” is impossible and inconceivable. Broadly speaking, it is widely accepted that Newton’s system, based on his three laws of motion accounting for the proximate physical reality in which humans live on this Earth coupled with the elaboration of the principle of universal gravitation to account for motion in the heavens of space beyond this Earth, makes no special axiomatic assumptions about physical reality outside the scale on which any human being can observe and verify for himself / herself (i.e., the terrestrial scale on which we go about living daily life). For example, Newton posits velocity, v, as a change in the rate at which some mass displaces its position in space; s, relative to the time duration; t, of the motion of the said mass. That is: ∂ ∂

(10.15)

This is no longer a formula for the average velocity, measured by dividing the net displacement in the same direction as the motion impelling the mass by the total amount of time that the mass was in motion on that path. This formula posits something quite new (for its time, viz., Europe in the 1670s), actually enabling us to determine the instantaneous velocity at any point along the mass’s path while it is still in motion. The “v” that can be determined by the formula given in equation [4.3] above is highly peculiar. It presupposes two things. First, it presupposes that the displacement of an object can be derived relative to the duration of its motion in space. Newton appears to cover that base already by defining this situation as one of what he calls “uniform motion”. Secondly, however, what exactly is the time duration of the sort of motion Newton is setting out to explain and account for? It is the period in which the object’s state of rest is disturbed, or some portion thereof. This means the uniformity of the motion is not the central or key feature. Rather, the key is the assumption in the first place that motion is the opposite of rest. In his First Law, Newton posits motion as the disturbance of a state of rest. The definition of velocity as a rate of change in spatial displacement relative to some time duration means that the end of any given motion is either the resumption of a new state of rest or the starting-point of another motion that continues the disturbance of the initial state of rest. Furthermore, only to an observer external to the mass under observation can motion appear as the disturbance of a state of rest and can a state of rest appear as the absence or termination of motion. Within nature, meanwhile, is anything ever at rest? The struggle to answer this question exposes the conundrum implicit in the Newtonian system: everything “works” — all systems of forces are “conservative” — if and only if the observer stands outside the reference frame in which a phenomenon is observed.

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In Newton’s mechanics, motion is associated not with matter-as-such, but only with force externally applied. Inertia , on the other hand, is definitely ascribed to mass. Friction is considered only as a force equal and opposite to that which has impelled some mass into motion. Friction, in fact, exists at the molecular level, however, as well as at all other scales — and it is not a force externally applied. It is a property of matter itself. It follows that motion must be associated fundamentally not with force(s) applied to matter, but rather with matter itself. Although Newton nowhere denies this possibility, his First Law clearly suggests that going into motion and ceasing to be in motion are equal functions of some application of force external to the matter in motion; i.e., motion is important relative to some rest or equilibrium condition. Following Newton’s presentation of physical reality in his Laws of Motion, if time is considered mainly as the duration of motion arising from force(s) externally applied to matter, then it must cease when an object is “at rest”. Newton’s claim in his First Law of Motion that an object in motion remains in (uniform) motion until acted on by some external force appears at first to suggest that, theoretically, time is taken as being physically continual. It is mathematically continuous, but only as the independent variable, and indeed, according to equation (4.3) above, velocity v becomes undefined if timeduration t becomes 0. On the other hand, if motion itself ceases— in the sense of ∂s, the rate of spatial displacement, going to 0 — then velocity must be 0. What has then happened, however, to time? Where in nature can time be said either to stop or to come to an end? If Newton’s mechanism is accepted as the central story, then many natural phenomena have been operating as special exceptions to Newtonian principles. While this seems highly unlikely, its very unlikelihood does not point to any way out of the conundrum. This is where momentum p, and — more importantly — its “conservation”, comes into play. In classically Newtonian terms: ∂ ∂

(10.16)

Hence ∂ ∂

∂ ∂

∂ ∂

∂ ∂

(10.17)

If the time it takes for a mass to move through a certain distance is shortening significantly as it moves, then the mass must be accelerating. An extreme shortening of this time corresponds therefore to a proportionately large increase in acceleration. However, if the principle of conservation of momentum is not to be violated, either: a. the rate of its increase for this rapidly accelerating mass is comparable to the increase in acceleration — in which case the mass itself will appear relatively constant and unaffected; or b. mass itself will be increasing, which suggests that the increase in momentum will be greater than even that of the mass’s acceleration; or c. mass must diminish with the passage of time, which implies that any tendency for the momentum to increase also decays with the passage of time.

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The rate of change of momentum (∂p/∂t) is proportional to acceleration (the rate of change in velocity, as expressed in the ∂2 s/∂t2 term) experienced by the matter in motion. It is proportional as well to the rate of change in mass with respect to time (the ∂m/∂t term). If the rate of change in momentum approaches the acceleration undergone by the mass in question, i.e., if ∂p/∂t → ∂2 s/∂t2, then the change in mass is small enough to be neglected. On the other hand, a substantial rate of increase in the momentum of some moving mass — on any scale much larger than its acceleration — involves a correspondingly substantial increase in mass. The analytical standpoint expressed in equation (4.4) and equation (4.5) above work satisfactorily for matter in general, as well as for Newton’s highly specific and indeed peculiar notion of matter in the form of discrete object-masses. Of course, here it is easy to miss the “catch”. The “catch” is the very assumption in the first place that matter is an aggregation of individual object-masses. While this may well be true at some empirical level at a terrestrial scale — 10 balls of lead shot, say, or a cubic liter of wood sub-divided into exactly 1,000 one-cm by one-cm by one-cm cubes of wood — it turns out in fact to be a definition that addresses only some finite number of properties of specific forms of matter that also happen to be tangible and hence accessible to us at a terrestrial scale. Once again, the generalizing of what may only be a special case — before it has been established whether the phenomenon is a unique case, a special but broad case, or a characteristic case — begets all manner of mischief. To appreciate the implications of this point, consider what happens when an attempt is made to apply these principles to object-masses of different orders and/or vastly different scales, but within the same reference-frame. Consider the snowflake — a highly typical piece of atmospheric mass. Compared to the mass of some avalanche of which it may come to form a part of, the mass of any individual component snowflake is negligible. Negligible as it may seem, however, it is not zero. Furthermore, the accumulation of snowflakes in the avalanching mass of snow means that the cumulative mass of snowflakes is heading towards something very substantial, infinitely larger than that of any single snowflake. To grasp what happens for momentum to be conserved between two discrete states, consider the starting-point: p=mv. Clearly in this case, that would mean in order for momentum to be conserved: − − −

which Means



(10.18)

(10.19)

At a terrestrial scale, avalanching is a readily-observed physical phenomenon. At its moment of maximum (destructive) impact, an avalanche indeed looks like a trainwreck unfolding in very slow motion. However, what about the energy released in the avalanche? Of this we can only directly see the effect, or footprint — and another aphenomenal absurdity pops out: an infinitude of snowflakes, each of negligible mass, have somehow imparted a massive release of energy. This is a serious accounting problem— not not only momentum, but mass and energy as well, are to be conserved throughout the universe.

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The same principle of conservation of momentum enables us to “see” what must happen when an electron or electrons bombard a nucleus at a very high speed. Now we are no longer observing or operating at the terrestrial scale. Once again, however, the explanation conventionally given is that since electrons have no mass, the energy released by the nuclear bombardment must have been latent and entirely potential, stored within the nucleus. Clearly, then, as an accounting of what happens in nature (as distinct from a highly useful toolset for designing and engineering certain phenomena involving the special subclass of matter represented by Newton’s object-masses), Newton’s central model of the object-mass is insufficient. Is it even necessary? Tellingly, on this score, the instant it is recognized that there is no transmission of energy without matter, all the paradoxes we have just elaborated on are removable. Hence, we may conclude that for properly understanding and becoming enabled to emulate nature at all scales, the mass-energy balance and the conservation of momentum are necessary and sufficient. On the other hand, neither the constancy of mass, nor the speed of light, nor even uniformity in the passage and measure of time are necessary or sufficient. This realization holds considerable importance for how problems of modeling Nature are addressed. An infinitude of energy and mass transfers take place in Nature, above and to some extent in relation to the surface of the earth, comprising altogether a large part of the earth’s “life cycle”. In order to achieve any non-trivial model of Nature, time itself becomes a highly active factor of prepossessing — and even overwhelming —importance. Its importance is perhaps comparable only to the overwhelming role that time plays in sorting out the geology transformations under way inside the earth.

10.5.6 Simultaneous Characterization of Matter and Energy The key to the sustainability of a system lies within its energy balance. In this context, equation (4.11) is of utmost importance. This equation can be used to define any process, for which the following equation applies: (10.20) In the above equation, Qin in expresses for the inflow of matter, Qacc represents the same for accumulating matter, and Qout represents the same for the outflowing of matter. Qacc will have all terms related to dispersion/diffusion, adsorption/desorption, and chemical reactions. This equation must include all available information regarding inflow matters, e.g., their sources and pathways, the vessel materials, catalysts, and others. In this equation, there must be a distinction made among various matter, based on their sources and pathways. Three categories are proposed: 1. Biomass (BM); 2. Convertible non-biomass (CNB); and 3. Non-convertible non-biomass (NCNB). Biomass is any living object. Even though, conventionally dead matter is also called biomass, we avoid that denomination as it is difficult to scientifically discern when a matter becomes non-biomass after death. The convertible non-biomass (CNB) is the

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one that due to natural processes will be converted to biomass. For example, a dead tree is converted into methane after microbial actions; the methane is naturally broken down into carbon dioxide, and plants utilize this carbon dioxide in the presence of sunlight to produce biomass. Finally, non-convertible non-biomass (NCNB) is a matter that emerges from human intervention. These matters do not exist in nature and their existence can only be considered artificial. For instance, synthetic plastic matters (e.g., polyurethane) may have a similar composition as natural polymers (e.g., human hair, leather), but they are brought into existence through a very different process than that of natural matters. Similar examples can be cited for all synthetic chemicals, ranging from pharmaceutical products to household cook wares. This denomination makes it possible to keep track of the source and pathway of a matter. The principle hypothesis of this denomination is: All matters naturally present on Earth are either BM or CNB, with the following balance: (10.21) The quality of CNB2 is different from or superior to that of CNB1 in the sense that CNB2 has undergone one extra step of natural processing. If nature is continuously moving to better the environment (as represented by the transition from a barren Earth to a green Earth), CNB2 quality has to be superior to CNB1 quality. Similarly, when matter from natural energy sources comes in contact with BMs, the following equation can be written: (10.22) Applications of this equation can be cited from biological sciences. When sunlight comes in contact with retinal cells, vital chemical reactions take place that results in the nourishment of the nervous system, among others (Chhetri and Islam, 2008). In these mass transfers, chemical reactions take place entirely differently depending on the light source, the evidence of which has been reported in numerous publications (e.g., Lim and Land, 2007). Similarly, sunlight is also essential for the formation of vitamin D, which is in itself essential for numerous physiological activities. In the above equation, vitamin D would fall under BM2. This vitamin D is not to be confused with the synthetic vitamin D, the latter one being the product of artificial processes. It is important to note that all products on the right hand side are of greater value than the ones on the left hand side. This is the inherent nature of natural processing – a scheme that continuously improves the quality of the environment, and is the essence of sustainable technology development. The following equation shows how energy from NCNB will react with various types of matter. (10.23) An example of the above equation can be cited from biochemical applications. For instance, if artificially generated UV comes in contact with bacteria, the resulting bacteria mass would fall under the category of NCNB, stopping further value addition by nature. Similarly, if bacteria are destroyed with synthetic antibiotic (pharmaceutical product, pesticide, etc.), the resulting product will not be conducive to value addition through natural processes, instead becoming a trigger for further deterioration and insult to the environment.

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Sustainable pathway CO2

Plants

Soil/sand

CH4

Bioreactor

Microbe converts to biomass or

Soil/sand

Plastic Non-biomass

Non-biomass

Figure 10.29 Sustainable pathwayfor material substance in the environment.

(10.24) An example of the above equation can be cited from biochemical applications. The NCNB1 which is created artificially reacts with CNB1 (such as N2, O2) and forms NCNB3. The transformation will be in a negative direction, meaning the product is more harmful than it was earlier. Similarly, the following equation can be written: (10.25) An example of this equation is that sunlight leads to photosynthesis in plants, converting NCBM to MB, whereas fluorescent lighting, which would freeze that process, can never convert natural non-biomass into biomass. The principles of the Nature model proposed here are restricted to those of mass (or material) balance, energy balance and momentum balance. For instance, in a nonisothermal model, the first step is to resolve the energy balance based on temperature as the driver for some given time period, the duration of which has to do with characteristic time of a process or phenomenon. This is a system that manifests phenomena of thermal diffusion, thermal convection and thermal conduction, without spatial boundaries but nonetheless giving rise to the “mass” component. The key to the system’s sustainability lies within its energy balance. Here is where natural sources of biomass and non-biomass must be distinguished from non-natural, non-characteristic, industrially synthesized sources of non-biomass. Figure  10.29 envisions the environment of a natural process as a bioreactor that does not and will not enable conversion of synthetic non-biomass into biomass. The key problem of mass balance in this process, as in the entire natural environment of the earth as a whole, is set out in Figure 10.30: the accumulation rate of synthetic nonbiomass continually threatens to overwhelm the natural capacities of the environment to use or absorb such material. In evaluating equation (4.12), it is desirable to know all of the contents of the inflow matter. However, it is highly unlikely to know all the contents, even at a macroscopic

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First organic Time, t=∞ First synthetic element

Non-biomass

Natural non-biomass (convertible to biomass, e.g. by sunlight) DDT, Freon, Plastic (Synthetic non-biomass, incovertible to biomass)

Figure 10.30 Synthetic non-biomassthat cannot be converted into biomass will accumulate far faster thannaturally-sourced non-biomass, which can potentially always be converted into biomass.

Beneficial Convertible CO2

Time, t=∞

Non-convertible CO2 Harmful Figure 10.31 Results from Carboncombustion in a natural reactor and an artificial.

level. In absence of a technology that would find the detailed content, it is important to know the pathway of the process to have an idea of the source of impurities. For instance, if de-ionized water is used in a system, one would know that its composition would be affected by the process of de-ionization. Similar rules apply to products of organic sources, etc. If we consider the combustion reaction (coal, for instance) in a burner, the bulk output will likely to be CO2. However, this CO2 will be associated with a number of trace chemicals (impurities) depending upon the process it passes through. Because, equation (4.12) includes all known chemicals (e.g., from source, adsorption/desorption products, catalytic reaction products), it would be able to track matters in terms of CNB and NCNB products. Automatically, this analysis will lead to differentiation of CO2 in terms of the pathway and the composition of the environment which is the basic requirement of equation (4.11). According to equation (4.12), charcoal combustion in a burner made up of clay will release CO2 and natural impurities of

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charcoal and the materials from the burner itself. Similar phenomenon can be expected from a burner made up of nickel plated with an exhaust pipe made up of copper. Anytime, CO2 is accompanied with CNB matter, it will be characterized as beneficial to the environment. This is shown in the positive slope of Figure 10.31. On the other hand, when CO2 is accompanied with NCNB matter, it will be considered to be harmful to the environment, as this is not readily acceptable by the eco-system. For instance, the exhaust of the Cu or Ni-plated burner (with catalysts) will include chemicals, e.g., nickel, copper from pipe, trace chemicals from catalysts, beside bulk CO2 because of adsorption/desorption, catalyst chemistry, etc. These trace chemicals fall under the category of NCNB and cannot be utilized by plants (negative slope from). This figure clearly shows that the upward slope case is sustainable as it makes an integral component of the eco-system. With the conventional mass balance approach, the bifurcation graph of would be incorrectly represented by a single graph that is incapable of discerning between the different qualities of CO2 because the information regarding the quality (trace chemicals) are lost in the balance equation.

10.6

Classification of CO2

Carbon dioxide is considered to be the major precursor for current global warming problems. The entire climate change hysteria is premised on the ‘vile of carbon dioxide’ as if CO2 is not a part of the ecosystem. This characterization is typical of New Science. The origin of this like of characterization goes back to Atomism5. Nobel Laureate Linus Pauling – prizewinner both for Chemistry and Peace, transmuted his work into the notion that humanity could live better with itself, and with nature, through the widest possible use and/or ingestion of chemicals. Essentially, his position is that “chemicals are chemicals,” i.e., that knowledge of chemical structure discloses everything we need to know about physical matter, and that all chemical combinations sharing the same structure are identical regardless of how differently they may actually have been generated or existed in their current form (his1954 Nobel Prize in Chemistry was "for his research into the nature of the chemical bond and its application to the elucidation of the structure of complex substances."). This approach essentially disconnects a chemical product from its historical pathway. Even though the role of pathways has been understood by many civilizations for centuries, systematic studies questioning the principle have only been a recent development. For instance, in matters of Vitamin C, this approach advanced the principle that, whether from a natural or synthetic source and irrespective of the pathway it travels, all vitamin C is the same. Whereas in 1995, Gale et al., reported that vitamin C supplements did not lower death rates among elderly people and may actually have increased the risks of dying. Moreover, carotene supplementation may do more harm than good for patients with lung cancer (Josefson

5 This notion goes back to Democratus, who introduced the notion of atomism and that notion was taken as fact by Aristotle, Newton and all contemporary scientists (see Islam et al., 2010 and Khan and Islam, 2016 for a detailed discussion).

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2003). Obviously, such a conclusion cannot be made if subjects were taking vitamin C from natural sources. In fact, the practices of people who live the longest lives indicate that natural products do not have any negative impact on human health (Haile et al., 2006). It has been reported that patients being treated for cancer should avoid antioxidant supplements, including vitamin C, because cancer cells gobble up vitamin C faster than normal cells which might give greater protection from tumors (Agus et al. 1999). Antioxidants present in nature are known to act as anti-aging agents. Obviously these antioxidants are not the same as those synthetically manufactured. The previously used hypothesis, “chemicals are chemicals,” fails to distinguish between the characteristics of synthetic and natural vitamins and antioxidants. The impact of synthetic antioxidants and vitamin C in body metabolism would be different than that of natural sources. Numerous other cases can be cited demonstrating that the pathway involved in producing the final product is of utmost importance. Some examples have recently been investigated by Islam and coworkers (Khan and Islam 2007; Islam et al., 2010; 2015; 2016; Khan and Islam, 2012, 2016). If the pathway is considered, it becomes clear that organic produce is not the same as non-organic produce, natural products are not the same as bioengineered products, natural pesticides are not the same as chemical pesticides, natural leather is not the same as synthetic plastic, natural fibers are not the same as synthetic fibers, natural wood is not the same as fiber-reinforced plastic, etc. However, it is the economics that drove scientists to by-pass this true science and focus on the most tangible aspects that would give the desired conclusions (Islam et al., 2018a). Once the entire history of materials is considered a different picture emerges. For instance, in addition to being the only ones that are good for the long term, natural products are also found to be extremely efficient and economically attractive. Numerous examples are given in Khan and Islam (2007) as well as Chhetri and Islam (2008), in which it is shown that natural materials are more effective than their synthetic counterparts, without any negative side-effect (and with positive impact). For instance, unlike synthetic hydrocarbons, bacteria easily degrades natural vegetable oils (AlDarbi et al. 2005). The application of wood ash to remove arsenic from aqueous streams is more effective than removing it by the use of any synthetic chemicals (Rahman et al. 2004; Wassiuddin et al. 2002).

10.6.1 Isotopic Characterization At present, there is consensus regarding the rate of fossil fuel combustion, which should account for an annual increase in CO2 by four ppm. However, the observed increase is only about two ppm. This discrepancy is explained in various ways. It is said that some CO2 dissolves in seawater. In pre-industrial times, the CO2 concentration of air was in equilibrium with the CO2 concentration of surface seawater. As atmospheric CO2 has risen, the equilibrium has been perturbed, such that the “excess” of CO2 in air now drives a flux of CO2 into the sea in an effort to re-establish equilibrium. It is also stated that the removal of CO2 from the atmosphere is related to the growth of forests and grasslands worldwide. This latter conclusion leads to the paradox that there has been severe deforestation, also attributed to industrial activities. This is countered by asserting that the rate of growth of large masses of vegetation (mostly forests) is higher than

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S(o/oo/ppmv) 0.03 0.02 0.01 0 0

1000 2000 3000 pCO2 ppmv

4000

Figure 10.32 The effect of pCO2 on C3land plant carbon isotope fractionation based on field and chamber experimentson a wide range of C3 land plant species (from Cui and Schubert, 2016).

that of deforestation. Of course, that poses the question, if forestation and vegetation is increasing, why is the CO2 concentration rising? To a first approximation, about half the CO2 emitted by combustion remains in the atmosphere, about 35% dissolves in the oceans, and 15% is taken up by the increase in the biomass of forests. It is recognized that CO2 absorption has declined in the ocean and at the same time general vegetation has not been using CO2 from combustion activities, rejecting a bulk amount to the atmosphere, thus causing overall rise. In this section, carbon dioxide has also been classified based on the source from where it is emitted, the pathway it traveled, and age of the source from which it came. It has been reported that plants favor a lighter form of carbon dioxide for photosynthesis and discriminate against heavier isotopes of carbon decades ago (Farquhar et al. 1989). They introduced a formulation, in which carbon isotopic composition is reported in the delta notation relative to the V-PDB (Vienna Pee Dee Belemnite, see Libes, 1992 for details) standard. δ13C (pronounced "delta c thirteen") is an isotopic signature, a measure of the ratio of stable isotopes 13C : 12C, reported in parts per thousand (per mil, ‰).

⎛



⎜ ⎝

⎞



⎟ − ⎠ ×



(10.26)

In Eq. 10.1, the standard is an established reference material. The value of δ13C varies in time as a function of productivity, the signature of the inorganic source, organic carbon burial and vegetation type. In essence, this term is a signature of the path traveled by a material or the time function. Biological processes preferentially take up the lower mass isotope through kinetic fractionation. Therefore, the fractionation itself becomes a measure of the quality of CO2. The following formulation is based on Farquhar et al. (1989) and was used by several researchers, who studied the kinetic fractionation process.



−

≈

−

(10.27)

in which, Δ13 is the C isotope discrimination, δ13Cair is the carbon isotope ratio of atmospheric CO2 (−7.8 2030) and δ13Cplant is the measured δ13C value of leaf material.

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Ever since the recognition that the past concentrations of atmospheric CO2 level (pCO2) is critical to plant metabolism and extent of photosynthesis, many research projects have been undertaken. These studies attempt to determine correlation between pCO2 with changes in carbon isotope fractionation (Δ13C) in C3 land plants6. Figure 10.32 shows the amount of carbon isotope fractionation per change in pCO2 (S, ‰/ppmv) as a function of pCO2. Note the similarity among the three S-curves. Circles are plotted as the midpoint of the range of pCO2 tested for each study. This sensitivity can vary under varying thermal conditions. Previous studies have reported that photosynthesis and plant enzyme activity can be strongly inhibited when grown at temperatures below 5C (Graham and Patterson, 1982; Ramalho et al., 2003). Some woody plants cannot withstand much below −6 C for any length of time and cease growth if the maximum daily temperature is below 9 C (Parker, 1963). For these low temperature conditions, thermal effects become the dominant limiting factors. Xu et al. (2015) reported variation in Δ13 with changing temperature. They observed a strong impact of mean annual temperature (MAT) on Δ13 in two mountain regions. MAT together with soil water content (SWC) in total accounted for a large proportion of the variation in Δ13 of the two mountainous regions. They observed that the impact of soil water availability on carbon isotope discrimination was limited for lower temperature values. In (Equation 10.2) , the fractionation process is controlled by the diffusion of CO2 through the stomata (Craig 1953) as well as CO2 fixation by ribulose bisphosphate carboxylase/oxygenase (RuBisCO; Farquhar and Richards 1984). These processes are highly sensitive to particulates of heavy metals as well as synthetic chemicals. Hartman and Danin (2010) reported strong correlation between dry season green plants and rainfall – attributed to the combined product of ground water availability, evaporative demand, and improved water use efficiency (unique to desert shrubs and trees). Escudero et al. (2008) demonstrated that long-lived leaves from lignified species have higher δ13C values than short-lived leaves, due to reduced transpiration. They argued that this adaptation was designed to combat seasonal and annual shortages of water by minimizing the risk of leaf desiccation. Few studies have been available on how this process is altered in presence of anthropogenic CO2. Fardusi et al. (2016) conducted meta-analysis with large amount of data. They concuded that the relationship between 13C and growth is better characterized at juvenile stages, under near-optimal and controlled conditions, and by analyzing 13C in leaves rather than in wood. Carbon isotope composition (13C) in plant tissues offers an integrated measure of the ratio between chloroplastic and atmospheric CO2 concentrations (Cc/Ca), and hence can be used to estimate the ratio between net CO2 assimilation rate (A) and stomatal conductance for water vapour, i.e., intrinsic water-use efficiency (WUEi) after making certain assumptions about mesophyll conductance and post-photosynthetic fractionations (Farquhar et al., 1984). Note that during an adaptation cycle – a term widely used by the scientific community since 1990s – plants

6 C3 carbon fixation is one of three metabolic pathways for carbon fixation in photosynthesis. This process converts carbon dioxide and ribulose bisphosphate (RuBP, a 5-carbon sugar) into 3-phosphoglycerate through the following reaction:CO2 + H2O+RuBP → (2) 3-phosphoglycerate

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and vegetations are likely to develop special water use efficiency skills in response to the surge of “toxic”7 CO2. In this process, photosynthesis activities are enhanced in presence of higher WUEi. However, if higher WUEi implies a tighter stomatal control, it tends to be inversely correlated with growth (Brendel et al., 2002). Intuitively, natural CO2 and anthropogenic CO2 should not behave the same way, mainly because anthropogenic CO2 is contaminated with various chemicals that are not found naturally. However, it is a topic that has eluded mainstream researchers. Few studies have been carried out to see how these two source affect long-term behaviour of CO2. Warwick and Ruppert (2016) attempted to document the relationships between the carbon and oxygen isotope signatures of coal and signatures of the CO2 produced from laboratory coal combustion in atmospheric conditions. This study unravelled some of the important justifications behind the intuitive assertion that natural materials cannot be the source of global warming. In their study, they took six coal samples from various geologic ages (Carboniferous to Tertiary) and coal ranks (lignite to bituminous). Duplicate splits of the six coal samples were ignited and partially combusted in the laboratory at atmospheric conditions. The resulting coal-combustion gases were collected and the molecular composition of the collected gases and isotopic analyses of δ13C of CO2, δ13C of CH4, and δ18O of CO2 were analysed by a commercial laboratory. Splits (~1 g) of the un-combusted dried ground coal samples were analyzed for δ13C and δ18O by the U.S. Geological Survey Reston Stable Isotope Laboratory. They reported that The the isotopic signatures of δ13CV-PDB (relative to the V-PDB standard) of CO2 resulting from coal combustion are similar to the δ13CV-PDB signature of the bulk coal (− 28.46 to − 23.86 ‰) and are not similar to atmospheric δ13CVPDB of CO2 (~ − 8 ‰). The δ18O values of bulk coal are strongly correlated to the coal dry ash yields and appear to have little or no influence on the δ18O values of CO2 resulting from coal combustion in open atmospheric conditions. There is a wide range of δ13C values of coal reported in the literature and the δ13C values from this study generally follow reported ranges for higher plants over geologic time. The values of δ18O relative to Vienna. Standard Mean Ocean Water, VSMOW8) of CO2 derived from atmospheric combustion of coal and other high-carbon fuels (peat and coal) range from + 19.03 to+27.03‰ and are similar to atmospheric oxygen δ18OVSMOW values which average + 23.8‰. For reference, note that the isotopic ratios of VSMOW water are defined as follows: 2

H/1H = 155.76 ± 0.1 ppm (a ratio of 1 part per approximately 6420 parts) H/1 hr = 1.85 ± 0.36×10−11 ppm (a ratio of 1 part per approximately 5.41 × 1016 parts) 18 O/16O = 2005.20 ± 0.43 ppm (a ratio of 1 part per approximately 498.7 parts) 17 O/16O = 379.9 ± 1.6 ppm (a ratio of 1 part per approximately 2632 parts) 3

7

The term ‘toxic’ implies that this CO2 contains particulates that make it inassimilable to the ecosystem. Vienna Standard Mean Ocean Water (VSMOW) is a water standard defining the isotopic composition of fresh water. 8

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–24 13 δ C-CO2 (R1, %o)

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13 δ C-CO2 (R2, %o)

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2 eo

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Coal sample

Figure 10.33 Plot of the isotopic signatures of δ13CVPDB for the original coal samples and carbon dioxide (CO2) and methane (CH4) of the gases derived from coal sample combustion (From Warwick and Ruppert, 2016).

Figure 10.33 shows results from Warwick and Ruppert (2016). As can be seen from this figure, the δ13CVPDB of the coal combustion CO2 ranged from − 26.94 to − 24.16‰. Figure 10.34 shows results as reported by Warwick and Ruppert (2016). In this figure, the value of oxygen isotopic signature of atmospheric CO2 (δ18OVSMOW =+23.88) is from Brand et al. (2014). Run 1 (R1) and Run 2 (R2) are from Warwick and Ruppert (2016). shows those for δ18OVSMOW of CO2 ranged from + 19.03 to+27.03‰. In this experiment, two runs were conducted (Runs 1 and 2). The CO2 gases collected during the second combustion run had slightly heavier values of δ13CVPDB and lighter values of δ18OVSMOW. Eight coal combustion gases (three from Run 1, and five from Run 2) produced sufficient quantities of CH4 for the measurement of δ13CVPDB of CH4, and these values ranged from − 33.62‰ to − 16.95‰. Two of the collected gas samples from Run two yielded δ2HVSMOW-CH4 values of − 243‰ and − 239.8‰. Figure 10.35 compares δ13CV-PDB values from effluents of a combustion in presence of atmospheric gases with combustion effluents in presence of high-purity combustion (brown squares in, as reported by Schumacher et al., 2011). The gases collected from the duplicate combustion runs indicate that the analytical results are generally reproducible. Schumacher et al. (2011) combusted samples of various organic materials (leaves, wood, peat, and coal) using controlled combustion temperatures (range 450 to 750 C) in the laboratory to study the effects of fuel type, fuel particle size, combustion temperature, oxygen availability, and fuel water content on the δ18O values of the produced CO2. The samples were combusted in high-purity oxygen with an isotopic signature of

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30 28 26 Co2 δ18O (R1, %o)

24 22

18 Co2 δ O (R2, %o)

δ18OVEMOW (%o)

20 18

Coal δ18O (%o)

16 Atms δ18O (%o) CO2 (Coplen et al. 2002)

14 12 10 8 6 4 2 2

1 ne

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Figure 10.34 Plot of the isotopic signatures of δ18OVPDB forthe original coal samples and carbon dioxide (CO2)derived from coal sample combustion (From Warwick and Ruppert, 2016).

δ18O =+27.2‰; however, to compare the results to those from atmospheric combustion, two samples (a charcoal and a peat) were combusted using laboratory atmosphere (brown squares on right side of). Schumacher et al. (2011) described the influences on carbon and oxygen isotopic fractionation during the combustion process and reported the major influences on the isotopic composition of combustion gases include the temperature of combustion, the carbon isotopic signature of the combusted fuel material, fuel particle size, and water content of the fuel material. Schumacher et al. (2011) also suggested the δ18O signature of the combusted organic material may influence the δ18O signature of the resulting combustion-derived CO2. While this is intuitively correct, they did not measure δ18O of the coal samples used in their study. Schumacher et al. (2011) chose to use high-purity oxygen for their combustion experiments because of the dampening effect of nitrogen and water vapor on the combustion process in natural atmosphere. Atmospheric components may also react with the combustion gases. The role of atmospheric gases in shaping the isotopic character of CO2 is confirmed in, which compares the two cases. It reveals that components otherwise not considered in conventional analysis (the ones we call ‘intangibles’) are the one made a difference in isotopic behavior of the two cases. Although preliminary, the results of our study may help to better characterize the oxygen and carbon isotopic character of CO2 derived from atmospheric coal combustion. Carbon has two isotopes, namely, 12C and 13C. Each has six protons in the nucleus of the atom, hence both are carbon. However, 13C has an extra neutron and thus a greater mass.

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–21 –22 Peat

δ13CVPDB (%o)

–23 –24

Coal Charcoal (500 ºC)

Charcoal

–25

Charcoal Coal

Coal Charcoal (750 ºC)

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Lignite

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High-purity oxygen combustion

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Atmospheric combustion

–29 –30

0

5

10

15

20

25

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δ OVSMOW (%o)

Figure 10.35 Plot of δ18OVSMOW-SLAP ofCO2 derived from combustion of coal andother carbon-rich fuels and δ13CVPDB valuesof the combustion-derived CO2 (from Warwick and Ruppert, 2016).

Adjacent atoms in molecules vibrate like balls attached to springs. In plain language, it means, in presence of an isotope, neighbouring atoms are more susceptible to interactions with the isotope. Lighter atoms vibrate more rapidly, and atoms vibrating more rapidly are easier to separate. Hence light atoms react more rapidly than heavy atoms in chemical and biochemical processes. In general, it is known that plant materials have less of the heavy isotope, 13C, than CO2 from which it is produced, in essence plants fractionate and accumulate 13C, which then get transferred to animals that eat them. Fossil fuels of biogenic origin would have the same feature. The addition of organic carbon to air causes the resulting CO2 mixture to have less 13C. So, for example, at night, the 13C/12C ratio of CO2 in air decreases as plant material decays, and as fossil fuel CO2 is added in populated areas. Similarly, in winter, the 13C/12C ratio of CO2 in air again decreases as vegetation slowly rots. The 13C/12C ratio of CO2 is presented as δ13C, which is the difference, in parts per thousand (tenths of a percent) between the 13C/12C ratio of a sample and a reference gas. The δ13C signature of bulk coal has been well studied and reported in the literature (Singh et al., 2012). Gröcke (2002) has compared the carbon isotope composition of ancient atmospheric CO2 to that of organic matter derived from higher-plants and suggested that both vary over geologic time. This observation confirms that CO2 is part of the organic cycle and as such should not create imbalance in the ecosystem. Carbon isotope ratios in higher-plant organic matter (δ13Cplant) have been shown in several studies to be closely related to the carbon isotope composition of the ocean– atmosphere carbon reservoir, the isotopic composition of CO2 being a reliable tracer. These studies

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have primarily been focused on geological intervals in which major perturbations occur in the oceanic carbon reservoir, as documented in organic carbon and carbonates phases (e.g., Permian–Triassic and Triassic–Jurassic boundary, Early Toarcian, Early Aptian, Cenomanian–Turonian boundary, Palaeocene–Eocene Thermal Maximum (PETM)). All of these events, excluding the Cenomanian–Turonian boundary, record negative carbon isotope excursions, and many authors have postulated that the cause of such excursions is the massive release of continental margin marine gas-hydrate reservoirs. That itself brings in Methane into the picture. In general a very negative carbon isotope composition (δ13C, around −60%%) is reported in comparison with higherplant and marine organic matter, and carbonate. The residence time of methane in the ocean– atmosphere reservoir is short (around 10 years) and is rapidly oxidized to CO2, causing the isotopic composition of CO2 to become more negative from its assumed background value (δ13C of about −7‰). Such rapid negative δ13C excursions can be explained with geological events. Notwithstanding this, the isotopic analysis of higherplant organic matter (e.g., charcoal, wood, leaves, pollen) has the ability to (i) record the isotopic composition of palaeoatmospheric CO2 in the geological record, (ii) correlate marine and non-marine stratigraphic successions, and (iii) confirm that oceanic carbon perturbations are not purely oceanographic in their extent and affect the entire ocean–atmosphere system (Grocke, 2002). The problem is, there are case studies that show that the carbon isotope composition of palaeoatmospheric CO2 during the MidCretaceous had a background value of −3‰, but fluctuated rapidly to more positive (around + 0.5‰) and negative values (around −10‰) during carbon cycle perturbations (e.g., carbon burial events, carbonate platform drowning, large igneous province formation). As such, fluctuations in the carbon isotope composition of palaeoatmospheric CO2 would compromise our use of palaeo-CO2 proxies that are dependent on constant carbon isotope ratios of CO2 (Grocke, 2002). Terrestrial plants can be divided into three groups on the basis of distinctions in photosynthesis and anatomy, namely: 1. C3 (Calvin–Bensen cycle, temperate shrubs, trees and some grasses, see Figure 10.36); 2. C4 (Hatch–Slack cycle, herbaceous tropical, arid-adapted grasses); and 3. Crassulacean acid metabolism (CAM, succulents). Figure  10.36 Is a depiction of the Calvin cycle. Note that the Calvin cycle (also known as the Benson-Calvin cycle) is the set of chemical reactions that take place in chloroplasts during photosynthesis. The cycle is light-independent in the sense that it takes place after light energy has been captured during photosynthesis. represents six turns of the cycle, each turn of the cycle representing the use of one molecule of CO2. Adenosine triphosphate (ATP) and nicotinamide adenine dinucleotide phosphate (NADPH, which is a reduced form of NADP+) are the products of the light-dependent reactions, which drive the Calvin cycle (ADP denotes adenosine diphosphate). The brackets after each element represent the number of molecules produced. It has been suggested that C4 plants were present in the geological record prior to the Miocene (Ehleringer et al. 1991). Evans et al. (1986) conducted experiments on the isotopic composition of CO2 before and after it passed through the leaves of a C3 plant and it was found that 12CO2 was preferentially incorporated into the leaf, although if

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Phosphoglycerate (12)

12 ATP 12 ADP Diphosphoglycerate (12) 12 NADPH

Ribulose biphosphate (6)

Calvin cycle 12 NADP+

6 ADP Glyceraldehyde phosphate (12) 6 ATP

Glyceraldehyde phosphate (10)

Glyceraldehyde phosphate (2)

Figure 10.36 A simplified version of the C3 Calvin cycle (From Grocke, 2002).

12

CO2 concentrations were low, then relatively more 13CO2 was incorporated into the leaf. Subsequently, it was shown that C3 and C4 plant groups have isotopically distinct δ13Cplant ranges: C3 plants range between −23 and −34%% with an average of −27%%, whereas C4 plants range between −8 and −16%% with an average of −13%% (Vogel 1993). Hence, the carbon isotope composition of ancient higher-plant organic matter, excluding environmental effects should provide researchers with a proxy for discriminating between these two main plant groups in the geological record. Similarly, such distinction can be made between CO2 from fossil fuel and CO2 from refined oil (e.g., gasoline). The fact that refining process adds many artificial chemicals, the Calvin cycle is affected. Figure 10.37 shows how the Calvin cycle can act as a fractionation column. In this figure, the term Σcontaminants is the collection of all contaminant molecules that come from artificial components (the ones termed ‘intangible’ by Khan and Islam, 2016). It includes the entire history of a particle/molecule. For instance, if CO2 came from plants that itself used pesticide and chemical fertilizer, this term will contain intangible amounts of the chemicals used in those processes. In the first phase, there will be components that will be rejected (Reject0) even before entering the Calvin cycle. It is similar to rejection or fractionation of 13CO2 molecules. This process of elimination continues at various stages, each corresponding to Rejecti, where i is the number of the cycle. Table 10.8 Shows δ18O of coal results represent the average of two analyses as reported by Warwick and Ruppert (2016). The isotopic results of the δ13CV-PDB of the coal combustion CO2 ranged from −26.94 to −24.16‰ and those for δ18OV-SMOW of CO2 ranged from +19.03 to+27.03‰. The CO2 gases collected during the second combustion run had slightly heavier values of δ13CV-PDB and lighter values of δ18OV-SMOW. Eight coal combustion gases produced sufficient quantities of CH4 for the measurement of

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contaminants Reject0

Reject4 Sage 1: carbon fixation

Reject1

3 ADP 6 ATP

3 ATP

6 ADP

Calvin cycle Sage 3: regeneration of RuBP

Sage 2: reduction

6 NADPH 6 NADP+ + H+

Reject2 Sugar

Reject3

Figure 10.37 The CO2 rejects due to contaminants.

δ13CVPDB of CH4, and these values ranged from −33.62‰ to −16.95‰. The coal combustion-derived δ13CVPDB-CO2 signatures were found to be similar to that of the δ13CVPDB of the bulk coal (−28.46 to −23.86‰) and are not similar to modern atmospheric δ13CVPDB of CO2 (−8.2 to −6.7‰; as reported by Coplen et al., 2002). The values of δ18OVSMOW of CO2 (+19.03 to+27.03‰) from the coal combustion gases from this study are similar to atmospheric oxygen δ18O values which average + 23.8‰ (Coplen et al., 2002). There is a wide range of δ13CV-PDB values of coal reported in the literature and the values obtained by Warwick and Rupert (2016) generally follow previously reported ranges for higher plants over geologic time. The isotopic signatures of δ13CVPDB of CO2 resulting from laboratory coal partial combustion are similar to and probably derived from the original δ13C signatures of the coal. The δ18OVSMOW values of coal show a strong correlation to the coal dry ash yields and appeared to have little or no influence on the δ18OVSMOW values of CO2 resulting from coal combustion. Coal burning is similar to crude oil burning. However, the same conclusion would not apply to refined oil burning and irrespective of the isotopic composition of the combustion products, the effect on the ecosystem will be long-lasting and irreversible. Warwick and Ruppert (2016) emphasized the need to develop better techniques for characterizing CO2 which results from the combustion of coal. Coplen et al. (2002) compiled a report on isotopic composition of a number of naturally occurring materials. The principal elements studied are reported in Table 10.9. Their report is a useful listing of major players of global warming.

E-0709002-063-2

SBT-19-R7

SBT-19-R7-2

07018-01314GBC

0701S-01314GBC- 2 2

MS-02-DU

MS-02-DU-2

PA-2-CN6

PA-2-CN6-2

PA-2-CN2

PA-2-CN2-2

Pennsylvanian OH

Permian India

Permian India

Cretaceous NM

Cretaceous NM

Paleocene MS

Paleocene MS

Paleocene TX1

Paleocene IX 1

Paleocene TX 2

Paleocene TX 2

2

1

2

1

2

1

1

2

1

2

1

E-0709002–063

Pennsylvanian OH

Run

Sample number

Sample

−26.77

−28,46

−25.73

−24,09

−23.86

— 26,57

δ i3Cvpob

Bulk coal

59.7

62.7

42

69.4

48

54.6

Mass fraction of C (%)

13.27

14,12

14.77

11,82

2.96

10,29

δ1SOvSMOW

21

21.4

25.5

11.3

9.2

15.5

Mass fraction of 0 (%)

−25.23

−26.01

−26.13

−26.94

−2416

−25.74

−24.95

−26.48

−25.68

−26.24

−25.2

−26.13

δ 13Cvpdb

C02

21.12

27.03

20.65

26.46

23.04

26.67

19.03

24.03

26.05

26.04

21.89

24.93

δ 1S0vsmow

−31.11

−17.46

−33.62

na

na

na

−25.39

−24.78

−16.95

na

−30.57

−25.89

δ 13Cvpdb

CH4

−243

na

−239.8

na

na

na

na

na

na

na

na

na

62Hvsmow

Collected gases from partially combusted coal

Table 10.8 Carbon and Oxygen Isotope Compositions in Bulk Coal and Gases Collected From Combusted Coal, All Isotopic Values Given in Per Mil (‰). (From Warwick et al. 2016).

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Table 10.9 The Minimum and Maximum Concentrations of a Selected Isotope in Naturally Occurring Terrestrial Materials (From Coplen et al., 2002). Isotope

Minimum mole fraction

2

0

.000 0255

0

.000 1838

7

0

.9227

0

.9278

11

0

.7961

0

.8107

13

0

.009 629

0

.011 466

15

0

.003 462

0

.004 210

18

0

.001 875

0

.002 218

26

0

.1099

0

.1103

30

0

.030 816

0

.031 023

34

0

.0398

0

.0473

37

0

.240 77

0

.243 56

44

0

.020 82

0

.020 92

53

0

.095 01

0

.095 53

56

0

.917 42

0

.917 60

65

0

.3066

0

.3102

0

.704 72

0

.705 06

H Li B C N O Mg Si S Cl Ca Cr Fe Cu

205

Tl

Maximum mole fraction

10.6.2 Isotopic Features of Naturally Occurring Chemicals Coplen et al. (2002) documented isotopic features of a number of chemicals that related to global warming and climate change. Following discussion relies on their report. Carbon monoxide (CO): In nature, oxidation of methane or other hydrocarbon can lead to the formation of carbon monoxide. This is inherent to fossil fuel burning. Also, biomass burning (including during forest fires), transportation, industry, heating, oceans, and vegetation, they will all generate certain volume of CO. The primary sinks of atmospheric methane are oxidation by the hydroxyl radical (OH) and uptake by soils. Its average residence time in the atmosphere is about 2 months. The values of δ13C of CO in the atmosphere in Antarctica (where the atmosphere is unpolluted) range between –31.5 ‰ and –22 ‰. Organic carbon: Organic carbon is the essence of vegetation and as such the driver of life on earth. Any biological assimilation of carbon by plants results in depletion of 13 C in the organism's tissues relative to the carbon sources (CO2 and HCO3 –). The magnitude of the 13C depletion depends on the species and the carbon fixation pathways

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utilized, environmental factors such as temperature, CO2 availability, light intensity, pH of water, humidity, water availability, nutrient supply, salinity, cell density, age of photosynthesizing tissue, and oxygen concentration. Based on our presentation in Chapter 4, such speciation will also depend on any artificial chemical that has been added to the pathway (e.g., pesticide, chemical fertilizer, refining catalyst). Plants assimilate carbon using two different pathways, which leads to a classification of three photosynthetic groups. The predominant fixation reaction is carboxylation of ribulosebisphosphate (RuBP) to the C3-product phosphoglycerate, which generally results in δ13C of plants between –35 ‰ and –21 ‰ , but as low as –35 ‰. C3 plants tend to grow in cool, moist, shaded areas and comprise 80 to 90 percent of plants. All trees, most shrubs, some grasses from temperate regions and tropical forests, and common crops such as wheat, rice, oats, rye, sweet potatoes, beans, and tubers utilize the C3 pathway. The second reaction involves the carboxylation of phosphoenolpyruvate to the C4 product oxalacetic acid. This fixation is more efficient leading to less depletion in 13C; the δ13C of C4 plants ranges between –16 ‰ and –9 ‰. C4 plants, such as maize, sugar cane, sorghum, and grasses in Australia, Africa, and other subtropical, savannah, and arid regions, tend to grow in hot, dry, sunny environments. Animals and microbial heterotrophs generally have δ13C values within 2 ‰ of their food supply. A wider range is possible for various organs and tissues within a single organism can have a wider range. It is the case because each organic part acts as a natural partitioning agent. The δ13C values of fresh tissues and the collagen and hydroxyapatite from bones and teeth have been applied to food web studies and reconstructions of prehistoric diet and vegetation patterns. For example, geographic variations of the δ13C values of hair in humans compares favorably with the 13C depleted diets of Germans (δ13C = –23.6 ‰), the seafood and corn diets of Japanese (δ13C = –21.2 ‰), and the corn diets of Americans (δ13C = –18.1 ‰), as reported by Nakamura et al. (1982). Isotope-ratio analyses of organisms found in the literature primarily have been confined to analysis of molecules or whole tissues. Brenna (2001) correctly pointed out that physiological history is retained in natural isotopic variability. Brenna (2001) suggested that a strong case that future studies of physiological isotope fractionation should involve position-specific isotope analysis and should reveal the relationship of diet and environment to observed isotope ratio. The δ13C value of sedimentary organic matter is affected by the local flora and fauna, the environmental conditions, secondary processes, recycling of older carbon-bearing sediments, and anthropogenic wastes. At this juncture, few studies have been reported on the role of anthropogenic wastes and their role in altering natural degradation. During diagenesis, the biopolymers of newly deposited sediments are biochemically degraded by microorganisms. Most of the organic matter is oxidized to CO2 and H2O or reused as biomolecules within living organisms. Within limited settings, terrestrial plant sediments tend to be more depleted in 13C than marine plankton sediments. For example, river sediments, with an average δ13C value of about –26 ‰, tend to become enriched in 13C at the river mouth, presumably because of increasing amounts of marine plankton (as opposed to terrestrial C3 plant) input (Deines, 1980). This can explain the nature of CO2 absorption in the ocean that shows decline in the presence of surplus anthropogenic CO2.

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Elemental carbon: As organic matter undergoes burial and thermal alteration, functional groups of organic compounds are lost, H2O and CO2 are produced, and methane is evolved. This process is simulated in a laboratory as pyrolysis. In a natural setting, the final product of this reduction is graphite, with δ13C ranging between –41 ‰ and +6.2 ‰. It appears that diamonds conform to this range with δ13C ranging between –15.6 ‰ to −4.4 ‰, in line with depth-related variations in the mantle. Ethane: Low temperature serpentinization of ophiolitic rocks generates free hydrogen along with minor amounts of methane and ethane. Studies indicate that the δ13C values of ethane as high as –11.4 ‰. Gases in the potash layers are highly enriched in 13 C with δ13C values as positive as +6.6 ‰. The mode of formation is still uncertain although hypotheses include (1) maturation of organic matter rich in 13C; (2) transformation of CO2 enriched in 13C to CH4; (3) unknown bacterial isotope fractionation; and (4) abiotic gas formation during halokinesis (including salt tectonics). The most negative δ13C found in the literature for a bacterially formed ethane is –55 ‰. This finding confirms the role of microorganisms in reducing isotopic fractions. Methane: The two major methane production processes are: (1) diagenesis of organic matter by bacterial processes; and (2) thermal maturation of organic matter. Biogenic methane follows one of two major pathways for biogenic methane production: (1) CO2 reduction, which dominates in marine environments; and (2) acetate fermentation, which dominates in fresh-water environments. The δ13C values of marine methane range from –109 ‰ to 0 ‰, whereas methane in freshwater sediments and swamps is more enriched in 13C, but have a smaller range in carbon isotopic composition, with δ13C values range from –86 ‰ to –50 ‰. The isotopic compositions of thermogenic methane are affected by the geological history of the basins and they depend on such factors as the extent of conversion of organic matter and the timing of gas expulsion, migration, and trapping. The δ13C of thermogenic methane that is associated with natural gas ranges from –74 ‰ to +12.7 ‰. The reason behind such positive δ13C is unknown but is indicative of the fact that kinetic of higher temperature is complex. Methane is an important atmospheric greenhouse gas with major natural and anthropogenic sources including swamps, rice paddies, ruminants, termites, landfills, fossil-fuel production, and biomass burning. The δ13C of atmospheric methane is relatively constant, generally ranging between –50.58 ‰ and –46.44 ‰. Nitrogen: Although nitrogen is about twenty-fifth in crustal abundance, it comprises 78.1 percent of the atmosphere by volume. A primary use of nitrogen gas is as an inert atmosphere in iron and steel production and in the chemical and metallurgical industry. Large quantities of nitrogen are used in fertilizers and chemical products. More moles of anhydrous ammonia are produced worldwide than any other nitrogenbearing compound. This ammonia is distinctly different from natural ammonia that is a common waste among living organisms. The natural abundance of stable isotopes of elements in animal tissue is influenced by both biotic and abiotic factors. Biotically, animals feeding at higher trophic levels are enriched in the ratio of 15N:14N (15N) relative to their food resources owing to the preferential excretion of 14N. Abiotically, increases in 15N may also reflect different sources of biologically available nitrogen, including nitrogen resulting from denitrification of chemical fertilizer. In Chapter 4, we discussed how chemical fertilizer would alter the overall nitrogen cycle, thereby

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contributing to imbalance in the ecosystem. Lake et al. (2011) variation in 15N among freshwater turtle populations to assess spatial variation in 15N and to determine whether this variation can be attributed to differences in nitrogen source or trophic enrichment. They examined nitrogen and carbon stable isotope ratios in duckweed (genus Lemna L.) and in Painted Turtles (Chrysemys picta) in aquatic ecosystems expected to be differentially affected by agricultural activity and denitrification of inorganic fertilizer. Across sites, C. picta δ15N was strongly correlated with Lemna 15N and was elevated in sites influenced by agricultural activity. Furthermore, trophic position of turtles was not associated with δ15N but was consistent with expected values for primary consumers in freshwater systems, indicating that differences in tissue δ15N could be attributed to differences in initial sources of nitrogen in each ecosystem. In all cases, δ15N was the lowest in absence of agricultural activities using chemical fertilizers. Since fossil fuel refining involves the use of various toxic additives, the carbon dioxide emitted from these fuels is contaminated and is not favored by plants. If the CO2 comes from wood burning, which has no chemical additives, this CO2 will be more favored by plants. This is because the pathway the fuel travels, from refinery to combustion devices, makes the refined product inherently toxic (Islam et al., 2010). The CO2 that the plants do not synthesize accumulates in the atmosphere. The accumulation of this rejected CO2 must be accounted for in order to assess the impact of human activities on global warming. This analysis provides a basis for discerning between natural CO2 and ‘toxic’ CO2, which could be correlated with global warming.

10.6.3 Photosynthesis For the ecosystem and sustainability of nature, photosynthesis is the most crucial occurrence. In term, the fact that photosynthesis occurs at visible wavelengths is of utmost interest. Any skewing of the light spectrum will have implication on photosynthesis. Chlorophyll a (C55H70O6N4Mg) and chlorophyll b (C55H70O6N4Mg) play major role in the absorption of solar energy for the sake of photochemical reactions of photosynthesis (Murray et al., 1986). In plants, it is the pigment chlorophyll a that is responsible for absorbing incoming solar radiation at selected wavelengths, and performing charge separation to gather electrons from an electron donor, such as H2S or H2O. While New Science presents these ‘electrons’ as uniform, homogenous, rigid entitities that cannot be affected by the presence of contaminants, Islam (2014) demonstrated that by using the galaxy model (see previous chapters), one can show that the presence of tiniest amoung of contaminants, one can affect the overall chemical reaction. The range of the spectrum, for which oxygenic photosynthesis occurs is largely restricted to the 400–700 nm range, called “photosynthetically active radiation” (Shields et al., 2016). The term, “Photosynthetically active radiation” (PAR) represents the spectral range of solar radiation from 400 to 700 nanometers, which is amenable to processing by photosynthetic organisms. Islam (2014) showed that this range is not a matter of artificially simulating the light component, it must have the same natural components, present in sunlight. Such conclusion cannot be reached using conventional Atomic theory. Certain organism, such as such as cyanobacteria, purple bacteria, and heliobacteria, can exploit solar light in slightly extended spectral regions, such as the near-infrared. While they are part of the overall ecosystem and necessary for total balance, the most

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important components are within the visible light region. As we have seen in previous chapters, Chlorophyll is the most abundant plant pigment, is most efficient in capturing red and blue light. Accessory pigments such as carotenes and xanthophylls harvest some green light and pass it on to the photosynthetic process, but enough of the green wavelengths are reflected to give leaves their characteristic color, green being the widest of the spectrum of visible lights. Even when chlorophyll is degraded during autumn (because it contains N and Mg), it remains essential to plants and remain in the leaf producing red, yellow and orange leaves. Chlorophyll a uses this PAR and cannot thrive in presence of contaminants. One the other hand, Chlorophyll b, which support activities of Chlorophyll a, is far less sensitive to contaminants. As shown in Chlorophyll a absorbs energy from wavelengths of blue-violet and orange-red light while chlorophyll b absorbs energy from wavelengths of green light. The characteristic wavelength for Chlorophyll a is 675 nm while for chlorophyll b it is 640 nm. It is known that higher plants and green algae contain chlorophyll a and chlorophyll b in the approximate ratio of 3:1. Chlorophyll c is found together with chlorophyll a in many types of marine algae. While, red algae (Radophyta) contain principally chlorophyll a and also chlorophyll d. α - carotene occurs always together with chlorophylls (Edarous, 2011). Chlorophyll are structurally originated from methyl phytolesters of dicarboxylic acid that consists of prophyrin head with four rings centrally linked to magnesium atoms and a phytol tail (C20H39OH) with long aliphatic chain of alcohol. The following distinctions between the two types of chlorophylls can be made. 1. Chlorophyll b is more absorbent while chlorophyll a is not. 2. Chlorophyll a is the reaction center of the antenna array of core proteins while chlorophyll b regulates the size of the antenna. It offers abundant energy to carry out the reactions of photosynthesis. 3. Specifically, Chlorophyll a (and other accessory pigments that vary by organism) absorbs strongly in the blue and also in the red region of the visible spectrum (Figure 10.38). The lower absorption coefficient in the green range of the spectrum is responsible for the higher reflectance of plants in this range, and their resulting green appearance to the human eye.

Chlorophyll b Absorbance

Chlorophyll a

400

500 600 Wavelength [nm]

Figure 10.38 Light spectrum for Chlorophyll a and Chlorophyll b.

700

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0.1

100 80

Quantum yield

60 40 20 0 400

Absorption spectrum

0.05

Action spectrum 0 500 600 Wavelength, nm

Quantum yield (photons/O2)

Absorbance action spectrum

700

Figure 10.39 Absorption spectrum and quantum yield vs. wavelength (From Gale and Wandel).

Figure  10.39 shows the absorption spectrum, as well as the action spectrum and quantum yield for chlorophyll while engaged in the process of oxygenic photosynthesis. Note the drop in the absorption coefficient in the green range of the spectrum (495–570 nm), and the sharp drop at 700 nm. Chlorophyll b: Magnesium [methyl (3S,4S,21R)-14-ethyl-13-formyl-4,8,18trimethyl-20-oxo-3-(3-oxo-3-{[(2E,7R,11R)-3,7,11,15-tetramethyl-2-hexadecen-1-yl] oxy}propyl)-9-vinyl-21-phorbinecarboxylatato(2-)-κ2N,N ] Structural compositions of Chlorophyll a and b are shown in Figure  10.40. Each of these is vulnerable to toxic chemicals that are added through chemical fertilizer or pesticides (Turkilmaz and Esiz, 2015; El-Aswed et al., 2008). Whereas, the loss of chlorophyll in response to aging resulting in natural senescence is an inevitable process in plant development, heavy metals or the presence of unusal isotopic concentration can accelerate the ageing effects. El-Said Salem (2016) identified following organic activities that are affected by chemical pollutants. 1. Formation of plastids; the small dense protoplasmic inclusion in the cell plant, and may act as a special centers of chemical activity. These plastids when exposed to light become pigmented and become chloroplasts. The presence of pollutants, even in intangible form (not detectable with conventional analytical tools) can alter plastid compositions. 2. Transformation of plastids to chloroplasts (in plastid containing chlorophyll, with or without other pigments embedded singly or in consider numbers in the cytoplasm of a plant cell. In this process, pesticides may interfere with the formation of plastids or chloroplasts. 3. Inhibition of pigments synthesis due to the accumulation of the carotenoids precursor phytofluene and phytoene, and the loss of chlorophyll, carotenoids. Chloroplast ribosomes and grana structure such accumulation resulted from the blockage of dehydrogenation reactions in the biosynthesis of the carotenoids in herbicide – treated leaves.

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Chl a

O

+ ++ + N.....Mg ..... N

+ ++ + N .....Mg ..... N

O

N

N O O

Chl b

N

N

O

521

O

O O O

O O H H

Figure 10.40 Chlorophyll a and Chlorophyll b (molecular structure)Chlorophyll a: Magnesium [methyl (3S,4S,21R)-14-ethyl-4,8,13,18-tetramethyl-20-oxo-3-(3-oxo-3-{[(2E,7R,11R)-3,7,11,15-tetramethyl-2hexadecen-1-yl]oxy}propyl)-9-vinyl-21-phorbinecarboxylatato(2−)-κ2N,N ].

In several studies, it was found that seed oil content (oil concentration) decreased or responded weakly to increase in N supply, due to the concomitant increase in heavier protein production under high N nutrition (Abbadi et al. 2008, Ghasemnezhad and Honermeier 2008). This could be a result of the competition between protein synthesis and fatty acid synthesis for carbon building blocks. Ghasemnezhad and Honermeier (2008) also suggested that fatty acid synthesis has higher carbo-hydrate requirement than protein. Consequently, the increased N supply would enhance protein synthesis at the expense of fatty acid synthesis for primrose seeds. Young et al. (2010) studied how chemical fertilizers affect the photosynthesis process. In this study, leaf gas exchange measurements and leaf nitrogen content were determined for four varieties of J. curcas, grown in the field or in pots. Based on stable carbon isotope analysis (δ13C) and gas-exchange studies, they reported the range of leaf photosynthetic rates (or CO2 assimilation rates) to be typically between 7 and 25 μmol (CO2) m–2 s–1 and light saturation beyond 800 μmol(quanta) m–2 s–1.

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10.6.4 The Effect on Carbon (114C and δ13C) The isotopic composition of carbon in atmospheric CO2 in oceanic and terrestrial carbon reservoirs fluctuate naturally. However, the introduction of anthropogenic emissions after the ‘plastic revolution’ has created imbalance the intensity of the fluctuation has increased. Naturally, Carbon-14 (14C) is continually formed in nature by the interaction of neutrons with nitrogen-14 in the Earth's atmosphere; the neutrons required for this reaction are produced by cosmic rays interacting with the atmosphere. Similar isotopes can be formed during testing of nuclear bombs, which was the case during 1950 s. On the other hand, in organic systems, the ratio of 13C and 12C isotopes fluctuates depending on the plant photosynthesis. Similarly, the 13C/12C ratio varies within sedimentary rock, leaving behind a signature, which can be used to characterize the rock. Fossil fuel burning decreases the proportion of the isotopes 14C and 13C relative to 12C in atmospheric CO2 by the addition of aged, plant-derived carbon that is partly depleted in 13C and entirely depleted in 14C (Graven et al., 2017). This process is referred to as the Suess effect following the early observations of radiocarbon in tree rings by Hans Suess (Suess, 1955). Suess (1955) pointed out that a decrease in the specific C14 activity of wood at time of growth during the previous 50 years. The decrease amounted to about 3.4% percent in two trees from the east coast of the United States. A third tree, from Alaska, investigated at that time, showed a smaller effect. The decrease was attributed to the introduction of a certain amount of C14-free CO2 into the atmosphere by artificial coal and oil combustion and to the rate of isotopic exchange between atmospheric CO2 and the bicarbonate dissolved in the oceans. In order to obtain more quantitative data concerning the effect, mass-spectrometric C13 determinations were made and used to correct for isotope fractionation in nature and in the laboratory. For this purpose a few cubic centimeters of C2H2 of each sample were converted to CO2 by recycling over hot CuO and the mass-spectrometer measurements were made. Eleven samples of wood from four different trees, each sample consisting of a small range of annual rings, were investigated; for comparison, three samples of marine carbon were also measured. Two independent sets of counting equipment were used. Suess observed marked variations among samples, always in the direction of a lower C14 content. The tree from the east coast of the United States showed the largest effect. The smaller effects noted in the other three trees indicate relatively large local variations of CO2 in the atmosphere derived from industrial coal combustion, and that the world wide contamination of the earth's atmosphere with artificial CO, probably amounts to less than 1%. Hence the rate by which this CO2 exchanges and is absorbed by the oceans was deemed to be greater than previously assumed. Carbon of marine origin is known to show a lower C14 content than expected when one assumes complete equilibration with the atmosphere. It is because in the atmosphere exchange with organic matter is far more intense and direct than in the ocean. The term Suess effect was also later adopted for 13C (Keeling, 1979). The magnitudes of the atmospheric 14C and 13C Suess effects are determined not only by fossil fuel emissions but also by carbon exchanges with the ocean and terrestrial reservoirs and the residence time of carbon in these reservoirs, which regulate the mixing of the fossil fuel signal out of the atmosphere (Keeling, 1979). The first measurements of the

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δ13C of dissolved inorganic carbon (DIC) of ocean surface waters were made in 1970 (Kroopnick, 1974) and serve as a baseline for assessing how the carbon isotopic composition of the oceans have changed in response to the burning of fossil fuel CO2 over the last decades. However, in order to gain a longer and more complete picture of the marine δ13C Suess effect, Black et al. (2011) suggested the use of indirect measurements of changes in surface water δ13C, most notably those preserved in carbonate secreting marine organisms. Recently, Swart et al. (2010) presented a compilation of coral δ13C records from throughout the global ocean and estimated that the average rate of change in δ13C in all of the records between 1900 and 1990 was −0.01 ‰ yr−1. Black et al. (2011) reported previous findings that the anthropogenic‐induced decrease in δ13C is 0.9 ‰ in the Arctic and 0.6 ‰ in both the eastern North Atlantic and the Southern Ocean. By combining data collected as part of the Cariaco Basin ocean time series study with data derived from a sediment core from the basin, Black et al. (2011) produced a annual record of δ13C in planktonic foraminiferal for the southern Caribbean for the last 300 years. Figure 10.41a shows pCO2 Mauna Loa atmospheric and Cariaco Basin water cases. Changes in Cariaco Basin pCO2 appear to be reflecting large scale changes in atmospheric CO2, rather than just local processes. In absence of direct measurements of the δ13C of surface water to asses how this increase in pCO2 over the previous 15 years is manifested as a change in the carbon isotopic composition of Cariaco Basin surface waters, Black et al. (2011) used the δ13C of planktonic foraminifera collected in sediment traps during this period as an indirect way of determining changes in surface water δ13C of dissolved inorganic carbon (DIC). Using this approach, they track back to 1700 by coupling the sediment trap results with a foraminiferal δ13C record derived from Cariaco Basin sediment cores. As shown in Figure 10.41(b) , by directly comparing coincident carbon isotope data for both sediment trap and box core samples for the period from 1996 through 2007, they could assess the fidelity of the G. ruber δ13C record preserved in the sediments. For this period of overlap the two G. ruber results indicate that the initial isotopic signature has not undergone postdepositional alteration. Over this 12 year interval, the sediment trap δ13C record decreases from 1.19 ‰ to 0.86 ‰ (−0.03 ‰ yr−1), while the box core record decreases from 1.23 ‰ to 1.00 ‰ (−0.02 ‰ yr−1). For comparison, the Mauna Loa atmospheric δ13C record also has a rate of change of −0.03 ‰ yr−1 for this time period Figure 10.41(b). This suggests that the Cariaco Basin G. ruber δ13C is not controlled primarily by local processes but rather can be used as a proxy for broad‐scale changes in the δ13C of surface water DIC associated with ocean-atmosphere exchange of CO2. Figure 10.42 shows that the atmospheric pCO2 increases slightly between the mid‐ 1800s and 1950, after which pCO2 values abruptly rise. The marine δ13C data become slightly more negative between the mid‐1800s and 1950, after which they become significantly depleted. The G. ruberδ13C sediment core record extends back to 1725 and is characterized by significant high frequency (annual to decadal) variability, as well as a long term trend of decreasing values towards the present day. Black et al., attributed much of the high frequency variability to interannual changes in upwelling intensity which causes large seasonal changes in surface water pCO2. While upwelling variability controls interannual‐ and decadal‐scale variations in the foraminiferal δ13C record from the Cariaco Basin, the long‐term trend appears directly related to similar‐scale

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The Science of Climate Change pCO2 (ppm) 480 440 Cariaco 400 360

Mauna Loa

320 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008

Figure 10.41 (a) Comparison of atmospheric CO2 and d13C to Cariaco Basin sediment trap and sediment core d13C. Mauna Loa atmospheric pCO2 and Cariaco Basin water pCO2 between 1996 and 2009. For both cases, DCO2/Dt = 1.95 ppm/yr. (From Black et al., 2011). G. ruber δCFDB (%o) 1.50 1.25

Mauna Loa annual average δ13C (Sediment trap) Δδ13C/Δt=–0.03 %o yr–1

7.5 (Box core 25–1) Δδ13C/Δt=–0.02 %o yr–1

1.00 0.75

7.75 8.0

Δδ13C/Δt=–0.03 %o yr–1 (Mauna Loa)

0.50

8.5 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008

Figure 10.41 (b) Comparison of atmospheric CO2 and d13C to Cariaco Basin sediment trap and sediment core d13C. All three data sets indicate the same rate of d13C depletion (determined by linear regression), indicating that trap and core samples faithfully represent atmospheric trends (From Black et al., 2011).

trends in atmospheric pCO2. Atmospheric CO2 concentrations, as determined from the Siple ice core are relatively stable from the mid‐ 1700s to the mid‐1800s, increasing by only about 10 ppm. Over the next century, this rate of change doubled, with atmospheric CO2 concentrations reaching 310 ppm in 1950. Since that time, CO2 concentrations have increased dramatically. The planktonic foraminiferal δ13C data follow the exact same temporal pattern. Meanwhile δ13C values remain relatively stable from the base of the record through the mid‐1800s, but begin to gradually decrease between 1850 and 1950. Between 1950 and 2008 δ13C values decreased by more than 0.75 ‰, in good agreement with the magnitude of δ13C changes derived from previous studies that compared planktonic foraminiferal shells collected from surface waters with those from surface sediment samples (See Black et al., 2011 for details). In general, carbonate ion concentration decreases as pCO2 increases and the 100 ppm increase in atmospheric CO2 between the start of the industrial revolution and today could result in a 60

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G. ruber δ13CPDB (%o)

400

G. ruber δ13C

1.5

360

2

320

Mauna Loa

280

Siple ice core

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240

1725

1750

1775

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Figure 10.42 Planktonic foraminifera d13C over the last three centuries compared to Siple ice core and Mauna Loa pCO2.

mmol/kg decrease in surface water carbonate ion concentration. Laboratory and field studies of carbonate ion concentration effects on stable isotopes in planktic foraminifera (Russell and Spero, 2000) indicate the estimated carbonate ion decrease would result in upwards of a 0.5 ‰ increase in G. ruberδ13C. This change is in the opposite direction of the anthropogenic δ13C decrease and suggests that magnitude and rate of marine δ13C depletion may be larger than estimated. However, we would then need a process that balances the carbonate ion effect to explain the identical rates of atmospheric and sediment trap/core δ13C depletion (Figure 10.41). A decrease in upwelling intensity over the last 300 years could create such a balance, but there is no evidence for decreased Cariaco upwelling over the last 300 years. Overall, Black et al. (2011) estimated the marine Suess effect to be −0.75 ‰. They showed that Foraminiferal δ13C began to decrease in the mid‐19th century, and accelerated towards even lower values in1950, coincident with the rise in atmospheric pCO2 as measured in ice cores and modern air samples. Naturally, biological and physical processes cause isotopic fractionation and the associated fractionation factors can vary with environmental conditions. Land use changes can also influence carbon isotope composition (Scholze et al., 2008). Any use of artificial chemical and energy sources will affect the environment, in turn affecting the carbon isotope composition. Gravel et al. (2017) point out that in addition to the perturbation from fossil fuel emissions, atmospheric Δ14C was also subject to a large, abrupt perturbation in the 1950 s and 1960 s when a large amount of 14C was produced during atmospheric nuclear weapons testing. The introduction of this “bomb 14C” nearly doubled the amount of 14 C in the Northern Hemisphere troposphere, where most of the tests took place. Most testing stopped after 1962 due to the Partial Test Ban Treaty, after which tropospheric Δ14C decreased quasi-exponentially as bomb 14C mixed through the atmosphere and into carbon reservoirs in the ocean and terrestrial biosphere that exchange with the atmosphere on annual to decadal timescales (Levin and Hesshaimer, 2000). Records of atmospheric Δ14C and δ13C have been extended into the past using measurements of tree rings and of CO2 in air from ice sheets. These records clearly show decreases in Δ14C and δ13C due to increased emissions of fossil-derived carbon following the Industrial Revolution and carbon from land use change. Ice cores, and tree ring and

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The Science of Climate Change Δ14C (permil) 900 800 700 600 500 400 300 200 100 0 1850 1870 1890 1910 1930 1950 1970 1990 2010

Figure 10.43 Historical atmospheric forcing datasets for D14C in CO2 (From Graven et al., 2017). δ14C (permil) –6.7 –7 –7.3 –7.6 –7.9 –8.2 –8.5 1850 1870 1890 1910 1930 1950 1970 1990 2010

Figure 10.44 Historical atmospheric forcing datasets for δ13C in CO2 (From Graven et al., 2017).

other proxy records, additionally reveal decadal to millennial variations associated with climate and carbon cycle variability, and, for 14C, changes in solar activity and the geomagnetic field (Damon et al., 1978). Figure  10.43 shows for Δ14C in CO2 throughout the industrial age until modern era. The only increase in Δ14C relates to nuclear testing. As reported by Black et al. (2017), after 1955, Δ14C increased rapidly as a result of nuclear weapons testing, reaching a maximum of 836 ‰ in the Northern Hemisphere and 637 ‰ in the Southern Hemisphere, where the values 836 ‰ and 637 ‰ are the maxima in the forcing data. The Δ14C was even higher in the stratosphere and some Northern Hemisphere sites. After 1963– 1964, tropospheric Δ14C decreased quasi-exponentially as the nuclear test 14 C mixed with oceanic and biospheric carbon reservoirs while growing fossil fuel emissions continued to dilute atmospheric 14CO2. Differences between the Northern and Southern Hemisphere reduced rapidly and were close to zero for the 1980s–1990s. The Northern Hemisphere deficit in Δ14C has been linked to a growing dominance of fossil fuel emissions in the Northern Hemisphere as air–sea exchange with 14C-depleted ocean water in C-depleted ocean water in the Southern Hemisphere weakened with decreasing atmospheric Δ14C (Graven et al., 2012). Figure 10.44 shows historical data for δ13C in atmospheric CO2 from ice core and firn records and from flask measurements to produce the historical atmospheric forcing dataset (Graven et al., 2017). There has been consistent decline in δ13C values with

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Millions of bbl;. 90. 80.

Alaska

70. 60. North sea

50. 40. 30. 20. 10. 0 1965

1970

1975

1980

1985

1990

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2000

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2010

Figure 10.45 Global oil production during 1965-2010 (from Rapier, 2012).

two distinct slopes. The fires slope that arises from 1850 remains constant until 1950, at which point the slope more than doubles. During the same time, there has been a consistent increase in oil production as North Sea and Alaska joined in the global oil production Figure 10.45.

10.7

The Role of Water in Global Warming

In overall functioning of the earth, water plays the most pivotal role. Water is ubiquitous and is plays a role at every stage of the carbon cycle, the important function being photosynthesis. Water is also the most potent solvent as well. In living cells, water is an ideal solvent as it is polar, meaning it can dissolve a variety of polar substances such as monosaccharides, amino acids, fatty acids, and vitamins and minerals, which can diffuse into the cells to help them survive by providing them with the metabolites to produce ATP for energy, allowing them to perform their particular functions. Minerals, in their natural form, are essential to metabolic activities. However, non-organic (as discussed in previous chapters) minerals (as well as vitamins) would disrupt normal functioning of all metabolic activities. In that sense, the composition of water is extremely important. Note that the composition should include so-called intangible components that are not detectible through conventional analytical tools. Ironically, at present, the most recent decadal increase in radiative forcing is attributable to CO2 (56%), CH4 (11%), N2O (6%) and CFCs(24%). Whereas, stratospheric H2O is estimated to have contributed only 4% (Shine et al., 1990). Another vital function of water is in thermal properties. It is a terrific heat sink and it is resistant to changes in temperature due to strong hydrogen bonding between water molecules. For organic functioning, it means any effect of ambient temperature is sealed off by each cells or an organism. Thermal properties of water can be affected by the presence of metal particles that are not naturally occurring. This alteration can lead to snow ball effects, triggering chain of undesirable events.

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Recently, Islam (2014) argued that water is the first material that resided on earth (and the universe). It means everything is ‘water-wet’. As a result, water can move along with great adhesion and cohesion properties. Water is highly cohesive. In fact, it is the highest of the non-metallic liquids. The positive and negative charges of the hydrogen and oxygen atoms that make up water molecules makes them attracted to each other. In a water molecule, the two hydrogen atoms align themselves along one side of the oxygen atom, with the result being that the oxygen side has a slight negative charge and the side with the hydrogen atoms has a slight positive charge. Thus when the positive side on one water molecule comes near the negative side of another water molecule, they attract each other and form a bond. This "bipolar" nature of water molecules gives water its cohesive nature. This property is also affected by the presence of artificial matter. The adhesive properties of water explain its capillary actions. Attraction to charged or polar surfaces allows water to flow in opposition of gravitational forces (capillary action). This capillary action is necessary to allow water to be transported up plant stems via a transpiration stream. Once again, metals play an important role in organic as well as non-organic systems, most notably in vascular systems. Studies over the past 40 years have revealed that the vascular system is much more than an organism’s “plumbing.” Rather than being a static series of pipes and tubes, the vascular system is extremely dynamic and plays a critical role, the functioning of which involves complex interactions among various vital parts, as discussed in many toxicology studies (Prozialeck et al., 2008). The exact behaviour is little known. Even less known is the extent of organic and non-organic chemicals affect organic functionalities. Water viscosity is one of the most mysterious properties. Apparently, it is a Newtonian fluid with high resistance to temperature change. However, more recent studies indicate that water viscosity is very complex and far from being Newtonian (see Islam, 2014 for details). It also is affected by heavy metals, particularly in microscale. Reported sources of heavy metals in the environment include geogenic, industrial, agricultural, pharmaceutical, domestic effluents, and atmospheric sources (Tchounwou et al., 2012). Living organisms require varying amounts of heavy metals. Although, all metals are toxic at higher concentrations, non-organic metals are toxic at all concentrations (Long et al., 2002). In presence of non-organic form of heavy metals, a rigid viscosity barrier is created at nanolevel, leading to disruption of vital organic functions. The beneficial functions of heavy metals had been recognized in ancient medicinal practices that sought out herbs, rich in certain heavy metals (Singh et al., 2011). Natural phenomena such as weathering and volcanic eruptions have also been reported to significantly contribute to heavy metal pollution but the role of these naturally occurring heavy metals has not been studied, mainly because New Science cannot distinguish between these metals and artificially processed metals. Non-organic heavy metals disrupt metabolic functions in two ways (Singh et al., 2011): 1. They accumulate and thereby disrupt function in vital organic bodies. 2. They displace the vital nutritional minerals from their original place, thereby, hindering their biological function.

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Phytovolatilization (The plant ability to remove toxic elements from the leaf surface once it have travelled through plant) (Direct accumulation of contaminants into plant shoots with subsequent removal of the plant shoots) Phytoaccumulation/ (Plants bind contaminated soil Phytoectraction which results in the immobalization of toxic contaminants) Phytostabilization

Phytodegradation

(Plants have natural substance in their roots, leaves and stem that can help them in breakdown of toxic contaminants)

M+

M+

M+ M+(Metal)

Uptake Rhizo(sphere) Degradation

Figure 10.46 Transition mechanism in plants for metal accumulation (From Singh et al., 2011).

In Point two above, it should be noted that anytime non-organic metal replaces organic metal components (within a nutrient body), it is far more damaging than an nonorganic molecule replacing another non-organic molecule. Figure 10.46 Shows various mechanisms that are involved in transition metal accumulation by plants.They are (Yang et al., 2002): – – – – –

Phytoaccumulation, Phytoextraction, phytovolatilization, phytodegradation, and phytostabilization.

All these mechanisms will produce metabolic products that will be contaminated and will continue to act as ‘cancer’ for rest of their pathways. This is the source of that is referred earlier as Σaccumulation, which leads to Rejects at various stages of Calvin cycle.

10.7.1 Water as the Driver of Climate Change The flow of water in different forms has a great role in climate change. Water is the main vehicle of natural transport phenomenon. A natural transport phenomenon is a flow of complex physical processes. The flow process consists of production, the storage and transport of fluids, electricity, heat, and momentum (Figure 10.47). The most essential material components of these processes are water and air, which are also the indicators of natural climate. Oceans, rivers, and lakes form both the source and the sink of

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Production of light Ashes gas

Electricity

Water Air Chemical and bilogical reaction

Lava

Production of vapor

Production of heat Motion

Heat

Figure 10.47 Natural transport phenomenon (Modified from Islam et al., 2010).

Efficiency Solar direct Wood Global efficiency

Biogas

Local efficiency

Wind

geothermal Wood

Nuclear

Hydropower oil Gas Coal

Nuclear Technology

Figure 10.48 Global and local efficiency of different energy sources.

major water transport systems. Because water is the most abundant matter on earth, any impact on the overall mass balance of water is certain to impact the global climate. The interaction between water and air in order to sustain life on this planet is a testimony to the harmony of nature. Water is the most potent solvent and also has very high heat storage capacity. Any movement of water through the surface and the Earth’s crust can act as a vehicle for energy distribution. However, the only source of energy is the sun and sunlight, the most essential ingredient for sustaining life on earth. The overall process in nature is inherently sustainable, yet truly dynamic. There isn’t one phenomenon that can be characterized as cyclic. Only recently, scientists have discovered that water has memory. Each phenomenon in nature occurs due to a driving force, such as pressure for fluid flow, electrical potential for the flow of electricity, thermal gradient for heat, and chemical potential for a chemical reaction. Natural transport phenomena cannot be explained by simple mechanistic views of physical processes described by a function of one variable.

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A simple flow model of natural transport phenomenon is presented in Figure 10.48. This model shows that nature has numerous interconnected processes, such as the production of heat, vapor, electricity and light, the storage of heat and fluid, and the flow of heat and fluids. All these processes continue for infinite time and are inherently sustainable. Any technologies that are based on natural principles are sustainable (Khan and Islam 2006). Water plays a crucial role in the natural climatic system. Water is the most essential as well as the most abundant ingredient of life. Just as water covers 70% of the earth’s surface, water constitutes 70% of the human body. Even though the value and sanctity of water has been well known for thousands of years in eastern cultures, scientists in the west are only now beginning to examine the concept that water has memory, and that numerous intangibles (most notably the pathway and intention behind human intervention) are important factors in defining the value of water (Islam, 2014). However, at the industrial/commercial level, preposterous treatment practices include the following: the addition of chlorine to “purify;” the use of toxic chemicals (soap) to get rid of dirt (the most potent natural cleaning agent) (Islam et al., 2015); the use of glycol (very toxic) for freezing or drying (getting rid of water) a product; the use of chemical CO2 to render water into a dehydrating agent (opposite to what is promoted as “refreshing”), then again to demineralize it by adding extra oxygen and ozone to “vitalize” it. The list seems to continue forever. Similar to what happens to food products (the degradation of the following chemical technology chain: Honey → Sugar → Saccharine → Aspartame), the chemical treatment technique promoted as water purification has taken a turn, spiraling downward (Khan and Islam, 2016). Chlorine treatment of water is common in the west and is synonymous with civilization. Similarly, transportation through copper pipes, distribution through stainless steel (enforced with heavy metal), storage in synthetic plastic containers and metal tanks, and mixing of ground water with surface water (collected from “purified” sewage water) are common practices in “developed” countries. More recent “innovations,” such as Ozone, UV, and even H2O2, are proving to be worse than any other technology. Overall, water remains the most abundant resource, yet “water war” is considered to be the most certain destiny of the 21st century. What Robert Curl (a Novel Laureate in Chemistry) termed as a “technological disaster,” modern technology development schemes seem to have targeted as the most abundant resource. Water vapor is considered to be one of the major greenhouse gases in the atmosphere. The greenhouse gas effect is thought to be one of the major mechanisms by which the radiative factors of the atmosphere influence the global climate. Moreover, the radiative regime of the radiative characteristics of the atmosphere is largely determined by optically active components, such as CO2 and other gases, water vapor, and aerosols (Kondratyev and Cracknell 1998). As most of the incoming solar radiation passes through atmosphere and is absorbed by the Earth’s surface, the direct heating of the surface water and the evaporation of moisture results in heat transfer from the Earth’s surface to the atmosphere. The transport of heat by the atmosphere leads to the transient weather system. The latent heat, released due to the condensation of water vapors, and the clouds play an important role in reflecting incoming short-wave solar radiation and absorbing and emitting long wave radiation. Aerosols, such as volcanic dust and the particulates of fossil fuel combustion, are important factors in determining

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the behavior of the climate system. Kondratyev and Cracknell (1998) reported that the conventional method of calculating global warming potential only accounts for CO2, ignoring the contribution of water vapor and other gases in global warming. Their calculation scheme took into account the other components that affect the absorption of radiation, including CO2, water vapor, N2, O2, CH4, NOx, CO, SO2, nitric acid, ethylene, acetylene, ethane, formaldehyde, chlorofl uorocarbons, ammonia, and aerosol formation of different chemical composition and various sizes. However, this calculation fails to explain the effects of pure water vapor and the water vapor that is contaminated with chemical contaminants. The impact of water vapor on climate change depends on the quality of the water evaporated, its interaction with the atmospheric particulates of different chemical composition, and the size of the aerosols. There are at least 70,000 synthetic chemicals being used regularly throughout the world (Icenhower 2006). It has further been estimated that more than 1,000 chemicals are introduced every year. Billions of tons of fossil fuels are consumed each year to produce these chemicals that are the major sources of water and air contamination. The majority of these chemicals are very toxic and radioactive, and the particulates are continuously released into the atmosphere. The chemicals also reach water bodies by leakage, transportation loss, and as by-products of pesticides, herbicides, and water disinfectants. The industrial wastes, which are contaminated with these chemicals, also reach water bodies and contaminate the entire water system. The particulates of these chemicals and aerosols, when mixed with water vapor, may increase the absorption characteristics in the atmosphere, thereby increasing the possibility of trapping more heat. However, pure water vapor is one of the most essential components of the natural climate system and has no impacts on global warming. Moreover, most of the pure water vapors end up transforming into rain near the Earth’s surface and have no effect on the absorption and reflection. The water vapor in the warmer parts of the earth could rise to higher altitudes since they are more buoyant. As the temperature decreases in higher altitude, the water vapor gets colder, and it will hold less water vapor, reducing the possibility of increasing global warming. Because water is considered to have memory (Tschulakow et al. 2005), the assumption of water vapor’s impact on global warming cannot be explained without the knowledge of memory. The impact depends on the pathway water vapor travels before and after the formation of vapor from water. Gilbert and Zhang (2003) reported that nanoparticles change the crystal structure when they are wet. The structure change that takes place in the nanoparticles of water vapor and aerosols in the atmosphere has a profound impact on climate change. This relation has been explained based on the memory characteristics of water and analysis of its pathway. It is reported that water crystals are entirely sensitive to the external environment and take different shape based on the input (Emoto 2004). Moreover, the history of water memory can be traced by analysis of its pathway. The memory of water might have a significant role to play in technological development (Hossain and Islam, 2008). Recent attempts have been made towards understanding the role of history on the fundamental properties of water. These models take into account the intangible properties of water, and this line of investigation can address the global warming phenomenon. The memory of water not only has impacts on energy and ecosystems but also plays a key role in the global climate scenario.

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Characterization of Energy Sources

10.8.1 Environmental and Ecological Impact Each process has an environmental impact, either positive or negative. The positive impacts are expected to keep an ecological balance. Most of the processes that are established to-date are disrupting ecological balances and produce enormous negative effects on all living beings. For instance, the use of Freon in cooling systems, disrupts the ozone layer, allowing vulnerable rays from the sun to penetrate the earth and to living beings. Burning of “chemically purified” fossil fuels also pollutes the environment by releasing harmful chemicals. Energy extraction from nuclear technology leaves harmful spent residues. The environmental impact of different processes has been discussed by Islam et al. (2010).

10.8.2

Quality of Energy

The quality of energy is an important phenomenon. However, when it comes to energy, the talk about quality is largely absent. In the same spirit as “chemicals are chemical” that launched the mass production of various food and drugs, irrespective of their origins and pathways, energy is promoted as just “energy”, based on the spurious basis that “photons are the units of all energy”. Only recently, has it come to light that artificial chemicals act exactly opposite to how natural products do (Chhetri and Islam, 2007). Miralai et al. (2007) recently discussed the reason behind such behavior. According to them, chemicals with exactly the same molecular formulae derived from different sources cannot have the same effect unless the same pathways are followed. With this theory, it is possible to explain why organic products are beneficial while chemical products are not. Similarly, heating from different sources of energy cannot have the same impact. Heating of homes by wood is a natural burning process, which was practiced since ancient times and did not cause any negative effects to humans. More recently, Khan and Islam (2007) extended the “chemicals are chemicals” analogy to “energy is energy”. They argued that energy sources cannot be characterized by heating value alone. Using a similar argument, Chhetri and Islam (2008) established a scientific criterion for characterizing energy sources and demonstrated that conventional evaluation would lead to misleading conclusions if the scientific value (rather than simply “heating value”) of an energy source was ignored. On the other hand, Knipe and Jennings (2007), indicated a number of vulnerable health effects to human beings due to chronic exposure of electrical heating. The radiation due to the electro-magnetic rays might cause interference with the human’s radiation frequency which can cause acute long-term damage to humans. Energy with natural frequency is the most desirable. Alternate current is not natural and that’s why there will be some vulnerable effects of this frequency to the environment and humans (Chhetri, 2007). That is why it can be inferred that heating by natural sources is better than heating by electricity. Microwave heating is also questionable. Vikram et al. (2005) reported that the nutrient of orange juice degraded highest by microwave oven heating as compared to other heating methods. It has been reported that microwave cooking destroys more than 97%

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of the flavonoids in broccoli and causes a 55% chlorogenic acid loss in potatoes. A 65% quercetin content loss is also reported in tomatoes (Vallejo et al., 2003). There are several other compounds formed during electric and electromagnetic cooking which are considered to be carcinogenic, based on their pathway analysis.

10.8.3 Evaluation of Process From the above discussion, it can be noted that considering only the energy efficiency based on input and output of a process does not identify the most efficient process. All of the factors should be considered and carefully analyzed to claim a process efficient in the long-term. The evaluation process of an efficient process should consider both the efficiency and the quality of a process. Considering the material characterization developed by Khan and Islam (2012), the selection of a process can be evaluated using the following equations:



−

 

(10.28)

Where Ereal is the true efficiency of a process when long term factors are considered, E is the efficiency at present time (t =”right now”), E0 is the baseline efficiency, and δ(s) is the sustainability index, introduced by Khan (2007), such that” δ(s) = 1, if the technology is sustainable; and δ(s) = −1, if the technology is not sustainable.





(10.29)

Where Qreal is the quality of the process. L (t) is the alteration of quality of a process as a function of time. When both Ereal and Qreal have positive values, this make the process acceptable. However, the most efficient process will be the one which has highest product value (Ereal × Qreal). After evaluation of efficient processes, economic evaluation can be made to find the most economical one. Today’s economic evaluation of any contemporary process, based on tangible benefits provides the decision to establish the process for commercial applications. However, decision making for any process needs to evaluate a number of criteria, as discussed earlier. Moreover, the economics of intangibles should be analyzed thoroughly to decide on the best solutions. Time span may be considered to be the most important intangible in this economic consideration. Considering the long-term, tangible and intangible effects, natural processes are considered to be the best solutions. However, to arrive at any given end-product, any number of natural processes may be available. Selection of the best natural one depends on what objectives have the greatest priority at each stage and what objectives can be accomplished within a given span of time. If the time span is considered important, it is required to find out the natural process which will either have a low pay back period or a high rate of return. , is this right?, However, irrespective of time span, the best natural process to select would be that which will base itself on the process which renders the best quality output, with no immediate impacts and no long-term ones.

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10.8.4 Final Characterization Various energy sources are classified based on a set of newly developed criteria. Energy is conventionally classified, valued, or measured based on the absolute output of a system. The absolute value represents the steady state of an energy source. However, modern science recognizes that such a state does not exist and every form of energy is at a state of flux. This section characterizes various energy sources based on their pathways. Each form of energy has a set of characteristic features. Anytime these features are violated through human intervention, the quality of the energy form declines. This analysis enables one to assign a greater quality index to a form of energy that is closest to its natural state. Consequently, the heat coming from wood burning and the heat coming from electrical power will have different impacts on the quality of heat. Just as all chemicals are not the same, different forms of heat coming from different energy sources are not the same. The energy sources are based on the global efficiency of each technology, the environmental impact of the technology, and the overall value of energy systems (Chhetri and Islam, 2008). Energy sources are classified based on the age of the fuel source in nature as it is transformed from one form to another (Chhetri et al. 2006). Various energy sources are also classified according to their global efficiency. Conventionally, energy efficiency is defined for a component or service as the amount of energy required in the production of that component or service, e.g., the amount of cement that can be produced with one billion Btu of energy. Energy efficiency is improved when a given level of service is provided with reduced amounts of energy inputs or when services or products are increased for a given amount of energy input. However, the global efficiency of a system is calculated based on the energy input, product output, the possibility of multiple uses of energy in the system, the use of the system’s by-products, and its impacts to the environment. The global efficiency calculation considers the source of the fuel, the pathways the energy system travels, conversion systems, impacts on human health and the environment, and by-products of the energy system. Islam et al. (2010) calculated the global efficiency of various energy systems. They showed that global efficiencies of higher quality energy sources are higher than those of lower quality energy sources. With their ranking, a solar energy source (when applied directly) is the most efficient (because the source is free and has no negative environmental impacts), while nuclear energy is the least efficient, among many other forms of energy studied. They demonstrated that previous fi ndings failed to discover this logical ranking because the focus had been on local efficiency. For instance, nuclear energy is generally considered to be highly efficient, which is a true observation if one’s analysis is limited to one component of the overall process. If global efficiency is considered, the fuel enrichment alone involves numerous centrifugation stages. This enrichment alone will render the global efficiency very low. Carbon dioxide is characterized based on normally-ignored criteria such as its origin, the pathway it travels, the isotope number and age of the fuel source from which it was emitted. Fossil fuel exploration, production, processing, and consumption are major sources of carbon dioxide emissions. Here, various energy sources are characterized based on their efficiency, environmental impact, and quality of energy based on the new criteria. Different energy sources follow different paths from origin to end-use and contribute emissions differently. A detailed analysis has been carried out on potential

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precursors to global warming. The focus is on supplying a scientific basis as well as practical solutions after identifying the roots of the problem. Similarly, this chapter presents an evaluation of existing models on global warming, based on the scenario of various protocols and agreements, including the Paris Agreement. Shortcomings in the conventional models have been identified based on this evaluation. The sustainability of conventional global warming models has been argued. Here, these models are deconstructed and new models are developed based on new sustainability criteria. Conventional energy production and processing use various toxic chemicals and catalysts that are harmful to the environment.

11 Conclusions

11.1

Concluding Remarks

We promised in the introduction, this book will have conclusions that are unlike any of the ones made before. Before, we show major conclusions under each of the chapters, it is important to recall the state of the art of climate change research. It will help the readership to understand the hopelessness of the current thrust both from the 97% left and 3% right. Table 11.1 shows major conclusions, compiled from Parry et al. (2007) and other IPCC publications. Comments are added in order to familiarize the readership with the conclusions of this book. The conclusions of Table 11 have been supported by the 97% consensus group through numerous research projects and voluminous annals of publications. The comments made in Table 11.1 are paramount. These conclusions set the stage for universal carbon tax and the erection of a UN-like body (the new version of IPCC) that would shape the future of the energy industry and global finances. The delivery of Nobel prize to IPCC and Al Gore in 2007 and to climate change economist and a world bank mentor this year are the events that exposes the motive of these conclusions that are touted to be scientific and objective. In conclusion, we can safely say that the above table shows how hollow the conclusions of the “97% scientific consensus” group has been. Their ‘evidence-based’ science has little real evidence and logic used to draw conclusions has little logic in it. The fact that the 3% who opposed this narration do not have any scientific explanation to support their opposition makes it clear that the debate has long moved from the scientific 537

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Table 11.1 Major conclusions from the ‘97% consensus’ camp. Major conclusions of IPCC

Comment

89% of 29,000 environment data series support Most data are terrestrial, concentrated on global warming Europe and North America. Global warming led to greatest reduction in ice extent that occurred in the Arctic, but some of the most obvious has been in tropical mountain environments such as on Mt Kilimanjaro.

Conclusion invalid unless global warming is the first premise.

The oceans have become increasingly acidic with an average pH reduction of 0.1.

Has no scientific validity whatsoever

The most vulnerable systems and sectors are: Some ecosystems, especially tundra, boreal forest, mountain, Mediterranean-type ecosystems, mangroves and salt marshes, coral reefs and the sea ice biomes; Low-lying coasts, due to the threat of sealevel rise; Water resources in low-latitude regions, due to decreases in rainfall and higher rates of evapotranspiration; Agriculture in low-latitude regions, due to reduced water availability; and Human health, especially in areas with low adaptive capacity. The most vulnerable regions are: The Arctic, because of high rates of projected warming on sensitive natural systems; Africa, especially the sub-Saharan region, because of low adaptive capacity and projected changes in rainfall; Small islands, due to high exposure of population and infrastructure to risk of sea-level rise and increased storm surge; and Asian megadeltas, such as the GangesBrahmaputra and the Zhujiang, due to large populations and high exposure to sealevel rise, storm surge and river flooding.

These are also the regions with least recorded data Predictions, based on models that are inherently flawed. Extension to human health and adaptive capacity has no scientific basis

Conclusions based on mathematical modeling, based on flawed premises.

(Continued)

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Table 11.1 Cont. Major conclusions of IPCC

Comment

There are very likely to be impacts due to altered frequencies and intensities of extreme weather, climate and sea-level events

This is not a scientific conclusion, it is a speculation that would fit the premise every major natural event emerges from manmade activities

Some large-scale climate events have the potential to cause very large impacts, especially after the 21st century

Absolutely useless and jejune statement of the obvious

The overall effect of climate change will be negative

This is not a conclusion, it is merely setting the false paradigm for a climate change agenda

Adaptation will be necessary to address impacts resulting from the warming which is already unavoidable, due to past emissions

This is preparing the public to spend on Adaptation projects and has no scientific backing

Even if emissions were stabilized now, global This is retrofitting DICE results that are decades old, long before the Climate data temperatures would increase on average by were collected. a further 0.6 °C by 2100. Furthermore, some current targets to reduce emissions assume a global average temperature increase of about 1.5 °C above present (i.e., 2 °C above pre-industrial temperatures). Some adaptation is occurring now, but on a limited basis, and more is needed to reduce vulnerability to climate change

Totally unscientific and illogical conclusion. Adaptation is a phenomenon that needs generations of studies – generations of humans as well as trees.

Vulnerability to climate change can be exacerbated by the presence of other stresses, including water extraction, commercial deforestation

First time a connection to overall industrial practices being made, albeit obliquely

Future vulnerability depends not only on climate change but also on development pathway

This is nothing for pandering for more funds for development agencies so they can ‘civilize’ the third world.

Sustainable development may reduce vulnerability to climate change and climate change may impede nations’ abilities to achieve sustainable development pathways

Has no meaning in absence of scientific definition of sustainability. This one is laying the groundwork for Universal carbon tax. (Continued)

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Table 11.1 Cont. Major conclusions of IPCC

Comment

Many impacts can be avoided, reduced or delayed by mitigation

This ‘conclusion’ actually is to counter the recent evidence that climate has stabilized and give credit to whatever has been done to ‘mitigate’

We will need a mix of adaptation and This ‘conclusion’ sets stage for more funding mitigation measures to meet the challenge to gather information and research of climate change, but this is hampered by a adaptation and justify eventual universal lack of information on the costs and benefits carbon tax. of adaptation This ‘conclusion’ is entirely a premise, which Human-induced climate change has is quickly becoming a cult-like ‘belief ’. contributed to changing patterns of extreme weather across the globe, from longer and hotter heat waves to heavier rains. From a broad perspective, all weather events are now connected to climate change. While natural variability continues to play a key role in extreme weather, climate change has shifted the odds and changed the natural limits, making certain types of extreme weather more frequent and more intense. Current level of global warming of 1.5 C above This conclusion is the same as predicted pre-industrial levels. decades ago and is as meaningless as it was then. Universal carbon tax will bring in the best result in mitigating global warming

This conclusion is actually a justification for implementing Paris Agreement and channeling funds for the new EU 2030 renewable energy target of 32%, and the new energy efficiency target of 32.5%, all focusing on creating a shift away from carbon and toward toxic alternatives.

arena to political one. It is only in media there remains a dispute over the scientific facts that implies ‘carbon is the enemy and non-carbon fuel is the panacea’ to global warming. In this book, we answer two key questions, which have eluded all climate scientists purporting to conduct evidence-based research. These questions are: 1. What is the impact of artificial chemicals on the fate of CO2 and other emissions? 2. What is the long-term consequences of the ‘renewable’ energy? 3. What is the real cause of global warming? 4. What measures must be taken to reverse the current trend?

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11.2

Conclusions of Chapter 2: State-of-the Art of the Climate Change Debate

1. For decades the climate change debate has moved on from scientific to political. 2. The scientific consensus has been in stating global warming and its cause are facts and the principal cause of global warming is anthropogenic CO2 as a result of burning of fossil fuels. 3. No analysis as to the nature of CO2 that is emitted or the role of artificial chemicals, such as the ones used in refining or gas or coal processing have been investigated, let alone following the pathway to global warming or rejection by the ecosystem. 4. Although the nature of greenhouse gas emitted from volcanic activities have not been identified and their role in global warming incorporated to conduct a sensitivity analysis, they have been ignored as a contributing factor to global warming. 5. The fraction of anthropogenic greenhouse gases, compared to naturally occurring gases has been reported to miniscule, but no scientific explanation has been provided as to determine why anthropogenic gases have been the main player. 6. Anyone that opposes the mainstream line of global warming has been denigrated as ‘climate denier’ and stigmatized as scientifically naïve – similar to the creationists in the context of evolution theory. 7. Skeptics of ‘scientific consensus’ have positioned themselves as deniers by stating that climate change is part of natural cycle and in fact, we may be very well be in a cooling cycle within the geologic timescale.

11.3

541

Conclusions of Chapter 3: Forest Fires and Anthropogenic CO2

1. Forest fires are entirely natural and hence beneficial to the environment 2. Any correlation between forest fire occurrence and global temperature is ill perceived and scientifically inconsistent 3. The misconception about forest fires arises from improper assessment of the role of water and carbon in maintaining harmony of the ecosystem 4. Modern science understanding of open fire and its nature is based on false premises that do not distinguish between real fire and artificial fire. 5. Correct assessment of global warming must include inclusion of intangible components of heat sources. These components behave differently in artificial energy sources from natural ones. 6. Every component of the sunlight spectrum is necessary for sustainability whereas each component of the artificial light spectrum is necessarily unsustainable and harmful to the environment.

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7. Carbon cycle and water cycle are complimentary and necessary combination for true sustainability. 8. Carbon sources are the next best energy sources to direct sunlight, which is a pre-requisite for photosynthesis. 9. Correlation between CO2 concentration in the atmosphere and forest fire occurrences is spurious and ill conceived.

11.4

Conclusions of Chapter 4: Role of Agricultureal practices on Climate Change

1. Water, energy and food form a nexus that can be either organic/sustainable or nonorganic/unsustainable, depending on the level of contamination. 2. Energy from sunlight is the purest form, whereas CO2 from organic sources is the purest. 3. Biofuel is not the best form of energy sources nor is it renewable. 4. The quality of CO2 emission from biofuel as well as crops is affected by chemical fertilizer as well as pesticides. 5. Minerals accumulated from chemical fertilizers and pesticides render the oxidation products unabsorbable by the environment, eventually contributing to global warming. 6. Chemicals from chemical fertilizers and pesticides create irreversible damage to plant metabolism, thus magnifying the level of pollution, resulting in a very large volume of CO2 becoming unacceptable to the ecosystem. 7. Any agricultural produce further affects the entire food chain the same it affects biofuels. 8. Heavy metals from pesticides are the most disruptive to the metabolic system for plants, which magnify the effect when consumed by animals and further contaminate through the food chain. 9. These contaminants act like cancer cells, thus threatening the entire organism. Similarly, the entire ecosystem is affected through chain reactions.

11.5

Conclusions of Chapter 5: Role of Biofuel Processing in Creating Gobal Warming

1. With currently used technologies, biofuels produce more toxic combustion gases than petroleum fuels. The contaminants of biofuels come from chemical fertilizers, pesticides, and chemicals that are added during processing. For petroleum products, only chemicals added during refining/processing affect adversely.

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543

2. The quality of biofuel can be improved by using natural chemicals as a catalyst. 3. The economics of biofuel can be improved by using waste vegetable oil. However, that would not improve the quality of CO2 produced at the end of combustion reactions. 4. The use of microwave, ultrasound, or other energy catalysts can affect the biofuel production rate but create pollution that cannot be quantified. 5. For any system to be renewable it must meet the long-term sustainability criterion. Such criterion can be met with fossil fuel more easily than biofuel.

11.6

Conclusions of Chapetr 6: Role of Refining on Climate Change

1. The current refining practices render crude oil unsustainable and resulting CO2 is no longer accepted by the ecosystem. 2. Scientifically, even energy from artificial sources can affect CO2, but conventional analysis is not equipped with to quantify the effect. 3. The theory that artificial nanomaterials behave opposite to natural materials can explain long-term impact of artificial chemicals on CO2 path. 4. If natural materials replace artificial or synthetic catalysts, the resulting refined products can be free from adding to the global warming as they will produce CO2 that will be absorbed by the plants, leaving behind no residue.

11.7

Conclusions of Chapter 7: Scientific Characterization of Petroleum Fluids

1. The current material characterization tools are inherently biased toward artificial chemicals and show natural chemicals to be inherently superior and necessary for long-term sustainability. 2. When petroleum fluids are properly characterized, petroleum fluids in their natural form are shown to be inherently sustainable, until artificial chemicals and/or energy sources are used to process/refine them. 3. The proper characterization tool must consider mass as the source of any energy and evaluate them as a whole, meaning artificial matter will create artificial energy and when that artificial energy is used in processing matter, it will be rendered artificial, incapable of returning to the natural system. 4. Petroleum fluids, both abiogenic and biogenic are inherently sustainable and offer no threat to the environment in its native form. 5. The transition between different forms of carbon-based fuel is continuous and cyclic. Therefore their development and usage are amenable to long-term sustainability, creating no stress on the ecosystem.

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6. The ranking of petroleum fluids and biofuel are (in descending order of utility): a. Basement oil b. Unconventional gas/oil c. Conventional gas/oil d. Biofuel (including vegetable oil) 7. The natural order of usage of carbon materials are: a. food b. fuel c. medicine 8. Biofuels are neither healthy nor economic 9. Biomass (including wood) is inherently sustainable

11.8

Conclusions of Chapter 8: Delineraized History of Climate Change Hysteria

1. The current climate change hysteria is not based on facts or science. All evidence is fictitious, exaggerated, or tweaked to fit the desired conclusions, befitting ‘climate change hysteria’. 2. The current climate change policies are similar to those made in UN. As such, the hidden intention behind climate change hysteria is not to bring about clean environment or healthy population, but bring about global control and economic dominance of the most powerful nations. 3. Every action item of the climate change 97% consensus group is based on false premises, akin to those based on Malthusianism regarding population and the Keynesian vision regarding economy. 4. The renewable/non-renewable boundary is fictitious. The ones purported as renewable are more toxic to the environment than fossil fuel. 5. Petroleum resources can be scientifically characterized and allocated for different applications, rather than focusing on running engines 6. Petroleum products should be considered for diverse applications rather than all refined the same way to produce gasoline first.

11.9

Conclusions of Chapter 9: The Monetization the Climate Science

1. Most popular predictive tools of climate change are devoid of scientific basis. 2. All economic tools for predicting impact of climate change policies are inherently biased toward non-carbon energy sources, which are inherently uneconomic, unsustainable, and toxic to the environmental health. 3. Conclusions made in various IPCC panels and international agreements, such as Kyoto, Copenhagen, Paris, and others are preposterous

The Science of Global Warming and geared to justify universal carbon tax and other means of global dominance.

11.10

Conclusions of Chapter 10: The Science of Global Warming

1. In the matter of global warming, the scientific protocol has followed the Honey → Sugar → Saccharine → Aspartame → Nothing (HSSAN) model, which symbolizes systematic decline while accumulating great amount of profit at the expense of global economic and environmental welfare. In this process, we have moved progressively from natural to artificial. Policies have been drafted first and science and engineering have been used to feel the justification of the policies. 2. Petroleum resources are 100% natural and as such are 100% sustainable. 3. Refining must be done with a sustainable process and with targeted applications, including medicinal applications. 4. A re-assessment of reserve based on scientific characterization of petroleum reservoirs can increase the current estimate of the global reserve.

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The Science of Climate Change. M. R. Islam, M. M. Khan. © 2019 Scrivener Publishing LLC. Published 2019 by John Wiley & Sons, Inc.

Index Absolute scale, 171 Absolute speed, 171, 303 Absolute energy, 469 Absolute binding nuclear energy, 473 Absorption, 421, 451, 456–60 Acetaldehyde, 176, 182, 230, 231 Acetic acid, 176 Adaptation, 34, 35, 251, 320, 422, 426, 428, 539, 540, 592, 599, 603, 611 Adaptive capacity, 347, 538 Adaptive risk management, 34, 36 Additive, 112, 114, 118, 144, 151, 164, 196, 229, 238, 245, 246, 251, 285 Aerosol, 5, 8, 22, 95, 97, 190, 241, 246, 282, 447, 464, 531, 532, 595 Agricultural activities, 6, 21, 103, 107, 142, 408, 411, 518 Agricultural land, 144, 556, 616 Agricultural Process, 103, 104 Agricultural practice, 104, 144, 180, 449 Algae, 113, 114, 143, 167, 322, 326, 519, 600 Amino acid, 128–30, 143, 157, 162, 166, 178, 331, 527, 577 Antioxidant, 165, 504 Aphenomenal, 5, 10, 17, 27, 94, 179, 266, 275, 295, 298, 377, 488, 490, 495, 498 Aquinas, Thomas, 171, 380, 382 Aristotle, 275, 314, 503, 549 Artificial aerosol, 8 Artificial boundary/barrier, 56, 64, 317, 467 Asymmetric, 252 Atomic absorption, 456, 460, 461 Atomic principle, 294 Atomic properties, 461 Atomic number, 146, 151, 153, 472, 476, 477 Atomism, 275, 322, 503 Atomic theory, 261, 264–6, 294, 299, 518 Avalanche model, 170 Avalanche theory, 171, 495, 498

Average temperature, 29, 364, 365, 375, 422, 431, 539 Biochemical, 264, 500, 501, 510, 561, 565 Biodiversity, 116, 135, 429, 598 Biofuel categories, 110 Biofuel conversion, 178 Biofuel feedstock, 179 Biological, 315, 319, 484, 485, 528, 547, 558, 585, 604 Biological carbon cycle, 449 Biological pathway, 572 Biomass, 6, 21, 22, 31, 50, 76, 77, 100, 104, 107, 112, 113, 115, 116, 118, 143, 167, 178, 233, 251, 332, 345, 360, 394, 500, 501, 515 Biomass-based diesel, 110 Biomass-based alcohol, 230 Biomass burning/combustion, 408, 485, 486, 517 Biodiesel combustion, 233 Biodiesel manufacturing, 183, 225 Biodiesel production, 228, 229, 230, 231, 234, 549, 555, 557, 549, 555, 557, 571, 577, 578, 580, 581, 584, 587, 588, 594, 601 Biodiesel synthesis, 189 Biofuel energy, 112 Biofuel generation, 114–6 Biofuel industry, 147 Biofuel market, 108 Biofuel manufacturing, 113 Biofuel plant, 117 Biofuel production, 178–80, 543 Bitumen, 237, 331, 360 Carbon monoxide, 45, 52, 118, 146, 193, 225, 245, 246, 247, 249, 255, 309, 330, 515 Carcinogen, 137–41, 147, 150 Carnot cycle, 493 Catalyst

619

620

Index

natural, 207, 232, 249 synthetic, 182, 238, 239, 291, 543 Catalytic cracking, 239, 244, 247, 249, 281, 284 Characteristic time, 171, 334, 380, 471, 501 Chloride Aluminum, 247 Barium, 310 Calcium, 249, 309 Copper, 311 Hydrogen, 247, 311 Methyl, 452 Methylene, 247 Sodium, 308, 310 Tin, 555, 559 Chlorogenic acid, 534 Cholesterol, 131, 176 Clean energy, 2, 3, 328, 332, 552, 593 CO2 from biomass, 404 Coal combustion, 142, 147, 152, 417, 422, 502, 507–9, 512, 513, 522, 548, 622 Coal-fired power plant, 417, 418, 419, 422 Coalbed methane, 332 Cobalt, 66, 70, 165, 238, 247, 249, 262, 277 Coke, 239, 242, 244, 283–5, 287, 291, 342, 385 Conventional refining, 236 Conventional resources, 339 Conventional theory, 261, 291, 297, 331, 340, 577 Conversion of energy (into mass), 57, 319 Corrosion, 186, 206, 227, 238, 386, 387, 482 Corrosion inhibitor, 246, 247, 249 Cracking, 204, 237–40, 244, 246, 248, 279, 284, 285, 290, 291 Criteria, 388, 534–6 Crop yield, 152, 178, 487, 488, 584 Crude oil production, 3, 23, 392, 398, 406 Dark matter, 299, 300, 603 DDT, 27, 132, 135, 138, 236, 351, 378, 502, 563, 613 Diabetes, 159 Diagenesis, 320, 516, 517 Diatom, 40, 42, 46, 50, 143, 321, 580, 582 Diffusion, 32, 227, 276, 277, 279–81, 284, 289, 303, 305, 467, 484, 500, 501, 506, 589 Dioxin, 141 Direct solar heating, 242 DNA, 47, 51, 163, 165, 176, 178, 246, 247, 318, 485, 487, 554 Drilling, 359, 360, 382, 386, 392, 572, 609

Ecology, 68, 84, 549 Efficiency Carbon, 348 Economic, 440 Energy, 54, 353, 413, 420, 421, 534, 535, 540, 568, 599 Fuel, 417 Global, 245, 331, 535 Local, 531, 535 Einstein, Albert, 350, 351, 365, 452, 493, 617 Electricity generation, 296, 297, 402, 403, 418, 419, 454, 455, 593 Electromagnetic, 58, 115, 268, 294, 298, 299, 308, 314, 489, 495, 534, 568 Energy balance, 422, 467, 493, 494, 499, 501, 502 Energy consumption, 1, 107–9, 181, 354, 409, 413, 421, 456 per capita, 344, 351–56 Energy crisis, 1, 314, 343, 344, 349, 357, 361, 363, 364, 375 Enhanced oil recovery (EOR), 263, 332, 357, 390, 393–7, 399, 400 Entropy, 494 Enron, 7 Environmental justice/injustice, 103 Environmental impact, 116, 183, 249, 282, 293, 294, 326, 338, 438, 533, 535 Enzyme, 30, 31, 113, 156, 164, 165, 167, 176, 177, 188, 227, 228, 319, 320, 506, 598, 614 Equilibrium condition, 483, 497 isotope, 482–4 point, 206 potential, 257 processes, 478 spurious, 443 Eurocentric, 361, 381 European union, 25, 357, 410, 412, 413, 416, 414, 420 Farming, 9, 135, 230, 449, 489, 594, 595 Fatty acid, 184–90, 199, 201, 203, 206, 208, 521 Fermentation, 176, 177, 230, 233, 455, 456, 517 Fertilizer Chemical, 9, 10, 78, 114, 121, 123, 126–8, 179–82, 186, 227, 368, 411, 487, 512, 517, 520, 542 Organic, 450, 487 Filter, 243, 593

Index Fish, 47, 132, 141, 150, 250, 363, 455, 487, 580 Fission, 472–4 Fluorescent, 63, 65, 69, 141, 174, 253, 261, 267 Freezing, 43, 531 Fructose, 131 Fuel cell, 323 Gas hydrate, 332, 340, 360, 390, 391, 511 Gas-gas separation, 276 Gas reserve, 357, 359, 360, 391, 393, 400 Gas separation, 280 Galaxy model, 169, 170, 173, 265, 300, 317, 471, 482, 484, 518 GDP Growth, 107, 437, 439 Genetic alteration, 179, 181, 368, 445 Genetic engineering, 179, 261 Globalization, 111, 410 GNP (Gross national product), 353, 354 Green revolution, 87, 119, 121, 378, 410, 487 Greenhouse effect, 9, 28, 29, 119, 193, 465, 466 Groundwater, 72, 128, 135, 144, 145, 146, 150, 153, 180, 324, 482 Health effect, 141, 159, 160, 533, 576 Heart, 136, 140, 423, 447 Heat dead, 294 Heat transfer, 29, 531 Heating value, 331, 339, 533 Heavy metal components, 127, 142, 144, 167, 287, 558, 567 Heavy metal contamination, 142 Helium, 46, 51, 55, 299, 328, 387, 448 Hepatic (liver) 136–41 Holistic, 251, 347, 355 Honey, 40, 339, 488, 489 Honey Sugar Saccharine Aspartame N othing (HSSAN) degradation, 531, 545 Hydrochloric acid, 188, 198, 205, 386 Incandescent, 46, 53, 63, 64, 307 Infrared, 29, 48, 56–8, 60, 63, 96, 99, 102, 205, 299, 313, 315, 318, 456, 458, 459, 466, 487, 518 Intangible components, 176, 177, 305, 527, 591 Intangible effects, 534 Intangible form, 250, 493, 520 Intangible mass, 492 Intangible particulates, 177 Intangible properties, 532

621

Japan, 26, 248, 352, 410–13, 416, 421 Johnson, Lyndon B, 437 Jojoba, 208 Jobs Automobile, 431 Green, 2 Industrial, 431 Manufacturing, 431 Judiciary, 7 Judgement, 7, 27, 434 Justification, 8, 14, 16, 36, 94, 100, 350, 435, 441, 540, 545 engineering, 389 testable, 101 Kelvin, Lord, 294, 314, 315, 432, 495 Kinetics, 191, 194–7, 483, 551 Kinetic effects, 483 Knowledge-based decision, 14 Knowledge-based technology, 575 Korean yin yang, 40 Least Developed countries (LDC) 424, 426–8, 488, 614 Life cycle, 153, 174, 229, 230, 270, 328, 329, 447, 497 Lipids, 123, 163, 165, 170, 325, 555, 569 Liposome, 261, 585 Liquid fuel, 109, 112, 117, 118, 119, 604 Liquid phase oxidation, 286 Liquid phase reaction, 214 Long run, 168, 360, 366, 381, 435, 440–2 Lung cancer, 503 Lung damage, 48, 52 Magnesium oxide, 189, 309 Marx, Karl, 378, 381, 382 Mass balance, 64, 179, 478, 484, 489, 492–4, 501, 503, 530, 561, 569 Mass conservation, 491, 495 Mass-energy balance, 467, 494, 499 Mass-energy-momentum balance, 489 Mass-energy discontinuity, 46, 49 Mass spectrometry, 149, 248, 467, 487, 522 Maxwell, 294, 308 Metallic oxide, 43, 46 Momentum, 268, 274, 372, 489, 494, 497–9, 529 Momentum balance, 501

622

Index

Monitoring, 73, 75, 96, 99, 111, 134, 207, 229, 449, 451, 548 Natural burning, 533 Natural frequency, 32, 254, 301, 303, 304, 471, 533 Natural processing, 31, 63, 173–5, 301, 320, 326, 328, 331, 333, 334, 337, 339, 358, 360, 394, 500 Natural processing time, 332, 338, 339 Natural source, 20, 53, 60, 62, 68, 78, 132, 141, 147, 157, 170, 234, 238, 290, 349, 366, 368, 480, 491, 500–4, 533 Nature science, 380, 490 Nervous system, 137–41, 145, 255, 500 Neurological, 136–41, 159, 160, 163 Neurotoxic, 254 Newton, Sir Isaac, 17, 90, 378, 468, 496, 503 Newtonian approach/mechanics/principle, 22, 94, 497 Newtonian fluid, 528 Nuclear bomb, 495, 522 Nuclear energy, 5, 16, 174, 294, 296, 413, 418, 488, 495, 535 Nuclear weak force, 308 Nobel laureate (Chemistry) 175, 48 Nobel laureate (economics) 7, 366, 380, 429 Nobel laureate (Physics) 315 Nobel laureate (Medicine) 132, 135, 378, 445 Non-linear density, 92 Non-linear viscosity, 44 Non-linearity, 94, 265, 489 Ocean bed, 24 Ocean-couple atmospheric, 72, 94 Octane rating, 113, 247 OECD, 357, 412, 415, 421 Offshore, 407 Oil in place, 392, 393 Oil shale, 326, 329, 386, 394, 397 OPEC, 384, 385, 393, 398, 407 Ozone, 9, 22, 34, 46, 50, 64, 73, 248, 319, 368, 372, 447, 448, 450, 453, 465, 531, 533 Pathway analysis, 6, 119, 263, 448, 534 Petroleum-based, 230, 409

Peak oil, 23, 343, 344, 349, 357, 361, 363, 376, 379 Permeability, 330, 386 Population growth, 351, 353, 355, 356, 370, 379, 412 Porosity, 254, 277, 290, 388, 484 Production process, 117, 179, 182, 183, 198, 229, 231, 233, 371, 517, 535, 588 Proven reserve, 333, 390, 391, 392, 394, 397, 399 Radioactive, 58, 169, 294, 296, 299, 472, 532 Radiocarbon, 522, 567, 583, 604 Radiation frequency, 298, 533 Radionuclide, 52 Real science, 5, 6, 7, 17, 36, 94, 346, 366, 431, 444 Refinery efficiency, 241 Shale formation, 385–8 Shale gas, 331, 332, 360, 388, 392, 398, 407 Solar radiation, 22, 24, 25, 28, 60, 73, 103, 317, 411, 465, 466, 518, 531, 582, 602, 613 Solar system, 73, 317, 319, 322 Solid fuel, 486 Quantum mechanics, 265, 270, 470, 585 Quantum equation, 468 Quantum physics, 266, 291, 294, 314 Subatomic particle activities, 31, 302 Subatomic particles, 171, 263, 264, 274, 294, 298–302 Subatomic structure, 31, 302 Synthetic crude, 383, 389 Sustainable development, 426, 427, 429, 539, 564 Supercritical conditions, 226 Sustainable growth, 105 Tangible, 8, 40–42, 249, 305, 306, 308, 352, 491 Tangible index, 354 Tar sand, 332, 389, 390, 394 Tight gas, 331, 332, 340, 360, 388, 391, 407

Index Ultraviolet, 30, 48, 56–8, 60, 299, 318, 319, 458 Ultrasonic, 225 Unconventional gas/oil, 332, 338, 544, 575 Uranium, 66, 70, 126, 295, 296, 308

623

Vacuum distillation, 231, 232, 237, 244, 386 Vacuum gasoil, 281, 283, 287 World Bank, 14, 15, 111, 366, 537 X-ray diffraction, 253, 280