Memoir II: The Elementary Chemical Composition of Marine Organisms 9781933789354

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The Elementary Chemical Composition of Marine Organisms

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MEMOIR

SEARS FOUNDATION FOR MARINE RESEARCH

Number II

THE ELEMENTARY

CHEMICAL COMPOSITION OF

MARINE ORGANISMS 4. P. VINOGRjIDOV

VERNADSKY LABORATORY FOR GEOCHEMICAL PROBLEMS Moscow, U. S. S. R. NEW HAVEN. SEARS FOUNDATION FOR MARINE RESEARCH, YALE UNIVERSITY

PUBLICATIONS OF THE SEARS FOUNDATION FOR MARINE RESEARCH, YALE UNIVERSITY The Sears Foundation for Marine Research at Yale University was established in 1937 by Albert E. Parr, director of Yale's Bingham Oceanographic Laboratory, through a gift from Henry Sears, to promote research and publication in marine sciences. The Foundation's Memoirs, inaugurated in 1948, remain important references. In 1959 the Bingham Oceanographic Collection was incorporated into the Yale Peabody Museum of Natural History. Distributed by Yale University Press www.yalebooks.com I yalebooks.co.uk MEMOIR I FISHES OF THE WESTERN NORTH ATLANTIC

Part One Lancelets, Cyclostomes, Sharks Part Two Sawfishes, Guitarfishes, Skates and Rays, Chimaeroids Part Three Soft-rayed Bony Fishes: Orders Acipenseroidei, Lepisostei, and Isospondyli Sturgeons, Gars, Tarpon, Ladyfish, Bonefish, Salmon, Charrs, Anchovies, Herring, Shads, Smelt, Capelin, et al. Part Four Soft-rayed Bony Fishes: Orders Isospondyli and Giganturoidei Argentinoids, Stomiatoids, Pickerels, Bathylaconids, Giganturids Part Five Orders Iniomi and Lyomeri Lizardfishes, Other Iniomi, Deepsea Gulpers Part Six Orders Heteromi (Notacanthiformes), Berycomorphi (Beryciformes), Xenoberyces (Stephanoberyciformes), Anacanthini (Gadiformes) Halosauriforms, Killifishes, Squirrelfishes and Other Beryciforms, Stephanoberyciforms, Grenadiers Part Seven Order Iniomi (Myctophiformes) Neoscopelids, Lanternfishes, and Atlantic Mesopelagic Zoogeography Part Eight Order Gasterosteiformes Pipefishes and Seahorses Part Nine, Volume One Orders Anguilliformes and Saccopharyngiformes Part Nine, Volume Two Leptocephali Part Ten Order Beloniformes Needlefishes, Sauries, Halfbeaks, and Flyingfishes MEMOIR II THE ELEMENTARY CHEMICAL COMPOSITION OF MARINE ORGANISMS

by A. P. Vinogradov

The Elementary Chemical Composition of Marine Organisms Translated from Vinogradatfs original Russian by JULIA EFRON and JANE K. SETLOW, with bibliography edited and newly enlarged by VIRGINIA W. ODUM, for the SURVEY OF EXISTING KNOWLEDGE OF BIOGEOCHEMISTRY AMERICAN MUSEUM OF NATURAL HISTORY

NEW

HAVEN

SEARS FOUNDATION FOR MARINE RESEARCH, YALE UNIVERSITY

Yale ISBN 978-1-933789-22-4 (pbk.) ISBN 978-1-933789- 35-4 (e-book) Issued in paperback by the Peabody Museum of Natural History, Yale University, New Haven, Connecticut 06511 USA First published in hardcover in 1953 by the Sears Foundation for Marine Research Bingham Oceanographic Laboratory, Yale University ISBN 978-0-912532-93-6 (cloth) Library of Congress Control Number: 55001070 Distributed by Yale University Press NEW HAVEN AND LONDON Printed in the United States of America Printed on acid-free paper

Table of Contents PREFACE

xiii

CHAPTER I. INTRODUCTION 1. History of the Accumulation of Analytical Data 2. Character of the Analytical Material 3. Elementary Composition of Living Matter 4. The Chemical Composition of Sea Water CHAPTER II. ELEMENTARY COMPOSITION OF NONPLANKTON1C MARINE ALGAE 1. General Remarks 2. The Water Content of Different Species of Phaeophyceae, Rhodophyceae, and Chlorophyceae 3. Ash Content 4. Carbon, Hydrogen, and Nitrogen 5. Phaeophyceae : Sodium, Potassium, Calcium, Magnesium, Phosphorus, Chlorine, and Sulfur 6. Phaeophyceae : Sodium and Potassium 7. Phaeophyceae : Calcium and Magnesium 8. Phaeophyceae: Sulfur, Chlorine, and Phosphorus 9. Phaeophyceae: Seasonal Changes in Sodium, Potassium, Calcium, Magnesium, Phosphorus, Sulfur, and Chlorine 10. Rhodophyceae: Potassium, Sodium, Calcium, Magnesium, Phosphorus, Sulfur, and Chlorine 11. Corallinaceae : Sodium, Potassium, Calcium, Magnesium, Phosphorus, Sulfur, and Chlorine 12. Chlorophyceae: Sodium, Potassium, Calcium, Magnesium, Phosphorus, Sulfur, and Chlorine 13. Iodine 14. Iodine in Phaeophyceae 15. Iodine in Rhodophyceae 16. Iodine in Chlorophyceae 17. Bromine 18. Arsenic

vii

i 10 13 14

17 20 22 26 35 40 44 45 49 49 53 62 69 73 94 103 106 no

viii 19. 2 o. 21. 2 2.

23.

Table of Contents Silicon and Aluminum in Phaeophyceae, Rhodophyceae, and Chlorophyceae Manganese Iron Other Elements: Copper, Zinc,Titanium, Lead, Molybdenum,Tin, Cobalt, Nickel, Mercury, Silver, Gold, Vanadium, Chromium, Boron, Bismuth, Antimony, Tungsten, Gallium, Germanium, Cadmium, Beryllium, Praseodymium, Neodymium, Samarium, Cerium, Lanthanum, Yttrium, Rubidium, Cesium, Lithium, Strontium, Barium, Thallium, Fluorine, and Radioactive Elements Gases

CHAPTER III. ELEMENTARY COMPOSITION OF MARINE 1. General Remarks 2. Chemical Composition of Cyanophyceae 3. Flagellata 4. Peridinieae 5. Diatomeae

IIQ xx

4

II6

118 128

PLANKTON 130 134 141 144 146

CHAPTER IV. ELEMENTARY COMPOSITION OF MARINE BACTERIA

155

CHAPTER V. ELEMENTARY COMPOSITION OF ZOSTERA AND OTHER MARINE FLOWERING PLANTS

15 8

CHAPTER VI. ELEMENTARY COMPOSITION OF PROTOZOA 1. Foraminifera 2. Xenophyophora 3. Radiolaria 4. Heliozoa, Infusoria, and Other Protozoa 5. Rarer Elements

163 164 171 172 174 j^

CHAPTER VII. ELEMENTARY COMPOSITION OF POR1FERA 1. General Remarks 2. Water, Ash, Carbon, Hydrogen, and Nitrogen 3. Class Demospongiae, Order Cornacuspongida 4. Tetraxonida 5. Class Hyalospongiae (= Hexactinellidae) 6. Aberrant Siliceous Sponges 7. On the Form of SiO2 in Sponges and Silicon Exchange in the Sea 8. Calcarea 9. Heavy Metals and Other Elements

!^g j^ j^g I gI jgi Xg2 jgo jg7 jgg

Table of Contents

ix

CHAPTER VIII. ELEMENTARY COMPOSITION OF COELENTERATA 1. General Remarks 2. Water, Nitrogen, and Carbon in Coelenterata and the Chemical Composition of the Skeletonless Forms 3. Hydrocorallina 4. Hexacorallia 5. Octocorallia 6. Heavy Metals and Other Elements 7. Halogens, Arsenic, and Radioactive Elements 8. Ctenophora

195 201 202 206 211 215 218

CHAPTER IX. ELEMENTARY COMPOSITION OF BRYOZOA

220

CHAPTER X. ELEMENTARY COMPOSITION OF BRACHIOPODA 1. Inarticulata (Calcium-Phosphate Brachiopoda) 2. Articulata (Calcareous Brachiopoda) 3. Other Elements

225 228 230

194

CHAPTER XL ELEMENTARY COMPOSITION OF PERMES 1. Water, Ash, Nitrogen, Carbon, Calcium, Phosphorus, Sulfur, Potassium, and Sodium 2. Composition of Calcareous and Phosphatic Tubes of Vermes 3. Heavy Metals 4. Nonmetallic Elements

231 232 235 237 240

CHAPTER XII. ELEMENTARY COMPOSITION OF PHORONIDEA

243

CHAPTER XIII. ELEMENTARY COMPOSITION OF ENTEROPNEUSTA

244

CHAPTER XIV. ELEMENTARY COMPOSITION OF ECHINODERMATA 1. Water, Ash, Carbon, and Nitrogen 2. Sodium, Potassium, Calcium, Magnesium, Phosphorus, Sulfur, Chlorine, and Silicon 3. Composition of the Skeletons, Particularly of Echinoidea 4. Composition of the Skeletons of Crinoidea 5. Composition of the Skeletons of Asteroidea 6. Composition of the Skeletons of Ophiuroidea 7. Form of CaCO3 and MgCO3 in the Echinoderm Skeleton 8. Composition of the Skeletal Parts (Spicules) of Holothuria 9. Heavy Metals 10. Other Metals i r. Nonmetallic Elements

245 246 246 250 254 255 257 257 259 261 267 268

x

Table of Contents

CHAPTER XV. ELEMENTARY COMPOSITION OF MOLLUSCS 1. General Remarks 2. Water, Organic Matter, and Ash 3. Carbon, Hydrogen, and Nitrogen 4. Sodium, Potassium, Calcium, Magnesium, Phosphorus, Sulfur, Chlorine, and Silicon 5. Sodium and Potassium 6. Calcium and Magnesium 7. Phosphorus, Sulfur, and Chlorine 8. Silicon 9. Composition of Shells ; Other Skeletal Formations 10. Composition of Shells of Cephalopoda 11. Composition of Shells of Lamellibranchiata 12. Composition of Shells of Amphineura, Scaphopoda, Pteropoda, and Heteropoda 13. Composition of Skeletal Parts of Gastropoda 14. Composition of Pearls 15. Manganese, Iron, Copper, and Zinc 16. Other Metals 17. Nonmetallic Elements CHAPTER XVI. ELEMENTARY COMPOSITION OF ARTHROPODA 1. General Remarks 2. Water, Ash, Nitrogen, and Chlorine in Crustacea 3. Composition of Entomostraca 4. Composition of Copepoda 5. Composition of Branchiopoda 6. Composition of Ostracoda 7. Composition of Cirripedia 8. Composition of Malacostraca 9. Composition of Stomatopoda 10. Composition of Amphipoda 11. Composition of Mysidaceae 12. Composition of Isopoda 13. The Carapace and Calcium Metabolism of Crustacea 14. Heavy Metals in Crustacea 15. Other Metals in Crustacea 16. Nonmetallic Elements in Crustacea 17. On the Composition of Some Fossil Arthropoda: Trilobita, Gigantostraca, and Xiphosura

271 272 280 283 285 286 290 295 296 3O1 3°3 309 311 318 319 360 368

375 376 381 381 386 389 390 390 397 397 399 099 400 403 408 ^II .x .

Table of Contents

xi

CHAPTER XVII. ELEMENTARY COMPOSITION OF TUN1CATA 1. General Remarks 2. Vanadium in Ascidiae

41 8 422

CHAPTER XVIII. ELEMENTARY COMPOSITION OF LEPTOCARDII AND CYCLOSTOMATA

430

CHAPTER XIX. HAEMOGLOBIN, HAEMOCYAN1N AND OTHER INVERTEBRATE RESPIRATORY PIGMENTS CONTAINING METALS 1. The Chemical Composition of the Blood and other Body Fluids of Invertebrates 431 2. Metallo-organic and other Special Compounds in Invertebrates 435 CHAPTER XX. MINERALOGICAL COMPOSITION OF THE SKELETONS OF MARINE ORGANISMS 1. Calcium and Magnesium Carbonates 2. Skeletal Parts with Other Salts of Calcium, Strontium, and Barium 3. Siliceous Skeletons 4. Phosphates and Apatites 5. Oxides and Metallic Hydroxides in Skeletons CHAPTER XXI. ELEMENTARY COMPOSITION OF PISCES 1. General Remarks 2. Water i n Fishes 3. Carbon, Hydrogen, and Nitrogen 4. Ash Residue 5. Potassium, Sodium, Calcium, Magnesium, Phosphorus, Sulfur, Chlorine, and Silicon 6. Potassium and Sodium 7. Calcium and Magnesium 8. Phosphorus and Sulfur 9. Chlorine 10. Silicon u. Manganese 12. Iron 13. Zinc 14. Copper 15. Aluminum 16. Mercury 17. Lead, Molybdenum, Nickel, Cobalt, Titanium, Chromium, Silver, Niobium and Vanadium in the Tissues of Fishes

454 458 458 460 462

463 483 494 497 5°3 5°4 5°5 5 12 51? 5*9 5*9 520 523 527 532 532 533

xii 18. 19. 20. 21. 22. 23. 24. 25. 26. 27.

Table of Contents Rarer Alkali and Alkaline Earth Elements Boron Strongly Radioactive Elements Bromine Fluorine Iodine Arsenic Composition of Fish Blood Composition of Bones and Other Skeletal Formations Gases

535 535 53 6 53 6 537 537 55 x 555 559 563

CHAPTER XXII. THE REGULATING INFLUENCE OF OCEAN SALT ON THE CHEMICAL COMPOSITION OF MARINE ORGANISMS

567

CHAPTER XXIII. FUNDAMENTAL CHANGES IN THE COMPOSITION OF MARINE ORGANISMS DURING GEOLOGICAL TIME

576

BIBLIOGRAPHY

ELEMENTARY

587

Preface

T

HE ELEMENTARY CHEMICAL COMPOSITION OF MARINE ORGANISMS constitutes one of the most important contributions that has yet been made to the study of the border line between biology and geochemistry. It may be compared in scope and learning with F.W.Clarke's DATA OF GEOCHEMISTRY and is doubtless destined to do for the study of the biochemical circulation of elements in the ocean what Clarke's work has done for the understanding of geochemical migration as a whole. As Professor Vinogradov's original work is available at present only in a Russian publication, which has a very limited distribution in libraries outside the Soviet Union, it was evidently incumbent to make this translation, prepared for the Survey of Contemporary Knowledge of Biogeochemistry, American Museum of Natural History, available as widely as possible throughout the English-speaking world. It is fortunate, therefore, that the publication of the work as one of the Memoirs of the Sears Foundation is now made possible through a generous grant from Mr. Henry Sears. The Russian original of THE ELEMENTARY CHEMICAL COMPOSITION OF MARINE ORGANISMS appeared in three parts, in 1935, J 937 anc^ X 944> *n the Travaux du Laboratoire biogdochimique de TAcademic des Sciences de 1'URSS. The third part contained numerous additions to the subject matter treated in the two earlier parts. In the preparation of this translation the later additions have been incorporated into the appropriate sections of the earlier part of the text. The whole of the English translation of the text was then read by Professor Vinogradov, who added some new information and made certain corrections. Further material, appearing during the process of editing and preparing the work for press, has been added mainly in the form of footnotes, which are distinguished by the letter "H." In a few cases where new material fitted conveniently into the text it has been incorporated without comment. The nomenclature of the sponges has been revised by Dr. Willard Hartman, that of the fishes by Miss Sarah B. Wheatland. Dr. Ralph Lewin has examined the lists of algae and made certain corrections. Professor M. Tatewahi of Sapporo has identified certain algae indicated in the literature only by vernacular Japanese names. Dr. Grace E. Pickford has most kindly examined the section on fishes and has provided numerous references to recent work. The editors have attempted to produce as accurate a text as xiii

xiv

Preface

possible and have taken great pains to avoid distortion of Professor Vinogradov's meaning. In some of the tables a complete rearrangement according to taxonomic principles has been possible, but in other cases this proved impracticable. Moreover, a number of other difficulties have arisen from time to time in the preparation of the work. These have been surmounted as far as possible, but errors undoubtedly remain; for these the writer craves the reader's indulgence. In the original work, dates were not used after authors' names in the text, so that reference to the bibliography was difficult. The enormous labor of completing the citations and of checking and completing the bibliography has been successfully carried out by Mrs. Virginia Odum. In a few cases in which names appear in the text without dates, it has not been possible to identify the work to which reference is made. As it stands, Mrs. Odum's bibliography is practically a new work and one which should be of extreme value to any investigator who consults it. This work should prove of value to geochemists, comparative physiologists and all who are concerned in any way with the utilization of marine products. On behalf of all such potential users, the writer wishes to express thanks to Professor Vinogradov for the immense labor that must have gone into the preparation of the work, to Mrs. Julia Efron and Mrs. Jane K. Setlow for the skill and patience of no common order that went into the translation, to Mrs. Virginia Odum for completing and editing the bibliography, to Mrs. Ann V. Vallentyne for meticulous editorial assistance, particularly on the galley proofs, to Mr. Yngve H. Olsen, editor of the Sears Foundation, for his expert care in preparing the work for the press, to Mr. Robert Earll McConnell and Mr. George Monroe Moffett whose generosity made the translation possible, and finally to Mr. Henry Sears who has ensured early publication. The writer also wishes to pay his tribute to the memory of the late V. I.Vernadsky, the founder of Biogeochemistry, who conceived the original program of which the present work forms so distinguished a part.

G. E. HUTCHINSON

* 15 Ayr March, 1952

American Museum of Natural History and Yale University. J

Chapter I

Introduction j. History of the Accumulation of Analytical Data ^ I ^O THOSE who are familiar with the problems of the elementary composition of A organisms it is quite apparent that the history of the study of this subject is inseparably tied to the history of the development of natural science. Apparent also is the fact that no complete science of elementary composition ever existed; although an interest in such a science has been shown in varying degrees by students of different branches of knowledge, a definite scientific center, where the problems of this particular subject might be studied systematically from year to year, has never existed. Furthermore, the data concerning the elementary composition of organisms or their parts— organs, tissues, and so forth—are scattered widely among numerous scientific books, journals and periodicals.1 Thus the collection of data, and the publication of such, proceeded independently in different fields of knowledge, and consequently the study of the elementary composition of organisms has not acquired an independent significance up to the present time, although the problems involved were familiar to investigators as far back as the early nineteenth century. First we shall make some remarks concerning the development of the knowledge of the elementary composition of all organisms in general, inasmuch as the history of this problem has not been presented elsewhere. But we will limit our remarks to only the primary essential facts which will aid in a better understanding of some of the material to be given subsequently. In the history of the problems which interest us there is still much that is not clear, although it is certain that future investigations into the history of chemistry will x. From 1822 there was the Jahresberichte Uber d. Fortschritte der Physischen Wissenschaften, d. Ckemie u. Mineralogie i>. Berxetius, and from 1847 to 1910, the Jahresbericht iiber die Fortschritte der Chemie und verwandter Teile anderer Wissenschaften^ begriindet von Liebig und Kopp. Later appeared the Chemisches Centralblalt, Chemical Abstracts, Biological Abstracts. I

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Memoir Sears Foundation for Marine Research

uncover more material. The following information, often fragmentary, was extracted from various treatises of the late eighteenth and early nineteenth centuries, the rest from the more recent works of physiologists, chemists, geologists, et al. The collection of data on this subject, chiefly during the last 150 years, may be divided into several stages. The first extends from ancient times to Lavoisier, that is, almost to the end of the eighteenth century; the second covers the years to the end of the nineteenth century, which in turn can be divided into separate trends; the third stage occurs in the last 30 to 40 years. The first stage is not of direct interest to us, although some of the ideas on the chemical composition of organisms elaborated during this period have persisted throughout the whole of the nineteenth century to the present time. However, the description of the relevant knowledge of this era is more difficult than that of any other, because the factual material is interwoven with the philosophical. A future historian will have to analyze in detail the complex picture built by the centuries. In ancient times knowledge was accumulated through results of practical experience of civilized peoples over many centuries. For example, the Egyptians, Greeks, Arabians, and later other people,2 knew that plants contain ash, which could be used as a fertilizer; later potash, the so-called vegetable alkali, was extracted from this ash and used for preparing soap. Something similar to this was prepared from brine and seaweeds by the inhabitants of the Mediterranean coasts, a material called barilla, containing chiefly sodium, or the mineral alkali, and potash. The alchemists, as for example Geber,3 discovered that potash was an important part of plants, as did Basilius Valentinus (Johannes Th6lde) in the seventeenth century. In 1579 Libavius extracted potash not only from plants but from parts of animals, although many other alchemists probably accomplished this before him.4 Animal bones were also used for fertilization in ancient times, it being known that they contained terra calcarea. The first information on the presence of lime in organisms is lost in remote antiquity.5 In the fifteenth to seventeenth centuries, discoveries made by the alchemists and somewhat later by the phlogistonists were added to knowledge acquired earlier. In 1669 Brand (see H. Peters, 1913) discovered phosphorus in urine, which element was later extracted from the ash of bones by Gahn (1769; see H.T. Scheffer, 1779) and Scheele (1771). Geoffroy (1706) and Lemery (1707) demonstrated the presence of iron in animals, though its presence in plants was known much earlier.6 In 1789 Abilgaard found silica in sponges (see O. Miiller, 1788—1806); in plants it was certainly known before, although only analyses of tabasheer by Macie (1791), Cavendish (see Macie, 2. From the time when the use of fire became known, man realized that plants, upon burning, leave an ash. 3. See Geber (1542). 4. For example, Geber extracted potash from yeast and alkali from animals (toads, frogs, and many others). See Olaus Borrichius (Olof Borch), 1674. 5. See the works of Dioscorides, first century (in Mellor, 1923: 619), on extracting lime from the shells of mollusks and other organisms. 6. See Lemery's (1707) citation of his father's discovery of the iron content of plants.

Chemical Composition of Marine Organisms

3

1791), and others7 are known. Priestley (1771) discovered oxygen and immediately showed that it is liberated by plants in light (1772). In 1774 Scheele found manganese in plants, and Vauquelin (i8o7-a) demonstrated its presence in animals. At the same time a number of chemists—Proust (1806), Klaproth (1804), GayLussac (1805), Berzelius (1807), Morichini (1805) and others—found fluorine in bones, and in 1793 there appeared the FLORAE FRIBERGENSIS by A. Humboldt, in which the author gave the first ample summary of all that was known at the time on the elementary composition of organisms. He named 13 chemicals8 which are always found in organisms, and he may have done the determinations of silica, potassium, and calcium in plants9 himself. On the eve of the nineteenth century, towards the end of the phlogiston period in chemistry, there were great and well known chemists in whose works the investigation of the elementary composition of organisms occupied a place. At that time no modern differentiation of knowledge existed. A chemist was primarily a naturalist, and his interests were diverse. We have already mentioned Priestley, Humboldt, and Vauquelin, Klaproth, Berzelius, and Gay-Lussac: let us also recall Davy (1818), Fourcroy (1793, 1804), Wollaston (1809), Bergman (1791), Berthollet (1798), Volta and many others10 in whose works we find investigations of the elementary composition of organisms. As a result of all the observations made before the beginning of the nineteenth century, there appeared in 1814 a publication called CHEMISCHE TABELLEN by John, in which many analytical data for plants, animals, and their organs were given. Nitrogen, sulfur, phosphorus, sodium, potassium, silicon, magnesium, calcium, and iron, as well as oxygen, hydrogen and carbon, were the substances dealt with by the investigator toward the beginning of the new century. Besides this, information appeared from different sources on the presence of heavy metals in plants (Hierne, 1753), but one needs to be critical of this information (see Sarzeau, 1830). However, the presence of iron and manganese was certainly known. At this time a great revolution and a new era in science occurred with the beginning of Lavoisier's precise quantitative studies of chemical phenomena. In a short period science was enriched by numerous discoveries. Over a period of two decades about 20 new elements were discovered, which is as many as were known towards the end of the nineteenth century. In 1812 Courtois discovered iodine in seaweeds, and 14 years later Balard (1826) found bromine in the same seaweeds. At that time it was 7. See Russell (1790) and Me*therie (1800). Cavendish (see Macie, 1791) determined the specific gravity of SiO, from tabasheer. 8. Different salts and other compounds of the following elements: oxygen, hydrogen, nitrogen, carbon, sulfur, phosphorus, sodium, potassium, silicon, aluminum, magnesium, iron, terra ponderosa (barium: see Scheele, 17741779) and terra richteriana (strontium?). 9. See page 174 and others of the 'Florae. 10. See Rouelle (1777), Riickert (1789-1791), and others. There is a discussion of the work of Lavoisier by his pupil S£guin (1801) on the analysis of organisms and their tissues. In 1796 (ed. 1804), S. Sniadecki, in Tkeorie der organischen Wesen, gave a list of the chemical elements found in organisms: nitrogen, hydrogen, oxygen, carbon, sulfur, phosphorus, potassium, sodium, calcium, and magnesium. See more details on Sniadecki in the works of V. I. Vernadsky (1934).

2

4.

Memoir Sears Foundation for Marine Research

acknowledged that not only organic matter but also various elements found in plant ash were necessary for plant nutrition (see Saussure, 1804), though some alchemists and phlogistonists had maintained this earlier. A discussion on the origin of potassium in plants went on for a long time. The question arose as to whether or not potash existed in plants before burning or only in the ash after burning,11 and similar questions arose with regard to other chemical elements found in organisms. Only later, when Lavoisier's ideas had penetrated into chemistry, were these problems solved. Every year interest in the salt nutrition of plants increased. Besides potassium and later phosphorus, which were the center of attention for a long time, many other chemical elements became the subject of somewhat systematic experiments. G.T. Fechner, an investigator and philosopher of wide interests, in his work RESULTATE DER BIS JETZT UNTERNOMMENEN PpLANZENANALYSEN (1829), gave information on the presence of iodine, bromine, and aluminium, in addition to the chemical elements that had been known earlier. In 1831 C. Sprengel indicated for the first time the significance of ash elements in plants, especially of chemical elements found in small amounts; this was confirmed with special emphasis by Liebig (1843), who also emphasized the physiological role of such chemical elements. From this time on, analyses of plants became an indispensable link in the chain of the investigations of agrochemists. In Germany, in the United States, and in other countries, the first experiment stations and laboratories were organized in the eight eenfifties. Thus an enormous amount of analytical material was gradually accumulated, which was summarized in 18 71 to 18 8 o by Wolff in the form of a detailed list of analyses in two volumes. This work then provided a background for the elucidation of some of the principal questions of the chemical composition of organisms. First, it became evident that organisms differ in their composition from the medium in which they develop, and second, that plants differ among themselves. It is interesting that Liebig himself did an analysis of Lemna trisulca and of the water in the pond where it lived. At the same time, Bezold (I857)12 and the botanist Rochleder (1854) suggested almost simultaneously for the first time the connection between the chemical composition of organisms and their systematic position.13 With the aim of establishing this relation, Bezold did analyses of various animals, which, by virtue of their completeness, are unique even at the present time. However, the relationship between the elementary composition of organisms and their position in the evolutionary scale was observed by many earlier investigators. For example, we find some remarkable ideas in John's book published in 1819-14 In the footnote on page 69 he says : 11. See the works of John (1819), Senebier, Palissy (1580), and others. 12. Bezold was a pupil of Scherer and had connections with Liebig's school. 13. At the present time there are many attempts to treat the questions of the classification of organisms on the basis of a study of the distribution of different molecular compounds found in them. As we mentioned above, we will not dwell on them in this exposition. 14. We find analogous views in the work of still earlier natural philosophers, such as Rouelle (cited by Diderot, ed. 1875) and Diderot (see Diderot, ed. 1875) at the beginning of the eighteenth century. V. I. Vernadsky has called our attention to the teachings of Grosseteste (1175-1253) on the different composition of natural bodies, including organisms.

Chemical Composition of Marine Organisms

5

Diese merkwurdige Entdeckung veranlasste mich; einen Aufsatz aufzuarbeiten, um zu zeigen, dass man vermogend sey, in einer grossen Anzahl von Pflanzen die charakteristichen und vorwaltenden Bestandtheile nach dem aussern Habitus zu bestimmen; ja, andere Versuche brachten mich selbst auf den Gedanken, dass es moglich sey, eine Art, freilich sehr einzuschrankenden, chemischen Pflanzensystems zu entwerfen.

Numerous investigations of the so-called stimulating or catalytic influences, because of the presence of traces of rare chemical elements in plants, were added to the unceasing flow of analyses of plants at the end of the nineteenth century due to the teachings of Liebig and Grando and the work of Wiegmann and Polstorf. These investigations, together with similar ones on animals, form a vast body of scientific literature and include data on the discovery of trace elements in the organisms studied. The study of the chemical composition of animals proceeded parallel with that of plants in the last century. These studies followed two main directions—one along the line of the geological and mineralogical sciences, another along the line of the biological sciences. The mineralogist was interested mainly in the composition of skeletal parts, since the participation of organisms in rock formation was known.15 The biologist was chiefly concerned with a study of the organic compounds found in the organs and tissues of organisms ; of course the newly-developing field of organic chemistry had great influence in this work. The skeletons of invertebrates, such as the shells of Mollusca, are composed chiefly of calcium carbonate, which was known even in ancient times. Vertebrate bones, as well as the skeletal parts of Crustacea, contain phosphates (see the bibliography in the work of Bibra, 1844); it was soon discovered that these participated in the formation of phosphorites. Forchhammer drew attention to these problems in the eighteen-fifties when he found a number of rare chemical elements16 in marine organisms, but his basic ideas were ahead of the times. At this stage it was suggested that not only calcareous rocks, but also dolomites, consisting of calcium carbonate and magnesium carbonate, were formed organogenically. Also, in the skeletons of some marine organisms considerable amounts of magnesium carbonate were found. Thus the attention of the scientist was drawn towards the study of the sea and marine organisms, and in 1908 Btitschli produced a critical survey of the available results on the chemical composition of invertebrate skeletons. The biological investigations were not only more complicated than the other studies, but they were performed by people of diverse education and specialties— hygienists, apothecaries, physicians, biologists, agronomists, zoologists, botanists, et al. Compared to the agrochemical and geomineralogical works, these investigations, done in many different countries, were much more widely scattered, so that the results of the investigations of some scientists were long unknown in scientific circles, and consequently a single discovery was often presented several times. Furthermore, the absence of a unified conception of the material was another characteristic of the work 15. See on this subject the ancient authors, such as Herodotus, fifth century, B.C. 16. Barium, boron, lead, zinc, strontium, and others.

2*

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Memoir Sears Foundation for Marine Research

done in this field before the beginning of the nineteenth century. However, in the textbooks of physiology, and later in books of physiological chemistry and similar works, there were special chapters devoted to the chemical composition of animals, such as those of C. Schmidt (1845) anc^ Schlossberger (1854), who, with few exceptions, gave data on compounds, protein, fat, carbohydrate, and ash. It is curious, then, that the ideas concerning the necessity of mineral salts for animals was finally accepted only after the experiments of Forster (1878) and Lunin. Concurrent with the idea of a single protoplasm, the notion became widespread at the end of the first quarter of the last century that animal organisms consisted of carbon, nitrogen, hydrogen, oxygen, phosphorus, sulfur, and a few other elements usually found in ash, namely potassium, calcium, magnesium, and iron. Although the study of organic metabolism (nitrogen, and to a lesser extent phosphorus and sulfur) in animals and man gradually achieved a certain importance between 1860 and 1880, and although exceptional progress was made in the study of the structure of proteins, fats, and so forth, mineral metabolism in general remained somewhat unnoticed. Consequently there were few analytical data available in regard to mineral metabolism in animals. But from time to time comparative studies were made of the chemical composition of skeletons of lower animals, of fish scales, turtle shells, vertebrate bones, and so forth: also, there were comparative studies of the blood of lower and higher animals, and of organs and whole organisms, such as the mammalian embryo, including that of man. Furthermore, interest had been aroused in the metabolism of separate chemical elements, such as calcium (E.Voit), iron and sodium (Bunge, i885~a, i885-b), and a vast amount of material was collected on the content of nitrogen and phosphorus as well as calcium, sodium, and iron. Over a short period of time there appeared treatises on the physiological chemistry of animals by Gorup von Besinez (1871), Krukenberg (1881-1882), and Griffiths (1892), as well as books by Quinton (1904) and Furth (1903) containing new data. Such new data as referred to separate parts of organisms, animal products, and so forth, were well summarized in 1903 by K6nig in his CHEMIE DER MENSCHLICHEN NAHRUNG UND GENUSSMITTEL.

But for over a century there existed among biologists and physicians an idea, which still has not disappeared entirely, that a limited number of chemical elements enters into the composition of organisms (Errera, 1887, called them biogenal). This conception distracted the attention of scientists from the chemical elements that are found in animals only rarely or in small amounts, since these were considered to be only of sporadic occurrence and were even considered to be harmful contaminations (pseudonormal and facultative). Thus one can understand why discoveries made in the beginning of the last century have only now become appreciated. As an illustration of the conflict of opinions, we might point to the history of the discovery of copper and iodine; to acknowledge the correctness of Sarzeau's assertions as to the presence of copper in organisms, special commissions of the Academy of Sciences in Paris had to be established, and likewise to acknowledge the investigations of Chatin (1859) on the

Chemical Composition of Marine Organisms

7

wide biological distribution of iodine. Nevertheless, copper and iodine and their physiological significance were forgotten until our time, when interest in the function of these elements in animals was again awakened.17 The same story pertains to the discovery of arsenic and other less common elements. However, towards the end of the nineteenth century it became known that boron, bromine, iodine, arsenic, fluorine, copper, and some other elements, in addition to the common ones, occurred in small quantities in animals (see Table i). Important discoveries regarding these lesser known elements have shown the great need for further investigations. In 1895 Baummann discovered iodine in the hormone of the thyroid gland; in 1896, Bertrand supposedly discovered manganese in laccase ; and it was found also that a number of enzymes important in oxidation contain iron. Parallel with the growing significance of the presence of small amounts of different elements, enzymes, hormones, vitamins, and so forth in organisms, there is a mounting interest in the distribution of traces of different chemical elements in the tissues. Heavy metals have been studied more thoroughly than others in this respect; in Table i it is seen that an exceptional output of this kind of investigation occurred during these last years.

TABLE i

DISCOVERIES OF CHEMICAL ELEMENTS IN NATURE, IN PLANTS AND IN ANIMALS

ELEMENT Carbon Sulfur* Sodium Potassium Calcium Magnesium Chlorine Phosphorus

Isolation of element

Occurrence in plants

Occurrence in animals

Native element known in antiquity Davy, 1807 (1808) Davy, 1807 (1808) Davy, 1808 Davy, 1808 Scheele, 1774 Brand

See Sodium B. Albinus, 1688

Iron

Known in antiquity

See Lemery, 1707

Silicon

Berzelius, 1824

Oxygen Hydrogen

Priestley, 1771 Cavendish, 1766

Known at least by seventeenth century Priestley, 1772 Occurrence in organisms evidently realized soon after discovery

Nitrogen

Rutherford, 1772

Known in organisms in the form of oxides or salts in antiquity Brand, 1669 (see Peters, 1913) Geoffrey, 1705; but indications of presence given by Pliny and Celsus (Lemery, 1707) Abilgaard, 1789

(continued next page)

17. There have been special government commissions which have investigated the content of trace elements in plant and animal products: for example, for arsenic, the Royal Commission on Arsenic Poisoning (England), and a similar one in Sweden for boron and iodine, and so forth. On aluminum, see £. £. Smith, Report of Referee Board of Consulting Scientific Experts created by Executive Order of President Theodore Roosevelt in 1908, referred to in Aluminum Compounds in Food (1928).

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Memoir Sears Foundation for Marine Research

ELEMENT

Isolation of element

Occurrence in plants

Aluminum

Oersted, 1824

Fluorine2 Manganese Copper Strontium2 Iodine Bromine Lead Titanium2 Arsenic

Saussure (?), 1804; mordanting properties of aluminum salts in some plant ash known earlier1* Wilson, 1849 Scheele, 1772 John,3 1814 Forchhammer, 1855 Courtois, 1812 Balard, 1826 See ftn. 4, Table I Aderholdt, 1852 Orfila, 1838 (1841)

Moissan, 1886 Scheele, 1774 Known in antiquity Davy, 1808 Courtois, 1812 Balard, 1826 Known in antiquity Gregor, 1791 Albertus Magnus, 1260 (see G. Gratarolus, 1561) Known in antiquity Malaguti, Durocher, Sarzeaud, 1850 Davy, 1808 Scheele, 1788 Arfverdson, 1817 (1818) Kirchoff and Bunsen, 1860

Silver Barium2 Lithium Thallium Rubidium Cesium Zinc Lanthanum Cerium2 Didymium* Yttrium2 Boron Argon Gold Radon Radium Samarium Vanadium2 Tungsten2 Nickel Scandium

Crookes, 1861 Kirchoff and Bunsen, 1861 Kirchoff and Bunsen, 1861 Paracelsus, 1570 Mosander, 1839 (1842) Berzelius and Hisinger, 1804 Mosander, 1842 (1843) Gadolin, 1794 Gay-Lussac and Ttenard, 1808 Rayleigh and Ramsay, 1895 (1896) Known in antiquity Dorn, 1900 M. and P. Curie and G. B&nont, 1898 Lecoq de Boisbaudran, 1879 Rio, 1801 (1804) Scheele, 1781 Cronstedt, 1751 Nilson, 1879

Boettger, 1863 Bunsen, 1862

Occurrence in animals

Morichini, 1805 Vauquelin, 1807 Vauquelin, 1807 Moretti, 1813 Fyfe, 1819 Hermbstaedt, 1827 Rees, 1834 Orfila,5 1838 (1841) Malaguti, Durocher, Sarzeaud, 1850 Forchhammer, 1855 Folwarczny (see Kirchoff and Bunsen, 1861) Sonstadt,6 1870

Lippmann, 1888

Sonstadt, 1870

Forchhammer, 1865

Lechartier and Bellamy, 1877 Schiapparelli and Peroni, 1879 Schiapparelli and Peroni, 1879 Schiapparelli and Peroni, 1879 Crookes, 1883 Jay, 1895

Cossa, 1880 Cossa, 1880 Cossa, 1880 Wittstein and Apoiger, 1857 Tolomei, 1897 Liversidge, 18978 Stoklasa and others, 1920 Stoklasa and others, 1920

Schloesing and Richard, 1896 Liversidge, 1897 Tommasina, 1904 Tommasina, 1904 Crookes, 1908

B6deker(?), 1855 Cornec, 1919 See ftn. 9, Table I Lippmann, 1925

Henze, 1911 V. Vernadsky, 1922

Chemical Composition of Marine Organisms ELEMENT Cobalt

Isolation of element

Occurrence in plants

Occurrence in animals

Brandt, 1733 (1735)

Legrip, 1844 Forchhammer,10 1855 Demar9ay, 1900 Stoklasa,12 1913 Cornec, 1919 Cornec, 1919 Demar9ay, 1900 Cornec, 1919

Bertrand and Michebceuf, 1925 Misk,11 1923 Mankin, 1928 Bishop,13 1928 Dutoit and Zbinden, 1929 Chapman,14 1930 Zbinden, 1930 Zbinden, 1930

Cornec, 1919 See ftn. 15, Table i See ftn. 16, Table i

Okajima, 1931 See ftn. 15, Table i Fox and Ramage, 1931

Tin Known in antiquity Molybdenum2 Scheele, 1778 Uranium 2 Klaproth, 1786 (1789) Germanium Clemens Winkler, 1886 Antimony Basilius Valentinus, 1611 Chromium Vauquelin, 1797 Gallium Lecoq de Boisbaudran, 1875 Bismuth Agricola, 1546 Thorium Berzelius, 1829 Cadmium Hermann (1818-b) and Stromeyer, 1817 (1818) Niobium2 Rose, 1844 Selenium Mercury Beryllium

9

Berzelius, 1817 (1818) Taboury, 1932 Known in antiquity Stock and Cucuel, 193419 Wahler, 1828; and Bussy, Sestini20 1828

Newell and McCollum,17 1931 See ftn. 18, Table i Stock and Cucuel, 1934

Tellurium, Zirconium,21 Indium, Tantalum,1" Hafnium, and Rhenium2" have not yet been found in organisms. Rare earths22 other than Holmium, Thulium, and Lutecium have been found in organisms. Members of the platinum group, Ruthenium, Rhodium, Palladium, Osmium, Iridium, and Platinum have not been found in organisms.3" The gases Helium, Neon, Krypton, and Xenon have not been studied in organisms. The radioactive elements, besides Uranium, Radon, Radium, Mesothorium I, and Thorium23 have not been studied in organisms. 1. Cadet (1769) apparently was one of the first to show that sulfur existed in organisms. Systematic determinations of sulfur in organisms were done later by Proust, from 1799 on. xa. See Hutchinson, 1943. 2. Known first in the form of oxides, salts, and so forth. 3. Demonstrations of the presence of copper in plants appeared earlier. See Hjarne (1753) and other phlogistonists. However, in their experiments the possibility of contamination from utensils was not excluded. John was the first to demonstrate that plants extract copper from the soil. 4. See Henkel (1755) on wormwood. These results are doubtful. 5. Probably arsenic was found before. See Couerbe (1834) for example. 6. The results are doubtful. See Ramage (1929) on rubidium in animals. 7. Didymium was separated into praseodymium and neodymium by Carl A. von Welsbach (1886). 8. Gold was indicated earlier by phlogistonists and by Stromm (see Hjarne), Levenheim, Tollius, Henull, Hain and Sage (see Rouelle and D'Arcet 1779) which proved to be erroneous. Data on gold in organisms given by Liversidge and more recent authors are doubtful, except for those of Haber (1927). 9. Apparently the first observations of nickel in plants were made by Forchhammer in 1855. 10. Shown by Henkel in 1750 in Genista (see Spartium jun. and others in Phisikalische Belustigungen, 1751, St. 2 x. Ill), but this is doubtful, it. See Bertrand's (1932) objections to the high figures of Misk. 12. Method of analysis not given. 13. Uranium occurs in plants growing in soil rich in uranium. 14. Brief note without precise data. In plants it was shown earlier. 15. The presence of thorium in organisms has been shown from radiometric analysis. See Burkser, Brun, and Bronstein (1927). A chemical determination of thorium has not been done. Possibly the radiation was from mesothorium I, not thorium: see also Brunovski (1932)(continued next page)

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Memoir Sears Foundation for Marine Research

16. General indications of the presence of cadmium in plants exist in the literature (see McHargue, for example), but original data are not given. Cadmium was discovered in coal in 1847. 17. All authors speak with great caution on the presence of niobium. 18. Taboury found selenium in plants growing near water which contained selenium. Gassmann (1916) was the first to insist he had found selenium in organisms, but his primitive methods are questionable. See Fritsch (1918, 1920). Robinson (1936) found selenium in poisonous varieties of wheat, and Sullivan (1933) detected it in cereals. 19. Mercury was recorded earlier by the phlogistonists, Hjarne (1753) and Hieronimus Ludolf. These data are erroneous. 20. In plants from soils containing beryllium. See Cornec (1919) on beryllium in algae. W. R. Fearon (1933) found beryllium in a number of plants. 21. Sprengel's (1828) demonstration of the presence of zirconium in plants has not been verified (however, see Rosenthaler and Beck, 1937-!)). 22. Indications of the presence of undifierentiated rare earths in organisms are given by Cherniak, I. D. BornemanStarynkevich, Borovik and Borovskit (1941), M. Belala (unpublished data), Robinson, Whetstone, and Scribner (1938), and Lux (1939). 23. See ftn. 15, Table i. 1 H. But see Rosenthaler (1938) for records of both niobium and tantalum in plant ashes, which may not have been properly cleaned. 2 H. See, however, Ishibashi and Sahara (1940) who claimed to find rhenium in a Japanese seaweed (v. p. 118, fb. uH ). 3 H. See Noddack and Noddack (1939).

The success of such investigations resulted from the introduction of the most refined and modern physico-chemical methods of investigation into biochemistry, spectroscopy, x-ray, radiometry, and so on. At the same time a tendency arose to investigate one chemical element in a number of representatives of the animal and plant kingdoms. Thus there has been a great change recently in the conception of the trace elements in organisms. This is reflected in special articles on the mineral composition of tissues and so forth (see Abderhalden [1946], Aron and Gralka [1924], Bottazzi [1925]) and in more or less complete surveys as the TABULAE BIOLOGICAE of Junk (1925—1947),18 the work of Linstow (1924) on plants, and the work of Mitolo (1932). Appearing also are monographs devoted to the biochemistry of one element—iodine, manganese, potassium, calcium, aluminum, or radium, and an attempt is now being made to unify the results of 150 years of uninterrupted work into a new branch of knowledge, biogeochemistry. 2. Character of the Analytical Material The basic requirements which we demand from analytical data follow from the essence of our problem, namely to determine as precisely as possible the elementary composition of an organism. Not all the possible data entered the lists mentioned above, for the dispersion of analytical material in the scientific literature of all countries makes the collection of data difficult. Also, even during the period of our investigation the methods of analysis and the mode of expressing data have passed through an evolutionary change, so that the involuntary mistakes of analysts of the last century have only now become evident. Thus, the absence of a universal method of expressing data sometimes prevents us from comparing the results of different investigators directly. For example, the content of a chemical element or compound was sometimes expressed 18. Periodical surveys have also appeared- Tabulae Biologicae Periodic a.

Chemical Composition of Marine Organisms

11

as percent of fresh weight, sometimes as percent of air-dried or even completely-dried weight, and sometimes as crude ash, pure ash, and so forth. Furthermore, difficulties are introduced by the absence of information as to names of species, number of specimens in a mean analysis, sex, age, place of collection, and so on. All these inadequacies can be overcome only when there are numerous repetitions of an analysis of the same material by different investigators. The chief misfortune lies in the fact that most of the figures refer not to whole organisms but to separate organs, tissues, or parts. From the point of view of an agricultural chemist or biochemist it is sufficient in one case to analyze the leaves and in another the roots, or in the case of animals, the liver, skeleton, flesh, or blood. This material proves to be especially valuable when we turn from the comparative chemical evaluation of whole organisms to a comparison of the composition of different parts and organs in an attempt to give a detailed chemical picture of an organism. But when the data must be used for comparison of the whole organism, recalculation is necessary, which lowers the value of the data. Since there are far fewer analyses of whole organisms than of their parts, and since the number of elements which the analyses include is very diverse, complete analyses of organisms or even of parts of organisms are lacking. The few complete analyses include, first of all, grains or air-borne parts of plants, and secondly some small animals, chiefly invertebrates, where it is necessary to use the whole animal because of the method of analysis used. The most complete analyses are those which include a maximum of 15 chemical elements : but there are very few of these. Usually analyses of plants are characterized as complete if they include nitrogen, phosphorus, sulfur, silicon, potassium, sodium, calcium, magnesium, iron and chlorine, but for animals, fewer elements have been determined, with more determinations of phosphorus, nitrogen, potassium, and iron than of other elements. Similar series of determinations have been done on copper, manganese, iodine, arsenic, and other elements, especially during the last years. But even if qualitative determinations of phosphorus and nitrogen in organisms are of no special interest at the present time, any determinations (even qualitative) of vanadium, chromium, nickel, cobalt or gallium and germanium would be of importance. There are few data for carbon, and oxygen is always determined by difference. Table 2, which includes the largest possible number of analyses, shows the degree to which those published reflect the chemical composition of all organisms.19 What is the result ? Only hundredths of a percent, or at best tenths of a percent, of the species of organisms described by zoologists and botanists have been analyzed chemically in any way. However, this does not mean that we know the complete chemical composition of those organisms in each case, but, on the other hand, with care we can transfer data from one species to another (for example, in bone composition). Also, in Table i we see that at the present time there are more than 60 of the total of 92 elements known 19. We found a number of species for which there are both qualitative and quantitative analyses, but the authors did not state whether the whole or only a part of the organism was used.

12

Memoir Sears Foundation for Marine Research

in organisms, but this list is not complete because it can be shown that all the inert gases20 are introduced into organisms in respiration; probably these gases do not enter into compounds, but this is not known for certain. Of the rare earths only holmium, thulium, and lutecium have not been discovered thus far in organisms, although they may reasonably be expected to occur with the other rare earths; the complexity

TABLE 2 ESTIMATES OF NUMBER OF SPECIES WITHIN DIFFERENT GROUPS OF ORGANISMS FOR WHICH CHEMICAL ANALYSES ARE KNOWN*

PLANTS

Bacteria Fungi Algae Lichens Bryophyta

I

Gymnospermae Angiospermae

Lycopodiales Filicales Equisetales

Number of species described up to the present

Number of species analyzed

70,000 40,000 5,000 18,000

c. 50 70 350 25 100

| I 7,000 J 500 160,000

(20 100 | 50 [ 30 100 3,500

ANIMALS

Protozoa Porifera Coelenterataf Echinodermata . t . . Vermes Bryozoa Brachiopoda Mollusca Crustacea Myriopoda Arachnoidea Insecta Tunicata Pisces Reptilia, Amphibia Vertebrata ( A Aves Mammalia

20,000 3,000 9,000 4,200 16,000 3,050 130 100,000 15,500 8,100 28,000 750,000 1?600

.70'000

50 70 250 150 100 25 20 330 100 200 45

40

100 50

° 100

* The number of species described is corrected according to Hesse and some other information. Compare former calculations (Bull. Acad. Sci. Ukr. Phys. Math., IV, Fasc. 5: 357, 1930). f Together with Ctenophora. 20. The authors, in reporting determinations of nitrogen in gases in the tissues and cavities of organisms, often add the note, "together with the noble gases.'*

Chemical Composition of Marine Organisms

13

of the analyses and the difficulty of their separation hamper such investigations.21 Finally, all other elements of the radioactive series are probably present in organisms in addition to those already discovered—radon, radium, thorium22 and mesothorium I. Up to the present time the elements of the platinum group (ruthenium, rhodium, palladium, osmium, iridium, and platinum) and some others, such as tellurium, zirconium, indium, tantalum, hafnium, and rhenium have not been found in organisms (see Table i). Actually, we must expect all the stable chemical elements and their isotopes which are found in the earth's crust to be present in living organisms, and it is primarily a question of determining the quantity in which they are usually found in organisms. 3.

Elementary Composition of Living Matter

The chemical composition of the medium in which an animal lives is reflected in one way or another in the chemical composition of the organism. In other words, organisms which contain calcium, silicon, iron, or any other element can live and develop only in a medium which contains these elements. Thus, in the regions of the biosphere where there are large masses of limestone, silicate rock, iron ore, and so forth, only such organisms can survive which assimilate these materials, using them for the construction of their skeletons, as oxygen carriers, and so forth. Numerous examples show that in the composition of each organism we find a certain realization of the geochemical role of the species. To put it in another way, no organism exists apart from the geochemical processes that take place in the biosphere. The geochemical role of individual organisms can be determined only quantitatively, for a single species alone is not geochemically significant. Rather, the significance lies in all organisms together, or in living matter. While one part of this living matter may be directly connected with the transportation of calcium, silicon, iron, and so forth, the other part may participate only indirectly through a long nutritional chain. Thus, the participation of organisms in the exchange of chemical elements in the crust of the earth will be called the geochemical functions of living matter. Obviously, certain geochemical functions are common to all the living matter of the planet, such as the oxygen-nitrogen functions, but others are more specialized and belong to the large army of organisms which concentrate elements, especially those which are in a dispersed state. These are the so-called siliceous, ferrous, and other concentrator organisms, which are, as a rule, rock-formers. Since an uninterrupted exchange of matter takes place between the medium and the organism, the geochemist needs to know in detail the chemical composition of all living matter, which in turn can be understood and explained with the use of geochemical concepts. As already mentioned, the question of chemical composition originally had no 21. In the spectrographic investigations done in the Vernadsky Laboratory for Geochemical Problems, lanthanum and yttrium were observed in organisms. 22. Probably mesothorium I, not thorium. See ftn. 15, Table i.

14

Memoir Sears Foundation for Marine Research

significance of its own and was useful only as an aid in solving numerous small problems. In 1916 Academician V. I. Vernadsky clarified the significance of the problem in a number of articles by using geochemical concepts as a starting point. He was the first to calculate the entire mass of living matter of the planet and to introduce the concepts of the average elementary composition of species, the biogenic migration of elements, and so forth. Since the basic concepts of the biosphere have become known outside the geological and mineralogical sciences, we will not deal with them here (see V. I. Vernadsky, 1934). However, we will dwell on the deductions which should be made with respect to a more specific problem, namely the chemical composition of organisms, and from the geochemical point of view this question can be answered fully. The first deduction we might make is the possibility of the presence of all chemical elements in living matter (i. e., the presence of different elements in different organisms) and the physiological significance of these elements. Thus, the question of which elements constitute living matter essentially loses its meaning, and therefore we might ask: In what quantities are elements found in each species of organism ? Is the chemical composition within taxonomic units as stable as the morphological characteristics of these organisms? In other words, could chemical composition be a characteristic of species ? The concept of genus, species, and so forth must include a certain geochemical definiteness. Also, it is clear to us that there is a close connection between the geochemical processes that continually take place in the crust of the earth and the evolution of the chemical composition of living matter. The geochemical point of view on this matter introduces us to the deepest biological problems, which we can tackle geochemically only if we possess all the related material. Therefore, we should attempt to obtain the following: complete knowledge of data on the chemical composition of organisms ; general ideas which could be deduced from these data; and a further comparative study of the chemical composition of organisms. At the present time both geochemists and biochemists are interested in this subject. In our work, LA COMPOSITION CHIMIQUE £L£MENTAIRE DBS ORGANISMES VlVANTS ET LE SYSTEME PfiRIODIQUE DES ^L^MENTS CniMIQUES, (THE ELEMENTARY CHEMICAL COMPOSITION OF LIVING ORGANISMS AND THE PERIODIC TABLE OF THE CHEMICAL ELEMENTS by Vinogradov, 1933), we have tried to show, on the basis of all the known analytic material, the connection between the distribution of atoms of different elements in organisms and the position of these elements in the periodic table. 4.

The Chemical Composition of Sea Water

Here we will present only data on the average chemical composition of sea water without entering into the history of the problem, the modern problems related to the origin of the ocean's salt, or the possible change in its composition during geological time. We cannot avoid completely the question of the composition of sea water, for ocean water, throughout all its expanse, has approximately the same inorganic composition. In the littoral zone, especially near the mouths of rivers, there is a dilution of

Chemical Composition of Marine Organisms

15

ocean water by fresh water, but while the total salt content, on the average close to 3.8 °/0, decreases, the relative amounts of ions remain without any considerable change. The chief components of sea water, in percent of inorganic residue (in ions) are given below, but besides these there are over 40 more elements that have been discovered up to the present time. Cl' .

. .

Br'

.

.

CO."

.

.

.

so; . .

.

.

55.29 0.19 7.69 0.21

Na' K' . . Ca" . Me" .

. . . . . .

.

30 59 1.06 - - - 1.20 . . . 3.79

The material contained in sea water is chiefly in ionic form, with only a small part of the other material in the form of colloids in different degrees of dispersion, these being chiefly clay particles and possibly some organic matter.23 Then there are the plankton organisms distributed in the water at various levels. Also, ocean water contains atmospheric gases all the way to the bottom, the amount of these gases varying with depth according to the solubility of the gases in the water.24 However, the form of some of the elements in sea water is far from being known, and various changes in sea water, such as CO2 content, influence the ionic equilibrium. Hence, a complete picture of the chemical composition of sea water is still not possible. The content of the chief components, changing upon dilution of the water, varies within multiples of ten, whereas the colloidal components, existing to a certain degree independent of the elements in ionic form, vary as much as a thousandfold. The amounts of the compounds of nitrogen (NO2, NH3), phosphorus (PO^), iron, silicon, and others are most easily disturbed by the seasonal development of plankton organisms which extract these elements from the water and in so doing change drastically the chemical picture in the upper layers of the water. Some of the elements are precipitated out by biochemical porcesses, in CaCO3 for example, so that a temporary lack of this compound is thus created. Other elements, such as oxygen from photosynthesis, increase in the zone of development of plankton. The presence of the microelements in sea water (boron, zinc, fluorine, strontium, and others) was noted for the first time by Forchhammer (1865), but the quantity of these elements has not been clarified until recently, and only recently have there begun to be observations on the annual changes in the content of different trace elements in sea water (silicon, iron, and phosphorus, for example). Sometimes changes can be noted in the content of some elements in relation to the distance from shore and in depth, the content of some elements increasing in the bottom layers. But there are so few data that it is impossible to draw a general picture of the distribution of trace elements in sea water, while many of the data we already have need verification, such as those for rubidium, cesium, lithium, fluorine, manganese and aluminum. Then too, for a certain 23. See Gran and Ruud (1926).

24. See V.I. Vernadsky, 1931: Classification of Natural Gases.

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Memoir Sears Foundation for Marine Research

number of elements there are only qualitative data, all attempts at quantitative determinations having been without results. Thus far, then, the geochemical history of these elements in the sea, except for silicon, iron, calcium, iodine, bromine, and aluminum, has not become the subject of special studies. Furthermore, the fate of some chemical elements (thalassophil25) is connected with their accumulation in the sediments so that much clarification is still needed in regard to the study of the elementary composition of marine organisms which extract a large number of elements from the sea and concentrate them a hundredfold or a thousandfold in the sediments, silts, and so forth. The development of geochemistry of the sea from this viewpoint is one of the achievements which, according to the plan of the author, should result from the present work.

TABLE 2 A ELEMENTARY COMPOSITION OF SEA WATER (1943) (IN '/oi CHLORINE = 19.00)

Oxygen Hydrogen Chlorine Sodium Magnesium Sulfur Calcium Potassium Bromine Carbon Strontium Boron Fluorine Silicon Rubidium Lithium Nitrogen* Iodine Phosphorus Zinc Barium Iron Copper Arsenic

; .

85.82 10.72 1.89 1.056 1.3 xlO" 1 8.8 XlO- 2 4.0xlQ- 2 3.8 X 10~2 6.5xlO~ 3 2.0 xlO' 3 1.3 X 10"s 4.5xlO~ 4 1.5xlO~ 4 5.0xlO~ 6 2.0xlO~ 6 1.5xlO~ 5 l.Ox 10~6 5.0 XlO- 6 5.0xlO~ 6 5.0 X l O - 6 5.0xlO~ 6 . 5.0xlO- fl 2.0xlO~ 6 1.5xlO~ 6

Aluminum Lead . „ , Manganese Selenium . Nickel . . Tin . „ , Cesium Uranium , Cobalt . . Molybdenum Titanium Germanium . Vanadium Gallium . , Thorium . Cerium Yttrium . . Lanthanum . Bismuth , Scandium . Mercury . Silver . Gold . . , Radium ,

5 XlO-5 5.0xlO- 7 4.0 X l O - 7 4.0 xlO- 7 S.OxlO- 7 S.OxlO- 7 2.0 xlO- 7 2.0 x l O - 7 l.OxlO- 7 l.OxlO- 7

y*

n

Chemical Composition of Marine Organisms No. of determinations

ALGAE

Chondrus crispus 99

99

"

99

99

99

99

99

*

Average

99

r>

99

99

2

27

36

2

Average Laminaria saccharina

99

99

99

r>

99

99

99

99

3 3

Laminaria saccharina* Laminaria saccharina*

Average /Y/«tf vesiculosus 99

»

99

99

r>

r>

N

Locality

Author

2.24 2.82 1.15 1.65 2.08

Brittany, France Rhode Island, U.S.A. India Canada (Atlantic)

Vincent, 1924 Wheeler and Hartwell, 1893 Greshoff, 1903 Butler, 1931 M. and A.Jolles, 1895

Japan Algiers Canada (Atlantic) Baltic Sea Brittany, France

Matsui, 1916-d Muller, 1894 Butler, 1931 Vibrans, 1873 Vincent, 1924

2.00

Gracilaria sp. Gracilaria armata Gigartina mammillosa Furcellaria fastigiata Rhodomela pinastroides Nitophyllum punctatum Solieria chordalis Polyides rotundas Ahnfeltia plicata Phyllophora membranifolia Ceramium rubrum Delesseria sanguinea Laurencia obtusa Liagora viscida Iridaea sp. Phaeophyceae Macrocystis pyrifera

29

3

1.45 1.63 3.54 1.07 1.72 2.53 0.85 1.59 3.30 1.69 3.07 1.99 2.0 1.31 0.51 2.72 1.57 1.58 1.07 1.7 1.28

r>

r>

»

rt

r>

n

99

99

T9

T9

99

99

Rhode Island, U.S.A.

Wheeler and Hartwell, 1893

T9

T9

T9

99

99

99

99

T9

T9

T9

99

99

99

99

99

99

Baltic Sea T9

Algiers

T9

Vibrans, 1873 Muller, 1894

T9

California, U.S.A. T9

T9

T9

T9

T9

T9

»9

T9

99

99

Burd and Hoagland, 1915 Turrentine, 1912 Burd, 1915 Stewart, 1915 Hoagland, 1915

1.75 1.59 1.73 0.73 1.09 1.38 2.60 3.03 2.29 1.80

Normandy, France Rhode Island, U.S.A. California, U.S.A. Brittany, France Japan Scotland Western Norway Baltic Sea

Wheeler and Hartwell, 1893

1.09 1.59 1.09 3.06 1.22

Scotland Rhode Island, U.S.A. North Sea Conn., U.S.A. Normandy, France

Wheeler and Hartwell, 1893

99

99

99

Turrentine, 1912 Vincent, 1924 Kinch, 1880 Hendrick, 1916 Werenskiold, 1900 Vibrans, 1873 Mohr, 1865-b

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

(continued next page)

Memoir Sears Foundation for Marine Research

3°

No. of determinations

ALGAE

0.99 2.01 1.84 2.43 1.37 1.09 2.29 1.22 (1-3) 1.64

Fucus vesicu/osus

Average Cystoseira fibrosa Cystoseira sp. »

»

Sargassum vulgare Sargassum bacciferum Cladostephus verticillatus Postelsia palmaef&rmis Egregia menziesii »

99

Desmarestia ligula f Air-dried.

N

4 3

2

1.14 1.21 1.23 1.23 0.80 0.77 1.29 2.56 2.75 1.99

Locality

Author

Scotland North Sea Baltic Sea Brittany, France Canada (Atlantic) Scotland England Normandy, France Adriatic Sea

Hendrick, 1916 Bergstrand, 1872 Vibrans, 1873 Vincent, 1924 Butler, 1931 Anderson, 1855 Barlow, 1911 Marchand, 1865 Sestini, et al., 1877

Brittany, France Algiers Japan Algiers Antilles (West Indies) Algiers California, U.S.A.

Vincent, 1924 Miiller, 1894 Kinch, 1880 Miiller, 1894 Corenwinder, 1865 Muller, 1894 Turrentine, 1912 Burd, 1915 Hoagland, 1916 Turrentine, 1912

Parts of algae.

of protein. The nitrogen content of P. laciniata and P. tenera, and of products prepared from them in various ways, reaches 7 °/0 of the dry matter compared to the usual nitrogen content of i to 3 °/o of dry matter in algae. Apparently the nitrogen is high also in all other Bangiaceae, since our analyses gave the following results for nitrogen: Porphyra umbilicalis. Gulf of Kola, 3.6% Bangia fuscopurpurea, „ „ „ , 4-°°/o Vedrinsky (1938-!)) found a maximum amount of nitrogen also in species of Rhodophyceae from the White Sea; in Ahnfeltia plicata there was 2.51%, and in Phyllophora interrupta there was up to 5. i3°/oIn the data of Reed (1907) and others14 it should be noted that a maximum amount of protein occurs in Porphyra. Of the other red algae, Rhodymenia palm ata must be grouped with those rich in nitrogen, which is in accordance with the data of Butler (1931), Schmidt-Nielsen and Hammer (1932), Tahara (see Oshima, 1905), Hendrick (1916), and others; however, the latter data often refer to the dry waterweeds which 14. See Kellner (in H. M. Smith, 1904), Konig (1879), K5nig and Bettels (1905), Nagai and Murai (1884), Smith (1904), and Nagaoka.

Chemical Composition of Marine Organisms

3i

TABLE 13 NITROGEN, WATER, AND ASH IN ALGAE

No. of determinations

ALGAE

HjOin •/.of living matter

Ash in •/.of dry matter

Phaeophyceae Laminaria japonica Laminaria saccharina Laminaria saccharina (stem) Laminaria saccharina (stem) Laminaria saccharina (growth cone) Laminaria saccharina (leaf) Laminaria digitata Laminaria digitata (stem) Laminaria digitata (growth cone) Laminaria digitata (leaf) Ascophyllum nodosum Desmarestia aculeata jllaria esculenta Fucus serratus Fucus vesiculosus

— — — — — — — — — — — — — — —

24.83 27.09 32.20 29.70 24.50 27.66 41.05 28.5 29.27 20.18 31.64 26.16 21.25 22.09

Rhodophyceae Rhodomela larix Rhodymenia sp. Callymenia sp. Porphyra sp. 99 99

— — — — —

24.80 12.8 21.6 15.7 15.7

99

99

Ptilota pectinata Iridaea sp. 99 99 Iridaea laminarioides Phyllophora sp. Phyllophora interrupta Ahnfeltia plicata 99 99 Turnerella sp. Gelidium corneum Eucheuma sp. Gracilaria sp. Corallina offainalis Furcellaria sp.

2 3

2 2

—

9.7

— — — 89.47 — — — — — —

21.6 28.6 14.80 16.08 11.52 8.35 22.5 9.85 30.0 12.49

— — — —

32.10 10.24 73.85 8.86

Nin

•/.of

dry

matter

Locality

2.12 1.41

Kiesewetter, 1936-b Far East White Sea Vedrinsky, 1938-a

.42 .90 .81 .61 .34 .88 2.0 1.19 1.05 1.29 1.59 1.48 1.15

2.9

3.00 3.23 5.00 5.00 5.40 3.40

1.9

2.20 3.28 4.50 5.13

4.4 2.3 4.9

2.55 0.78 1.13 1.00

—

Author

99

99

9.

99

99

99

99

99

99

99

I

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

9,

99

I

Far East

Kiesewetter, 1936-a

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

Nagai and Murai, 1884 Kiesewetter, 1936-a 99

99

Lebedev, 1936 Ellegood, 1939 Lebedev, 1936 White Sea Vedrinsky, 1938-a Far East Kiesewetter, 1936-a White Sea Vedrina, 1936 Far East Kiesewetter, 1936-a Nagai and Murai, 1884 Greensh, 1936 99

99

99

99

99

99

White Sea Vedrinsky, 1938-a 99

99

99

99

32

Memoir Sears Foundation for Marine Research

are rich in nitrogen and which are prepared and used for food." Other red algae, Phyllophora, Gigartina and Chondrus, are also distinguished by a larger nitrogen content. In the Phaeophyceae a similar division of species according to nitrogen content is much more complicated, in spite of the large range of data and the possibility of comparing the series of analyses. In various Phaeophyceae from the Gulf of Kola we

TABLE 14 NITROGEN IN CORALLINA SQUAMA TA

Season

N in «/0 of dry matter, free from lime

January March

5.406 5.428

Season

N in °/0 of dry matter, free from lime

April May

5.327 4.678

Season

N in •/. of dry matter, free from lime

Season

of dry matter, free from lime

July August

4.658 4.078

September October

4.22 5.11

found only 1.5 to 2°/ 0 nitrogen, with rare exceptions. Vincent (1924) has noted the large nitrogen content of Fucaceae as compared with that of Laminaria, and according to Muller (1894) all the algae of the coast of Algiers are poorer in nitrogen and in phosphorus than the algae of colder regions. Moreover, the giant waterweeds are not distinguished by an especially high nitrogen content, for according to all data they contain less than Laminaria and other species of algae of the European coasts. There is a certain decrease in the nitrogen of giant waterweeds from the north to the south, as for example along the California shore, but the geographical variation has not been clarified. Burd (1915), in analyses for different parts of Macrocystisy Nereocystis and Pelagophycus, found that the highest concentration of nitrogen occurs in the leaf, and according to Weren-

TABLE 15 NITROGEN IN PORPHYRA

ALGAE

N in °/0 of dry matter

Locality

Author

Porphyra tenera

4.9 -6.43 2.83-5.08 0.66-4.13 3.61 4.1

Japan Gulf of Tokyo Japan Canada (Atlantic) U.S.A.

5.19-5.8 5.4

Japan

Okuda and Nakayama, 1916 Matsui, 1916-a Kinch, 1880 Butler, 1931 Reed, 1907 (U.S. Dept. Agric.) Smith, 1904 Tahara (see Oshima, 1905)

Porphyra laciwata n

w

19

19

w

»»

9»

»

19

19

*

* *

• Percent of air-dried matter. 15. In Japan, especially Porptyra and Rhodymenia pcrtusa. See Miyabe (1902), Tondo (193°), and Nadson.

Chemical Composition of Marine Organisms

33

skiold (1900) the same is true of some Laminaria. Stigeoclonium, possibly a parasitic green alga, contains a good deal of nitrogen. In the majority of Chlorophyceae the nitrogen is somewhat higher on the average than in the majority of Phaeophyceae (see Table 12). This apparently follows from the data of Sestini (1876), Oshima (1902), Tahara (see Oshima, 1905), and Reed (1907); comparatively they contain a larger amount of protein (for example Enteromorpha linza, E. compressa and Ufoa lactuca)^ But there are few data for Chlorophyceae, and they are contradictory. Seasonal variations in nitrogen were studied in a number of algae by Anderson (1855), Wheeler and Hartwell (1893), Toms (1905), and Freundler, Laurent, and Manager (1922). From Table 16 it is seen that the maximum in nitrogen content occurs in the winter months (January, February, and March) and at the beginning of the spring, with the minimum in autumn. Butler (1931) determined the amount of nitrogen in Chondrus crispus at different times of the year; he gave his results in graphs. In March and April there is an increase in nitrogen in calcareous algae such as Corallina squamata from the coast of Dorset, England, as shown by Haas, Hill and Karstens (1935) in Table 14. The existence of seasonal variations partly explains a certain discrepancy in the tables, but apparently the maximum in nitrogen occurs at the time of maximum growth and spore formation. Kiesewetter (i936-a) found the following amounts of nitrogen (in °/o of dry matter) in Porphyra sp. of the Pacific Ocean: December 6.61, January 6.63, February 6.07, March 1.85. Vedrinsky (1938-!)) found the following changes in the nitrogen of Laminaria of the White Sea during the year: Months

January . February March . April May . Tune .

L. saccharina

L. digitata

.

. . . 1.57 . .

. .

. . . . . 2.34 . . . . . . 1.87 . . -

2.33 2.26 2.18 1.78

Months

July . . August . September October . November December

. . . .

L. saccharina

„ . . . .

1.53 1.18 1.54 1.54 1.76 1.80

„ . „ . „ „

„ „ . . ,

L. dig* tola

. . . „ .

1.57 1.18 1.50 1.53 1.88 1.55

This is the same picture as before; the nitrogen maximum occurs in the beginning of spring, the minimum in the summer and fall." 16. See Loew and Bokorny (1887) on freshwater Spir&gyra which contains up to 32 °/0 protein as opposed to the usual 5- I 5°/o> however, see Pennington (1897) on Spirogvra. See Whipple and Jackson (1899) on freshwater Chlorophyceae. 2 H. Black (1948-3, b, c) found in species of Laminaria ocurring on the coast of Scotland that the ash content is highest early in the year, from January to March, or in the case of L. cloustonii, May, when the old frond is cast. In the latter species the ash reached 41.3 °/0 of the dry weight or 6.1 % of the wet weight in May, at which season the water-soluble ash was 36.35% of the dry weight. In November the total ash was 12.6% of the dry weight and 2.46 °/0 of the wet weight and the water-soluble ash 9.09 % of the dry weight. The water-insoluble ash obviously varies little and may be largely contaminant material. The great fall in the ash over the sommer is due to osmoregulatory processes that occur when carbohydrate, mainly mannitol, is accumulated during the summer. In the Fucaceae (Black i948-d, 1949) of the same region the major components all showed maxima relative to the wet weight twice a year, in the late spring or early summer and in the autumn. No compensatory loss of ash

Memoir Sears Foundation for Marine Research

34

The nitrogen in algae is found chiefly in the form of protein, but water-soluble nitrogen is also abundant; Hoagland (1915) found that up to half of all the nitrogen is found in the latter form. The question of the distribution of nitrogen in different fractions of the organic matter has been the subject of numerous investigations by Shunichi Tases (1931) and Okuda and Nakayama (1916). Butler (1931), who gave the distribution of nitrogen in various fractions, found that up to 67°/ 0 of all nitrogencontaining matter is water soluble.17 Nathansohn (1906) showed the presence of NOi in many algae.

TABLE 16 CHANGES IN NITROGEN OF ALGAE DURING THE YEAR (IN °/§ OF DRY MATTER) NAME

Jan.

March

May

Laminaria laccharina Lamlnaria diptata

2.26

1.85

1.99 2.27

— —

»

»

Fucus vesiculosus »

»

Ascofhyllum nodosum Chmdrus crispus Phyllophora membranifolia

— 2.03 — 1.50 2.84 —

3.06 1.93 1.91 1.28 3.10 2.78

1.94 — 1.98 — — —

Sept.-Oct. Author

0.94

1.34

0.96 0.82 1.16 0.64 1.32 3.36

Wheeler and Hartwell, 1893 »

»

»

W

W

W

W

W

»

»

»

»

(Rhode Island) Toms, 1905 (Island of Jersey) Wheeler and Hartwell, 1893 Toms, 1905 (Island of Jersey) Wheeler and Hartwell, 1893

A common characteristic of Rhodophyceae is the content of diverse and usually easily-hydrolyzed polysaccharides, sometimes in considerable amounts, such as agar, carrageenin, algin, and other derivatives of polygalactouronic acids. The most primitive species of Rhodophyceae, as for instance the Bangiales, Corallinaceae, and possibly some others, contain almost no cellulose but do have pectin in the outer wall. All the Phaeophyceae contain cellulose tissue and diverse pectic materials (algin, fucin, and others), the greatest amount of pectin being found in the primitive species of Phaeophyceae, namely the Ectocarpales. Among the Chlorophyceae, the Siphonales, Codium, Bryofsis and others, have organic walls containing chiefly pectic material or polysaccharides; in these species the content of combined nitrogen is larger. Some species of Siphonales, such as Vaknia^ as well as of Cladophorales (Cladophora\ are distinguished from other Siphonales by their morphological characteristics, particularly their cellulose walls. relative to wet weight occurred as the products of photosynthesis accumulated. The ash maximum may be later than the dry weight maximum owing to accumulation of ash in the reproductive parts of the plant. In all the seaweeds studied by Black there was a tendency for the protein content to be maximal in late winter; this is attributed mainly to the fact that at this time a maximum amount of nitrate is available in the medium for protein synthesis. Iodine content, which is greater in the Laminariaceae than in the Fucaceae, tends to be maximal, at least in the former group, when the ash is highest, but the variations are not very regular. 17. See Kapeller-Adler and Csat6 (1930) and Yahagigawa on the form of nitrogen in algae.

Chemical Composition of Marine Organisms

35

5. Phaeophyceae: Sodium, Potassium, Calcium, Magnesium, Phosphorus, Chlorine, and Sulfur Although the Phaeophyceae have been investigated more than other plants, chiefly the species of two large and widespread families, Fucaceae and Laminariaceae, the analyses of one are more complete and accurate than those of the other, and comparisons are hindered by circumstances previously mentioned, most of the data not including any indication of the method of analysis, the time and place of collection, and so forth. In the analyses of different investigators, the compositional variations which actually take place in nature seasonally, the age of the specimen, and so forth, are augmented by the variations which result from the methods of analysis. So analyses done by different investigators on the same species are rare, and these acquire special value. Only for Fucus vesiculosus do we find up to 15 more or less complete analyses ; for only about ten species are there series of analyses. The most complete analyses of Phaeophyceae, and of the algae in general, usually contain data on 7 to 10 elements, namely potassium, sodium, calcium, magnesium, sulfur, phosphorus, chlorine, silicon and iron, rarely iodine and bromine. The first extensive analysis was done by Bouvier (i79i-a) for Fucus helminthochorton (Alsidium helminthochorton}. Somewhat later analyses of the ash of Fucus buccinalis were done by Brandes (1818) and Driessen (i823).18 More modern analyses are given elsewhere. Many more series of determinations are known for nitrogen, potassium and phosphorus than for other elements, particularly in connection with the use of seaweeds for food, fertilizer, extraction of potassium salts, and so forth.19 These are discussed in the works of Fagerstrom (1823), Forchhammer (1844), M'Crummen (1847), Yeats (1853), Kinch (1880), Johnson (1872), Storer (1887), Hendrick (1892, 1898), Wheeler and Hartwell (1893), Russell (1910), Woods (1901), Barlow (1911), Doherty (1918), Karrer (1916), Brandt and Raben (1919-1922), Wurdack (1923), Riviere (1924), and Burd (1915). First let us attempt to analyze the distribution of the first seven elements mentioned above in different species of algae. Analyses of kelp or varech as a whole, without indication of the names of species, will not concern us.20 Table 17 shows only analyses in which seven or more elements are included. Iron, aluminum, silicon and all other elements, inasmuch as there are few data for them, will be discussed together later. The analyses refer mainly to algae of the temperate and cold regions of the European and North American coasts. For those species, such as Fucus vesiculosus, for which there are a number of analyses, we have given the mean content. So far as possible, all analyses 18. Probably F. vesiculosus. See Jodin (1888) on freshwater algae. 19. On the utilization of seaweeds, see Nadson (1903), Zinova (1928, 1935), Eratov (1928), Averkiev (1926-1928; U.S.S.R.), Sauvageau (1920), Vincent (1924), Mangenot (1883), Matignon (1914), Gloess (1919$ France), F. Cameron (1912; U.S.A.), Davidson (1840), Smith (1904), Miyabe (1902), Yendo (1901), Perrot and Gatin (1911), Rein (1889; Japan), Rapson, Moore and Elliott (1942; New Zealand), Saint-Yves and Desmoires. 20. See Guthrie (1899), Sterkers (1914), Tressler (1923) and Herve*-Mangon. We regret that some Japanese work is known to us only by reference, such as the work of Atsuki and Tomada (1926). For preliminary brief surveys of data on algae, see Kutzing (1843) and Senebier. For recent data, see Galletti (1931), Klason (1935), and Mayer.

Memoir Sears Foundation for Marine Research

36

TABLE COMPOSITION OF ASH

ALGAE Macrocystis fyrifera Nereocystis luetkeana Pelagophycus porra Laminaria digitata Laminaria digitata (stem, fall) Laminaria digitata (stem, spring) Laminaria digitata (leaf, fall)

Na,0

K,0

MgO

CaO

so,

35.62 50.57 52.66

13.75 14.12 11.1

34.0 36.90 39.39

3.58 2.42 2.65 7.44 2.85 12.91 6.06 6.01 5.18

6.70 2.76 2.74 11.86 7.52 5.45 7.48 10.02 10.87 8.78

6.40 3.62 3.79 13.26 2.33 8.56 9.03 12.71 22.01 11.08

18.64

45.22

35.10

w

w

— 17.34

„

„ Average .

Laminaria saccharina

,

w

w

w

w

Laminaria Laminaria Laminaria Laminaria

saccharina saccharina saccharina saccharina

. (stem) (base of leaf one year old) , (middle of leaf one year old) (old leaf)

w

(stem) (base of leaf one year old) (middle of leaf one year old) . (old leaf)

28.80

18.26

25.87

6.74

8.74

11.28

7.56 13.49

21.86

12.91 8.14

22.08

23.89

24.62

4.6

4.44 1.35 2.32 2.58 6.91

32.67

36.54

14.49 5.27 7.80 9.06 2.95 2.15 3.34 2.78

24.58

5.83

9.55

12.95

33.90 23.35 37.39 26.64

6.69 6.80 2.30 3.66 3.98 2.63 6.17 5.19 7.16 15.19 6.94 6.62 5.96 10.54 6.61 10.91 10.91 14.45

4.027

5.18 12.63 6.37 7.80 10.83 9.29 15.98 14.98 28.16

—

33.47 36.82

38.61

37.47

46.15

30.64

11.48 40.78

31.14 32.12

43.23

11.83

—

13.89 12.33

—

„

w

w

,

34.11

30.06

16.0

(5.67)

„

22.4

44.74

27.72

— 15.19 16.88 16.18

„

8.45 12.09 16.73

6.81 18.48 24.51

—

Laminaria /atifto/ia Laminaria cloustonii Laminaria cloustonii Laminaria cloustonii Laminaria cloustonii Ecklonia buccinalis Ecklonia exasperata Fucus vesiculosus

24.09

26.55 23.89

(31.55) Average .

(in '/„ of

Ash in dry matter

15.30

(15.71)

* Under P2O6 Forchhammer gave the total amount of phosphate. f Of crude ash. Contains 11.09% san(i.

24.39

18.98 4.79 15.72 22.04

20.13 16.43 20.1 18.27 9.42 14.46 14.75 24.40

21.14 14.51 20.20

18.15

24.54 20.34 23.45 20.47

19.70 18.92

22.44

9.63 34.12 8.67

23.78

15.01

37.86 29.84

32.01

25.1

29.31

35.69 22.66 24.59

15.23

— 14.65 6.24 21.41 8.67 16.97 8.98 17.25 10.06

?

11.04 10.64

13.91 4.75 1.48 4.28 2.49 26.16

5.5

9.78 16.77 10.90 14.59 9.12 14.93 7.18 25.77

7.49 19.49

19.51 10.18

4.15 5.88 5.71 5.08 9.48

30.94 24.03 26.27 28.64 32.56 22.76 26.22

13.46 13.44

Chemical Composition of Marine Organisms

17

37

OF PHAEOPHYCEAE

pure ash0 p

*°* 1.65 1.35

1.55 2.56 2.52 2.06 2.73 3.14 4.47 1.88 2.76 2.12 4.31 4.01 2.79 2.41 2.72 2.19 1.67 2.07 2.70 2.23 7.17 1.54 4.91 2.42 2.19 3.69 0.75 1.36 -—

2.26 2.23 2.19 2.19 2.38 5.18 5.46 5.86

a

Fe,O$ (AljO,)

33.70 38.50 38.58

0.40 0.16 0.24 0.62 0.21 0.53 0.51 0.23

17.23

38.67 28.35

32.14

33.29 20.80 29.30 28.54

0.53

28.88 20.46

5.94 32.17

35.77

34.12

34.63

31.16

24.85 26.40 20.99 32.76

31.04 27.81 33.01 1.09 15.62 15.24 6.00 16.40 26.11 15.10 1.90 21.46 2.10 15.03 24.52

— 0.57 0.44

1.06 0.08 0.38 0.22

0.073 0.062 0.067 0.074

0.56 0.39

0.605

— 0.05

0.035 0.024

0.041

0.33 4.42 0.56 1.11 0.37 8.26 0.18 H

—^

2.35

SiO,

— —

1.56 0.34 1.42 1.01 3.10 0.48 — 1.32 —_

1.14 0.56 1.11 — 0.21

— 0.37

Author

Locality

. Hibbard, 1915

California, U. S. A rt

n

rt

rt

Scotland (west) Scotland (?)

. Godechens, 1845 . Anderson, 1855

France (Fecamp) Helgoland White Sea

. Marchand, 1865 . Forchhammer, 1844* , Northern Iodine Lab., 1933

North Sea France — Baltic Sea (Varnov) Norway

. . , . .

,

Witting, 1858-b Marchand, 1865 Schweitzer, 1845 Vibrans, 1873 Werenskiold, 1900

— 0.67

White Sea

. Northern Iodine Lab., 1933

3.34f

Japan Denmark (Hoffmansgave) Norway

. Oshima, 1902 . Forchhammer, 1844 , Werenskiold, 1900

0.69

— — — — 4.05

1.35 7.69 1.38 2.62 0.70 0.27 11.00

1.40f

Cape of Good Hope New South Wales Scotland (west) England (near Liverpool) England La-Manche-F6camp . Scotland Denmark (Taarbeck) Greenland Baltic Sea (Esel)

. *

.

-

-

, . . . , . , . .

. . . . . . . . .

Forchhammer, 1844 White, 1907 Godechens, 1845 James, 1845 Griffiths, 1883 Marchand, 1865 Anderson, 1855 Bergstrand, 1872 Schweitzer, 1845 Forchhammer, 1844 Sengbusch, 1894 (continued ttext ftgc)

*•

Memoir Sears Foundation for Marine Research

3»

Ash in dry matter

ALGAE Fucus vesiculosus ,

»»

.

.

.

.

*

,

.

-

.

»»

Average . Fucus serratus

Average , Fucus^ sp dscophyllum nod osum w

»

'

w

»

.

»

»

"

.

.

.

.

.

.

..

Cystoseira sp Sargassum vulgare

»»

»»

Sargassum bacciferum w

.

12.98 11.66 4.43 7.21 11.52 10.10 9.65

18.70 16.36 9.76 9.25 18.99 14.33 14.56

22.74

8.1 17.68 26.59 21.78 25.89 22.98

17.1 10.65 10.07 21.53 13.65 13.97

2.26 6.91 10.93 7.10 8.12 8.26

5.21 7.46 12.80 10.25 7.63 9.28

— 32.04 26.62 23.47 25.76 26.97

-—•

7.61 4.68 23.72 6.96 33.40 15.49 28.73 4.97 21.11 0.77 5.3

5.07 4.20 20.40 0.78 2.83 15.41 12.57 4.46 1.66 1.63 20.5

5.66 3.70 4.02 5.85 13.03 7.55 0.87 — 9.99 3.78 1.38

39.99 56.8 17.90 47.05 13.42 10.12 14.89 22.8 13.56 63.97 2.47

17.14 18.85 14.65 19.11 13.15 17.89 20.65 21.13 31.71 9.12 2.2

w

Halidrys siliquosa DuruilUa utilis , Cladostephus verticil/atus Chorda fluminis Padina pavonia Desmarestia\ sp

Laminaria digitata Laminaria saccharina Laminaria cloustonii Saccorhiza bulbosa Fucus vesicu/osus Fucus serratus Ascojhyllum nod osum Cystoseira fibrosa Halidrys siliquosa Himanthalia lorea Pelvetia canaluulata Chorda filum

*

— — — — — — — — —— — —

3.08 — — — 4.38 4.96 5.08 3.16 2.03 6.07 4.95 6.45

4.17 10.12 7.47 — 5.40 6.71 4.66 5.40 4.03 9.42 3.27 14.22

Not as oxides but as percent of elements.

16.05 . 15.52

, 24.58

.

. 28.25§

.

. (58.90)

.

*

— . — . 14.51 . 17.51 23.14

,

. . .

,

. . . . . . . , . . .

. 11.62 . 19.39 . 11.19 — . 17.56

. . . . , . . . . . .

so, 11.42

14.14 4.51 7.99 15.22 5.64 4.85 8.72

. 18.39

Average .

CaO

11.31 31.37 29.67 24.00 14.32 29.30 23.33

. 15.16 ,

MgO

7.62 4.85 11.99

13.89 17.41 — 14.19 —

,

'

KjO

3.53 28.45 14.00

^

»»

»

Na,0

0.84 9.17 8.77

(25.34) 27.22 . 16.37

26.29 15.70. 20.35

a Vincent gives H2SO4 in all analyses.

1.04 0.91 0.37 1.66 0.644 0.32 0.56 1.865 0.81 0.378 0.783 1.08

1.02 2.37 1.65 2.09 1.038 1.29 1.505 3.55 1.315 2.06 1.50 2.965

20.26

25.21 29.39 21.0S 19.34 17.43 29.QB 20.30

(in»/,rf 2.08« 5.5(11 2.64 2.03 5.94 3.12 5.53 3.89 4.13 3.51 9.80 5.74

Chemical Composition of Marine Organisms P2°6

C1

(AW

SiOt

2.86 1.66 3.05

18.68 19.92 15.03

8.58 0.93 2.71

16.55 2.04 4.49

1-74 4.40 2.46 2.42 2.03 3.80

8.23 11.39 27.62 23.53 20.04 15.42

1.98 0.34 0.72 0.32 1.09 0.49

1.12 0.43 1.38 0.38 1.16 1.46

2.81

17.60

0.82

0.99

0.78 0.88 1.52 1.83 1.66

17.34 13.32 12.24 14.77 18.39

1.48 10.86 0.29 0.28 0.49

— 0.12 1.20 0.41 3.09

1.47

14.68

2.98

1.20

2.17 1.92 1.84 3.33 1.08 2.95 2.61 1.37 2.07 1.59 2.6

1.39 1.75 17.47 14.30 26.63 37.24 19.68 1.09 18.30 0.93 19.34

1.81 2.66 — — 2.60 2.39 — (10.0) 0.22 8.47 5.18

19.47 5.85 — 1.63 — 1.50 — (10.0) 4.37 9.63 —

Locality

Author

Lagoons of Venice Baltic Sea (Varnov)

Sestini, 1877 Vibrans, 1873

Baltic Sea (Rugen I.) Scotland (west) Normandy, France :

Beckmann and Bark, 1916 Godechens, 1845 Marchand, 1865 Schweitzer, 1845 Vibrans, 1873 Griffiths, 1883

Baltic Sea (Varnov) England White Sea Norway Scotland (west) Scotland „ Algiers „ Gulf of Campeche „ „ „ Antilles, West Indies La-Manche-F6camp Chile Algiers Baltic Sea Algiers White Sea

Northern Iodine Lab., anal. 1933 Beckmann and Bark, 1916 Godechens, 1845 Anderson, 1855 Jenkins, 1877 (see Wolff, 1871-1880) Miiller, 1894 Forchhammer, 1844 Corenwinder, 1865 Marchand, 1865 Forchhammer, 1844 Miiller, 1894 Vibrans, 1873 Miiller, 1894 Northern Iodine Lab., anal. 1933

dry weight) 0.41 0.65 0.09 0.383 0.458 0.532 0.25 0.38 0.25 0.21 0.16 0.34

— — — — — — — — — — —

0.55 1.75 2.06 0.75 0.85 1.145 0.43 — 0.30 — — 0.76

— — — — — — — — — — —

39

Brittany, France „ „ „ „ „ „ „ „ „ „ „ „ „ „ English Channel Finisterre English Channel Brittany, France

Vincent, 1924

*

„ „ „

* n

„ „

4o

Memoir Sears Foundation for Marine Research

were recalculated, on the basis of pure ash, as oxide in percent of ash. It is impossible to recalculate the majority of results in percent of living weight, but the use of ash as a basis for calculation permits one to use the maximum number of analyses.21 From Table 17 it is seen that the chief mass of the ash (around 1/3) consists of alkalies ; next in order are the alkaline earths. Even a cursory inspection makes it clear that a difference exists between the ash composition of different families and genera, as for example between all Laminariaceae and Fucaceae. 6. Phaeophyceae: Sodium and Potassium Both sodium and potassium are accumulated by marine algae in amounts that vary in different species and within the same species. While the sodium content of marine algae is high, the amount sometimes reaching 30% or more22 whether in the form of Na2SO4 or Nad, many algae actually contain more potassium than sodium, although the potassium salts occur in sea water in amounts that are one-tenth (or less) the concentration of sodium salts. From Table 17 it appears at first glance that there is no regularity in the ratio of sodium and potassium in different species, particularly in the Phaeophyceae, for even within the same species either sodium or potassium may predominate.23 However, after an examination of many determinations of potassium and sodium, we have concluded that in many species the predominance of potassium is quite stable, as in the majority of the Laminariaceae.

TABLE 18 SODIUM AND POTASSIUM IN BROWN ALGAE AND OTHERS (IN °/0 OF ASH) ALGAE

Na

K

Phaeophyceae Laminaria saccharina 3.264 Pelvetia canaliculata 8.221 Padina pavonia 4.03 Ascophyllum nodosum 19.24 17.16 Fucus serratus 18.59 Fucus vesiculosus 13.85 Fucus serratus 13.14

20.804 12.034 4.91 11.70 14.27 15.63 18.21 18.0

Rhodophyceae Rhodymenia palmata

37.78

0.485

Locality

Author

Banyuls-sur-Mer, RoscofF, France (England) RoscofF, France (England)

Bertrand and Perietzeanu, 1927 „ „ „ „ Bertrand and Rosenblatt, 1928 „ „ „ w Barlow, 1911 Bertrand and Rosenblatt, 1928 Barlow, 1911

Bertrand and Perietzeanu, 1927

21. Vincent's results cannot be recalculated as percent ash, and therefore we give them as they are, in percent of dry matter. Unfortunately the author does not indicate the method of analysis. 22. Sodium was found in organic salts by Hassid (1933). 23. In Table 18 the potassium content of different Phaeophyceae is given in a number of other series of analyses besides those in Table 17. For additional determinations of potassium, see the works of Johnson (1872), Frisby (1880), Shutt (1894), Cuniasse (1900), Skinner and Jackson (1913), and Hendrick (1919).

Chemical Composition of Marine Organisms

41

Actually the data for potassium24 are probably more accurate than those for sodium, the latter often being determined by difference, or even less precisely by the amount of chlorine f5 at the same time the quantity of NaCl may fluctuate considerably depending on the method of collection and on the preparation of the seaweed for analysis. Sea water, containing an average of approximately 3.8 % NaCl, cannot be entirely removed from the surface of fresh seaweeds, but this would not present difficulties if only a single method of procedure were used for its removal. However, some workers only shake the water off the plant, others remove it with the aid of filter paper, and so forth. Consequently there are few direct determinations of sodium. Of special interest,

TABLE 19 COMPOSITION OF THE SOLUBLE PART OF THE ASH OF GIANT SEAWEEDS AND OF THE SALT CRYSTALLIZING ON ALGAE DURING THE PROCESS OF DRYING

ALGAE

coa

Nereocystis luetkeana (lamina) Nereocystis luetkeana (salts) Pelagofhycus porra (lamina) Pelagpphycus porra (salts)

Cl

K

KCl

0.52

0.08 0.83

S04 5.26 0.09 6.77

46.52 47.74 45.72

36.55 — 31.41

0.00

0.79

47.22

51.62

71.0 — 49.24 (+12.47KSSO4) 98.72

therefore, are the analyses of Bertrand and his collaborators (1927, 1928 ; given in part in Table 18), first because sodium was determined directly and second because the preparation of seaweeds for analysis was uniform. An indirect proof of the prevalence of potassium over sodium in algae has been noted many times. The prevalence of potassium over sodium in species of Phaeophyceae was noted in the beginning of the nineteenth century. There is no doubt that the majority of Phaeophyceae, like the terrestrial flora, are richer in potassium than in sodium, but difficulties of method still prevent one from making the same generalization concerning all representations of the marine flora.26 From the experiments of Stanford (1862) and others, in which Laminaria and Fucus were soaked in water and in which an almost complete extraction of soluble salts took place, it became clear that the sodium salts washed out first; presumably the salts from the surface of the algae, which are part of the sea water, are washed out first. It is characteristic for potassium salts to wash out less rapidly than sodium salts, the difference in the permeability of the tissues to sodium and potassium evidently being responsible for this. However, in both Fucus and Ascophyllum, which live in the tidal zone and hence remain outside of the water part of the time, the potassium and sodium 24. Phosphorus and potassium are often determined at the same time. 25. Or from NaCl. See early determinations of alkali given by Cadet (1767). 26. Concerning the sodium and potassium content of Cyanophyceae, see below. See also the experiments of Vincent (1924) with cultures of Laminaria which extracted almost all of the potassium from the medium.

42

Memoir Sears Foundation for Marine Research

salts are generally difficult to wash out because of a more solid epithelial layer. (Other ions are also difficult to wash out, as for example iodine.) Of the numerous experiments that have been performed, a few may be noted here. Potassium proved to be the dominating element in the results obtained by Balch (1909) and by Burd (1915) (see also F. K. Cameron, 1912) in removing salts from the giant seaweeds of the Lessonioideae from the California Coast, most of the soluble salt con-

TABLE 20 COMPOSITION OF WATER-SOLUBLE PART OF THE ASH OF DIFFERENT ALGAE (IN «/o OF SOLUBLE SALT, WITHOUT CO,) ALGAE

NajO

Laminar ia cloustonii (stem) Laminaria cloustonii (leaf) Laminar ia flexicaulis (stem) Laminaria flexicaulis (leaf) Laminaria saccharina** Laminaria japonica Fucus serratus . Fucus vesiculosus Ascofhyllum nodosum . Cystoseira barbata^ Various algae (varech)P ,

18.14

22.69 16.83 27.83 21.30 18.22 27.23 26.67 30.93 23.44 11.54

so, 36.89 — 9.68 27.45 — 17.49 39.62 — 6.15 24.22 — 12.88 38.72 — 6.41 41.22 — 6.24 22.42 — 23.11 18.43 — 34.51 30.93 15.86 — 23.61 24.72 0.42 29.53 0.33 7.91 KjO

CaO

Cl

Locality

35.28 32.15 37.36 35.05 31.68 32.86 27.23 20.39 20.28 26.82 49.62

Scotland.

Author .

Hendrick, 1916

Pacific (near Kalishchev, 1926* Vladivostok) Liasota, 1926 Scotland . . Hendrick, 1916

Black Sea . Shkatelov, 1917 Spain , . Bode ?

a Eight analyses. * In the analyses, the CO2 content is given. § MgO - 0.41; values for this compound not given for other species. P Two analyses.

sisting of pure KC1 crystals that formed on the organisms during drying. In Hendrick's (1919) interesting analyses of the soluble part of the ash of Phaeophyceae, the predominance of potassium over sodium in Laminaria is seen. Kalishchev (1926), Liasota, and others gave analagous analyses of other algae (see Tables 20 and 32). Bertrand and his collaborators (1927, 1928) determined alkali after numerous washings and got the results given in Table 21. Balch (i 909) analyzed kelp from different localities and found that the kelp from the Pacific Coast of the United States and Canada proved to contain the largest quantity of salt. In 1909 this same author was the first to find algae with an exceptionally high potassium content as compared with sodium (4:1), the algae in this instance being the giant seaweeds of California and Alaska—Pelagophycus porra, Nereocystis luetkeana and Macrocystis pyrifera. According to the data of F. K. Cameron (1912) and of Parker and Lindemuth (1913), the K2O reaches 40% of the ash, or 2°/ 0 of the living weight, with Nereocystis (the northern form) being richer in KC1 than the more southern Macrocystis and Pelagophycus\ although Turrentine's (1912) average data for potassium are somewhat higher for Macrocystis than for Nereocystis^ there is no

Chemical Composition of Marine Organisms

43

real contradiction in results, since the potassium content of the latter species, for which he gives only six analyses, apparently varies more than in other algae. The author himself notes instances of large amounts of KC1 in Nereocystis^ which contains more potassium than any other algae. Other Laminariaceae are somewhat less rich in

TABLE 21 EXTRACTION OF SODIUM AND POTASSIUM FROM BROWN ALGAE WITH DISTILLED WATER

NAME

Washings

Padina pavonia . 99

99

W

W

W

»

*

*

Pelvetia canaliculata 99

H

19

11

»

»

'

Ascophyllum nodosum »»

99

w

99

99

99

Fucus serratus . 99

19

.

.

.

99

»

.

.

.

W

»

'

Fucus piaty carpus Fucus tu€siculosus Cystoseira fibrosa Himanthalia lorea . Laminaria flexicaulis Laminar ia saccharina *

. . .

. . . . . . . . .

. .

. .

. . . .

.

.

.

,

. . .

. . . . . . . . .

. . . . . . . . . . . . . . , .

. . . . . . . . . . . . . . . .

Initial alkali content in °/0 of ash 1st 2 n d 3rd Initial alkali content in °/0 of ash 1st 2nd

5th

Initial alkali content in °/0 of ash 1st 2 n d 5 t h Initial alkali content in °/0 of ash 1st 2nd 5 t h 1st 1st . 3 r d 3rd 3rd 3rd

Na

4.03 1.14 0.94 0.42 15.41 15.66 15.88 15.75 19.24 18.80 18.63 18.68 18.59 16.14 15.65 15.36 17.77 14.87 2.76 13.88 13.03 12.27

K

4.91 3.79 3.95 1.51 9.25 9.27 9.80 9.77 11.70 12.83 10.95 10.56 15.63 17.61 16.53 17.39 15.18 20.63 18.79 24.77 12.36 17.15

potassium than giant seaweeds, but the prevalence of potassium in certain species, such as L. digitata and L. saccharina, undoubtedly exists (see Table 17). Trofimov (i938-a,b,c) performed an analysis of salt extractions on Gulf of Kola algae (Laminaria saccharina and L. digitata) consisting of pure KC1, which formed 2 to 2.5°/0 of the dry weight of the algae (see the data on KC1 in Laminariaceae from the shores of the Pacific Ocean given by Kiesewetter, 1936). According to Merz (1914), the stems of Nereocystis and Macrocystis are richer in potassium than the leaves. At the present time both of these species are used in the United States for the production of potassium salts.27 27. Alum schists, occurring in the Permian and found in various places, for example Scandinavia, contain the remains of algae and a great deal of potassium.

44

Memoir Sears Foundation for Marine Research

In species of Fucaceae the predominance of one element or the other does not occur (compare the amount of potassium in Pelvetia and in Cystoseira^\ and in general they are less^rich in alkali than Laminaria. For other families of Phaeophyceae no adequate observations exist, but it is very probable that among them there would prove to be species with a distinct prevalence of potassium; Lessonia might be an example. Sauvageau and Deniges (1921) observed crystals of pure potassium chloride in Cystoseira opuntioides> C. stricta and C. sedoides> while mannite was found instead of potassium chloride in C.fibrosa and C.foeniculacea. In C. myriophylloides and C. abrotanifolia, both were found together. With all the known facts at our disposal, we may conclude that Phaeophyceae are usually richer in potassium than in sodium, and that in a number of families the potassium content is large, evidently predominating over that of sodium. Such algae, though living in a medium rich in sodium, concentrate potassium. A sharp decrease in alkali, particularly in potassium, occurs in species encrusted with CaCO3, which are present mostly in the lower latitudes. According to the amount of potassium, the Phaeophyceae may be divided into four groups: 1. Concentrators of potassium . . . . genera Macrocystis^ Pelagophycus> Nereocystis> and so forth. 2. Rich in potassium. . . . Laminaria and other genera in which K>Na. 3. With the usual amount of potassium . . . . many Fucaceae. K «Na. 4. With little potassium . . . . rare, chiefly encrusted forms such as Padina pavonia. 7. Phaeophyceae: Calcium and Magnesium The amount of calcium and magnesium in the ash of marine algae varies rather widely (Table 17) and is of the order of n x i °/o- In general calcium predominates over magnesium, but there are no special determinations which give us their ratios. Besides the analyses in Table 17, data for calcium are found also in less complete analyses, such as those of Brandt and Raben (1919-1922), but these do not alter the general picture. Series of magnesium determinations (Table 22) were done by Javillier (i93o)' Magnesium, which does not go above 5 to i o % of the ash, or 0.5 °/0 of the living matter, has a certain uniformity and has a considerably smaller range of variation than calcium. Similar Ca/Mg ratios occur in terrestrial plants.29 The amount of magnesium is not greater in Phaeophyceae even if they become enriched in calcium, and the amount may even be somewhat smaller, as in Padina pavonia^ Sargassum vulgare, and Cystoseira (see Table 17). Larger calcium content than the average does not often occur in species of Phaeophyceae, 28. The peculiar ratios of sodium and potassium in Pelvetia and Cystoseira may be explained either as a species-specific characteristic, or as differences conditioned by age, season, and so forth. 29. An exception are the seeds, where magnesium predominates over calcium.

Chemical Composition of Marine Organisms

45

and calcification30 occurs in few species of this class. This is to be expected, inasmuch as most species of the genera Laminaria, Fucus, Desmarestia, and others occur in high latitudes of the temperate and arctic regions, where the exchange of calcium is not so intense as in the tropics; such Phaeophyceae as do occur mainly in warm or tropical seas do have a tendency to accumulate CaCO3.

TABLE 22 MAGNESIUM IN ALGAE (IN °/0 OF ASH)

ALGAE

M

Phaeophyceae Fucus vesiculosus Atcophyllum nodosum Laminart a digit ata

ALGAE

M

Rhodophyceae 4.29 6.55 4.48

Chondrus crispus Geranium rubrum

6.81 1.14

From the data in Table 17 it is seen that Padina pavonia and possibly other Dictyotaceae (and to a limited extent Sargassum and Cystoseira) often contain relatively more CaCO3 than other Phaeophyceae.31 However, only Padina pavonia is known to take part in the formation of calcareous sediments, since analyses are not available for other species of Dictyotaceae. Apart from species of the genera just mentioned, brown algae from warm seas generally contain calcium in amounts comparable to those of the other Phaeophyceae.32 Although the mineralogical character of the CaCO3 in Phaeophyceae (Padina pavonia) is not known, according to the composition of the ash it is probably an amorphous form, or aragonite. Magnesium and calcium protein compounds and calcium pectinate have been discovered by Wille (1899), Molisch (1926), Kylin (1929), Bird and Haas (1931); and Read and How* (1927) have analyzed different forms of calcium in algae (calcium organic compounds, and so forth). In summary we must note that the metabolism of calcium and magnesium does not play as important a role in Phaeophyceae as it does in other classes, nor can it be compared with potassium metabolism, which constitutes the exclusive geochemical function of the majority of Phaeophyceae. 8. Phaeophyceae: Sulfur', Chlorine, and Phosphorus From analyses of soluble ash and also from analyses of cell sap, it is seen that phosphorus and sulfur occur in part at least in the form of PO4 and SO4 ions. However, organic compounds of phosphorus and sulfur in algae are less known, although Sira30. See details on encrustation, calcification, and so forth, in Chapter XXI. 31. Forchhammer (1844) found 72.72% CaO in the ash of Padina pavonia. 32. In the work of Forchhammer (1844), Vibrans (1873), Wheeler and Hartwell (1893), and others it is shown that the algae of the Baltic Sea contain relatively more calcium. Contamination might have occurred in these determinations, but still one must note the regular increase in CaCO, and FeaO3 in algae of freshened basins.

Memoir Sears Foundation for Marine Research

46

hama (i938-a) isolated phosphorus organic compounds from brown algae. Determinations of phosphorus, sulfur and chlorine, as usually performed on the ash, do not show the actual amount of these elements, both phosphorus and sulfur being lost during combustion (see Berthelot and Bertrand). Therefore, since everyone working with algae has noticed H2S coming off the ash when acids are used, all determinations of sulfur, and of phosphorus to a lesser degree, should be regarded as suspect. The experiments of Hoagland and Lieb (1915) showed the loss of sulfur in algae, which is observed even when they are carefully dried. -

°/0 of S after drying

/t of S before drying

Macrocystis pyrifera Iridaea laminarioides Ul*ua fasciata

. . ,

1«20 8.97 4.49

. . . . . .

1.08 8.76 4.36

Sengbusch in 1894 noted an increase in sulfur in the analysis of Fucus vesiculosus when he used a method which involved combining the sulfur with alkali, thereby preventing the loss of this element; he determined sulfur in the ash and found about 2 °/0 SO3 relative to the dry matter, whereas on analyzing the dry matter, using alkali, he found up to 8°/o* Church (1877) observed the same for Chondrus crispus*3 obtaining 2.64% sulfur in the ash and 6.41 °/o in the dry matter. Hoagland and Lieb (1915) and Read and How (1927) gave series of determinations of sulfur in the dry matter. Also,

TABLE 23 SULFUR IN DIFFERENT ALGAE (IN •/• OF DRY MATTER) No. of determinations

ALGAE

Macrocystis pyrifera (stems) , Macrocystis pyrifera (leaves)

,

.

.

Nereocystis luetkeana (steins) Nereocystis luetkeana (leaves)

.

,

,

.

.

.

w

»

,

.

,

. . . . 2 . . . . 2 . . . . 3 . . . . 2

Pelagophycus porra (steins) . Pelagophycus porra (leaves) . , » it . . . . . . Laminari a andersonii . Laminaria japonica Laminaria religiosa Egregia menziesii Sargassum si/iquastum Iridaea s p . (Rhodophyceae) . . . . 33. Rhodophyceae.

s

Author

0.77 1.20 1.04 0.45 1.27 0.55 0.71 1.03 0.93 2.12 0.65 0.63 1.17 0.70 8.16

Hoagland, 1915 19

»

»

M

It

W

Turrentine, 1912 Hoagland, 1915 Turrentine, 1912 Hoagland, 1915 Turrentine, 1912 Hoagland, 1915 Read and How, 1927 » » »» »» Hoagland, 1915 Read and How, 1927 Hoagland, 1915

Chemical Composition of Marine Organisms

47

TABLE 24 Laminaria japonica

Laminaria religiosa

Sargassum nliquastum

Freely water-soluble SO^' . . . . 0.0 Acid-soluble SO^' 0.6 Thio-ethers (SOJ 1.04 Neutral S (protein) (SO4) , . . . 0.29

0.05 0.0 1.64 0.2

0.35 0.53 0.64 0.55

Hoagland and Lieb (1915) noted the predominance of sulfur in the form of organic compounds. The amount of sulfur in marine algae puts them among the first in the ranks of organisms which take part in the geochemical exchange of sulfur in nature. Actually it is difficult to find other organisms as rich in sulfur except for the sulfur bacteria. Although it is known that the algae extract SO^ from the sea and partially reduce the sulfates to organic sulfur,34 further than this the history of sulfur in marine algae has been little studied, and the question of the history of the sulfur after the death of the algae is almost untouched (see Forchhammer, 1844).

TABLE 25 PHOSPHORUS IN PHAEOPHYCEAE (IN •/. OF DRY MATTER) FROM CALIFORNIA, U.S.A.

ALGAE

No. of determinations

Macrocystis pyrifera . . . . 4 Afacrocystis pyrifera (leaf) . . . 19 Macroeystis pyrifera (stem) . . . 19 Nereocystis luetkeana . . . . 2 Nereocystis luetkeana (leaf) . . . 13 Nereocystis luetkeana (stem) . . 13 Pelagophycus porra — Pelagophycus porra (leaf) . . . 5 Pelagophyeus porra (stem) , 5 Egrtgia laevigata 2 Egregia menziesii 3 — Postelsia paI mata — Laminaria andersonii . . . . —

P

, . . . . . . . . . . .

. . . . . . . . . . .

0.44 . 0.38 . 0.24 . 0.34 .0.37 . 0.23 . 0.22 . 0.36 0.24 0.49 . 0.55 . 0.78 . 0.45 . 0.33

Author

. . . . . . . . . . .

. . . . . . . . . .

-

.

. , . . . . , . . .

Cullen (see Turrentine, 1912) Burd, 1915 „ „ Cullen (see Turrentine, 1912) Burd, 1915 „ „ Cullen (see Turrentine, 1912) Burd, 1915 „ „ „ „ „ „ . Cullen (see Turrentine, 1912) „ „ „ „ . Burd, 1915

.

34. Haas (1935) supposed that the sulfur in algae is found in the form of

OSO2O

R

where R is a carbo-

Ca,

OS020 hydrate. According to Nelson and Cretcher (1931) the sulfur occurs as R—O—SO2—(OH), methyl pentose sulfate. See Neuberg and Ohle (1921).

48

Memoir Sears Foundation for Marine Research TABLE SEASONAL CHANGES IN COMPOSITION _ V f\ _

Jan.

ALGAE Laminaria saccharina Laminaria digitata rt

rt

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

.

4scophy1turn nodosum Fucus vest cutosus i>

rt

.

Chondrus erispus Phyllophora membranifolta

*

3.92 2.93 2.05 5.11 2.28

Mar.

Sept. Oct.

2.83

0.80 0.68 2.34 2.74 3.14 2.50 3.69 3.62

3.45 2.77 2.77 2.62 3.67 2.80

Mar.

Sept. Oct.

1.55

—

1.39 1.30

1.54 1.24

1.50 1.34

1.54 1.22

1.37 2.03

1.49 2.34

— 1.37 1.66

Jan.

1.88

—

—

The difference in chlorine and sulfur content of the two genera Laminaria and Fucus is very noticeable, the chloride content being greater and the sulfate less in the former than in the latter. The large amount of potassium in the giant seaweeds and in Laminaria is essentially an enrichment in KC1. From this it follows that the Fucaceae are probably richer in sulfur generally and in SO^ particularly. Tables 23 and 24 confirm these conclusions, and these differences stand out even -more in Hendrick's (1916) analyses (see Table 20). Thus different marine algae contain combinations of ions which are peculiar to them. Read and How (1927) obtained results given in Table 24. We have already noted the dependance of the chloride content on that of SO^ and the relation between the amounts of these ions to the potassium content. Trofimov (i938-a) showed that the ash of Laminaria of the White and Murman seas contains 32.6% chloride, Ascophyllum nodosum from 13.5 to 23.28%, If we exclude Forchhammer's (1844) data on phosphorus (since they refer to impure precipitates) and some data on Japanese algae which refer to seaweeds used as food (for example, it is claimed that Cafe a elongata contains up to 11.22% P2O5 !),35 then the average phosphorus content of Phaeophyceae would be about 2 % P2O5 in the ash, or about o.i % phosphorus in the living matter. Fluctuations are not usually large, being somewhat like those in the magnesium content. There are a number of determinations, besides those shown in Table 2 5, and data for them may be found in more complete systematic analyses of individual species. But separate series of phosphorus determinations in algae are almost unknown (Cullen, 1912; see Turrentine, 1912). In Fucus, Laminaria and Pe/vetia from Saint-Servan-surMer, L. Cayeux (i 933) found from 0.23 to i .46 % P2O5 in the dry matter (see Table 25), In the analyses of Schweitzer (1845), Marchand (1865), Russell (1910), Brandt and Raben (1919-1922), Vincent (1924), and other investigators, the Laminariaceae are 35. Evidently it was the product and not the seaweed that was analyzed in this case. See Warington, 1879 (Porphyray etc.) on the high phosphorus content of cultivated waterweeds.

Chemical Composition of Marine Organisms

49

26 OF ASH (IN «/o OF DRY MATTER) f^^^^^^^—

Jan.

—

2.87 — 2.03 1.67 — 2.68 15.71

- CaO Mar.

2.76

— 1.96 2.10 2.04 1.30 1.09 19.20

Sept. Oct.

3.28 2.57 1.65 2.28 1.84 1.30 2.07 8.99

Jan.

— 0.58 — 0.38 0.45 — 0.69 0.39

-P.O.-^^^"^^^^fc,. Mar.

Sept. Oct.

Jan.

0.46

0.35 0.23 1.65 0.30 0.40 0.85 0.40 0.48

12.15 12.66 — 21.13 24.81 — 28.61 35.76

—

1.29 0.38 0.60 0.36 0.57 0.41

• Dry matter • Sept. Mar. Oct.

6.10

7.06 13.0 19.76 16.51 22.6 17.88 37.68

17.78 17.78 18.0 27.32 29.02 23.6 25.39 28.03

Author

Wheeler and Hartwell, 1893 1* w w ii Toms, 1905 Wheeler and Hartwell, 1893 n rt it »» Toms, 1905 Wheeler and Hartwell, 1893 w

w

w

1*

as a rule somewhat richer in phosphorus than other Phaeophyceae; this is particularly true of Egregia laevigata and E. menziesii, as indicated by the analyses of Turrentine (1912), Cameron (1912) and Burd (1915). Kylin (1929) did a qualitative study of the distribution of phosphates in algae. 9. Phaeophyceae: Seasonal Changes in Sodium, Potassium, Calcium, Magnesium, Phosphorus, Sulfur, and Chlorine Parallel with changes in water and ash content during the year (see pages 22,25), there are also yearly changes in the amounts of different elements, but these problems have not been sufficiently studied (see Table 2 6). According to the few data at our disposal, the content of potassium, phosphorus, and calcium generally increases in the spring months (April and March) and probably decreases gradually until winter, after which an increase in water content begins (March) and with it the entry of the salts soluble in sea water. The changes occur seasonally according to latitude and they probably change also in relation to the time of spore formation, which varies from species to species. Kalishchev (1926) did analyses of Laminaria from the Pacific Coast, near Vladivostok, from July to October, and it is shown that there are no sharp changes in the composition of the soluble ash of Laminar* a. Vedrinsky (i938-b) found no regularities in the amount of phosphorus and sulfur in Laminaria in the course of the year. 10. Rhodophyceae: Potassium, Sodium, Calcium, Magnesium, Phosphorus, Sulfur, and Chlorine There are far fewer analyses of the red algae than of the Phaeophyceae, and moreover, the various single analyses refer to different species. Consequently it is much harder to form a conception of the relation of some definite substance to a given species of Rhodophyceae than is possible in the Phaeophyceae, even though it may be difficult

5o

Memoir Sears Foundation for Marine Research TABLE COMPOSITION OF ASH

Ash in % of dry matter

ALGAE

Chondrus crispus Chondrus plicatus Furcellaria fastigtata

............

20.61 8.37 18.92 29.28 11.61

Polyslphonia elongata ............ Gracllaria armata ............ Gracilaria confervoides (sphaerococcus) Iridaea edulis .............. Ctramum rubrum ............ Galaxaura fragilis ............ Laurencia obtusa ............. tiagora visdda .............

15.17 (12.12) — 9.86 14.34 — (42.60) (64.7)

Deltsstria sangumea

............

............

............. ............. ............

39.52

.......

Na^O

K^O

MgO

CaQ

18.73 26.93 23.47 15.71 23.17

17.32 9.08 20.24 9.24 14.90

11.35 8.12 10.46 8.23 6.46

7.16 16.50 7.25 17.35 4.35

13.33 6.91 26.37 16.93 23.94 1.56 3.36 1.96

22.61 8.09 3.94 23.42 7.08 2.18 2.52 1.41

15.30 3.55 2.00 ? 1.91 0.85 4.18 0.72

20.59

8.61

1.87

16.53 4.47 26.98 6.25 20.46 17.44 88.6 63.35 82.38

(in o/f of Chondrus crispus Furcellaria fast( giata Rhodomela pinastrotdts Nitop hyllum punctatum SMiria chorda/is Rhodymenia falmata

............. ............ ........... ........... ............. ............

— — ~ — — _

9.15 8.23 4.62 8.76 18.15 3.00

3.03 8.16 11.74 11.63 17.75 10.80

1.090 0.72 0.382 0.526 0.66 0.83

even in the case of some Phaeophyceae. The only obvious characteristic of many Rhodophyceae is the calcium function, which is more strongly developed than that in the Phaeophyceae. As already mentioned, in the Phaeophyceae the potassium metabolism is of great importance, in addition to that of sulfur, iodine, and some other elements more or less common to all algae; in Rhodophyceae, however, the most significant element is calcium, and for certain species magnesium also, but the calcium function is specifically differentiated in some Rhodophyceae. One can thus divide all Rhodophyceae into three groups with respect to calcium content. First group. The majority of Rhodophyceae. Calcium content similar to that of Phaeophyceae (the usual amount in algae). Genera Chandrus, Delesseria, Pofysiphonia and Nitophyllum. Second group. Concentrating calcium and precipitating it as deposits of CaCO3, probably as aragonite; species of the genera Ga/axaura, Laurencia, and Liagora. Third group. Calcium or more precisely calcareo-magnesian algae concentrating CaCO3 and MgCO3 in the form of calcite. Species of the Corallinaceae.

0.655 0.88 4.85 0.287 0.459 1.75

Chemical Composition of Marine Organisms

51

27 OF RHODOPHYCEAE

of ash)

PA 0.41 5.35 2.21 1.94 2.36 46.49 1.76 4.20 4.61 13.01 2.95

SO,

41.24 19.69 30.92 36.62 44.18 2.44 30.54 25.58 7.61 25.20 30.89 (2.27) 13.70 10.69

2.11 0.99

Cl 3.79 14.33 5.24 8.39 4.58 3.31 8.84 2.39 23.53 0.98 17.65 2.50 trace 0.52

Fe0

SiO,

— — — 1.17 — 0.63 — 7.20 14.96 — 1.02 — 4.18 0.79

— — 0.21 2.75 — 0.30 3.15 15.37 14.60 — 1.05 2.03 6.60 0.34

—

—

Locality

Author

Kattegat ........ Denmark (Hoffmansgave) Kattegat Baltic Sea ........ Kattegat ........ Baltic Sea ........ Denmark (HofFmansgave) Algiers ......... Lagoons of Venice Kattegat ........ Baltic Sea (Varnov) Antilles, West Indies . . Algiers ......... „

. . . ........

Forchhammer, 1844 „ „

Vibnms, 1873 Forchhammer, 1844 Vibrans, 1873 . . . Forchhammer, 1844 MiiLler, 1894 ..... Sestini, 1877 Forchhammer, 1844 ..... Vibrans, 1873 . . . Damour, 1851 Muller, 1894 .........

dry matter) 8.64 6.22 8.710 1.22 8.03 1.423

0.367 0.088 0.362 0.254 0.567

^"^

0.628

—

Brittany, France

......

Vincent, 1924

»

»

......

»

»

»

w

......

»

«

»

»

„

„

w

»

»

»

„

„

*

,

*

• ......

•

*

......

We shall first examine the former two groups.36 Some species which we have placed in the first or second group should not be separated either chemically or systematically from species of the other group. That is, species are found whose calcium content is between that of groups one and two (Geranium, Iridaea, Rhodomela, and so forth), so that often a number of species of one genus or family are placed in the first group while other species of the same genus or family are placed in the second. Furthermore, morphological differences are stressed by peculiarities in chemical composition, which is usually related to differences in latitude also (compare, for example, different species of Laurencia and Polysiphonia). As already mentioned, the first group contains calcium and magnesium in amounts similar to those of the overwhelming majority37 of Phaeophyceae.8H Warm water species 36. For qualitative analyses, see the work of Bley (1832), O'Shaugnessy (1834-1837), Schmidt (1845), Fr£my (1923, on freshwater species), Herberger, Riegel, and Nygord. See also Table 32. 37. In the so-called tengusa \Gcliciium\ yegenori [Camphyllopkora hypnaecoides\ and ogonori [Gratilaria], Matsui (i9i6-d) found more magnesium than calcium. 3H. Illari (1944) records in Gclidium corneum from the Straits of Messina 15% HSO, 20.03°/0 protein, i3-99*/o cel~ 5

52

Memoir Sears Foundation for Marine Research

of Rhodophyceae which can be classified in the first group have some tendency to become enriched in calcium, the amount varying greatly, as in Gracilaria and Phyllophora (see Miiller, 1894); also, Actinotricha of the Indo-Australian Sea are able to concentrate CaCO3. But the situation is different for species of the second group. Schweigger in 1819, and Kiitzing in 1843, noted the CaCO3 inclusions of Liagora viscida, and Damour (1851) made the first analyses of a red alga of the second group, namely GaJaxaura*8 Many other species closely related to the above, such as Laurencia, Peyssonne/ia calcea, Cruoriella and a number of species of Nemalionales, Galaxaura^ Liagora^ Batrachosfermum and Wrangelia penicil/atay concentrate CaCO3. But unfortunately there are no quantitative determinations. CaCO3 is precipitated in Galaxaura** in the form of aragonite, according to Meigen's (1901) analyses, but in relation to the increase in calcium, this alga contains smaller amounts of other constituents (alkalies, chloride and sulfate).

TABLE 28 PHOSPHORUS IN RHODOPHYCEAE (IN »/p OF DRY MATTER) ALGAE

Rhodymenia palmata* Polyides rotundus Iridaea sp

P

.

,

, 0.30 0.26 0.30

Locality

Author

Rhode Island, U.S.A. „ „ „ California, U.S.A.

Wheeler and Hartwell, 1893 „ „ „ „ Burd, 1915

* Two determinations.

The ratio of potassium to sodium in the red algae of the first and second groups cannot be determined from the analyses at our disposal (see Table 27). The alkali is similar to that of Fucaceae, i. e., there is no exclusive accumulation of potassium as in the giant Laminariaceae, or even in Laminaria. It is probable, however, that in many species a predominance of potassium will be observed, for example in Rhodymenia^ where 12.22 °/0 of the dry matter was potassium according to the analyses of Bertrand and Rosenblatt (1928), Wheeler and Hartwell (1893), Vincent (1924), and Butler (1931). Weevers (1911) found potassium histochemically in the spores of Ceramium and Callithamnion and in the tissues of other red algae. Apparently an increase of calcium in algae leads to a decrease in potassium and vice versa (in Laminaria^ for example), these inverse relationships having not only physiological significance but also important geochemical significance. The phosphorus content of Rhodophyceae is often higher than is usual in other algae,40 this being especially clearly seen when calculations of phosphorus are done lulose, and 3-38°/o ash. The latter contained 32.47 °/0 SiOa, 28.32°/0 SO,, 2.41 °/o P»O6, 1.57 °/o FeaO8, 29.870/0 CaO, 2.70 °/0 MgO, and 1.09 °/o NaaO. Most of the material unaccounted for analytically is galactan. 38. See Kohl (1889) on Galaxaura rigida, G, rugosa and G. lapideseens. 39. The mineralogical character of other species is unknown. Very probably it is also aragonite. 40. We have not given the analyses of red algae prepared for food, in which the PaOB reaches io°/0 or more of the dry matter as a result of the preparation. See also Tetsunosuke and Yahagigawa.

Chemical Composition of Marine Organisms

53

in percent of dry matter, which depends partly on the relatively small amount of water in these species, such as in Phyllophora membranifolia. Haas and Russell-Wells (1935) showed that the amount of phosphorus in algae changes month by month and is different in different fractions. The total phosphorus proved to be as follows: Iridaea (= Dilsea) edulis caspica Chondrus crispus * Polysiphonia fastigiata

0.41 °/0 P in dry matter 0V'**** 22 w w w w 0.22

Lemberg (1928) found calcium, magnesium, phosphorus, and iron in pigments isolated from Porphyra tenera and Rhodomela (see Table 26 on seasonal changes in composition). In Rhodophyceae, especially in species not concentrating calcium, i. e., those of the first group, the amount of sulfur evidently reaches a maximum, so that they contain more sulfur than all other algae. In Iridaea^ Hoagland found an exceptionally high amount of sulfur, as did Church (i 877) in Chondrus crispus^ Vincent (1924) in Rhodomela pinastroides, Chondrus crispus^ Solieria chordalis^ and others (see Tables 23 and 27). Compare the amount of sulfur in Chondrus given by Butler (1931), Vincent, Sarazin and Hervieux (1935). According to their data there is an average of 0.65 °/0 SO3 in Laminariaceae, and in Fucaceae an average of i.6o°/0 SO3. Masters and McCance (1939) found up to 5.46 °/0 sulfur in dry Chondrus crispus. Sulfur is present in these organisms in the form of sulfates, of ethero-sulfuric acids, related in turn to carbohydrates and other compounds, of thio-protein and other compounds; in other words, sulfur is present at all stages of oxidation and in many different compounds, which presumably vary from species to species. 11. Corallinaceae: Sodium^ Potassium^ Calcium^ Magnesium^ Phosphorus^ Sulfur', and Chlorine The Corallinaceae are widely distributed in all seas from arctic latitudes to the tropics, and they inhabit depths down to 400 m, where light penetrates only slightly. Although the first two groups of Rhodophyceae (p. 50) are closely related to each other systematically, the third group, the Corallinaceae, is distinguished from them both morphologically and chemically. Most of the available data relate to calcium and magnesium, with but little about other elements. Bouvier (i79i-b) presented an analysis of Corallina officinalis\ Merat-Guillot in 1797 investigated the calcareous Corallina articulea^ and in 1800 Hatchett found that the skeleton of Corallina opuntia (which was classified as a calcareous sponge) contained CaCO3 and little phosphate. That the Corallinaceae are algae was established by Schweigger in 1820. More complete analyses by Payen appeared in 1843. There are qualitative indications of the presence of CaCO3 in the work of Klitzing (1843) on JAM* rubens\ Melnikoff (1877) and Kohl (1889) gave surveys of plants which concentrate CaCO3, the Corallinaceae being among them f

54

Memoir Sears Foundation for Marine Research TABLE COMPOSITION OF CORALLINACEAE

ALGAE

NajO

^O

MgO

CaO

SOS

Ltthothamntum ramulosum * Lithothamnium sp Ltthothamntum nodosum Ltthothamntum glaciate Lithothamnium kaiseri Ltthothamntum erubescent Lithothamnium crassum Lithothamnium calcareum Lithophyllum sp Lithophyllum pallescens Lithophyllum craspedium f. mayorii Lithophyllum craspedium Lithophyllum daedaleum Lithophyllum antillarum Lithophyllum encodes

— — — — 1.10 — — — 0.55 — 2.06 — — — —

— — — — 0.24 — 0.96 — 0.27 — 0.25 — — — —

3.06 1.90 2.66 4.78 7.69 7.52 1.90 2.13 5.89 6.42 8.0 8.64 8.14 7.24 8.07

45.88 48.09 47.14 45.41 40.76 42.96 40.60 48.35 43.32 40.39 42*22 41.56 40.48 43.34 42.57

— — — 0.14 0.78f 0.61 6.89f 0.96f 0.95 0.71 0.81 f 0.15 0.44 0.57 0.27

— — — — — —

7.25 8.81 6.47 10.69 6.54 7.09

42.55 41.07 42.60 37.66 44.88 45.92

0.02 0.69 0.59 0.79 0.71 0.00

Goniolithon strictum (young) Goniolithon strictum (old) Goniolithon frutescens

2.78 — — — — — — — —

0.34 — — — — — — — —

3.88 5.93 4.02 8.27 10.39 10.93 9.64 10.26 6.29

40.31 44.80 38.19 40.60 38.54 38.03 37.64 38.25 46.16

0.97f 0.53 0.52 0.62 0.60f 0.61 f 0.63 0.67 0.00

Goniolithon orthoblastum Amphiroa tribulus Amphiroa fragilissima Amphiroa foliacea Melobesia sp

— 0.89 — — 1.75

— 0.39 — — 0.65

5.71 8.83 6.71 7.53 6.41

42.39 39.74 34.82 39.02 32.76

0.00 1.05 0.56 l.OSf 1.25

Lithophyllum Lithophyllum Lithophyllum Lithophyllum Lithophyllum Lithophyllum

intermedium tarniense pachydermum pachydermum (young) pachydermum (old) kaiseri

Lithophyllum proboscideum drchaeolithothamnium episporum Phymatholiton compactum Goniolithon acropetum Goniolithon strictum

• Fe2Os without A12O3. t S04.

1.42

0.45

2.83 1.91

0.49 0.87

— — — — — —

1.57

0.38

6.65

7.84 7.28

7.28

43.78

40.28 41.76

41.76

P20,

—— 0.06 trace 0.46 trace 0.03 trace 0.32 0.11 0.38 0.03 trace trace 0.08

0.87f

0.25

0.94f 0.90f

0.38 0.48

0.91f

0.46

trace trace 0.00 trace trace trace

0.30 trace 0.10 0.18 trace trace 0.00 0.00 trace

trace 0.27 trace 0.35 0.38

Chemical Composition of Marine Organisms

55

29 (IN •/« OF DRY MATTER)

Cl

— —

FeA

{+ AljO,)

Si02

C02 + organic matter Locality

0.41 • 0.28"

1.91 1.59

44.98 44.93

— —

0.23

—

1.93 0.9 0.08 0.22

—

— 0.60 — — — — — •— •— — — — — „ .— — — -— -— — — —.

—

0.12

— 0.09 0.08 0.10 0.12 —

0.21

0.16 0.08 0.11 0.14 — — 0.64* 0.89 0.23 0.04 0.01

— —

0.32 0.57

— — — 0.53

—

0.34

O OC £. j\J

0.28

0.05 0.07 0.11

A(\

0.41 0.02 0.19 — — — 1.01 0.28 0.03 0.18 0.04 0.09 0.06 0.27 0.12 0.04 0.04 0.09 0.18 0.16 8.38 1.47 0.10 0.06 0.02 0.02 0.08 0.22 .

1.31 0.64* 0.20

2.82 0.32 —

Author

Gulf of Naples 99

99

99

C(\

99

99

Newfoundland Tutuila, Samoa Timor (Indian Archipelago) Normandy, France Concarneau, France Mediterranean California, U.S.A. Rose Atoll Palmyra I. (Pacific) Puerto Rico 99

99

Coetivy I. (Indian O.) Tutuila, Samoa Jamaica, B.W.I. New Guinea Bahama Is. 99

99

Cocos-Keeling I. (Bahamas) Tutuila, Samoa 99

99

California, U.S.A. Panama Newfoundland Puerto Rico Bahama Is. Florida Bahama Is. 99

99

Cocos-Keeling I. (Bahamas) Tutuila, Samoa Murray Isle, Australia Antilles (W. Indies) Puerto Rico Tutuila, Samoa Algiers

99

99

1 Q*7 1 Lr umbel, lo/l Clarke and Wheeler, 1922 Lipman and Shelley, 1924 Clarke and Wheeler, 1922 Vincent, 1924 O - — U->1

T"Z.DZ

48.0 49.09 47.89 10.39 0.45 44.17 49.94 46.95 48.37 49.99 48.11 47.96 47.29 48.63 48.77 49.55 50.64 47.51 45.72 49.79 48.71 42.31 45.69 55.42 49.56 49.91 49.91 51.14 48.76 46.7 48.85 50.97 45.73 48.78 50.87 49.88

Schwager (see Walther, 1885)

99

19

Damour, 1851 Clarke and Wheeler, 1922 Lipman and Shelley, 1924 Clarke and Wheeler, 1922 99

99

99

99

99

99

99

99

99

99

99

99

Lipman and Shelley, 1924 Clarke and Wheeler, 1922 99

99

99

99

9>

W

19

99

Kamm (see Clarke and Wheeler, 1922) Chambers (see Vaughan, 1918) Lipman and Shelley, 1924 99

99

99

99

9>

9»

99

)»

Clarke and Wheeler, 1922 W

W

99

99

99 99

W

99

W

9

9

W

99

W

99

99

99

99

99

Kamm (see Clarke and Wheeler, 1922) 99

99

99

Chambers (see Vaughan, 1918) Lipman and Shelley, 1924 Chambers (see Vaughan, 1918) Damour, 1851 Clarke and Wheeler, 1922 Lipman and Shelley, 1924 Damour, 1851

w

56

Memoir Sears Foundation for Marine Research TABLE 30 MgC03 AND CaCQ, IN CORALLINACEAE FROM DIFFERENT LOCALITIES (IN °/0 OF ASH)

MgCO, CaCOj Lat.f

ALGAE Lithothamnium sp. . . . soriferum . glacial* . sp. . fornicatum . polymorphism n Coralfina . officinalis Lithothamnium caltareum » »

• •

Lithophyllum . incrustans Lithothamnium calcareum crassum . glaciate . Phymatolithon . compactum Lithophyllum tortuosum . expansum . tortuosum . Lithothamnium polymorphum Coralfina officinalis rt

•

Lithophyllum incrustans . Lithothamnium ramulasum . racemus . ramulosum . sp. . tortuosum . (calcareum) . Lithophyllum . proboscideum

. . .

. . . .

8.67 9.56 13.19 9.94 10.09 9.10 15.15 12.06

84.83 78° N 80.90 75

83.10 75 74.26 72 88.61

74.22

83.4

57 57

86.68 49°33'

. 12.04 84.60 48°5' . 12.4 85.1 48°5' - 12.52 87.48 48 . 11.14 87.10 48 .

12.70' 87.30 48

. 5.30 94.70 . 10.93 88.11 48 .

10.93 87.21

48

Long.

Author

Locality

.

99

*

— —

12 12

99

Bering o I. . Norway . Kattegat . 99

•

9°E 7 3

- 13.76 74.15 43

3

99

99

. 11.13 72.12 43 . 10.09 68.36 —

3

99 99 99

15.90 84.10 43

9.46 11.33 6.81 4.19 . 12.35 . 12.76 . 8.15

. . .

63.00 77.39 86.90 90.30 87.65 86.36

72.0

41 41 41 41 41 40 37

*

. .

— 3 14 14 14 14 14 —

»

n

n

n

99

99

Charf (see Lemoine, 1910) . H6gbom, 1894 Vesterberg, 1900-01 • Pay en, 1843

T12'W Saint-Wast, Normandy 4°W Jlenan Isle . (Finisterre) English Channel — — Roscoff(Finisterre) 3 English Channel (Gatteville) 3 Concarneau, France 3 ? 53 Topsail, . , , Newfoundland Torbay, . 55 Newfoundland

. 9.83 77.58 44 . 13.11 75.99 44 . 14.12 73.91 43

.

Hdgbom, 1894*

(20° E) Spitzbergen . Arctic O. .

Charf (see Lemoine, 1910) 99

99

99

99

Chalon, 1900 Charf (see Lemoine, 1910) Vincent, 1924 Clarke and Wheeler, 1922 99

99

99

99

Genoa, Italy . Charf (see Lemoine, 1910) Villefranche , Novacek, 1930 Banyuls-sur-Mer, France 99

99

99

99

99

99

99

99

99

99

99

99

99

'

Naples, Italy

Hegbom, 1894

»

99

99

99

rt

*

• 1

99

99

'

• I

»

Schwager (see Walther,

1885)

Chalon, 1900 99 » Mediterranean . Damour, 1851 12?°W Monterey, . Lipman and Shelley, 1924 Calif. U.S.A.

Chemical Composition of Marine Organisms ALGAE

MgCO, CaCO, Latt

Melobesia sp. . Lithophyllum . incrustans Lithothamnium sp. racemus . Goniolithon strictum strictum ° . strictum P . Lithophyllum pachydermum ° pachydermum P pachydermum , Goniolithon strictum Lithophyllum . pallescens Lithothamnium sp.

14.44 84.36 36 10.73 85.08 33 12.73 5.35

82.44 32°N

—

25

Long. Locality

57

Author

3°E Algiers , 7°W Mazagan,

Damour, 1851 Charf (see Lemoine, 1910)

Morocco 65°W Bermuda . Hogbom, 1894 Bahamas (B.W.I.) Nichols, 1906 75

24.00 74.85 25 22.98 75.42 25 23.74 74.29 25

75 75 75

Clarke and Wheeler, 1922 Kamm, 1922 (see Clarke and Wheeler, 1922)

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

24.95 15.43 15.08 25.17

73.65 83.06 83.68 73.63

25 25 25 24

75 75 75 81

15.46

81.48

24

110

25.32

73.23 23

80

Amphiroa tribulus Lithothamnium sp. Goniolithon acropectum Lithophyllum . daedaleum ant illarum .

19.29 9.39 19.24

79.81 20 84.01 20 79.05 18

— 161 68

19.03

79.85 18

68

16.35

82.46

18

68

intermedium Amphiroa . fragilissima Lithophyllum craspedium . Lithothamnium kaiseri . Goniolithon frutescens . Porolithon craspedium . encodes . Lithophyllum kaiseri Amphiroa fo/iacae Lithothamnium sp.

16.59 17.47

82.85 18 76.23 18

72 68

16.82

72.77

18

150

Tahiti

16.15

72.80

15°S

172

Tutuila, Samoa . Lipman and Shelley, 1924

15.29

74.57

15

172

16.80 13.75 16.46 15.80 36.36 19.47 13.80

75.39 15 78.20 15 71.93 15 69.64 15

172 172 172 172 175 175

15.33

84.38

Goniolithon frutescens Lithophyllum kaiseri .

—

74.4 86.13

13 13

Clarke and Wheeler, 1922

Soldiers' Key, Fla., U.S.A. Bay La Paz, . . Calif., U.S.A. South Florida, , Phillips (see Clarke and Wheeler, 1922) U.S.A. Antilles (W.Indies) Damour, 1851 Honolulu, T.H. Hogbom, 1894 Culebra I., . , Clarke and Wheeler, 1922 Puerto Rico Salinas Bay, . Puerto Rico Culebra I., . . Puerto Rico Kingston, Jamaica Lemon Bay . (Puerto Rico)

99

Rose Atoll . . Tutuila, Samoa . 99 99

Samoa 99

99

99

99

9?

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

9>

»»

99

99

99

J9

99

99

99

99

99

99

99

99

99

99

99

99

96°5'E Cocos Is. . (Bahamas)

12°5'

96°5'

»»

99

99

12°5'

99

99

99

- * .

99

. . Charf (see Lemoine, 1910)

.

99

99

.

.

\ Phillips (see Clarke and f Wheeler, 1922) Chambers (see Vaughan, 1918) 99

99

99

99

(continued next page)

58

Memoir Sears Foundation for Marine Research

ALGAE Goniolithon orthoblastum Lithothamnium

CaC03 Lat.t

Long.

Locality

Author

13.66

86.22

10

145

Murray Isle . (Australia)

Chambers (see Vaughan,

16.96

81.59 10

123

Timor (Indian Archipelago)

Clarke and Wheeler, 1922

13.09 5.85

83.47

10

8

80 178

Panama , Funafuti .

18.17 19.60

80.93

7

56

MgCOs

.

erubescent Archatolithothamnium episporum Lithothamium.

—

* .

phillipi var. funafutiensis Lithophyllum encodes , craspedium . tarniense Lithothamnium sp.

nodosum

20.02

72.92 78.43 72.03 83.60 83.75

3.76 6.53 12.17 6.06 91.04

5°5'N

5°S 5 0 0 —

Madagascar .

172°W Palmyra I. . 145°E New Guinea — Java Sea . 90°W Galapagos Is.

90 —

—

1918)

Skeats (see Royal Society of London, 1904)

Clarke and Wheeler, 1922

»

»

Hogbom, 1894 Vesterberg, 1*900-01 Giimbel, 1871

* Analyses of Mauzelius, Sahlbom and Guinchard. t For analyses in which only the geographical name was given, we have calculated the approximate latitude and longitude, a Young. P Old.

(see also Violette and Archambault).41 Damour (1851) apparently was the first to note that the skeletons of Corallinaceae, for example Lithothamnium^ contain not only CaCO3 but also considerable amounts of MgCO3,42 these being the only plants with such a skeleton. At that time it was suggested that organisms participate in the formation of dolomites (see Forchhammer [1850, 1852], Ludwig [1862], and BischofF[i847]), but the question of the significance of Corallinaceae for dolomite formation was not raised. Only at the end of the last century, and during the last 30 years, has there been a large series of analyses on Corallinaceae in connection with this possible function (see Table 29). The geochemical role of the Corallinaceae is now known to be great. In Paleozoic times the So/enoporay which are believed to be genetically connected with the Corallinaceae, formed reefs. Unfortunately there are no analyses of Solenofora remains, but it would be interesting to know if they contained MgCO3. In the Corallinaceae we find in fact for the first time organisms with large amounts of magnesium, up to 36 °/o MgCO3 and 60 to 90% CaCO3 in the ash, the ash residue reaching almost 50% of the living weight. But the amount of water has not been established. According to Putter (1908), in Corallina mediterranea there is 79.8 °/0 41. See Wallner (1938) on CaCO, in algae from freshwater basins, forming sediments: Desmidiaceae-Ooftzn/f'am, Cosmarium nitidum and Hydrurus crystallophorus. Frlmy (1923) indicates incrustations of CaCO, in Batrachospermum; see Wallner, 1938, on calcium in Riirularia. 42. There was some information before in the data of Bouvier (1791) and Payen (1843) on the MgCO3 content.

Chemical Composition of Marine Organisms

59

H2O, 9.8 °/0 organic matter, and 10.4 °/0 ash ; in Lithothamnium racemosum there is 11.8 °/0 H2O, I4.8°/ 0 organic matter, and 73.4% ash in the living matter. Thus the Corallinaceae are calcium-magnesium organisms, with the amount of CaCO3 and MgCO3 in different species varying comparatively little; where there are repeated analyses it is possible to get an idea of the range of variation in the ratio of CaCO3 and MgCO3 within one species. There have been attempts to correlate the amount of MgCO3 with the temperature of the habitat of these algae, as in the cases of marine animals whose skeletons are chemically analogous (see the section on Echinodermata; also Table 30). But the rule that species with the habitats closer to the equator

TABLE 31 CaCO3 AND MgCO3 IN CORALLINACEAE OF DIFFERENT AGES

MgC08

ALGAE

Lithophyllum pachydermum 1. young parts 2. old parts . , . . Gontolithon strictum 1. young parts . ,

2. old parts .

,

,

,

,

CaC08

CaS04

.

. . 24.95 1543

73.65 8306

1 24 1 27

,

.

75.42 7429

1.22 1.25

* 22.98 - 23.74

contain larger amounts of magnesium does not always prove to be valid, as in Lithothamnium racemosum and other species. For example, Lithothamnium from Java contains up to 3.76 °/0 MgCO3,43 while Lithothamnium glaciale from the arctic contains as much as I3.i9°/ 0 . Furthermore, Clarke and Wheeler (1922) got up to 24% MgCO3 for a Bahama species of Goniolithon and up to 25.17 °/0 for a Florida species of Goniolithon, while in an Australian specimen there was only 13.66 °/o MgCO3. But taking into consideration all the exceptions to the rule, such as cases where species from warm seas contain small amounts of MgCO3 and cold water species contain much magnesium, one can still state that the overwhelming majority of species follow the rule of dependence of MgCO3 content on the temperature. In arctic seas species do not contain MgCO3 in amounts higher than 13.19%) and it follows then that the majority of species with a small amount of MgCO3 are from arctic or temperate regions. Clarke and Wheeler (1922) posed the following question: Could the differences in composition noted above be connected with the age of the algae? The results of analyses are shown in Tables 31 and 32, but the question remains unsolved and needs further study. It is interesting to note the Mg/Ca ratio in connection with the form of seaweeds, from more compact weeds such as species of Lithothamnium to more delicate ones such 43. This is possibly erroneous.

60

Memoir Sears Foundation for Marine Research TABLE 32 COMPOSITION OF ALGAE; RECENT DATA (IN «/o OF ASH)

ALGAE

Ash

Ns^O K2O MgO

Ulvasp.* . 28.55 — Stigeoclonium sp. . . . 3.78

»

With the discovery of the concentration of iodine in the thyroid gland of animals (Baummann, 1895), the iodine problem began to penetrate into all branches of biological science, and finally during recent years the question of the distribution of iodine, particularly in organisms, was re-examined from the point of view of the geochemistry of iodine in numerous investigations of Fellenberg (1924), Hercus and Roberts (1927), history of the use of sponges in medicine is set forth in the work of Richter (1907), Arndt (1924), Sturm (1931), and Viel. Although almost nothing has been written on the history of the use of algae in the Orient, in particular for goiter, it is evident that this cure was known there long before it was in Europe.

Chemical Composition of Marine Organisms

j i

Lunde (1928), Wilke-Dorfurt (1928), and Closs (1931). Thus considerable material was collected on the cycle of iodine in the sea. Material appeared in the earlier works of Marchand (1866), Bourcet (1899), Gautier (1899-!), c), and many others, and in the dozens of recent works to which we will refer later. Thousands of samples of different minerals, soils, water, and organisms were analyzed for iodine. It became clear that the ocean as a whole contains more iodine than the land, and that the distribution of iodine on land is irregular, depending on the character of soils and in particular on the amount of iodine in the rocks from which soils were formed [see Fellenberg (1924), Wilke-Dorfurt (1928), and Bleyer (1926)]. Furthermore, soils can absorb iodine,

TABLE 40 IODINE IN WATER, ROCKS, ORGANISMS, AND SO FORTH, ON LAND AND IN THE SEA (IN °/0)

On land

Air Water Rock Soils (silts) Plants (algae) Animals Thyroid gland of

In the sea 8

fish

nxlOnx KT7 nxlO- 6 nxlO- 4 nx 10~5 nx 10~6 nx 10"1

nx 10~fl (y/m*) nxlO'6 — nxlO' 2 nx 10~3 nx 10~4 nx 10"1

either in the form of salts (chiefly iodides60), or bound with organic matter, or as elementary iodine. Oxidizing substances such as oxides of iron, manganese, and other metals, and probably O2 and O3, liberate iodine from its compounds. Rivers, lakes and other freshwater basins contain little iodine, whereas the sea and its inhabitants contain many times as much. A reliable estimate of the amount of iodine in sea water has been possible during recent years;8" on the average it is about 50 y per liter (see Table 39).61 Iodine is distributed throughout the biosphere, as seen in Table 40, with the silty ocean bottoms proving to be rich in the element (see A. P. Vinogradov, 1938-a). Besides that, one should note that the northern hemisphere, with a greater length of shoreline and consequently with more littoral-zone algae, among which are found such exceptional iodine concentrators as the Laminariaceae, must have a larger supply of 60. Deniges (1932) suggests the formation of iodate and iodide in the sea from free iodine in the presence of calcium bicarbonate. 6 H. For recent work, see the summary by £. M. Low and G. £. Hutchinson which will appear in Survey of Contemporary Knowledge of Biogeochemistry, V, Bromine and Iodine, Bull. Amer. Mus. nat. Hist. 6z. We have selected only the most accurate data on iodine in the water of the open sea. As a rule there is more iodine in such water than in that near the shore; this variation parallels the differences in chlorine content. The amount of iodine apparently changes with depth, and determinations have been made down to 900 m or more. See also the data of Boussingault (1825), Macadam (1852), Marchand de Fecamp (see Mohr, 1865), Thorpe and Morton (1871), Sonstadt (1872), Koettstorfer (1878), Itallie (1889), Gautier (1899-!), c), Stoklasa (1911)) Freundler (1924^), Heymann (1925), Hercus, Benson and Carter (1925), Bleyer (1926), and Closs (1931) on different seas.

72

Memoir Sears Foundation for Marine Research

iodine than the southern hemisphere. The entire history of the iodine industry is a history of the utilization of the northern hemisphere seaweeds.62 The question then arises as to whether or not this concentration is compensated in the warm seas by the accumulation of iodine by the Alcyonaria and sponges, which are widely represented there. Also, there has been much discussion on the origin of iodine in the sea. From the time of the origin of the biosphere, the massive7" rocks which contain n X io~5°/0 iodine evidently fed the rivers with iodine during erosion, the latter depositing it in the ocean which thus became enriched with iodine. Of course, iodine is extracted from sea water by marine organisms, chiefly by seaweeds and invertebrates, in which the element is distributed more or less regularly throughout the body, while in the more organized vertebrates iodine becomes concentrated in separate organs, such as the

TABLE 41 IODINE IN THE THYROID GLAND OF VERTEBRATES OF DIFFERENT AGES (IN °/0 OF DRY MATTER)

Homo sapiens Gal/us gallus

Young

Mature

Author

0.01 (at birth) 0.2 (7 weeks)

0.3 0.6 (14 weeks)

Fellenberg, 1924 Choudhury

thyroid gland. Also, the silty ocean floors become enriched in iodine which is deposited with the remains of marine organisms, but the latter process has only begun to be studied. In the silts of the sea the concentration of iodine reaches io~~2°/0. Oil-bearing and salty vadose deposits rich in iodine have their origin in the silty water of ocean bottoms accumulating iodine. The first link in the biogenic migration chain of iodine in the sea is constituted by the phytoplankton organisms and by all benthic seaweeds ; in these the concentration of iodine is one thousand times greater than that in sea water. Numerous Mollusca, Crustacea, and other organisms consume algae, which, in turn, become food for fish and other vertebrates. In vertebrates the iodine is concentrated in the thyroid gland, and high iodine content has also been found in the fat of fish liver. The thyroid gland of marine vertebrates, such as fish, is richer in iodine than that of terrestrial forms, and the amount of iodine in the thyroid gland changes during the year, with the curve representing the iodine of the thyroid gland of vertebrates being similar to the curve of the iodine content of seaweeds. The maximum in both cases occurs in the spring or summer, the minimum in winter. This is of interest because it proves once more the nutritional dependence between organisms. Let us note that the iodine in the thyroid gland of vertebrates, 62. All the centers of the iodine industry are situated in the northern hemisphere: Scotland, Normandy, Norway, and the northwestern shores of Germany, Sweden, Denmark, Murman, and Spain; in Asia, on the Pacific Ocean, Hokkaido (Japan), and near Vladivostok in the U.S.S.R.; in America from the Isle of Cedros in California to Alaska. 7 H. As with the other halogens, the amount derived from this source would appear to be rather too small; iodine may have been added from volcanic vents and hot springs.

Chemical Composition of Marine Organisms

j3

which is minimal in the young, increases with time (see Table 41); this is the reverse of what we know of the content of a number of heavy metals in the organs of animals, such as copper, iron, and manganese, which are present in the liver of the embryo but which are used up during development. Organisms with their different amounts of iodine assume varying iodine levels in the separate links of the nutritional chain. Although the physiological role of iodine is important, it has not yet been studied thoroughly and it is not our aim to examine it here. Iodine is present in the thyroid gland in the form of thyroxin: ^Cl—CH

CI=CH

OH-C

C-O-C X

CI=CH

/

C-CH.CHCNHJCOOH

\I-0/

As Swingle (1922) has shown, tetrabromothyronine, in which iodine is replaced by bromine, does not have the physiological action of the iodine compound.63 14. Iodine in Phaeophyceae The contemporaries of Courtois showed that the largest amounts of iodine can be found in seaweeds, their determinations referring chiefly to brown algae, which are most widely distributed in European seas; of all algae they are actually the richest in iodine. In different species of Fucus and Laminaria, iodine was found qualitatively by Davy (1814), John (1814), Ancum (1814), Gaulthier de Claubry (1815), Fyfe (1819), Gay-Lussac (1814), Kriiger (1821), Driessen (1823), and later by Wheeler (1882), Bergstrand (1872), Fluckiger (1887), Herzog, Babiy (1913), and Molisch (1926). At the present time there are data on the presence of iodine in more than 250 species, and we must conclude that all marine algae contain iodine.64 Although quantitative determinations have not been done for all the species investigated, the data on the iodine content of algae are expressed in various ways— as percent of living weight, as percent of air-dried material or dry matter, or as percent of ash. Since it is not always possible to make these data uniform by recalculation, we sometimes have to leave them as they were first given by the author. Furthermore, the analyses are not of equal value, perhaps because the determination of iodine in ash does not give large enough values. For greater details, the reader is referred to Tables 42 and 43 which contain extensive data on this element. These tables could be extended even farther with analyses of algae for which the names of the species are not given (Foslie [1884], Meyer [1891], Weis [1903], Averkiev [1915, 1926], Forbes [i9i6-a, b], Fellenberg [1924], 63. See Harms on the significance of iodine in the development of organisms and their evolution. 64. Zora Klas (1932) determined iodine qualitatively in Adriatic algae, Anadyomene stellata, Cladostephus verticillatus, Phyltitis fascia, Zanardinia collaris, Spy ricfia filament osa, Chylodadia clavellosa, Rytiphloea tinctoria, Vidalia volubilis, and in more than 50 other species, but he was unable to detect iodine. This was due to the method he used. See the qualitative iodine determinations given by Roman (i93O-a, b), Narasimham and Pal (1939), and others.

74

Memoir Sears Foundation for Marine Research

Bleyer [1926], Sugimoto [1928], Glimm and Isenbruch [1929], Niesenmann, Pisarzhevsky, and others).65 The picture of the distribution of iodine in brown algae includes data chiefly concerning two families of Phaeophyceae, namely the Laminariaceae and the Fucaceae. These data refer to many different species living at different depths in various places from the littoral zone and the open sea and collected at different times of the year. Shown also in these data is the iodine content of the same species found in different parts of the globe, mostly in the northern hemisphere. There are analyses of algae from the shores of the Atlantic Ocean and seas adjoining the British Isles, from the east coast of America, from the shores of Scandinavia and the North Sea, from the shores of France, Spain and the Mediterranean, from the inner seas of Europe, from the shores of the Arctic Ocean, the Barents Sea and the White Sea, from the Pacific Coast of Alaska to southern California, along the Japanese shore, including the Okhotsk and Japanese seas, and the shores of China and the Hawaiian Islands. For other localities a few determinations have been made, for example those on the algae of the Indian Ocean and Australia by Dixit (1930), and those of Averkiev (i926)66 on the algae of the Caspian Sea. Unfortunately these analyses gave no information as to species. Gaulthier de Claubry (1815), and later many others such as Morid£ (1866), Pellieux and Allary (1880), and Weitzig, noted a considerably higher iodine content in Laminaria than in other Phaeophyceae, which fact is evident by a mere glance at Tables 42 and 43 ; of the brown algae as well as all other species, those of Laminaria are the richest in iodine and rank in first place; of the European species, the richest are L. digitata and L. saccharina, as well as L. cloustonii, L. flexicaulis, and L.bullata; of the American species from the Pacific shore, there is L. andersonii; and of the Japanese species, L. bullata, L.japonica, and L.religiosa. The amount of iodine in L. digitata^ for example, reaches 5°/o °f ^e ash> or x °/o °f the dry matter, which is equal to 0.2 °/o iodine in the living algae. The second place in the scale of iodine concentrators is occupied by giant seaweeds from the subfamily Lessonioideae, including Macrocystis pyrifera, Pelagophycus 65. Averkiev gave analyses of 149 specimens from the Pacific Ocean, the North, White, Black, Azov, Baltic and Caspian seas (see Zinova's [1935] remarks on the collection of these algae). According to Fellenberg (1924), in the Japanese seaweed preparation "nori," there is 0.00587%; in "kombu," 0.2640%; in an alga from Chile (Lache), about 0.001%; in unknown algae, 0.09%. Bleyer (1926) found 0.065% m the same algae from Japan; Glimm and Isenbruch (1929) found 0.0098% (of dry matter). Simpson (1932) found 0.20-0.86% iodine in the dry matter of an alga of the Australian Coast; Hercus and Roberts (1927) gave 0.0048% for algae of New Zealand; according to Bode, in the algae (varech)from Asturia (Spain), there is 0.60-0.0915% in the ash (see Bauchdeker); according to Sugimoto (1928), in the dry matter of "nori" there is 0.01% and in that of "kombu" 0.03 %. Gautier (i899-a) gave Allary's data. Probably Yendo (1901) gave data from European authors, as did Doherty (1918), in the part concerning Laminaria digitata, L. saccharina, and Fucus. Beckmann and Bark (1916) gave 0.3 % of the dry matter in an analysis of Fucus of the North Sea. See Gail (1930) on iodine in algae of the Pacific Coast of the U.S.S.R. See Happ (1822), Holl (1826), Tressler and Wells (1924), Adolph and Whang (1932), Rasmussen and Bjerreso (1941), and Kollo and Anitescu (1942). 66. Averkiev found the following amounts of iodine, in percent of ash, in algae from various localities: from the Baltic Sea, traces to 0.04%; from the Caspian, traces to 0.004%; fr°m the Azov Sea, traces to o.ooi %,—all small amounts. In view of the fact that the iodine was determined from ash, it is desirable that the analyses should be repeated on fresh algae.

Chemical Composition of Marine Organisms

75

TABLE 42 IODINE IN PHAEOPHYCEAE

ALGAE

f\J-t\Jf\Xs

Laminariaceae Laminar i a i < sficcfiorifiQ it

No f . « •' ° determinations

matter

dry matter

•^^~—

0.230

living

Author

Locality

Q 01

0.288

99

0.279t 0.0488 • — 0.049 — 0.405 12 -

11

ash

~~

0.09

— 0.378

—

— —

France 11 Brittany, France 11

99

91

Normandy, France 0.714 North Sea — 0.1885 0.6494 North Sea (Helgoland) — Kristineberg, — Sweden — „ — — — „ — Norway 0.303

99

0.496

99

99

2 (stem)

w

-

0.15

(lamina) 0.03 (growth zone) 0.09

I

2 0.043 -

0.264

?4

2 3

0.14 0.32 0.28§

_

* In percent of fresh matter. § Average.

— 1.67 —

-

5

—

——

—

West Coast, Norway Baltic Sea Gulf of Kola

Barents and White seas 0.933 Murman Coast 0.55 Solovki Isle, White Sea White Sea 0.63

Sarphati, 1834 Schweitzer, 1845 Wallace (see Wolff, 18 71 -1880) Stanford, 1877 Allary, 1881 Gautier, 1899-a Freundler and Menager,

1922

Vincent, 1924 Marchand, 1865 Witting, 1858-b Albert and Krause, 1919 Kylin, 1929 99

11

99

99

Beckmann and Bark, 1916 Krefting, 1899 Vibrans, 1873 Vinogradov and Bergmann, 1938 BruVevich,Trofimov and Hartmann, 1933 Varaksin, 1924 Averkiev, 1926

Northern Iodine Lab., 1933 Nanaimo, Canada Cameron, 1915 Puget Sound, Turrentine, 1912 (see U.S.A. F. K. Cameron) Doherty, 1918 _ Ossendovski, 1 906 0.4 1 7 « Okhotsk Sea(?) f Air-dried. a Not clear how this was calculated. (continued next page}

76

Memoir Sears Foundation for Marine Research

Laminariaceae Laminaria saccharin a

No. of determinations

,— living matter

•/. of——«^™^^»» dry matter ash

5.0P

Locality

Author

Baltic Sea (Sweden) Scotland

Weibull, 1917

—

—

. — — — — — —

0.122 0.209 0.135 0.119 0.577 0.444

— — — — — —

99

0.454 0.295 0.625

—

99

99

— — —

2.81

99

—

0.954

5.50

— — —

0.1 08§ 0.154 0.518

—

0.19

— —

0.59 0.51

digitata (stem) „ (lamina) 99

(stem)

99 99

„

(lamina) (stem)

(stem) (lamina) 99

„

(stem)

„ „

(lamina) (rhizoids)

2

(lamina) 99

99

„ „

— 0.765 — 1.7P 0.122Y — 0.109Y —

(young leaf) (stem)

0 Ofil Y

(lamina) (stem, rhizoids) (rhizoids)

P Maximum.

— — — — —

1.46

— — — —

0.123 0.114 0.095 3 0.15

0.595 0.438 0.461 —

— — — —

2 0.045

—

—

4 0.554

—

—

—

0.347

—

—

—

6 99

—

0.84

Anderson, 1855

99

99

99

Sarphati, 1834

99 99 99

99

99

99

99

Wallace (see Wolff, 1871-1880) Stanford, 1877

99

99

99

Godechens, 1845

West Coast, Scotland Normandy, France

Marchand, 1866 Tunmann, 1907

Normandy, France Norway Beckmann and Bark, 1916 North Sea (near Eschle, 1897 Schleswig-Holstein) 99

99

North Sea (Helgoland) 99

99

Brittany, France France 99

99

99

Albert and Krause, 191 9 99

99

99

Vincent, 1924 Allary, 1881 99

Oslo Fjord

99

99

99

Gautier, 1899-a Lunde and Closs, 1930

99

99

99

99

99

99

99

99

99

99

99

99

Kristineberg, Sweden Gulf of Kola West Coast, Norway Barents and White seas White Sea

y Fresh varech.

Kylin, 1929

Vinogradov and Bergmann, 1938 Krefting, 1899 Bruievich, Trofimov and Hartmann, 1933 Northern Iodine Lab., 1933

Chemical Composition of Marine Organisms ALGAE Laminariaceae Laminaria digitata

. .™- U I determinations

uym

e matter

0.074

99 99

99

stenophylla

—

99

cloustonii (stem) „ (lamina) (stem) „ „

(leaf) (growth zone)

2 2

0.72 0.11 3 -

2

„ flexicaulii (lamina) (stem)

7 bullata

— — 0.23

3 4

3

andersonii

—

0.235

— —

0.80 0.678

0.008

,^__

—

—

lejolisii

3

—

angustata longissima

6 3

— —

japontca

2

0.17 0.37 0.41

"

Imgicruri*

0.513

Author

Locality

0.758 Murman Coast

1.201 « Okhotsk Sea(?) — Halifax,

—

— 0.501

— -

ash

0.0996 — 0 • 407^0 T£,J\J 1.40 1.828

—

—

99

—

0.45 — 0.349

0.1*

2 hyperborea (lamina)

ory matter

— — — —

77

Nova Scotia France

Varaksin, 1924 Doherty, 1918 Ossendovski, 1906 Butler, 1931 Allary, 1881 Ossendovski, 1906 Hendrick, 1916

Scotland 99

Kristineberg, Sweden

Kylin, 1929 "

Roscoff, France

Freundler and Manager, 1922 Vincent, 1924 Beckmann and Bark, 1916 Lelievre and Manager, 1925

Brittany, France Norway France

— — 0.995Y Brittany, France Freundler and Manager,

„

1.285 — —

2.06

99

France Nanaimo, Canada Puget Sound, U.S.A. Okhotsk Sea

99

99

1922 Allary, 1881 Cameron, 1914 Turrentine, 1912

Pentegov, Niankovski and Plaksina, 1927 Albert and Krause, 0.6603 2.9703 North Sea (Helgoland) 1919 — California, U.S.A. Turrentine, 1912 0.60 — Burd, 1915 0.48 — New Brunswick, Butler, 1931 0.737 Canada Roscoff, France Freundler and Manager, 0.623 — 1922 Hokkaido, Japan Oshima, 1902 0.99 0.18 99

99

-

0.173 0.073

0.634 — Cape Atoiya,

—

0.25

0.75

99

99

Japan Tatarski Strait, Okhotsk Sea

99

99

McClendon and Takeo Imai, 1933 Liasota and Pavlov (continued next page)

Memoir Sears Foundation for Marine Research

7» ALGAE

Laminariaceae Laminaria japonica

»» » ochotensis

religiosa »» fragilis dentigera sachalinensis coriacea sp» Saccorhiza bulbosa Chorda filum

No. of determinations

living matter

—

0.48

5

-

0.106 1.234 0.128

4

—

0.188 0.206

— ~

-

1.158 0.127 0.419

— —

0.262 0.177

— — —

0.229 0.232 0.192

0.007

0.068

3

11 4 2 2 4

0.01

0.018 »»

»

2

»» ticydis radiata

5

exasperata kurome Egregia laevigata

—

0.141 0;089

99

sp. Ecklonia cava

• •/. ofdry matter

2

ash

Locality

Author

Pentegov, Niankovski and Plaksina, 1927 0.619 Hokkaido, Japan Oshima, 1902 Read and How, 1927 China Hokkaido, Japan McClendon and Takeo Imai, 1933 Oshima, 1902 0.922 McClendon and Takeo Hokkaido, etc., Imai, 1933 Japan Read and How, 1927 China 0.679 Hokkaido, Japan Oshima, 1902 McClendon and Takeo Japan Imai, 1933 1.063 Hokkaido, Japan Oshima, 1902 Alaid, Kurile Is. McClendon and Takeo Imai, 1933 Sokobetsu, Japan Hokkaido, Japan —

Okhotsk Sea

—

Brittany, France

Vincent, 1924

—

Kristineberg, Sweden Brittany, France

Kylin, 1929

—

Vincent, 1924 Sarphati, 1834 McClendon and Takeo Imai, 1933 Stanford, 1877 Varaksin, 1924

"""

0.002

—

—

0.120 —

0.287

Murman Coast

—

—

0.478

—

0.187 —

Chiba, Yamaguchi, Japan

0.531 Chiba, Yamagu- Oshima, 1902

0.06

0.209 0.40

1.5

— —

0.027!

—

0.03

Matsu Bay (Japan)

Oshima, 1902 Okuda and Eto, 1916

chi, Japan

0.89

Sydney Heads, Australia New South Wales Seto Mar. Biol. Sta., Japan

Okuda and Eto, 1916 Doherty, 1918 White, 1907 McClendon and Takeo Imai, 1933

California, U.S.A. Burd, 1915

Chemical Composition of Marine Organisms

79

living matter

•/• ofdry matter

r»

3 3

— —

0.03 0.09

— —

California, U.S.A. Burd, 1915 „ Turrentine, 1912

fimbriatum j%

8 2

— —

0.151 0.09

— —

0.097

—

Nanaimo, Canada Cameron, 1914 Puget Sound, Turrentine, 1912 U.S.A. Halifax, Canada Butler, 1931

ALGAE Laminariaceae Egregia

No. of determinations

menziesii

Agarum

turneri Costaria turneri

—

ash

Author

Locality

2

— —

trace 0.029

— —

California, U.S.A. Turrentine, 1912 Nanaimo, Canada Cameron, 1915

29

—

0.27

—

— — — —

—

0.13 0.18 0.20

0.66 —

r>

4 18 18 23

Puget Sound, Turrentine, 1912 U.S.A. — Balch, 1909 California, U.S.A. Burd, 1915

r»

4

—

0.22

—

6

—

0.14

—

— — — —

— 0.07 0.1 0.22

0.26 -

T»

3 13 13 16

Pelagophycus porra

5

—

0.36

—

5

— — —

— — 0.26

0.233

1.132

—

Hokkaido, Japan

—

0.14

—

California, U.S.A. Turrentine, 1912

w

Macrocystis pyrifera w

„

(stem) (lamina)

Nereocystis luetkeana r>

„ *

(stem) (lamina)

(stem) (lamina)

91

Arthrothamnus tifidta

Postelsia palmaeforms Dictyoneurum californicum Pleurophycus gardneri

3

— 2

—

—

'

—

»

T>

fl

fl

Freshwater Bay, Parker and Lindemuth, Calif., U.S.A. 1913 Nanaimo, Canada Cameron, 1915 Puget Sound, Turrentine, 1912 U.S.A. California, U.S.A. Balch, 1909 „ „ Burd, 1915 n

r>

w

w

Freshwater Bay, Parker and Lindemuth, Calif., U.S.A. 1913

Puget Sound, Turrentine, 1912 U.S.A. 0.555 „ Balch, 1909 0.85 — California, U.S.A. Burd, 1915 Oshima, 1902

0.09

w

»

»

»

0.12

t»

»

»

w

5 Percent of salt solution. (continued next page)

Memoir Sears Foundation for Marine Research

8o AT_A1? ALGAE

Laminariaceae Cymathere triplicate! Alaria lanceolata

No.of determinations

esculenta

dry matter

ash

2

—

0.03

—

2

— — —

trace 0.06 0.101

— — —

2

—

0.059

—

— — —

trace 0.08 0.0435

— — —

— —

0.045 0.027

— —

— — — — —

0.001 — 0.02971 — — 0.18 — 0.225 — 0.269

— — —

0.1 0.008 0.112

— —

— 0.02

—

0.011

fistulosa

valida macroftera dolichorachis tenuifolia

living matter

2

Locality

Author

California, U.S.A. Turrentine, 1912 r>

r>

Alaska Halifax, N. S., Canada Barents and White seas Nanaimo, Canada Alaska Cape Atoiya, Japan Toshirari, Japan Nanaimo, Canada

99

99

99

99

Butler, 1931

BruIevich,Trofimov and Hartmann, 1933 Cameron, 1915 Turrentine, 1912 McClendon and Takeo Imai, 1933 99

99

99

Cameron, 1915

99

Fucaceae Fucus vesiculosus 99 99 99

*

99 99 99 99

r> r>

2

— —

Scotland 99

West Coast, Scotland — Roscoff, France 0.028 Brittany, France 0.74 Normandy, France North Sea 1.4 Schleswig— Holstein Baltic Sea —

— — 1.05 0.0405 0.2023 Helgoland — (old lamina) 0.0027 — — Kristineberg, Sweden 0.003 0.003 — 0.015 0.12P Baltic Sea (Sweden) 0.031 — 0.0113 — White Sea 2 — 0.026 2

Sarphati, 1834 Stanford, 1877 Anderson, 1855 Hendrick, 1916 G6dechens, 1845 Oswald, 1911 Vincent, 1924 Marchand, 1865 Fagerstr6m, 1823 Eschle, 1897 Beckmann and Bark, 1916 Vibrans, 1873 Albert and Krause, 1919 Kylin, 1929

Weibull, 1917 Marsson, 1851 Itallie, 1889 BruIevich,Trofimov and Hartmann, 1933

Chemical Composition of Marine Organisms ALGAE

Fucaceae Fucus vesiculosus

No. of determinations

living matter

0.003

serratus

dry matter

— 0.058 0.154

furcatus 9»

evanescens

(macrocephalus) sp.

inflatus Ascofhyllum nod osum

Locality

— 0.055 Murman Coast 0.0127 — New Brunswick, Canada — 0.109" — — 0.741« Okhotsk Sea(?) 0.124 — — 0.177 0.99 West Coast, Scotland 0.0565 — — 0.0865f

sfiralis

ash

—

0.213 Scotland 0.224 0.88 Normandy,

France Kristineberg, 2 0.0075 Sweden Brittany, France 0.043 — 0.01 0.1026 0.5083 Helgoland 2 — — 0.56 Baltic Sea 0.06 — Oneghski Gulf, White Sea — 0.796* Okhotsk Sea (?) — 0.2 P Baltic Sea (Sweden) Kristineberg, 0.002 — — Sweden California, U.S.A. — trace — Nanaimo, Canada 0.023 — 6 Puget Sound, 4 0.05 — U.S.A. Nanaimo, Canada 0.017 8 — Alaska trace — Porbundar 0.0271 (Indian O.) Barents Sea — 0.031 — _ —

_ 0.36 0.0396 — 0.05721 — 0.074 0.41

Scotland — West Coast, Scotland

81

Author

Varaksin, 1924 Butler, 1931 Schweitzer, 1845 Ossendovski, 1906 Sarphati, 1834 G6dechens, 1845 Wallace (see Wolff, 1871-1880) Stanford, 1877 Hendrick, 1916 Schweitzer, 1845 Marchand, 1865 Kylin, 1929 Vincent, 1924 Albert and Krause, 1919 Vibrans, 1873 Bruievich,Trofimov and Hartmann, 1933 Ossendovski, 1906 Weibull, 1917 Kylin, 1929 Turrentine, 1912 Cameron, 1914 Turrentine, 1912 Cameron, 1915 Turrentine, 1912 Dixit, 1930 Bruievich,Trofimov and Hartmann, 1933 Anderson, 1855 Wallace (see Wolff, 1871-1880) Stanford, 1877 G6dechens, 1845 (continued next page)

82

Memoir Sears Foundation for Marine Research

ALGAE

No. of determinations

living matter

Fucaceae Ascophyllum nodo sum

_ 0.022 2 0.011 — 2

Himanthalia lorea 2 2

Halidrys siliquosa

Cystophyllum geminatum Turbinaria fusiform* Pelvetia canaliculata Cystoseira barbata discors fibrosa siliquosa Sargassum linifolium siliquastrum enerve horneri

_ 0.004 _

_ — _ _

' •/• ofdry matter

ash

Locality

Author

_

0.415

Hendrick, 1916

0.084 —

— —

0.062

—

West Coast, Scotland Brittany, France Kristineberg, Sweden Norway

0.1984 0.7934 Helgoland — 0.056 Murman Coast 0.1362 — Halifax, N. S., Canada 0.089 — — 0.0087 — — 0.001 0.004 Helgoland _ 0.03 ?

_

_

0.08

—

0.075

0.65

0.021 0.086 0.0083 —

— —

Stanford, 1877 Allary, 1881 Albert and Krause, 1919 Malchevski, 1915 Weibull, 1917

— —

0.264 1.030 0.2131 —

—

0.25

—

Alaska

Turrentine, 1912

—

0.06

—

Enoshima, Japan

Okuda and Eto, 1916

0.021

—

Brittany, France

Vincent, 1924

—

0.0077 0.0478 Crimean Coast, Black Sea 2 — — 0.027 Bay of Naples 0.0027 0.011 — Brittany, France _ 0.142 — —

2

Beckmann and Bark, 1916 Albert and Krause, 1919 Varaksin, 1924 Butler, 1931

Baltic Sea (Sweden) Normandy, France Brittany, France Kristineberg, Sweden Helgoland ?

0.004

2

Vincent, 1924 Kylin, 1929

— _ — —

— 0.339 0.126 0.081

0.072 — — —

Marchand, 1866 Vincent, 1924 Kylin, 1929 Albert and Krause, 1919 Stanford, 1877

Shkatelov, 1917 Scurti, 1906 Vincent, 1924 Sarphati, 1834

Bay of Naples Scurti, 1906 China Read and How, 1927 Kanazawa, Japan Okuda and Eto, 1916 Misaki, Japan

Chemical Composition of Marine Organisms • °/o ofary matter

. .™- 01 determinations

uvm

6

—

0.130

—

ringgoldtanum tosaense

2 2

— —

0.120 0.0175

— —

patens aquifolium micracanthum tortile thunbergit confusum

4 2

— — — — ——-

0.021 0.0039 0.0035 0.034 0.041 0.0095

— — — — — —

piluKferum

2

—-

0.0113

—

sp.

7 3

-

0.058 0.038f

— —

0.054 0.029

— —

ALGAE

Fucaceae Sargassum serratifolium

4 5

e matter

99 99

Dictyotaceae Padina arborescens pavonia Haliseris undulata Zonaria diesingiana Dictyota dichotoma Sphacelariaceae Sphacelaria bipinnata Encoeliaceae Scytosiphon lomentarius Colpomenia sinuosa

sp.

ash

2

—

0.0025

—

2

—

0.003

—

—

0.007

— —

83

Locality

Author

Misaki, Japan

McClendon and Takeo Imai, 1933

n

»

Seto Mar. Biol. Sta., Japan

w

w

w

r>

w

w

99

99

99

w

w

w

99

99

w

n

11

11

r>

r>

r>

n

n

i) 11

»

r>

r>

11

n

w

r>

w

n

n

n

w

n

11

11

11

11

n

n

11

Matsu Bay (Japan) Seto Mar. Biol. Sta., Japan Japan Bombay, Okha (Indian Ocean) — —

Seto Mar. Biol. Sta., Japan

Dixit, 1930 Smith, 1904 91

99

McClendon and Takeo Imai, 1933

r>

r>

w

99

99

99

—

r>

r>

r>

99

99

99

0.021

—

r>

n

r>

99

99

99

0.0043

—

99

99

99

—

—

Kristineberg, Sweden

—

0.014

—

Nanaimo, Canada Cameron, 1915

—

0.006

—

—

0.006

—

Matsu Bay (Japan)

0.1

Matsu Bay (Japan)

r>

w

Kylin, 1929

McClendon and Takeo Imai, 1933 99

99

99

(continued next page)

84

Memoir Sears Foundation for Marine Research

ALGAE

No. of determinations

living matter

• •/• of' dry matter

—

0.0046

Dictyosiphonaceae Dictyosiphon Kppuroides

0.063

—

Desmarestiaceae Desmarestia acuteata

0,12

Encoeliaceae Punctaria latiftolia

2

viridis

-

Mesogloiaceae Mesogloia vermiculata Chordaria flagelliformis

—

Matsu Bay (Japan)

McClendon and Takeo Imai, 1933

—

Kristineberg, Sweden

Kylin, 1929

Kristineberg, Sweden Barents and White seas Kristineberg, Sweden Nanaimo, Cai

Kylin, 1929 BruievichjTrofimov and Hartmann, 1933 Kylin, 1929

0.463

—

0.0076

—

—

—

0.026

—

—

0.058

0.09

—

Puget Sound, U.S.A.

0.012

—

—

Kristineberg, Sweden

Kylin, 1929

0.0011

—

—

Kristineberg, Sweden

Kylin, 1929

—

Spermatochnaceae Stilophora rhizoides

Author

—

—

tigulata herbacea

Locality

ash

— 0.05

0.019

0.281 1 —

Cameron, 1915 Cameron, 1914 Cameron, 1915 Turrentine, 1912

0.023 0.0027

— —

Canada (Pacii Matsu Bay (Japan)

Stanford, 1877 Kylin, 1929 Cameron, 1915 McClendon and Takeo Imai, 1933

—

0.011

—

Canada (Pacific)

Cameron, 1915

Ectocarpaceae Pylaiella littoralts

0.0036

—

—

West Coast, Sweden

Kylin, 1929

Ectocarpus tomentosus

0.019

—

—

— —

firma

Corynophlaeaceae Leat hesia difformis

3

r>

Chemical Composition of Marine Organisms

85

TABLE 43 IODINE IN PHAEOPHYCEAE (RECENT DATA)

ALGAE Laminaria digitata digitata f. complanata (lamina) digitata f. complanata (stem) digitata f. complanata (lamina)a digitata f. complanata (stem)a saccharina saccharina f. butbata (lamina) . saccharina f. butbata (stem) . sp sp. (lamina) P sp. (stem)P religiosa japonica w

japonica (lower part of lamina) japonica (middle part of lamina) japonica (top part of lamina) bull at a (young) bullata (old) bondardina Desmarestia plicata Sargassum fusiforme

w

.

.

.

.

.

thunbergii*

siliquastrum hemiphyllorum horneri pallidum a Three determinations. * Together with Sphacelaria suifosa.

.

dry matter

0.24 — — 0.798 0.643 0.20 — — 0.25 0.307 0.427 0.024(?)

f

s

Locality

0.87 0.97 0.91

White Sea

—

0.63 L03 0.94 — — — —

0.58 0.235

— —

0.415 0.194 0.202 0.44 0.50 0.28f

— —

—

0.52

0.0321 0.031 0.079 0.1074 0.110 0.053 0.0384 0.022

— — — —

0.0223 0.094 0.039 0.0268

Author

ash

— — — —

— — — — — — — —

w

w

w

w

Vedrinsky, 1938-a Muraviev, 1935

Gulf of Kola W

W

W

White Sea w

w

w

w

Hokkaido, Japan Gulf of Kola »

w

w

w

w

»

w

w

w

w

Trofimov, 1938 Vedrinsky, 1938-a Muraviev, 1935

Nagata, 1936 Trofimov, 1938

w

Adolph and Whang, 1932 Primorie, U.S.S.R. Gail, 1930 Basargin, Kiesewetter, 1936-b Cape Primorie China Sea

w

w

w

w

w

w

w

w

w

w

w

n

w

w

w

w

w

w

JJ

W

White Sea

Vedrinsky, 1938-a Muraviev, 1935

China Sea w

w

w

w

w

w

w

w

w

w

w

w

Tsingtao, China Sea China Sea w w

w

Tsingtao, China Sea

Tang and Whang, 1935 Tang and Chang, 1935 Tang and Whang, 1935 Tang and Chang, 1935 W

W

W

W

Tang and Whang, 1935 Tang and Chang, 1935 Tang, Kou and Tang,

1936 Tang and Chang, 1935 w

»

w

w

w

w

w

»

Tang, Kou and Tang, 1936

p Eight determinations, •f Maximum. (continued next page)

86

Memoir Sears Foundation for Marine Research dry matter

ALGAE Sargassum

so

*

Endarachne binghanida Eckloma cava INereocarpus dl'VQTlCQtUS

.

ash

0.0462

—

0.0046

—

0.38

—

0.005

—

Locality

Author

Tsinetao, China Sea China Sea

Tang, Kou and Tang, 1936 Tang and Chang, 1935

r>

r>

Tsingtao, China Sea

Masuda, 1933 Tang, Kou and Tang,

1936

porra, Nereocystis luetkeana, Lessonia, Dictyoneurum californicum and Postehia palmaeformis; the amount of iodine which they contain varies, however, according to American investigators (see Table 44). Also, compared to the amount of iodine in Laminaria and the Lessonioideae, the amount in other genera of Laminariaceae is somewhat smaller, although in individual cases some species prove to be especially rich. (Within a certain genus or among several genera which are relatively rich in an element, some species are found which contain a large amount of the element. We will say more about this later.) The third place is occupied by the genera Ecklonia, Agarum and Alaria, in which iodine fluctuates from 0.03 to 0.2 °/0 of the dry matter, which is several times less than in Laminaria, although in general they all contain a considerable amount of iodine. For other genera and species of Laminariaceae a relatively high iodine content is no less characteristic, as in Egregia^ Arthrothamnus and Pleurophycus; however, analyses of these are not sufficiently numerous to enable one to draw conclusions. Another family, the Fucaceae, which is better represented by analyses, contains on the average five to ten times less iodine than the above-mentioned species of Laminaria. Among Fucaceae which are relatively rich in iodine we find the genera Fucuf1 and Cystophyllum.

TABLE 44 VARIATIONS IN IODINE IN GIANT SEAWEEDS (IN °/o OF DRY MATTER)

ALGAE

No. of determinations

Macrocystis pyrifera Nereocystis luetkeana

29

23 72

49

16

Min.

Max.

Av.

0.15

0.41

0.27

0.14 0.10

0.01

0.13

Author

Turrentine, 1912 Parker and Lindemuth, 1913 Burd,* 1915 0.30 0.17 Cameron,* 1915 0.30 0.215 Parker and Lindemuth, 1913

0.27 0.20 0.41 0.17

* Determinations of various parts of the algae. 67. Fucus furcatus and F. spiralis usually are poorest in iodine.

Chemical Composition of Marine Organisms

87

For other families of Phaeophyceae the data are isolated. Desmarestia aculeata is richer than other species of the family Desmarestiaceae; from the other families, Chorda filum and Dictyosiphon hippuroides are richest. In regard to the Fucaceae, it has been observed that species from different localities have approximately the same iodine content; for example, for Fucus vesiculosus it is about o. i °/0 of the dry matter, for F. serratus o. i %, for Cystoseira about o. i %, and for others somewhat less. Fluctuations in iodine content were noted as being greater for species of Fucaceae than for Laminaria of different localities, which may be the result of differences in time of collection and of the depths from which they were taken.8"

TABLE 45 IODINE IN ALGAE IN RELATION TO VERTICAL DISTRIBUTION IN THE SEA (IN «/0 OF DRY MATTER)* Depth Arctic Ocean (m) Barents Sea

0 "I Rhodymenia palmata (R)f

£ Fucus vesiculosus 2 Ascophyllum nodosum k 5 Fucus serratus Gloria esculenta Laminaria saccharina 10 > Laminaria digitata "5 Delesseria sinuosa (R) | Ptilota plumosa (R)

I

0.001 0.02 0.03 0.06 0.05 0.3 0.3 0.05 0.4

Atlantic Ocean Scotland, France

I

Fucus vesiculosus Fucus siliquosus Ascophyllum nodosum Himanthalia I orea Laminaria saccharina Laminaria flexicaulis Saccorhiza bulbosa

0.02 0.02 0.08 0.01 0.40 0.3 0.1

Pacific Ocean California

I

Enteromorpha linxa (C) Fucus evanescens Gigartina mammillosa (R) Polysiphonia sp. (R) Alaria valida Laminaria bullata Laminaria saccharina Costaria costat a Nereocystis luetkeana

0.02 0.05 0.02 0.01 0.08 0.4 0.3 0.03 0.2

* Average data are given for some typical algae. f (R) = Rhodophyceae, (C) = Chlorophyceae; others are Phaeophyceae.

In general, Phaeophyceae collected near the shore and at relatively shallow depths contain less iodine than those taken from the open sea, as in the case of Fucaceae, which, as a rule, are found in the tidal zone near the shore. As a rule, the greater the depth of habitat of the Phaeophyceae the higher their iodine content (see Table 45 where the depths at which the species usually live are given together with the iodine content of the listed species). To check this observation we have taken a cross section of the algae of these coasts at different latitudes, and in all cases this rule is valid for the Phaeophyceae (see Table 46). The iodine level is typical for individual species, characterizing at the same time species living under the same conditions. Thus, in the same species of Phaeophyceae, the further out they are in the sea the greater the iodine content. Apparently latitude also affects the iodine content of a species. The typical Sargassum and Cystoseira among others from tropical seas are the richest in iodine of the Phaeophyceae, yet these differ little in iodine content from the 8 H. Weber and Gerhard (1938) indicate that Fucus vesiculosus, serratus, platyearpus, and mytili from the North Sea are higher in iodine than Baltic plants, which contain only 0.033 °/o dry.

88

Memoir Sears Foundation for Marine Research

usual northern Fucus. Along the coasts of Japan or the fjords of Scandinavia, for example, the distribution of algae is associated with numerous variations in condition of habitat; that is, every species is adjusted to a certain temperature, salinity, and so forth, and it is very probable that the intensity of iodine accumulation is relative to these conditions. But unfortunately there are no data. A general rule, formulated by many investigators, is that more saline seas and arctic zones favor the accumulation of iodine in algae (see Pellieux and Allary, 1880), as for example in Laminaria, which are richest in iodine but which do not extend further south than 30° N. However, Turrentine (1912) and Parker and Lindemuth (1913) did not find any striking differences in the

TABLE 46 IODINE IN ALGAE (PHAEOPHYCEAE AND RHODOPHYCEAE) FROM NEAR THE SHORE AND FROM THE OPEN SEA (IN °/0 OF DRY MATTER)

ALGAE

Near the shore

I

Open sea

I

Laminari a japonica

Vladivostok, Okhotsk Sea Sebastopol, Black Sea Kristineberg, Sweden

approx. 0.2 approx. 0.10 0.13

Tartar Strait

approx. 0.3 approx.

Phyllophora rubens .

,

.

,

,

,

Trailtiella intricata .

,

.

.

,

,

Black Sea West Coast of Sweden

0.3 0.53

iodine content of giant algae along the California Coast from the southern islands to Alaska, while Cameron (1915) indicates that the more southern Macrocystis has twice the iodine content of Nereocystis, a more northern species. Among the algae of the warm seas there are no representatives similar to the Laminariaceae in the amount of iodine concentration. Species of the temperate zones of both the northern and southern hemispheres contain similar amounts of iodine. Hooker (1847) found that Lessonia nigrescens from the southern tip of South America (Cape Horn) is less rich in iodine than the algae of the northern hemisphere. Species living in freshened seas of temperate or arctic regions contain somewhat less iodine, as for example Fucus vesiculosus from the North and Baltic seas (see Krtiger [1821], Sundvik [1903—I9O4]).68 The iodine content of brown algae (forming the chief mass of varech) of the French Coast (Brittany and Normandy) is on the whole highest. Then come the brown algae of Scotland and Ireland, of the Scandinavian shores and Murman, and also of the Atlantic Coast of America. The iodine of algae from the Okhotsk Sea69 and the Japanese islands is similar to that of the algae of Scotland. Brown algae of the Pacific Coast are, on the whole, less rich in iodine, and the Phaeophyceae of the Algerian Coast of the Mediterranean are the poorest. 68. A verification of this is needed since these data are qualitative. 69. On the iodine of algae from the seas of the U.S.S. R., see also Ivanov (1927), Zinova (1928), Marzinovski, Niesenmann, and Magidson.

Chemical Composition of Marine Organisms

89

Freundler, Menager, Laurent and Lelievre (1925-!)) tried to explain in physiological terms the concentration of iodine in deepwater forms as an assimilatory process compensating for an insufficiency of light (see Table 47). But rather than discuss in detail the significance of iodine in the development of algae, we will note the peculiarities in the distribution of iodine, since these peculiarities are intimately connected with the biology of every species. As in the case of other elements, the iodine content of Phaeophyceae and other algae changes during the year. Hollard (1926) found a maximum for Laminaria flexicaulis (coast of France) in August and September. In the Norwegian algae, Wille (1899) found that the maximum occurred in July (see Table 48). According to Averkiev (i 926), the maximum in Phyllophora rubens from the Black Sea occurs during the May to August period. According to Trofimov (i938-a) the iodine in Laminaria saccharina of the Gulf of Kola varies as follows (in °/0 of dry matter): January February March April

. . . .

. . . .

. . . .

. . . .

0.350 0.365 0.280 0.270

June70 July August December

. , . .

. , .

. . . .

0 225 0.260 0.315 0.412

The maximum in iodine, ash, and chlorine occurs in January to April, the minimum in June to July. The maximum spore-bearing is in July to August. Usui, Sukegawa and Matumoto (i 936) observed changes in the amount of iodine in two algae of the Japanese Sea, namely Turbinaria fusiformis and Ecklonia bicyclis. In Turbinaria the maximum iodine content occurs in February-March, coinciding with a maximum in spore production. In Ecklonia, the iodine curve is different, March to April being the months of minimum iodine content, December to January the maximum. Vedrinsky (i938-b) observed the following seasonal changes in the iodine of Laminaria from the White Sea (in °/0 of dry matter): L. saccharina

. 0.93

January February April . May . Tune .

L. digitata

. .

. .

. -

. 0.23 . 0.20

068 0.67

0.42 0.27

L. saccharina JJuly **V

. .

August September October . November December

0.19 0.17 0.19 0.30 0.78 0.80

L. digitata

0.26 0.18 0.20 0.30 0.75 0.78

In Laminaria of the Pacific shores, the maximum iodine occurs during the period of ripening of the zoospores, or somewhat earlier. Gail (1930) found for the same algae a second iodine maximum in the early spring. Thus the amount of iodine in different algae during the year depends not only on the time of arrival of spring in the sea (see Okuda and Eto, 1916) but also on the species 70. January to June in the year 1932; the remaining months are in 1931.

Memoir Sears Foundation for Marine Research

go

TABLE 47 IODINE IN ANNUAL AND PERENNIAL ALGAE (IN °/0 OF DRY MATTER)

Annual Saccorhiza bulbosa , Saccorhiza bulbosa (stem) . Himanthalia I orea . . , Perennial Laminaria cloustonii (leaf)

, . .

Perennial Laminaria cloustonii (stem) Lamnaria flexicaulis (leaf) Laminaria flexicaulis (stem) Lamnaria saccharina (leaf)

0.07 0.08 0.02 0.88

0.68 0.64 0.39 0.30

of algae concerned (see Kemp, 1862) ; furthermore, it depends on the time of maximum growth when spore formation and reproduction take place. However, the variations in iodine in algae during the year are still not clearly known. In so far as variations within individual specimens are concerned, Sarphati (i 834), Anderson (1855), Allary (1881), Wille (1899), and Struve noted a larger amount of TABLE 48 IODINE IN PHAEOPHYCEAE DURING THE YEAR (IN °/0 OF DRY MATTER)

ALGAE

Remarks

Laminaria bull at a (young) saccharina — v> — V) flexicaulis cloustonii lejolisii Fucus furcatus evanescens Nereocystis luetkeana

» Cystoseira discors * Sargassum linifolium* Ecklonia cava 9»

bicyclis

I— III

IV

V

0.605

—

—

— —

— — —

0.738 0.455 0.546

— — —

— —

—

— —

— —

(leaf) (stem)

—

—

—

— —

—

—

— —

, Months • VII VI

0.27 0.206 0.078 — — 0.712 — — —

VIII

0.06

0.156 0.176

IX—XII Author

—

—

0.826 0.782 — 0.571 0.502 — 0.568 0.756 — — —

0.015 0.016

—

—

0.272 0.250 0.305 0.133

— —

0.079 0.065

— —

—

—

0.0064 —

—

0.0068 —

—

—

0.0054 —

0.0029 —

—

9»

9!

0.760 0.468 Freundler and Menager,

0.042 0.028

—

Cameron, 1915

—

1922

9»

9»

9>

9»

9»

9>

9)

9)

9>

Cameron, 1915 9>

9)

9>

n

9>

9)

Scurti, 1906 9>

9>

0.255 0.216 0.142 0.267 Jap. Bur. of Fisheries (H. M. Smith, 1904) (old leaf) 0.101 0.114 0.076 0.294 0.294 0.142 0.592 n 9> 9> 9> 0.178 — 0.202 0.348 0.155 Okuda and Eto, 1916 — — (old stem) 0.118 0.118 0.147

* Bay of Naples.

Chemical Composition of Marine Organisms

91

TABLE 49 IODINE IN DIFFERENT PARTS OF PHAEOPHYCEAE (IN °/0 OF DRY MATTER) ALGAE

Laminaria digitata ..

. . . . . . . Laminaria lejolisii .

Laminaria saccharina na

.

. . . . . . .

.

. . . . . . .

.

.

. . . . . . .

.

Lamina

Stem

Author

0.2946

0.4535 0.209 0.113 0.59 0.084 0.492 0.0765 0.416 0.56 0.46 0.301 0.58 0.57 0.6603 0.248

Stanford, 1877 Anderson, 1855 Tunmann, 1907 Eschle, 1897 Hendrick, 1916 Lunde and Closs, 1930 Albert and Krause, 1919 Brulevich, Trofimov, and Hartmann, 1933 Albert and Krause, 1919

0.137 0.084 0.19 0.094 0.36 0.051 0.452 0.76 0.56

. . . 0.446 Laminariaflexicaulis is** . . . 0.74 Laminaria cloustonii/' . . . 0.755 Laminaria hyperborea •ta . . . 0.7346 Nereocystis luetkeanaa . . . 0.2550 r»

r»

n

19

r>

»

BruTevich, Trofimov, and Hartmann, 1933 Albert and Krause, 1919 Freundler and Manager, 1922 Albert and Krause, 1919 Cameron, 1915

* Seven analyses.

iodine in the leaf than in the stem of Laminaria?* This was noted in other algae also, but it was especially evident in the Laminaria^ which are more highly differentiated morphologically. Kylin (1929) found just the opposite to be the case in fresh Laminaria (see also Michaelis, 1878). Vedrinsky (i938-b) also determined the amount of iodine in different parts of algae (in °/0 of dry matter) : Stem Growth cone Lamina

L. saccharina

L. digitata

0.26 0.37 0.18

. 0.256 . 0.38 - 0.144

Differences in iodine concentration are not observed (see Balch [1909], Parker and Lindemuth [1913], Burd [1915], and others) between the lamina and the stem of giant algae. The same is true of Fucaceae (see Kylin, 1929). Kylin's data show that the growth area of Laminaria is richest in iodine. The age of the algae also influences the iodine content, the younger specimens containing more of the element. Some data indicating the reverse of this are known, but these may be erroneous because of a neglect to take into account the season in which the collecting occurred. The question of the form in which iodine occurs in algae is still not settled. The loss of iodine when algae are kept a long time was noted by those working in the 9H. Rinck and Brouardel (1949) found that adjacent strips of 5 cm1 area of the same leaf may differ by 25°/ 0 in their iodine content.

g2

Memoir Sears Foundation for Marine Research TABLE 50 IODINE IN YOUNG AND OLD PHAEOPHYCEAE (IN °/0 OF DRY MATTER)

ALGAE

Laminar ia digitata . Laminaria saccharina Ecklonia cava * In May.

Young

- 0.122 - 0.652* . 0.084

Old

Author

0.057 0.451f 0.076§

Allary, 1881 Freundler and Manager, 1922 Jap. Bur. of Fisheries (see H. M. Smith, 1904)

f Without spores.

§ Spore-bearing.

seaweed industry (see Thiercelen [1880], Pellieux and Allary [1880]); such a loss occurs when the plants are left lying on the beach, since the iodine is partly washed away by rainwater. From Laminaria, iodine is removed almost entirely (90%) by the first washing, since they normally live under water, but from Ascophyllum, which is out of water part of the time, during low tide, iodine is washed out with great difficulty (75°/o after seven days). Dorvault in 18 50 suggested that the iodine in algae occurs in the form of salts of HI, chiefly KI, and this opinion was shared by many others, such as Pellieux and Allary (1880), Itallie (1889), Oswald (1911), Segers-Laureys (1913), Kylin (1929), and Kay (1929). According to them, the iodine is found in some inorganic form and is water-soluble. Freundler (1924^) suggested that iodine is bound with rubidium and he gave some good reasons for his viewpoint.10" Eschle (1897) showed the presence of organic compounds of iodine in algae. Okuda and Eto (1916) investigated Ecklonia and showed that most of the iodine is bound in an organic complex; in Ecklonia TABLE 51 EXTRACTION OF IODINE FROM ALGAE WITH WATER (IN °/§) Washing time n

3 6 12 24 2 3 4 5 6 7

hours hours hours hours days days days days days days

Laminaria digitata

(0.528 \ 0.057 0.020 0.021 0.023 0.020 0.023 0.021 0.022 0.020 0.019 0.021

IOH. However, this view is probably quite inacceptable.

Ascophyllum nodosum

0.060 0.051 0.040 0.032 0.025 0.024 0.019 0.019 0.018 0.017 0.016 0.013

Chemical Composition of Marine Organisms

93

bicyclis there was from 50 to 8o°/0 bound organic iodine (see also Weis, 1903, on Fucus vesiculosus). The majority of modern investigators assume the presence of iodine in both forms, the ratio of inorganic to organic iodine varying according to species; and they believe also that iodine is able to change from one form into the other (see Okuda and Eto [1916], Fellenberg [1924], Lelievre and Manager [1924], Freundler, et al. [1925^], Kylin [1929], Lunde and Closs [1930], Closs [1931]). Trofimov (1933) found more than 6o°/0 mineral iodine in Laminaria saccharina and L. digitata of the Kola peninsula, and he also observed the formation of free iodine in these algae. Both forms of iodine compound dissolve easily in water and other media. In different parts of Laminaria digitata Lunde and Closs (1930) found the following amounts of different forms of iodine in percent of the total iodine. Water-soluble

Stem Leaf Rhizoids

89.2 89.9 58.1

Water- and alcohol-soluble

96.4 93.0 61.5

Iodide

89.4 (36.0) 49.2

Bound with calcium compound

Bound with alginic acid

Residue

(0.5) 1.1 4.4

(3.3) 2.2 7.0

(2.1) 3.7 27.1

According to Okuda and Eto (1916), who got similar results for Eckknia bicyclis, the iodo-organic compound is not a protein. However, Toryu (1933) considers that the alcohol-insoluble iodine in algae is bound with protein; in Laminaria ochotensis, in which the total iodine is o.345°/o> he found the following (in °/o of total iodine): alcohol-soluble iodine 94.26 alcohol-insoluble and nonprotein iodine 1.02

alcohol-insoluble iodine protein iodine

,

,

. , 5.735 4.714

Furthermore, Toryu (1933) considers that the protein iodine occurs in the form of di-iodotyrosin, but he was unable to isolate this compound.1111 Tsukamoto and Furukawa (see Okuda and Eto, 1916), suppose that iodine is bound with unsaturated acids, but it has also been suggested that iodine is bound with carbohydrates in algae. Golenkin (1895) anc^ Robertson (1897) demonstrated the loss of elementary iodine from Bonnemaisonia asparagoides and other red algae, the phenomenon being discovered with starch paper. Soon, more investigators, such as Sauvageau (1925) and Mangenot (1928), confirmed these observations, chiefly by work with algae from the French coasts. Dangeard (1928) also did a number of experiments which showed that living algae could give off elementary iodine; according to him, iodine in the form of iodide was found in special epithelial cells71 (in the so-called vacuole iodique] from which iodide could be lost by volatilization as elementary iodine. He also showed in numerous qualitative determinations that the loss of iodine occurs more noticeably in I I H . Roche and Lafon (1949^) found di-iodotyrosin in Laminaria ftexieaulis and L. saccharina. 71. See Tunmann (1907).

94

Memoir Sears Foundation for Marine Research

Laminariaceae and Rhodophyceae, i. e., from algae rich in iodine.72 However, Dangeard's (1928) views were not accepted by other investigators, including Kylin (1929), Chemin (i928-a, 1928-!)), Chemin and Legendre (1926), Lunde and Closs (1930), who repeated his experiments but did not obtain the same results. Chemin (i928-a, 1928-b) and others suggested that the formation of free iodine is connected with a change in oxidation potential within the algae, especially when they are cut. Since Gertz' (1926) discovery of iodo-oxidase (a substance in algae which splits iodine from the salts of HI), investigators such as Kylin (1929) and Dillon (1929) have considered the possibility of the participation of oxidizing substances in the liberation of iodine. Lunde and Closs (1930) suggested that the liberation of iodine occurs without the participation of enzymes, and that O2 and O373 may be the oxidizing agents. Suneson (1932), who worked with algae from the coast of Sweden, repeated the experiments on algae from French shores; his results showed that the algae of the French coast lose iodine and that the other ialgae lose little or none. Like Kylin (1929), we are inclined to regard the difference in the behavior of the algae as caused by differences in habitat. For example, the algae of the French shores, richer in iodine than the others, live under conditions of greater tidal changes; thus their cellular tissues are more permeable, which in turn facilitates the liberation of iodo-oxidase. Kylin (1929) distinguished three groups of algae according to the way in which iodine is bound and according to the ease with which it is removed. The first group consists of algae containing iodine in the form of iodide, which is easily extracted but with an unknown compound in the vesicular cells; the majority of Rhodophyceae (Bonnemaisonia, Trailliella, and Falkenbergia) fall in this group. The second group, which includes Laminaria, contains iodides almost exclusively. Finally, according to Kylin (1929), the third group (Sphacelaria) contains iodo-organic compounds. Thus iodine occurs in different compounds in algae, and the character of the compounds of various species differs even when there is an equal amount of iodine present, as in Laminaria and Sphacelaria^ 15. Iodine in Rhodophyceae The qualitative determination of iodine in red algae (easily detected with histochemical methods; see Dangeard on Nitophyllum and SoKeria1^) was begun as early as 1814 in the same period in which iodine was discovered in brown algae and others (see Davy [1814], Bley [1832], Herzog, Grosse, Winkler, Wanneberg, Kreyssig, and Riegel [i 853] ; see also Pasquier [i 843] and Itallie [i 889] on Rhodymenia palmata). But 72. Lelievre and Menager (1924) did not find volatile compounds of iodine. Deniges and Chelle extracted iodine from algae directly with organic solvents. 73. See Lami (1930) and Kay (1929). 12 H. Roche and Lafon (1949^) found i.55°/ 0 of the protein of Laminaria JUxicaulis and L. saccharina to be diiodotyrosin. Masuda (1935) has apparently found tri-iodo-acetaldehyde in seaweeds. 74. See Dangeard also for lists of algae qualitatively examined for iodine. For investigations of free iodine, see Chemin and Legendre (1926), Sauvageau (1926-!), 1927), and Kylin (1929).

Chemical Composition of Marine Organisms

95

quantitatively the iodine in red algae has been studied less than that in the brown ones. This is understandable, since they are small and live at greater depths than the brown algae and were therefore »not a source of the element for industry. However, during the last few years such species as Nitophyllum rupestris and N. violaceum have been studied and have been found rich in iodine (see Cameron, 1914), but red algae are generally regarded as second to brown algae in iodine content (see Scurti, 1906). In 1914, L. Pisarzhevsky and Averkiev discovered another species in the Black Sea which is rich in iodine, namely Phyllophora rubens*™ later Kylin (1929) and Vinogradov and Bergmann (1938) found a number of new species of Rhodophyceae rich in iodine (see Tables 52 and 53). From these tables it is easy to pick out one group of Rhodophyceae which is especially rich in iodine and another group which has a normal amount. In the first group are: Phyllophora rubens (Black Sea) P. brodiaei (Barents Sea) P. interrupt** (Pacific Ocean) Trailliella intricata (Atlantic Ocean, Norway) Ptilota plumosa (Pacific Ocean, Barents Sea) P. pectinata (Pacific Ocean) Nitophyllum rupestris (Pacific Ocean, America) N. violaceum (Pacific Ocean, America) Solieria chordalis (Atlantic Ocean, France) Before iodine was quantitatively determined in the species of the first group, Kylin (1929), Chemin (1929), and Dangeard showed histochemically that there is a great deal of iodine in Trailliella and that it can be detected easily (it is present in special epithelial cells). Because the iodine in this genus occurs primarily in the form of iodides, Kylin (1929) placed Trailliella in his first group; he also indicated that Trailliella taken in the Bay of Kristineberg contains less iodine (0.13 °/0) than specimens found in the open sea. Furthermore, it is interesting to note that Trailliella often is an epiphyte of Phyllophora^ which in turn is epiphytic on Laminaria. Phyllophora of the Black Sea, both littoral specimens and those of the open sea, were investigated in numerous analyses by L. Pisarzhevsky and Averkiev; they were also investigated qualitatively by Dangeard who determined the large amount of iodine present in these organisms.75* But Muraviev's observations of the small amount of iodine in Phyllophora interrupta from the White Sea conflict with those of many other investigators who showed that all species of Phyllophora from different seas were exceptionally rich in iodine. Vedrinsky (i938-a), investigating the same alga from the White Sea, found that it contains the largest amount of iodine in comparison to other 75. Phyllophora rubens forma nervosa. 75 a, Molisch (1926) did not find iodine in qualitative analyses of Phyllophora rubens, but he evidently was not sure that he had used this species.

96

Memoir Sears Foundation for Marine Research

algae (see Table 53). Also, it has been shown that Phyllophora is less rich in iodine in the littoral zone than in the open sea; in the ash of Phyllophora rubens from the open sea up to 2.82% iodine was found,76 while in the ash of specimens collected in a bay there was < 0.5%. At the bottom of the Black Sea, Phyllophora rubens lives at depths of from 6 to 60 m and forms algal meadows.77 Since Phyllophora does not become fixed to the bottom, entire fields of it move from one place to another, its specific gravity holding it near the bottom (see V. Lipski, 1932). Similar beds of red algae are formed by other species rich in iodine, such as Ptilota plumosa, found in the North Sea and in the Pacific shore zones. Phyllophora brodiaei of the Gulf of Kola, according to our analyses, contains iodine of the same order of magnitude as local Laminaria. Ptilota plumosa from four different localities is equally rich in iodine. Vincent (1924) notes only traces of iodine in Nitophyllum punctatum. Dixit (1930) found that Asparagopsis contained more iodine than various other algae, and Sauvageau (i926-b) and Kylin (1929) also classified these plants with the Rhodophyceae, which, like Trailtiella, are rich in iodine. Plumaria elongate^ according to qualitative determinations by Kylin (1929), is also rich in iodine, although Molisch (1926) had described Plumaria before this as the only red alga of all those analyzed by him which was rich in iodine. Dangeard found qualitatively a considerable amount of iodine in Plumaria and in a number of other Rhodophyceae. However, lists of species of Rhodophyceae rich in iodine are far from being complete, since quantitative determinations of iodine for many Rhodophyceae are not known. Hence, among these will be discovered many more species rich in iodine.78 It should be remembered that the loss of elementary iodine (see Golenkin [1895], Robertson [1897]) was noted first for Rhodophyceae, as was also the loss of iodooxidase (Gertz, 1926), which indicates the large amount of iodine in these species. As mentioned above, many investigators have noted how easily iodine may be detected in Trailliella^ Plumaria and Ptilota?* iodine evidently being found in the form of iodides in these plants. But figures higher than average, such as those for Rhodymenia palmata given by Vincent (1924) and Butler (1931), are isolated cases, according to some investigators. From the ash analyses of these algae an increase in chlorine and alkali became evident (see also Solieria} ; regardless of the usual amount of iodine in the species, the greater the chloride content the greater the amount of iodine in Rhodophyceae. Having considered the first group, which is especially rich in iodine, we may now turn briefly to the second group, which contains the majority of Rhodophyceae with an average content of o.oi°/0 of the dry matter. Those poorest in iodine prove to be 76. The maximum iodine in the ash of Phyllophora was 3.5 */Q. Averkiev (1928) gave an average figure of 1.32 '/0. According to the data of the 1927 expeditions, the seaweed contains 0.72 % iodine; collections made in 1915, partly from gulfs, average 0.65 °/o> anc^ X 9 l 6 collections from the gulfs averaged 0.2 •/„• 77. Opotz'kii, in a popular book on Phyllophora from the Black Sea, gave numerous data on iodine in these organisms. 78. Varaksin (1924) found 0.044 °/o iodine in fresh specimens of an unknown red alga from the Murman shore (0.66 •/„ in the ash), i.e., as much as in the local Laminaria. 79. E.g., Ptilota asplemoides.

Chemical Composition of Marine Organisms

97

TABLE 52 IODINE IN RHODOPHYCEAE '/.of-

ALGAE

Bangiaceae Porphyra I acini at a

N

of

. . °" determinations

umbilicalis vulgaris (ladniata)

Uying

matter

—

ash

Locality

0.0085

—

0.009

—

New Brunswick, Butler, 1931 Canada Kristineberg, Kylin, 1929 Sweden Nanaimo, Canada Cameron, 1914

0.0008 4

—

Helminthocladiaceae Nemalion multifidum 0 verTwculare

4

—

0.0013

2

—

0.092 0.0135

Gelidiaceae Gelidium amansn j a pom cum subcostatum

Prionitis lyallii Furcellaria fastigiata

2

ocellat us

—

2

Kristineberg, Sweden Matsu Bay, Japan

Kylin, 1929 McClendon and Takeo Imai, 1933

Nanaimo, Canada Cameron, 1914 Seto Mar. Biol. McClendon and Takeo Imai, Sta., Japan 1933 W

»

Matsu Bay (Japan)

V»

T>

„

»

W

T>

0.0075 0.043

Gigartinaceae Chondrus crisfus

—

0.0215 0.032

2 2

Author

matter ^

—

Canada (Pacific)

Kristineberg, Sweden — English Channel (France) 0.06 Baltic Sea (Sweden)

0.0012

—

—

—

trace

—

—

0.0018

—

—

0.0069

—

—

— —

0.0765 0.3 0.0736

— _

0.009 0.0023

Kristineberg, Sweden Gulf of Kola

Cameron, 1914 Kylin, 1929 Vincent, 1924 Weibull, 1917

Kylin, 1929 Vinogradov and Bergmann, 1938 Albert and Krause, 1919 Butler, 1931

Helgoland Nova Scotia, Canada Nanaimo, Canada Cameron, 1915 Matsu Bay McClendon and Takeo Imai, (Japan) 1933 (continued next page)

Memoir Sears Foundation for Marine Research

98

No. of determinations

Gigartinaceae Chondrus sp. Gigartina radula spinosa mammillosa

brodiaei Halosaccion ramentaceum „

dry matter

ash

—

0.0045

—

—

trace 0.006 trace 0.016

— — — —

0.0083

—

—

2

—

0.036

33

—

22

—

0.27 — 0.457

6

3

w

Iridaea (Dilsea) edulis Iridaea laminarioides Phyllophora rubens

living matter

-

— — —

—

0.1237

2 0.026

—

— 2 0.0033 — 0.029

—

Locality

Matsu Bay, Japan McClendon and Takeo Imai, 1933 California, U.S.A. Turrentine, 1912 Nanaimo, Canada Cameron, 1914 California, U.S.A. Turrentine, 1912 Nanaimo, Canada Cameron, 1914 Nova Scotia Butler, 1931

Kristineberg, Sweden — Sapporo, Hokkaido, Japan 0.65 Black Sea 1.31 — — Black Sea

— — —

Author

Kylin, 1929

McClendon and Takeo Imai, 1933 Averkiev, 1915 Averkiev, 1928 Komarovski, Tiulpina and Fisher, 1934 Gulf of Kola Vinogradov and Bergmann, 1938 „ » » w w w New Brunswick, Butler, 1931 Canada Alaska and Calif., Turrentine, 1912 U.S.A. Nanaimo, Canada Cameron, 1914

glandiforme

—

trace

—

„ GyTnnogongrus furcellatus Constantinea sitchensis

—

0.006

—

—

0.015

—

—

0.019

—

— —

0.023 0.085

— —

Okha (Indian O.) Dixit, 1930 Seto Mar. Biol. McClendon and Takeo Imai, Sta., Japan 1933

— —

Brittany, France Kristineberg, Sweden ? Gulf of Kola

Sphaerococcaceae Gracilaria sp. Hypnea sp.

2

Rhodymeniaceae Rhodymenia palmata

0.012 0.081 — 0.0008

— 0.712(!) — 2 0.0009 — —

2 (linearis)

—

0.021

—

— —

0.0231 (0.122)

— —

—

0

—

Matsu Bay (Japan) Canada (Pacific)

McClendon and Takeo Imai, 1933 Cameron, 1915

Vincent, 1924 Kylin, 1929

Stanford, 1877 Vinogradov and Bergmann, 1938 Murman Coast BruYevich, Trofimov and (Tokanga Gulf) Hartmann, 1933 Canada (Atlantic) Butler, 1931 Canada (Pacific) Cameron, 1915 Alaska Turrentine, 1912

Chemical Composition of Marine Organisms ALGAE

. No ' of determinations

Rhodymeniaceae Euthora fruticulosa Chylocladia wrightii champia parvula

Nanaimo, Canada Cameron, 1915 Matsu Bay (Japan) Seto Mar. Biol. Sta., Japan

McClendon and Takeo Imai, 1933 —

Kristineberg, Sweden Gulf of Kola

Kylin, 1929

—

0.0017

—

0.0015

—

—

0.011

—

—

0.0036

—

—

0 — — —

Rhodomelaceae Rhodomela pinastroides 99

2

0.158 0.127

trace

— 0.012

0.038

0.0015

— 0.014

— ~

Nanaimo, Canada Sapporo, Hokkaido, Japan Kristineberg, Sweden

—

—

0.0048 0.002

— — —

0.009 0.007

—

0.009

—

—

0.010

—

—

0.078

—

—

99

— Brittany, France Kristineberg, Sweden

0.0056

—

99

— — —

0.0205

99

Nanaimo, Canada Cameron, 1914 Brittany, France

— —

Vinogradov and Bergmann, 1938 Kylin, 1929 99

—

— —

0.001 —

Kristineberg, Sweden 99

0.071 — 0.0018

subfusca

A uthor

—

2

0

Locality

0.053

—

99

7)

ash

0.0012

Lament aria clavelLosa Nitophyllum ruprechtianum violaceum punctatum

99

• »/. ofdf y matter

—

sinuosa

violace a elongata nigrescens tenuistriata tubulata Odonthalia dentata

* matter

2

Delesseriaceae De/esseria sanguinea

•uirgata larix sp. Polysiphonia urceo/ at a

livin

99

99

99

99

Vincent, 1924

Stanford, 1877 Vincent, 1924 Kylin, 1929 99

99

Cameron, 1914 McClendon and Takeo Imai,

1933

Kylin, 1929

99

99

99

99

99

99

99

99

99

Nanaimo, Canada Cameron, 1915 99

99

Kristineberg, Sweden Gulf of Kola Gulf of Onega, White Sea

99

99

Kylin, 1929 Vinogradov and Bergmann, 1938 BruYevich, Trofimov and Hartmann, 1933 (continued next page)

i oo ALUAU,

Memoir Sears Foundation for Marine Research No. of determinations

Rhodomelaceae Odonthalia corymbifera Laurencia pinnattfida

sp.

Brongniartella byssoides

living matter

matter

ash

0.043

—

—

—

-

0.046

—

0.0036

—

—

2

— 0

4

0.0009

—

—

0.0038

—

—

— trace

r>

Ptilota plumosa

0.06 2 0.042

2

-

r>

Grateloupiaceae Halymenia sp. Schizymenia dubyi

Author

Sapporo, Hokkaido, Japan West Coast, Sweden Matsu Bay (Japan) Kristineberg,

McClendon and Takeo Imai, 1933 Kylin, 1929 McClendon and Takeo Imai, 1933 Kylin, 1929

OWCUCIl

r>

Rhodophyllidaceae Cystoclonium purpurescens Eucheuma papulosa Richocarpus crinitus SoKeria chordalis

Locality

C M» Afl A W\

Ceraminaceae Ceramium rubrum

pecttnata Antithamnium plumula Jsparagopsis sanfordiana

dry

2

— 0

—

—

trace Helgoland — Baltic Sea —

—

—

0.23

—

0.40

—

0.285

—

—

Kristineberg, Sweden Gulf of Kola

—

0.092

—

—

—

Kylin, 1929 Vinogradov and Bergmann, 1938 Albert and Krause, 1919 Vibrans, 1873

Kristineberg, Sweden Gulf of Kola

Kylin, 1929

Karaginski Is., Bering Sea Murman Coast (Takanga Gulf) Sapporo, Hokkaido, Japan Kristineberg, Sweden Okha (Indian O.)

Treumann, 1931

Kylin, 1929

Vinogradov and Bergmann,

1938

Brulevich, Trofimov and Hartmann, 1933 McClendon and Takeo Imai, 1933 Kylin, 1929 Dixit, 1930

2

—

0.0035

—

2

—

0.0056

—

0.024

0.158

—

Kristineberg, Sweden Seto Mar. Biol. Sta., Japan Sapporo, Hokkaido, Japan Brittany, France

—

0.035

—

Okha (Indian O.) Dixit, 1930

—

0.0011

—

Matsu Bay (Japan)

0.002 1

2

McClendon and Takeo Imai, 1933 »»

r>

r>

r>

Vincent, 1924

McClendon and Takeo Imai, 1933

101

Chemical Composition of Marine Organisms ALGAE

. N°' of determinations

Grateloupiaceae Grateloupia affinis filicina divaricata ligulata sp. Rhizophyllidaceae Chondrococcus homemanni

livin

£ matter

Locality

Author

Matsu Bay (Japan)

McClendon and Takeo Imai,

—

0.0037

—

2 2 2

— — —

—

0.0021 0.0075 0.0067 0.0310

— — — —

—

0.0105

—

Seto Mar. Biol. Sta., Japan

McClendon and Takeo Imai, 1933

—

—

Kylin, 1929

—

—

Kristineberg, Sweden Gulf of Kola

0.012

—

Dvina Gulf (Pangama Bay)

— —

0.005 0.0033

— —

— —

0.0071 0.0067

— —

Canada (Pacific) Matsu Bay (Japan)

2

0.0017 0.0017 J m

99

jfmphiroa sp. Cheilosporum sp.

ash

2

Spongiocarpeae Polyides rotundus*

Corallinaceae Cora/Una officinalis sp.

dry matter

^ ~

3 4

* Classified with Gelidaceae.

1933

9»

99

9»

it

9»

yj

9»

99

99

»

»

1j

»»

9»

»

»

»

M

w

»

w

»

Seto Mar. Biol. Sta., Japan

9»

99

Seto Mar. Biol. Sta., Japan

Vinogradov and Bergmann, 1938 Brulevich, Trofimov and Hartmann, 1933 Cameron, 1914McClendon and Takeo Imai, 1933 w » » » y>

r»

?>

9*

Halosaccion, Polyides, and Chondrus crispus, the species which live in the littoral and tidal zones. This biocoenosis of red algae with low iodine might be shown to differ from the biocoenoses of red algae rich in iodine (represented by species of Trailliella^ Phyllophora, Ptilota^ and so on) living in the sublittoral zone. Here, as in the case of the Phaeophyceae, the rule that the deeper algae are richer in iodine is valid to a certain degree. However, exceptions exist which show the significance of iodine as a characteristic of species independent of the living conditions. Thus, Polysiphonia, Porphyra and other Bangiales, and Gracilariafb often living together with algae of the first group, are poor in iodine. Therefore, in the distribution of iodine among the species of Phaeophyceae and Rhodophyceae a similarity is observed, for in both classes all the algae contain iodine but 80. The presence of iodine has been shown qualitatively in 15 to 20 species of Rhodophyceae, besides the ones mentioned. 8*

i o2

Memoir Sears Foundation for Marine Research TABLE 53 IODINE IN RHODOPHYCEAE (RECENT DATA)

dry

ALGAE

matter

Rhodomela larix Rhodymenia sp. . Callymenia sp. . Porphyra sp. , Porphyra tenera Porphyra suborbiculata . Ptilota pectinata Iridaea sp. Iridaea laminarioides , Phyllophora sp. . Phyllophora interrupta . 99

Ahnfeltia piteata

99

99

99

99

n

Gloeopeltis sp. . 99

"

99

Gelidium divarication * 99

Gelidium amansii

'

99

99

"

99

99

'

99

99

'

99

99

'

Digenea simplex

0.042

0031

m

,

ash

—

Locality

Author

Primorie, Far East

Kiesewetter, 1936

—

99

99

99

. . . . .

0.070 — 99 99 99 0.062 — 99 99 99 China Sea 0.0018 — 0.0021 — 99 99 Primorie, Far East 0.240 — 0092 — 99 99 99 0.036 — 99 99 99 . 0.0024 0.015 U.S.A. . 0.58 — Primorie, Far East White Sea . trace — Primorie, Far East . 0.451* —

. 0.126

—

. 0.73

—

0.035

. 0.0072 . 0.0053 . 0.0029 . 0.0033 . 0.026 . 0.0242

. 0.16

Gracilaria confervoides . Corallina pilulifera . Eucheuma gelatina * Eucheuma muricatum . Chondrus sp. , Polysiphonia sp. . Turner ella sp. (May) . Turnerella sp. (June) , Turnerella sp. (August) Furcellaria sp. , Maximum.

.

.

Gloeopeltis furcata .

99

'/ O of

. . . . . . . . . . . . . .

0.1776 0.047 0.0231 0.026 0.0588 0.0018 0.0155 0.0009 0.0024 0.0357 0.044 0.056 0.032 0.062

. 0.081

—

— — — — — —

—

— — — — — — — — — — — — — —

—

99

White Sea 99

99

99

99 99

99

99

99

99

99

99

99

Adolph and Whang, 1932 Tang and Whang, 1935 Kiesewetter, 1936 Lebedev,j 1936 Ellegood, 1939 Lebedev, 1936 Muraviev, 1935 Vedrinsky, 1938-a Kiesewetter, 1936 99

China Sea 99

99

99

Muraviev, Tang and Tang and Tang and

99

99

99

99

99

99

99

99

99

99

99

Tang Tang Tang Tang

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

and and and and

99

1935 Chang, 1935 Whang, 1935 Chang, 1935 Whang, 1935 Chang, 1935 Whang, 1935 Chang, 1935

Tang and Whang, 1935 Tang and Chang, 1935

Pamban (Indian Ocean) Narasimham and Pal, 1939 Primorie, Far East Kiesewetter, 1936 99

99

99

99

rt

99

99

99

99

9)

99

99

n

Vedrinsky, 1938-a

Chemical Composition of Marine Organisms

103

in different amounts, and in both there are families and genera which are rich in the element: Phyllophora, Trailliella, and Ptilota among the Rhodophyceae; Laminariaceae and Lessonioideae among the Phaeophyceae. Finally, genera or species, such as Laminaria digitata^ Phyllophora rubens, and so on, appear among them with an exceptional ability to concentrate iodine. Rhodophyceae which tend to accumulate CaCO3, and the magnesium-calcium Corallinaceae (groups 2 and 3 according to the amount of CaCO3) contain little iodine. For example, in Laurencia pinnatifida Kylin (1929) did not find any iodine. In other species the presence of iodine was demonstrated qualitatively by Vincent (1924) and others. Fujikawa and Kitayama (1935) found that Porphyra tenera from the shores of Korea contains a maximum of iodine in December, the amount then decreasing after the middle of January. The maximum in iodine occurs at the time of spore formation. Kiesewetter (i936-a) found the following amounts of iodine in Porphyra from the shores of Primorle of the Far East (in °/0 of dry matter): December 0.137, January 0.059, February 0.027, March o.ooo. In conclusion we must point out that, among the Rhodophyceae, species and genera exist which are exceptionally rich in iodine, and inasmuch as Rhodophyceae are represented in warm seas by numerous species, one may suppose that they are the chief concentrators of iodine there, thus replacing Laminaria which are absent in these same latitudes. 16. Iodine in Chlorophyceae Among the Chlorophyceae we do not find species with really high contents, the amount of the element which they contain being equivalent to that found in those brown and red algae which are classified in the group of algae poor in iodine. Nevertheless, they are many times richer in iodine than the terrestrial flora. For qualitative data, see Courtois (i 813), Davy (i 814-a, 18 H-b), Fyfe (1819, 1820), Straub (i 820), Sarphati (1834; on Solenia and Uha\ Henry (1844; on "Conferva"\ Chatin (i85O-a, i85O-b; on freshwater "Conferva crispata"\ Fetter (1862; on Cladophora glomerata\ and Dangeard (who showed qualitatively a considerable amount of iodine in Bryopsis hypnoides and B. plumosa). Quantitative data on Chlorophyceae are scarce. McClendon and Takeo Imai (1933) found Codium intricatum to be exceptionally rich in iodine, while other species of Codiaceae contained less than one hundredth as much. The problem of the iodine content of Chlorophyceae, such as Cladophora and Vaucheria which live not only in the sea but in saline, semisaline, and freshwater basins as well, is obviously of interest. In Tables 54 and 55 are given some data which bear on this question. According to Budrik (1927), Vaucheria dichotoma f. marina from the saline Lake Tambukan81 contained 1.3 x io"2°/0 iodine in the dry matter, the plants extracting the element from the water of the lake. On the other hand, according 81. The lake water contains io~*°/ 0 iodine.

104

Memoir Sears Foundation for Marine Research TABLE 54 IODINE IN CHLOROPHYCEAE

ALGAE

N °* °f determinations

Uvin&

2

—

Ulvaceae Enteromorpha compressa

matter

°dry matter

rt

"

rt

~~~

0.006 trace 0.0007

— —

0.0026 0.02

intestinalis linza U/va lactuca

—•

0

rt

„ ( v. latissima) „ (rigida) 2 „ conglobata 2 Monostroma fuscum 6

""

— — — —

0.055 0.021 0.008 0.003 0.0022

— 0.0008

0.008

—

Locality

Author

Nanaimo, Canada Brittany, France Matsu Bay, Japan

Cameron, 1914 Vincent, 1924 McClendon and Takeo Imai, 1933

Nanaimo, Canada

Cameron, 1915-a

Kristineberg, Sweden

Kylin, 1929

«

rt

rt

— Nanaimo, Canada rt

rt

Brittany, France Seto Mar. Biol. Sta., Japan Nanaimo, Canada Gulf of Kola

Codiaceae Codium fragile v. califomicum mucronatum

2

— —

0.003 0.0007

Nanaimo, Canada Matsu Bay, Japan

cylindricum

2

—

0.0045

mamTnillosum intricatum

2 2

— —

0.020 0.146

Seto Mar, Biol. Sta., Japan

0.027

—

Cladophoraceae Cladophora rupestris sericea stimpsonii wrightiana

2

glaucescens

2

sp.

0

— —

— 0.009 0.061 0.002

—

0.0014

rt

rt

rt

rt

Sarphati, 1834 Cameron, 1914 Cameron, 1915-a Vincent, 1924 McClendon and Takeo Imai, 1933 Cameron, 1914-15 Vinogradov and Bergmann, 1933

Cameron, 1915-a McClendon and Takeo Imai, 1933 rt

rt

rt

rt

rt

rt

rt

rt

rt

n

rt

rt

rt

rt

rt

«

Kristineberg, Sweden rt

Kylin, 1929 rt

rt

Nanaimo, Canada Cameron, 1915-a Misaki Mar. BioL McClendon and Takeo Imai, Sta., Japan 1933 Matsu Bay » rt rt rt (Japan) rt

rt

w

Chemical Composition of Marine Organisms ALGAE

No. of determinations

Cladophoraceae Cladophora glomerata* fragtlis* Acrosiphoma pallida

living matter

"/oof dry matter

Locality

Author

0.023 0.00098 0.0021

—

Zenger, 1875 Gautier, 1899-a Kristineberg, Sweden

* Fresh water.

105

Kylin, 1929

to Fellenberg (1924), Vaucheria from Aare contained 3 x io~ 4 °/o iodine in air-dried matter, which is considerably more than the amount in other freshwater algae.82 Even freshwater forms of algae, the green ones particularly, are richer as a rule in iodine than flowering water plants (see Zenger's [1875] analyses of freshwater algae and other plants). Thus it apparently follows that the development of these algae is related to the amount of iodine in the basin.

TABLE 55 IODINE IN CHLOROPHYCEAE (RECENT DATA)

ALGAE

Ulva lactuca

„

Enteromorpha tubulosa Enteromorpha prolifera Enteromorpha lima Codium fragile Monostroma sp

°/o of

dl

7 matter

0.0031

0.004 0.0033

0.0054 0.0054 0.0224 0.0067 0.0016

(Akiaki)

0.041

(Huka)

0.0002

(Kohu)

0.0005

(Lipoa)

0.0085

(Alaula) (Eleele) (Huluhuuwaena) (Kala)

(Lipeepee) (Manaula)

(Opihi)

(Palahalaha)

Locality

Author

China Sea »» »»

Tang and Whang, 1935 » » » »

„ „

„ „

»»

W

w

„

Hawaiian Is.

Tang, Kou and Tang, 1936 Tang and Chang, 1935 »

»

T»

»»

Tang, Kou and Tang, 1936

Ripperton, 1934

0.013 0.0006 0.015

0.048 0.013

0.0148

0.0089

0.0005

82. In the aerial alga Protococcus w^° was the first to describe deposits of iron hydroxide in 94. Considering that there is more aluminum than iron in algae, data for iron without any indication of the separation of aluminum must be taken as approximate.

Chemical Composition of Marine Organisms

117

"Conferva" distinguished between external and internal accumulation, outside and inside the cells. Other authors distinguish facultative concentrators and obligatory concentrators, or siderophilous and siderophobous organisms. Not only does the presence of iron in the external medium create conditions for precipitation of iron in algae, but the character of the cellular medium, such as the pH and so on, also plays an important role. We will call "iron organisms" those whose iron concentration is hundreds and thousands of times greater than the usual amount in other organisms ;95 from the geochemical point of view this is the only proper definition. Lists of iron algae have been made by Dorff (1934), and to these lists must be added Frdmy's (1936) discovery of the precipitator and concentrator of iron, the cyanophycean Microcoleusferrugineus Fr&ny.

TABLE 65 IRON IN VARIOUS ALGAE (°/0 OF DRY MATTER) ALGAE

I

Laminaria jafonica . . . . 0.085 Lammaria religiosa . ... 0.149 Sargassum siliquastrum . . . 0.093

Locality

. . .

. . China . . . „ „

Author

, Read and How, 1927 . . . . „ „ „ „ . . . . „ „ „ „

Iron in algae is found in the form of soluble compounds and as various hydroxides. Although the role of freshwater algae in the formation of marsh iron ore is widely known, the process of iron concentration in algae is not clearly understood; however, as we have already said, a concentration of iron in some seaweeds has been observed, especially in the Chlorophyceae. Deposits of iron hydroxide in marine algae, besides Cyanophyceae and other unicellular plants, were noted by Harder (1919), Molisch (1926), and Naumann (1930) ; they were also the subject of a special study by Sj6stedt (1921), who made numerous analyses of 120 species from the Baltic Sea. The formation of deposits of iron hydroxides reaches different magnitudes; for example, they are little developed or even absent in Dilseay Odonthalia, Rhodymenia palmata, Ceramiumy Delesseria and Polysiphonia (i. e., chiefly in the red algae), but they are especially well developed in some species of Pilayella (P. littoralis\ Sphacelaria cirrhosa, S. racemosa, Chaetopteris plumosa and in the Chlorophyceae (Enteromorpha aureola f. ochracea, E. torta^ E. tubulosa^ E. prolifera, Cladophora rupestris, and Diplonema). In these species, deposits of iron hydroxide have been found inside the cells. In Sestini's (1877) analyses, some Chlorophyceae from Venetian lagoons were shown to be extremely rich in iron, due to the influence of freshening (see Table 35), and it is possible that bacteria, Cyanophyceae, and so forth, participate in the formation of iron deposits in algae. There are larger amounts of iron in older specimens than in the young. It is still uncertain whether or not the deposits of iron and manganese hydroxides in algae are connected 95. See the discussions of iron organisms by Cholodny (1928) and Naumann (1930). 9*

11 8

Memoir Sears Foundation for Marine Research

with the CaCO3 deposits. Molisch (1926) noted traces of manganese in Acetabularia mediterranea^ Amphiroa crypth., and Corallina rubens. SJ6stedt (1921), who found iron in a number of Corallinaceae, supposed that these processes are connected, as for example in Cladophora and Enteromorpha. To summarize, some species of Rhodophyceae, Phaeophyceae, and Chlorophyceae, particularly the latter group, accumulate iron. Freshening evidently speeds up this phenomenon. In typical marine algae such as Laminaria, accumulation of iron is not observed. 22. Other Elements: Copper', Zinc, Titanium, Lead, Molybdenum, Tin, Cobalt, Nickel, Mercury, Silver, Gold, Vanadium, Chromium, Boron, Bismuth, Antimony, Tungsten, Gallium, Germanium, Cadmium, Beryllium, Praseodymium, Neodymium, Samarium, Cerium, Lanthanum, Tttrium, Rubidium, Cesium, Lithium, Strontium, Barium, Thallium, Fluorine, and Radioactive Elements™* Information as to the content of these other elements in algae is scarce. The first demonstrations of the presence of lead, silver, copper, zinc, and other elements were performed chiefly by Malaguti, Durocher and Sarzeaud (1850), and Forchhammer (1844); the last-mentioned worker gave a number of analyses of algae and posed the question of the presence of trace elements in marine organisms. His observations aroused great interest at that time and became the foundation for further investigations. However, there still is much less information for these elements in seaweeds than in terrestrial plants. COPPER. Malaguti, Durocher and Sarzeaud (1850), as well as Forchhammer (1844), demonstrated qualitatively the presence of copper in Fucus vesiculosus. Lehmann (1895) found 6 mg Cu per kg dry Fucus crispus (Chondrus crispus?). Hiltner and Wichmann (1919) found traces of copper in unknown algae. Cornec (1919) found copper spectroscopically in Laminaria, and Newell and McCollum (1931) detected it in kelp. Webb (1937) found 0.3 °/0 copper in the ash of Ufoa lactuca and 0.003% copper in X4H. Ishibashi and Sahara (1940) record in "wakame" [which according to Professor Tatewaki is Undaria pinnalifida] minute amounts of bismuth, tin, barium, strontium and lithium; in "hondawara" [Sargassum enerve} moderate amounts of lithium and minute amounts of mercury, bismuth, tin, barium, strontium, rubidium, titanium and vanadium; in "kuromo" (Myrioehladia kuromo] minute amounts of mercury, bismuth, tin, chromium, barium, strontium, lithium and rhenium; and in "kogaimo" ["kogaichirimo"—Pleurotcumium nodulosum] moderate amounts of lithium and minute amounts of mercury, bismuth, tin, barium, strontium and rubidium. These algae contained respectively 17.63 '/0, 26.67 */0, 23-43 °/oand 3 2 - J 3 °/o ^ *n t^ie dry matter, potash being the dominant metallic oxide present. The aluminum contents are given as 1.68 °/0, 3.52 •/„> 0.76 °/0 and 4.64 °/0 Al in the ash but these values appear high; the manganese contents are given as 0.04 °/Q, 0.45 •/„» 0.80 °/0 and 0.68 •/„ Mn in the ash respectively. It is to be noted that the material of the third alga contained the lowest amount of aluminum and is therefore the least likely to have been contaminated. This alga provided what appears to be the first biological occurrence of rhenium. Ishibashi and Sahara make no comment on this discovery. They state that they were unable to ascertain if silver, copper, zinc, lead, indium, gallium, ruthenium, tellurium and tungsten were present or absent. In carrageen from northern France, Rosenthaler and Beck (1937^) found, besides the ordinary major ash constituents, manganese, aluminum, nickel, and chromium and in smaller traces lithium, bismuth, arsenic and cobalt. Scandium was detected in the oxalate precipitate.

Chemical Composition of Marine Organisms

119

Fucus serratus. According to Miller and Robbins (1936), there was 0.00045% copper in the fresh matter of an alga from the Hawaiian Islands, known under the name of "limu-kohu." It is probable that drilling Mollusca and Crustacea get copper from algae, there being an allusion to this in the work of Elmhirst and Paul (1921). Oy (1940) found i.i to 1.4 x io~ 4 °/ 0 copper in the dry matter of Laminaria digitata^ 5.8 to 17 x io~ 4 °/ 0 in that of Fucus serratus, and 3.4 to 8.4 x io~ 4 °/ 0 in dry F. vesiculosus* Wilson and Fieldes (1942) noted less than 2 x io"3°/0 in the dry matter of Macrocystis pyrifera?* ZINC. There are almost no determinations for this element. Forchhammer (1844) found zinc in Fucus vesiculosus and in the marine flowering plant Zoster a. Javillier (1930) did some isolated analyses on algae, finding 0.007 °/o zinc in the ash of Laminaria saccharina and 0.008 °/o in that of Fucus vesiculosus, which amounts are somewhat less than are usually found in terrestrial plants and considerably less than the amounts in marine animals. Wilson and Fieldes (1942) found a comparable quantity of 0.003% zinc in the dry matter of Macrocystis pyrifera. Bertrand (1932) records 0.00077% in the dry agar of Gelidium and Gracilaria. Qualitative determinations of the presence of zinc in algae are given by Cornec (1919) and by Newell and McCollum (1931). Lagrange and Tchakirian (1939), in a spectroscopic analysis of Lithothamnium calcareum, detected zinc, manganese and copper as well as silver, germanium, beryllium, molybdenum, nickel, lead, tin, titanium, vanadium, tungsten, and arsenic, TITANIUM. Titanium was detected spectroscopically in Laminaria by Cornec (1919). Later Bertrand and Voronca-Spirt (1930) determined the element in a number

TABLE 66 TITANIUM IN ALGAE 01

ALGAE

Laminaria flexicaulis Laminaria saccharina Laminaria digit at a . Himanthalia lorea Ptlvetia canaliculata . Ascophyllum nodosum Fucus vesiculosus . Fucus platycarpus Fucus serratus Cystoseirafibrosa. Lithothamnium sp. Rhodymenia palmata

dry matter

.

. . . . . . . . . . .

.

. . . . . . . . . . .

6 X 10 -i 5.4x 10 -4 2.4x 10 -4 2.4x 10 -8 6 x 10 -4 3 x 10 -44 9 x io3 x 10 -48 1.8x io3.9 x10 -4 2.5x 10 -3 5 x 10 -4

„«•

ash

4.8 x 103.64 x 107.2 x 102.52 x 101.6 x 103.56 x 101.04x 10-2 l.OSx io- 8 9.2 x io—

* Unpublished data. 96. For isolated analyses of freshwater algae, see Quartaroli (1928).

Author

Bertrand and Voronca-Spirt, 1930 99

99

99

99

Kaminskala, 1933* Bertrand and Voronca-Spirt, 1930 99

99

99

99

99

91

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

Kaminskala, 1933* 9>

99

120

Memoir Sears Foundation for Marine Research

of seaweeds. During recent years Sh. Kaminskai'a (193?) has found titanium in marine organisms from the Barents Sea. She also found the following amounts of titanium in algae from the same place (in °/0 of living matter) : 5.2 x io~ 4 in Bangia fuscopurpurea, 4.4 x io~* in Fucus serratus, and 1.3 X io~* in Ascophyllum nodosum. The amount of titanium is rather high in Lithothamnium, and thus its presence in some limestones has been clarified.97 Titanium was determined qualitatively in algae by Newell and McCollum (i 931). Wilson and Fieldes (i942) were unable to identify titanium in their spectrograms of Macrocystis pyrifera. LEAD. Malaguti, Durocher and Sarzeaud (1850) were the first to determine this element in the following algae: Fucus serratus I Fucus ceranoides \ o.ooi8°/o Ascophyllum nodosum} The spectroscopic studies by Webb (1937) showed 0.04 °/0 lead in the ash of Fucus serratus. Forchhammer (1844) also found lead in Fucus vesiculosus and Freundler (1925^) detected it in Laminaria. The element has been detected spectroscopically in algae by Cornec (1919) and Newell and McCollum (1931). The question of the distribution of lead in algae and other organisms has not yet become a subject of study. The quantitative data need verification; Wilson and Fieldes (1942) concluded that Macrocystis pyrifera contained less than 0.0002 °/0 in the dry matter. MOLYBDENUM. Molybdenum was detected qualitatively by Cornec (1919) in Laminaria. In a chemical analysis of the ash of Laminaria digitata and L. saccharina we succeeded in getting a qualitative positive reaction to it. Ter Meulen (1931) gave numerous determinations of molybdenum in plants and in other terrestrial organisms, in which the amount of molybdenum proved to be about io~ 6 °/ 0 ; he also attempted to determine the element in seaweeds (species not given) and found 0.16 mg molybdenum per kg of dry seaweeds (1.6 x io~ 5 °/ 0 in the dry matter), while in the freshwater plant Azolla, a waterfern, there was 1.13 x io~ 4 °/ 0 . Anabaena, a cyanophycean which fixes nitrogen,98 lives in symbiotic relationship to Azolla. Bortels (1939) showed that addition of molybdenum to the medium of Anabaena increases nitrogen fixation. Ter Meulen (1931) was unable to detect molybdenum" in 40 liters of sea water. Bertrand (1940) obtained the following results for it in algae (in °/0): Algae

Pelvetia caniculatus U/»

91

91

>»

91

»

»

91

dphanixomenon sp. . »

» •

»

91

•

Riiwlaria bullata . Calothrix pulvinata Nostoc communis . n

9i

Oscillatoria sp. . Chlorophyceae folvox globator . » 99 Ankistrodesmes sp. Hydrodiction sp.

•

— 4.47 43.78 6.28 — 5.51 42.18 43.37 5.43 6.84 5.85 7.00 8.01 10.98 6.10 10.66 7.84 48.0 2.42 63.0 1.5 . 15.0 2.8 6.50 • — 6.20 25.07 _

99

99

71

0.80 n » » n 0.89 0.69 0.70 — 0.75 Caspian Sea, 1937 1.20 Sea of Azov, 1934 — — — — — —

6.2t —

14.50 4.30 — 8.32 21.43 2.48

99

Vinogradov, 1939

— — 0.42

99

n

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

Sant-Malo 99 99

Payen, 1938

99 99

Staroselie, Kiev, 1936 Lake Tambukan

Vinogradov, 1939

Knauthe, 1907 Mytishchi, Moscow region Vinogradov, 1939 Birge and Juday, 1922 Shiori and Mitui, 1935

• For comparative purposes, some figures for other algae are shown in Tables 76 and 77. f In percent of ashless matter.

Chemical Composition of Marine Organisms

137

TABLE 76 NITROGEN IN DIATOMEAE AND CHLOROPHYCEAE (IN °/0 OF DRY MATTER). COMPARE WITH CYANOPHYCEAE ORGANISM

N

Author

Diatomeae Spiragyra Cladophora

3.66 3.47 2.77

Birge and Juday, 1922 „ „ „ „

Asterimella Spirogyra

2.30 4.50

Whipple and Jackson, 1899

W««

7.61

„

„

„

(tuberculosa ?) which becomes encrusted with CaCO3 and which therefore must be classified with the forms rich in calcium, participating in rock formation.12 Many other Cyanophyceae living in the sea (certain species of Lyngbya, Scytonema, Schizothrix, Calothrix and Hyella caespitosa v. spirorbicola—see Hansgirg, 1892) also concentrate CaCO3. The formation of Pre-Cambrian limestones has been attributed to the activity of fossil species of Cyanophyceae. Freshwater forms of these organisms precipitate CaCO3 on their surfaces and thus form travertines, this being true of Phormidium, Chroococcus, and Gloeocapsa (see Hansgirg [1892], Geitler [in Rabenhorst, 1932], Prat [1929]* Fritsch [1929], and Sernander [1916]). Also, many species of Cyanophyceae take part in the destruction of limestone; these are the so-called drilling blue-green algae, Hyella, Mastigocoleus, and others (see Nadson, 1900). Often the same species apparently participate in both processes. The Ca/Mg ratio is not known for most species. According to H6gbom (1894), one specimen of Rivularia sp. contained 84.88°/oCaCO 3 and 0.69°/o MgCO3.13 Calcium carbonate crystals were found in the body of many species, apparently as calcite14 (on the formation of calcite in cultures of Cyanophyceae, see Prat, 1929). Although many investigators have noted that limestones formed by freshwater Cyanophyceae are relatively poor in magnesium, there are few analytical data. Calcite sediments connected with the activity of Cyanophyceae are poor in MgCO3, being in this respect like the calcite skeletons of many other plankton organisms, such as Foraminifera. Cohn (1892) found aragonite crystals in Rivularia sp. (Euactis calcifera\ but this requires verification. Thus, it is apparent that the process which leads to the accumulation of CaCO3 and formation of deposits by the above-enumerated Cyanophyceae, is not yet clearly known. The calcium content of species which are not accumulators is also unknown, with the 12. See Rothpletz (1891) on Rivularia Jura, Danin (1932) on Rivularia polyotis, and Meyen (1837-1839). 13. A freshwater form from Gotland, analyzed by N. Sahlbom; Oscillaforia Seiwell and Seiwell (1937), Cooper (i937-b), and Fleming (1939); according to their analyses the ratio N/P varies within the same limits. Redfield (1933) stated that in general the ratios N/P, Fe/P, and so forth, are similar to the ratios of these elements in sea water, but this is only roughly so. We have always claimed that the chemical composition differs considerably in different plankton, as is seen in the analytical data given in the present work. Kalle (1933) found 10.9 mg plankton-bound phosphorus per m3 of sea water, TABLE 86 SOME ELEMENTS IN DIATOMS (IN °/0 OF ASH) GENERA and SPECIES

No. of analyses

1. Rhizosolenia

Chaetoceras Sceletonema Thalassiothrix

Fe2Oa CaO

9* 4.49

PjO6

5.67 4.98

SiO2

64.44

AljOg Locality

—

Bay of Kiel

Author

Brandt and Raben, 1919-1922

and others

2. Sceletonema Chaetoceras Thalassiothrix

If

1-62

—

2.38

3. Rhizosolenia Chaetoceras Thalassiothrix

1§

—

—

—

4. Melosira granulata Cyclotella compta (soil)

1*

—

2-27

—

45.73f —

Gulf of Kola Vinogradov, 1933

St 157, Chal- Anderson (see lenger Exped. Murray and Renard, 1891) 83.66 3.5 Lake Baikal Samoilov and Roshkova, 1925 (+ Fe,03) 78.38 1.76

* Percent of ash without soluble salts. f Calculated in percent of ash without removal of NaCl and other soluble salts, which constitute about 40 °/0 of the analyzed material. § Percent of dry matter. Organic matter - 16.75 %; HgO - 4.87 °/0. 30. Navicula ostrearia gives off a phosphorus pigment into sea water, according to Ranson (1933). 31. He gives no weight data. Data are calculated in terms of number of specimens and volume of fresh plankton. n*

150

Memoir Sears Foundation for Marine Research

when the total phosphorus was 27 to 30 mg. Analogous observations were made by Cooper and others. Buch and Gripenberg (1938) constructed a curve of the phosphorus content of the water in relation to the number of specimens of Sceletonema^ and they found that when one liter of water contained i .3 million specimens of Sceletonema there was no phosphorus in the water; also, according to their estimate, every Sceletonema cell collects i x io~ 8 mg phosphorus. According to Atkins (1923), each specimen of Nitschia closterium collects 0.52 x io~ 9 mg phosphorus, and Lauderia borealis 2.2 x io~ 8 mg phosphorus, per day. We have determined the calcium, magnesium, silicon, iron, and other elements in diatoms (see Table 87), but of all these elements silicon is present in the largest quantities,32 up to 23-32°/o of the dry weight, or about $o°/0 SiO2. The ash contains 96—99 °/0 SiO2; for example, Rogall (1939) found for Biddulphia sinensis (in °/0 of ash) SiOa FeaOs » Residue

96.80 1.26 1.92 (heating loss),

and for Coscinodiscus concinnus (in °/0 of ash) SiOa FeaO8 Residue

96.16 1.80 1.98 (heating loss).

Einsele and Grim (1938) obtained interesting determinations of SiO2 in individual cells of various diatoms, their analyses being made on freshwater forms of German lakes. We give below several mean data (in grams per cell): Asterionella formosa Fragilaria fenestrata Tabellaria fenestrata Synedra acus angustissima Synedra ulna danica Diatoma elongata Melosira granulata Melosira italica

.

(Xio- 8 ) 6.5 9.0 18.7 57.0 100.0 12.0 8.0 15.0

Melosira islandica he/vitica . Cyclotella glomerata Cyclotella melosiroides Cyclotella socialis Cyclotella comta Cyclotella bodanica Stephanodiscus astraea Mallomonas mirabilis

,

.

(Xio~ 8 ) . 27.0 10.0 35.0 47.5 90.0 150.0 400.0 40.0

Thus it is seen that different species of diatoms contain different amounts of SiO2, which is related to their morphology.34 In the past some investigators thought that the diatom skeleton consisted of SiO2 entirely, but now we know that some forms lack silicon and that those which 32. Hensen (1887), using direct methods, found 2.83 Vo SiO, and 93.43 •/. H,O, the dry residue being 6.57 °/0} see data on Frustalta satina(l)\ Schmidt (1845) found 45.1% sioi »n the dry matter. 33. Together with Al,Ot. 34. There is a relationship between the amount of SiO, in the water and the development of diatoms. Note the development of diatoms in volcanic ash regions containing alumosilicates and SiO,.

Chemical Composition of Marine Organisms

151

possess a siliceous exoskeleton may lose it under certain conditions. Also, we know that northern forms are richer in silicon than other forms (see Pia, 1926), and that the Centricae, the more primitive of the diatoms, represented chiefly by the marine plankton, have a light SiO2 skeleton. Furthermore, the freshwater diatoms, mostly Pennatae, have a heavier SiO2 skeleton, the most massive skeleton with a large SiO2 content being found among the benthic species of Pennatae, both marine and freshwater; SiO2 occurs also in the skeletons of the terrestrial forms belonging to the Pennatae. TABLE 87 COMPOSITION OF DIATOMS (IN °/0 OF DRY MATTER), FROM VINOGRADOV, 1939 ORGANISM

Ash

Ca

Mg

Si

P

Fe

Locality

Rhnosolema calcar-avis

60.38 52.15 54.22 59.17 51.47

0.9 1.17 0.63 0.36 —

0.32 0.26 0.38 0.32 —

21.78 19.35 19.14 23.32 —

0.61 0.53 0.31 0.90 1.27

0.16 0.23 0.10 0.10 0.63

Caspian Sea

Coscinodiscus sp.

Liebisch (1929—1930) supposed that the skeleton consists of two membranes, one of pectinous matter and another of hydrated SiO2. At the present time the presence of organic matter (pectin) as well as silica in diatom skeletons is accepted by all investigators. At first the majority believed this material to be cellulose (see Weiss, 1871), but later Mangin (1908) and Liebisch (1929—1930) showed that this pectinous substance is a complex polysaccharide which is widely distributed in the plant kingdom and is the important factor in the formation of jelly when fruit is boiled. Some investigators, such as Bachrach (1927), believed this substance to be hyalin (a general name given to certain proteins whose structures are unknown35), which has no relation to the polysaccharides. The presence of pectin distinguishes Diatomeae from the Chrysomonadina, although they are often considered to be related. Pfitzer and many others (see Kolbe [1932], Richter [1911]) presumed that SiO2 occurs not in the form of SiO2 or one of its hydrates, but rather in a compound with organic, or sometimes inorganic, matter. At the present time, however, it is supposed that silicon occurs as amorphous silicic acid; x-ray study of SiO2 in diatoms by Vinogradov (1939) for Rhizosolenia and by Kahane (1935) anc^ Rogall (1939), showed that it is amorphous (see also Brieger, 1924). From the work of Murray and Irvine (1890—1891) the source of silicon in diatoms became known. It was shown that kaolin particles suspended in sea water are split by diatoms into hydrates of SiO2 and A12O3, and experiments by other investi3£. From the determinations of protein, fat, and carbohydrate in diatoms no decisive conclusions can be drawn (see Brandt and Raben, 1919-1922, and Emmons). Hahn (1925) reported the discovery of a proteinous substance in deposits of kieselgur, the so-called cornuite.

152

Memoir Sears Foundation for Marine Research

gators, Vernadsky (1940) and Coupin (1922), have confirmed the fact that the kaolin nucleus is split in the presence of diatoms and bacteria.36 Furthermore, Vinogradov and Bolchenko (1942) showed that diatoms destroy kaolin (nacrite) with liberation of aluminum hydrate by the action of their slime, composed of pectin. Thus the SiO2 is utilized by diatoms, and the other part containing A12O3 remains in the water or in the silt. Free hydrated aluminum oxide has been found in silt, but the fate of this material is not clear, since the problem of the biogenic migration of aluminum has been neglected. From the analyses of Anderson (see Murray and Renard, 1891) and the author, it is seen that aluminum is present in diatoms ; according to Samoilov and Roshkova (1925) there is aluminum in diatom skeletons from the bottom of Lake Baikal. The aluminum data are given together with those of iron. Ktitzing (1844) suggested the possibility of the presence of hydrates of aluminum and iron oxide in the skeletons. Other elements in diatom ash have been little investigated. Naumann (1930) and Richter (1911) found iron in freshwater forms, for example in Eunotia impressa, and Richter (1911) and SJ6stedt (1921) found deposits of iron in Cocconeis scutellum var. ornata and in C.pediculus var. baltica. Molisch (1926), Weiss (1871), and Schneider (1897) also found iron deposits in the organic base of the skeleton, some species showing more (Pinnularia, Navicula, and Nitschia] and others less (Fragillaria, Synedra, and Gomphonemus}. Usually, however, there is from I to 5 °/o Fe2O3 in the ash, or from 0.5 to 2.0% in the dry matter (see Tables 86 and 87). Thompson, Bremner and Jamieson (1932) observed that if a sample of sea water is allowed to stand for some time the iron disappears from it, this element being almost completely extracted by the diatoms. Hence, iron is more concentrated in filtered sea water below the level of diatoms. Cooper (i937-b) found the ratio Fe/P equal to i.o in Coscinodiscus excentricus, and in the mixed plankton from the English Channel (1939) and in plankton consisting chiefly of diatoms (i 935-c) he found approximately the same ratio, 4.2 to 4.4. According to our data, the ratio Fe/P in Lauderia borealis is 25/360, in Nitschia 1/175 (?)• ^ *s possible that in different parts of the sea at different times of the year these Fe/P ratios change somewhat, depending on the physico-chemical conditions. In any case the ratio is considerably lower ( from calcareous pieces of shells, from spicules of sponges, and from other skeletal particles of Protozoa. D'Orbigny (1826), Schultze (1856), Reuss (1859), and later many others, described such sandy or agglutinating forms of Foraminifera. The division into calcareous and arenaceous forms is still used. It has been observed that under certain conditions, changes occur in the shells of Foraminifera; not only is the magnitude and thickness altered but also the chemical composition. The strictly freshwater forms, Lieberkuhnia wagneri> Plagiophrys cylindrica^ Rhynchogromia variabilis^ and Diplogromia brunneri> have an organic scleroprotein 3. Trichosphaerium rieboldti is a marine form; many others are known but not adequately distinguished.

Chemical Composition of Marine Organisms

165

skeleton which sometimes collects foreign material. Marine forms, transferred into slightly saline waters, lose their mineral skeleton and exist with an organic membrane, become agglutinating forms, or forms containing SiO2; this is true of Gundriella sp., G. irregulariS) Rotalia beccarii, Polystomella, Miliolina oblonga^ and other species of Miliolina. Others at great depths in the sea have an organic membrane; they exchange the calcareous shell for a sandy one, which activity is possibly caused by the dissolving action of sea water under great pressure on the calcareous shell. Thus skeletal isomorphism occurs among Foraminifera in connection with change in habitat, so that similar forms possess skeletons of different chemical composition.1" Known also are forms which are half sandy and half calcareous, as for example Endothyra, and certain calcareous forms which are more closely related to some arenaceous forms than they are to other calcareous forms. However, this does not diminish the significance of the chemical composition of the shell of Foraminifera for genetic comparison, and it does show the diverse paths which their evolution can take. First we will examine the composition of arenaceous Foraminifera which have an organic skeleton with properties similar to a chitinous one and which agglutinate particles of sand and similar bodies. Then we will consider the siliceous and calcareous Foraminifera. A. ARENACEOUS FORAMINIFERA. The first material analyzed chemically was the collection of Foraminifera obtained by the CHALLENGER Expedition. Brady (1884) quotes analyses by Wright and Dunn for two families of Foraminifera from the Atlantic Ocean—Astrorhizidae and Lituolidae. In 1911 Faurd-Fremiet added to these analyses a number of determinations of calcium and iron for the same families in the Mediterranean Sea (see Table 93). The basis of the mineral part of the skeleton of these Foraminifera is SiO2, sand, and so forth, which is cemented by CaCO3, by hydroxides or carbonates of iron (giving the shells a brownish red color), and by organic matter.4 The amount of silica in the sandy forms is high, and in the skeletons of some of them there are hydrates of silica formed by the organisms and not by agglutination of siliceous material from without. Foraminifera such as Cystammina (= Ammochilostoma) pauciloculata have been described as having skeletons containing SiO2, the pseudoquartz of Penard; according to Rhumbler (i 892) this is also true of Allogramiidae, which are transitional forms between the sandy forms and the specifically siliceous forms (see Averinzev on the discovery of similar phenomena in Nebela and other freshwater species). The cement in the organic part of the skeleton of arenaceous species is a mixture of hydrated iron oxide and CaCO3 in different proportions. According to Faurd-Fremiet (1911), the iron is in oxide form, but it may well prove to be carbonate.5 Brady (1884) i H. Cushman (1940) believes that records of siliceous tests in the Miliolidae are based on errors of identification. He accepts the thickening of the organic layer in such organisms in brackish waters. 4. The material agglutinated by the sandy Foraminifera varies with the sediments of the ocean bottom; in turn, the distribution of these organisms is in accordance with the sediments. 5. CaCO, apparently occurs as calcite (see Lister [1903] and Stromer Reichenbach [1909]), so the iron is probably

12*

166

Memoir Sears Foundation for Marine Research

supposed it was Fe(OH)3. The precipitation of iron and CaCo3 is an active physiological process in the Rhizopoda. Faurd-Fremiet (1911) found iron in the cytoplasm of Rhizopoda, and a little earlier Rhumbler (1897) showed qualitatively that iron as well as sulfur are present in the sandy Foraminifera. The concentration of iron in the skeleton of sandy Foraminifera is especially great in two species, Haflofhragmina and Cyclammina. In some regions the Foraminifera cover enormous areas of the ocean bottom. In the Barents Sea, according to the data of the PERSEUS Expedition, they form a layer, several centimeters thick covering the western part of this sea (see T. I. Gorshkova). We have studied Rhabdammina ooze from the Barents Sea, from St. 1119 e/s PERSEUS, and according to our data, fresh Rhabdammina cores collected from this ooze contain 2.4O°/0Fe2O3 in the ash.6 Gorshkova found a good deal of Fe2O3 in a similar deposit. Hence, in regions dominated by these organisms there is apparently a biochemical enrichment of iron in the silt. Thus Rhizopoda play a role here that is analogous to that of the iron bacteria which form the iron manganese concretions in the sea. Manganese was found in the arenaceous Foraminifera by Faurd-Fremiet (1911), and aluminum was found by Brady (1884); we found manganese, aluminum, and titanium in these organisms.211 Sh. Kaminskala (1937) found 3 X io~ 2 °/ 0 titanium in the ash of Rhabdammina^ or 1.5 x io~ 2 °/ 0 in the dry matter. The relatively high titanium in Rhabdammina reminds us of the iron bacteria. Probably we would also

TABLE 93 COMPOSITION OF SHELLS OF SANDY FORAMINIFERA (IN •/, OF ASH) SPECIES

SiOa

CaCO, Fe2O8 Locality

Author

Rhabdammina abyssarum .

94.7

2.9

Wright and Dunn

Hyperammina friabilis

88.26 4.01 — 1.9 93.63 3.95

Haplophragmina latidorsatum Cyclammina canceltata.

jfstrorhiza crassatina .

.

.

2.4*

North Atlantic

7.41 2.40 Barents Sea 2.02* North Atlantic

76.1 84.8

7.3 5.5

16.3* 9.4*

—

6.8

8.55

1 Q l.O

Z.J

OR*

(see Brady,

»

»

»

Vinogradov, 1933 Wright and Dunn (see Brady,

„ „

1884)

„

„

1884)

„

Prince Albert of Monaco, Faur^-Fremiet,

St. 1017,2717 „

1911

„

• With a small quantity of A1,O,. in the form of FeCOa, isomorphous with calcite, although this is unverified. Iron has been qualitatively determined in many freshwater species of Foraminifera by Averinzev (1907) and Schneider (1897). 6. In the older samples of Foraminifera cores there was a larger quantity of Fe,O8. 2H. Mention may also be made of the extraordinary case of Ealhysiphon argenteus which, according to Dick (1928), regularly incorporates minute acicular crystals of rutile (TiO2) apparently derived from the titaniferous schists. These are accompanied by some platey material soluble in HC1.

Chemical Composition of Marine Organisms

167

find the same amount of this element in organogenic iron ore.7 The accumulation of iron in Rhabdammina, Hyperammina, and others is certainly related to specific conditions of habitat, aeration, pH, and so forth, which is interesting from the paleobiological and taxonomic standpoint.8 B. SILICEOUS FORAMINIFERA. Turning to the siliceous species, which are as yet inadequately studied, we find that their skeletons consist of silicate and organic matter only and that they sometimes have the same form as the lime-magnesium Foraminifera. The relationship of the siliceous to the arenaceous species is not clear, since forms occur which are transitional between the two. The parts of the skeletons containing SiO2, pseudoquartz and opal (SiO2 • nH2O), are formed biochemically. These substances, in the form of balls of uniform size, plates and similar particles, are secreted as a bound organic compound and form the skeletons of the freshwater Foraminifera, such as Euglypha globosa and Quadrula. Rhizopoda have been described also as having a homogeneous skeleton of opal. The optic properties of the skeletons are used to determine SiO2. Schmelck (see Brady, 1884) found io,6°/ 0 SiO 2 in Biloculina ringeus, and in another case, 7-6i°/o SiO2, the residue being CaCO3. The acid-insolublfe residue was taken as SiO5. However, Biloculina is actually a calcareous species, with 92.05 °/0 CaCO3 in the skeleton; the presence of an insoluble residue may be explained as contamination, the shells having been taken from the ocean floor. Recently there have appeared some further observations on SiO2 and SiO2 + CaCO3 in Foraminifera. Penard was the first to describe several forms with a siliceous skeleton, including the freshwater species Quadrilella symmetrica; to use Penard's expression, this skeleton was "isomorphous" with that of another, Quadrilella irregularly the latter consisting of CaCO3. Averinzev suggested at that time that there was convergence of form in shells of different composition. Also, Chapman (1904) described similar nonagglutinating species as "isomorphous"—Miliolina oblmga var. arenacea with an SiO2 skeleton and M.oblonga with a CaCO3 skeleton. Heron-Allen and Earland (1930) established for M. oblonga var. arenacea the genus Miliammina^ from Antarctic waters. Though Cockerell (1930) assumed that the Miliolina of Chapman and the Miliammina of Heron-Allen and Earland were the same genera, an investigation by the latter authors showed that Miliammina has a shell with three layers (an inner layer, an intermediate layer of CaCO3, and an outer layer of hydrated SiO2) which is not found in Miliolina.*11 All these examples show the complexity of the chemical composition of some foraminiferal shells of siliceous species. The form of the SiO2 is not clearly under7. According to Vlodavets, there is 0.27 °/0 TiO, in iron bacteria. In the iron manganese concretions, there is from 0.13 to 1.05% TiO,, according to the data of Greiner, Gibson (see Murray and Renard, 1891, Appendix II), Tshurina and Gorshkova. 8. See Averinzev (1907) on iron and SiO, in freshwater rhizopods, in particular the species with SiO, in some parts of the skeleton. 3 H. Several fossil genera from the Mesozoic and Eocene are grouped with Miliammina to form the family Silicinidae (see Cushman, 1940).

16 8

Memoir Sears Foundation for Marine Research TABLE COMPOSITION OF SHELLS OF MAGNESIUM-CALCIUM

SPECIES

CaCO,

MgCOs

Fe2O,

GMgerma bulges

93.14 91.32 92.54 77.02 93.60 84.38 92.85 86.46 88-2 88.74 87.91 89.01 89.76 90.11 88.76 88.70 92.05

0.57 0.30 0.87 3.67 4.8 1.79 4.9 12.52 8.8 9.55 10.50 10.55 10.04 9.33 11.22 11.08 —

1.72 2.72 1.25 3.98 0.1 4.94 trace 0.68 — — 0.13 0.09

I I ! Pulvinulina menardn Opereulina complanata Sphaeradina dehiscent JmpKstegina lessonn Orbitolites complanata var. lacimata „ . OrbitoKtes marginal Orbiculina adunca Quinqueloculina auberiana Polytrema mineaccum Tinoporus baculatus Eiloculma sp

0.19 —

SiOa

0.56 0.02

1.57 1.83 1.36 (15.33) 0.9 8.89 0.3 058 0.3 0.14 0.11 0.31 0.11

stood; probably it is opal, but there are no data to confirm this supposition. Because of a superficial likeness in the siliceous Foraminifera between individual particles of skeletal SiO2 and quartz, Penard called the substance pseudoquartz. C. CALCAREOUS FORAMINIFERA. These organisms are usually divided into the Perforata with a glass-like shell and the Imperforata with a opaque porcelain-like shell. The calcareous nature of the shells has been known for a long time and has been confirmed by many investigators, who supposed that the shells consisted only of CaCO3. But their true composition was made clear only after analyses by Wright and Dunn (see Brady, 1884) and later by Clarke and Wheeler (1922) and others. Actually the Foraminifera investigated sometimes contain considerable amounts of MgCO39 in addition to the CaCO3. Thus, they are magnesium-calcium rather than calcareous organisms. The MgCO3 may reach 12.52 °/0, especially in species living at the bottom of the sea. On the other hand, Globigerina^ and the species closely related to them, which, according to some investigators, are those of the families and subfamilies Rotuolidae, Sphaeroidinae, Pulvinulinae, and others, contain noticeably less MgCO3 (see Table 94); this is especially true of those present in the plankton,10 such as Globigerina bulloides. 9. See the composition of fossil forms and limestone. Compare the MgCO, of the nummulite limestone with that of the fusulina limestone. 10. Compare with the magnesium content of other plankton organisms and Mollusca. As a rule, in pelagic invertebrates, if the skeleton contains any CaCO3, there is also a small amount of MgCO,. In the early stages the shells of

0.03 —

Chemical Composition of Marine Organisms

169

94

AND CALCAREOUS FORAMINIFERA (IN '/• OF ASH) Form

Locality

Author

Perforata (pelagic)

Perforata

„

40°34'N, 66°09'W

Imperforata (benthic) » » »

Brady, 1884

»

Imperforata Imperforata (benthic) Imperforata (benthic)

•

.

'

.

. . . . . . • - . . .

•

. . . ,

.

.

.

Philippine Is Cape Verde Is Fiji, Pacific

. . . . . . , . . . . . .

.

w

•

,

w

„

„

»

»

.

.

,

Tortugas, Fla., U.S.A. Key West, Fla., U.S. A. Tortugas, Fla., U.S.A. Bahamas, B.W.I Australia

.

,

,

. . , . . . . , .

Clarke and Wheeler, 1922 Wright and Dunn (see Brady, 1884) Clarke and Wheeler, 1922 Wright and Dunn (see Brady, 1884) „ » » w >? »» w Gibson (see Brady, 1884) »

»

w

»>

Clarke and Wheeler, 1922 „ Chambers (see Clarke and Wheeler, 1922) Clarke and Wheeler, 1922 „ „ Schmelck (see Brady, 1884)

The qualitative analyses done by Btitschli (1908) showed that Globigerina contains a small amount of MgCO3, Amfhistegina a larger amount. In the fossil Nubecularia novorossica up to 26 % MgCO3 was found. The question now arises as to whether or not a genetic relationship can be traced in species which form a series according to the increasing or diminishing amount of MgCO3 in the shells. Although there are only 17 analyses of calcareous Foraminifera, we can list two groups according to the amount of MgCO3. The first calcareous group has a small MgCO3 content of only 0.3 to 5 °/o> while the second has an MgCO3 content of from 5 to I2.5°/0, According to recent data, the first group consists of Foraminifera with a porous glass-like shell, such as Globigerina^ Pulvinulinae, Operculinae, and others, and the second group consists of genera with a solid porcelain-like shell, such as Orbitolites, Biloculina, and others. One would expect that limestone formed by the first group, as for example chalk, would be poor in magnesium, and that limestone formed by the second group would show signs of dolomitization. Foraminifera with a porcelain-like shell, the Imperforata, are benthic forms, while the Perforata, which have a glass-like shell, are mostly plankton forms. Hence, sediments of the skeletons of the pelagic forms should be poor in magnesium with the other forms containing more. But this assumption, inasmuch as it has practical Sphaeroidinae, Pulvinulinae, and others in Table 94 are like those of the Globigerina, although they are classified in different families. Taking into account the chemical composition of the shells, one can assume a close genetic relationship.

170

Memoir Sears Foundation for Marine Research TABLE 95 SKELETONS OF FORAMINIFERA

Types of skeleton

Families

Protein

Allogramidae and others (most primitive, often freshwater forms) Saccamminidae Miliolidae

Protein+agglutinated material Protein-(-agglutinated material with calcareous cement Protein+agglutinated material with CaCO3 and Fe cement Protein-(-agglutinated material with SiO2 cement*H Protein+individual particles of SiOa Protein-(-homogeneous SiOa*H Protein +CaCO3 Protein+CaCO3+Mg CO3

Astrorhizidae, Lituolidae (Haplophragminae), Hyperamminae, and others Silicinidae Miliolidae and others Globigerinidae, Sphaeroidinae(P), Orbitoididae, and others

*H. No examples of these categories are given in the original tables.

significance, should be verified. According to Brasier (see Murray and Renard, 1891), the globigerina silt of the open sea contains only 0.87 to 1.3 °/0 MgCO3, and according to Gebbing (i 927) i .4 °/0, Thorp (i 931) analyzed the globigerina and other foraminiferal silts from the Karaib Sea; his analyses show that the smallest amount of MgCO3 (i to 1.6 %) is found in the globigerina silts, while an average of 3 °/0 MgCO3 or more is found in other silts. Mineralogically the shells do not differ. By x-ray analysis Mayer (1932) confirmed the presence of calcite in all the calcareous and magnesium-calcium Foraminifera in the species from the families Globigeriniidae, Nummulinidae, and Miliolidae. Sollas (1885), Sorby (1879), and even earlier investigators, supposed, from the specific gravity of the CaCO3 of the shells, that the majority of Foraminifera contain calcite,

TABLE 96 COMPOSITION OF SKELETAL PROTEIN OF INVERTEBRATES

C

Pseudochitin Spongin Cornein Conchiolin Byssus protein Fibroin

H

— 48.51 49.4 52.87

—

48.39

—

6.30

6.8

6.54

—

6.51

N

o

8(?!) 14.79 17.2 16.6 13.0 18.40

,—

— — — —

26.0

s —

0.73

—

0.85

— —

I „_ 1.5 7.8 — — —

Foraminifera Porifera (Euspongia) Octocorallia (Gorgonia) Mollusca (Pinna) Mollusca Insecta (Bombyx)

Chemical Composition of Marine Organisms

171

although they admitted the presence of aragonite in some forms. Only calcite was found by Biitschli (1908) in Globigerina and Amfhistegina^ in Polytrema by Meigen (1901), in some Perforata by Kelly (1900), in Lagena, G/obigerinay and others by Schmidt (1924). Averinzev (1907) investigated the optic properties of a number of calcareous foraminiferal shells and demonstrated the presence of calcite. Furthermore, Rhumbler (1892) regarded certain specific characteristics observed in the investigation of optic properties of these shells as important. The form in which MgCO3 occurs is unknown, but it is doubtful whether dolomite is present in the shells. The hexagonal calcite crystals differ from those of MgCO3 and do not produce isomorphous mixtures ; they produce only double salts of a definite composition such as dolomite. However, in no case of foraminiferal or other invertebrate skeletons has MgCO3 and CaCO3 been found in a ratio equal to that of these elements in dolomite, which suggests that MgCO3 is in some other form. In magnesium-calcareous foraminiferal shells Mohr (i865-a) found traces of phosphorus and fluorine. 2.

Xenophyophora

A peculiar chemical composition distinguishes this group of preponderantly deepwater Rhizopoda, called Xenophyophora by Schulze (1873, 1898—1899, 1906, 1912), who obtained them from the collections of the CHALLENGER, SIBOGA, ALBATROSS, and VALDIVIA Expeditions. With the aid of the data of these expeditions, the range of Xenophyophora in the sea can be clearly pictured. All these organisms are found in a narrow strip along the Equator, between latitudes 39°22' S and 38°N, at depths of 981 to 5,000 m. Schepotieff (1911-1912^, b) described their presence also at depths of i to 5 m at a locality near Ceylon. In the same region, near Colombo, peculiar concretions containing BaSO4 were found by Jones (1888) at the bottom of the sea (1,235 m)> an(i similar concretions were found by B6ggild (1930) in material collected

TABLE 97 SKELETONS OF HELIOZOA, RADIOLARIA, AND XENOPHYOPHORA Type of Skeleton

Organisms

Protein? ......... Heliozoa (fresh water) Protein + SiO 2 .nH 2 O ..... Heliozoa, Radiolaria Protein .......... Thalassophysa (deep water) Protein + agglutinated material . . - Caementellidae (siliceous skeleton) Protein+SiO2.nH2O ..... Spummellaria (marine) Protein +SrSO4 ....... Acantharia (marine; Podactinelius among aberrant forms) Protein + Paluminosilicate . . . . Acantharia (marine, deep water) Protein +BaSO4 ....... Xenophyophora (marine, deep water) Protein and other types ..... Infusoria

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Memoir Sears Foundation for Marine Research

by the SIBOGA Expedition from the ocean floor in the region where Xenophyophora were found.11 Thierfelder, when investigating various inclusions of several Xenophyophora with Schulze (Schulze and Thierfelder, 1905), showed that they consist mostly of BaSO4; these inclusions, called "granellen," reach 3 H in dimension. They have been found in many species of the families Psammonidae and Stammonidae, such as P same fa erythyrocytomorpha and Stamona dendroides. Besides BaSO4, these bodies sometimes contain CaSO4. Andrde (1909), Samoilov (1910), and others thought it possible that organisms similar to Xenophyophora took part in the formation of concretions and other deposits of barites. Apparently some deposits of barites are of marine and organic origin. Sulfur and iodine were also found in the Xenophyophora, which apparently concentrate the latter element. These organisms have an outer protein sheath. Finally, one may reasonably suppose that the arenaceous skeletons with different ratios of iron, calcium, and silica, the magnesium-calcium skeletons with different MgCO3/CaCO3 ratios, pure siliceous skeletons, or those with calcite, and skeletons with BaSO4 inclusions, do not exhaust all the possibilities for diversity of composition of the skeletal parts of Foraminifera. 3. Radiolaria The Radiolaria, of microscopic dimensions, attract attention because of their regular handsome forms. Their remains are found in the most ancient fossiliferous sediments, and the spicules, such as those of the Spummelaria and Nassellaria, contain SiO2 as shown by Ehrenberg in 1838 (see Meigen). The form and composition of the skeletal organic capsule of primitive Radiolaria are like those of freshwater Heliozoa. Among the deepwater Radiolaria there are also forms whose skeletons remain purely organic, as for instance in Thalassophysa pe/agica. Almost all of the analyses of Radiolaria are qualitative. There are those by Hensen (1887) of unknown Radiolaria, and those by DelfF (1912) on Collozoum inerme which contain 0.38 °/0 nitrogen in the dry matter or 4.28 % *n the ashless dry residue ; Vernon found the dry residue in Collozoum smaller than i °/0.12 These data remind us of the analyses of diatoms.

TABLE 98 CHEMICAL COMPOSITION OF RADIOLARIA (IN »/o OF DRY RESIDUE)

Dry matter

ORGANISM

Collozoum inerme Radiolaria . .

, ,

. 12.22 . 67.27

Soluble + insoluble ash

Locality

Author

86.5+1.28* 32.73

Naples Bay of Kiel(?)

DelfF, 1912 Hensen, 1887

* Some of the insoluble ash may be foreign matter. 11. Depth 304m. The silts contain BaSO4, according to N. Bj err urn's analyses (see Bjerrum and Unmack, 1929). 12. Which is doubtful, because sea water contains > 3 °/o

Chemical Composition of Marine Organisms

173

TABLE 99 COMPOSITION OF SKELETON OF ACANTHOMETRA PELLUCID1UM (IN °/0)

CaO MgO Fea03 (+A1203) SiO2 loss

31.4 trace 17.6 21.6 29.6

100.2 The organic capsule of most species of Radiolaria contains spicules or complicated lattices of skeletal SiO2 *nH2O (see Immermann). Borgert (1909) describes cementing forms (Caementellidae) that contain silica. Schr6der (1901—1903), describing the species Cytodadus gracilis and C. major from the Atlantic Ocean, points out that the parts of skeletons of those forms that contain silica, the so-called "stacheln," are not as easily dissolved in HF and H2SO4; the middle part of the spicule is easily dissolved, but the inner and outer parts dissolve with great difficulty. Miiller (1858), who believed that the skeletons of the majority of Radiolaria contain silica, was the first to examine the character of the crystals present in a radiolarian, Collosphaera Huxley; the crystals could not be dissolved in cold acids and alkalies, and certain signs indicated that the material had properties like those of SrSO4 and BaSO4. Brandt (1885) also showed that the inorganic part of the skeleton of Acantharia is not SiO2. Averinzev (1903), and later Biitschli, found that the skeletons of some Acantharia (Acanthochiasma and Xiphicanta) show double refraction, a property not characteristic of SiO2 -nH 2 O (opal). Sheviakov (1902) investigated the composition of the skeleton of Acanthometra pellucidum, which dissolved in H2SO4 without giving off gas ; according to Schr6der (1901-1903) it consisted of various chemicals (see Table 99). On the basis of this analysis, Sheviakov concluded that the skeleton consists of a hydrated calcium aluminosilicate. The loss in the analysis is explained by the presence of water and alkali, which were not determined. Biitschli (1907), who obtained material from Schr6der that was collected during the South Pole Expedition, and which consisted of an atypical sessile form of Radiolaria, Podactinelius sessilis, did an analysis of the skeleton. From spectroscopic analysis, as well as from the form of the salt crystals of the skeletal matter, he concluded that the skeleton consisted of SrSO4.13 Other Acantharia, from the Bay of Naples, also gave a clear strontium reaction. Besides this element, silicon, iron, calcium, and sulfur were found in small quantities. Popofsky (1904—1906), studying the chemical composition of the skeletons of Acantharia, suborder Acanthophracta (for instance Astrocapsa tritonis and other Astro13. Up to 7°/0 SOa was found.

i 74.

Memoir Sears Foundation for Marine Research

capsidae) from the Antarctic, found that the skeletons dissolved easily in sulfuric and hydrochloric acids and that with barium chloride they showed the presence of SO4. A flame test gave the coloring produced by strontium salts. Popofsky concluded, therefore, that the skeletons of the Astrocapsidae which he investigated contain strontium. Schmidt (1924) found that the skeletons of Acanthometridae, such as Amfhiloncha, exhibited double refraction in polarized light. Sheviakov (1902), in his monograph on the Acantharia, returned to this subject and confirmed his former hypotheses. He pointed out that the form Podactinelius is not typical of the radiolarians; according to Mielck they should be classified with the Heliozoa. However, the composition of the skeleton remains an open question.411 Interest in this problem has increased since the possibility of an organic origin of celestines has been recognized (see Samoilov, 1910); apparently only the southern Acantharia contain celestine. As we shall see shortly, marine organisms contain 0.5% strontium or more, especially in the CaCO3 skeletons. In some Radiolaria Sheviakov (1926) found crystals of calcium phosphate.14 Iron was indicated qualitatively by Schneider (1897). Shepherd (1940) found o.oi to 0.05 °/0 fluorine in Radiolaria silt. 4. Heliozoa, Infusoria, and other Protozoa HELIOZOA. The freshwater organisms have an organic protein capsule and spicules or a net of amorphous SiO2 "nH2O. This is true of Clathrulina elegans and Acanthocystis turfacea, which were analyzed for silicon by Hertwig (see Schulze and Kunike, 1923). Mangin also found SiO2 in the skeletons of the Chalarothoraca.** We know of no other data on the composition of these organisms. INFUSORIA. The marine Tintinnoidea have an organic sheath which is probably protein, and there are unverified indications of the presence of hemicellulose in some Infusoria. In the freshwater Infusoria the presence of crystalline calcium phosphate has been indicated but not confirmed.15 Halliburton (1885) gave an analysis of colonies of the ciliate Ophrydium versatile, containing 0.07 °/0 ash. Some Infusoria are iron organisms (see Molisch [1926] on Vorticella and others). Sulfur has been found in the forms living in sulfur springs (see Cohn, 1892). One observation on SiO2 is especially interesting; according to Weineck (1931) SiO2 is found in the form of a siliceous gel in the pellicula of Ophryoscolecidae, which live in the stomach of ruminants (see Eber4 H. Celestine determined by x-ray diffraction, spectrographic and chemical analysis, and containing very little Ca contaminating the Sr, has been found forming the skeleton of an Acantharian from the North Atlantic off Delaware Bay by Odum (1950). 14. This has been questioned. 5H. Penard (1904) indicates that of the various genera of Chalarothoraca, Heterophrys has organic spicules, the others siliceous. The Desmothoraca appear to have organic skeletal elements. 15. Trichosphatrivm neboldti and other organisms, at certain periods of development, contain little needles of CaCO, situated radially. Luce and Pohl (1935)) on the basis of certain analyses, suppose that the crystals, which are often found in Protozoa, for example Amoeba, may be calcium chlorophosphate. See Needham, Needham, Yudkin and Baldwin (1932) on phosphorus in Glaucoma sp., as well as some Flagellata, Eodo eaudatus and Polytoma uvella.

Chemical Composition of Marine Organisms

175

lein, 1895). Some analytical data exist for Paramedum caudatum\ Grobicka and Wasilevska (1925) found up to 12.81 °/0 N2 in the dry matter. Sheviakov (1894) indicated that calcium phosphate is present in Paramedum. Thus it is apparent that there are no systematic observations of these organisms, and all the examples quoted are obviously atypical cases. 5. Rarer Elements Traces of iodine were found by Cameron (1914) in Prorocentrum, and we should note the presence of boron (0.05 °/o), selenium (< o.oooi °/0) and yttrium (< o.ooi °/o) in the Globigerina and Radiolaria silts, according to Goldschmidt and Peters (1932). Engelhardt (1936) found o.oi to o.O3°/ 0 BaO in Globigerina and Radiolaria silt.

Chapter VII Elementary Composition of Porifera I. General Remark*

I

N THE beginning of the last century there was established a method of classifying sponges according to the chemical composition of the skeletons, namely horny, siliceous, and calcareous sponges. The main lines of this division are still used. The classification of sponges followed here was employed by Alander (1942). Three classes are recognized in the Phylum Porifera. These are: Demospongiae, Calcispongiae (Calcarea), and Hyalospongiae (Hexactinellida). This primary subdivision is based on the chemical composition of the skeleton of sponges. The Demospongiae have skeletons consisting of organic matter only or of a combination of organic matter in varying amounts together with siliceous spicules (one- to four-rayed). The Calcispongiae bear calcareous skeletons. The Hyalospongiae have siliceous skeletons made up of six-rayed spicules. Spongin is absent from the last two classes. The Demospongiae may be broken down into two orders: Cornacuspongida, which always possess spongin and may or may not contain one- or two-rayed siliceous spicules; Tetraxonida which lack spongin, have a radiate skeletal architecture, and have one-, two-, and (or) four-rayed spicules. In modern taxonomy, one part of the skeleton, known as the spicule, has acquired great significance. Hence, classification of the species of Porifera is based on (i) the morphological character of the spicules, which are uniaxial, tetraxial, 3- or 6-rayed, or even more complicated in form, and (2) the history of the formation of the spicules, primary spicules, secondary spicules, and so forth. Since the chemical composition of spicules and of sponges has not been adequately considered, there has not been any division of sponges beyond siliceous and calcareous forms. However, we will try to draw the attention of the reader to such characteristics of the chemical composition of Porifera, chiefly of the skeleton, which could be used in the taxonomy of these organisms.

i76

Chemical Composition of Marine Organisms

177

Early investigators did not know the basic substances in the common horny sponges.1 In 1706 Geoffroy found NaCl, MgCl2, and salts of iron in the bath sponge (genus Sfongia)\ Levis (1771) repeated these observations. Lavoisier (1784) investigated for the first time the organic composition of the sponge. Somewhat later, in the beginning of the nineteenth century, we find more detailed analyses of the bath sponge by Ragazzini (1835), Herberger (1835), Sommer (1834), Bley (1834), who analyzed sponge concretions, Sommer and Preuss (1837), and Heyl (1847); Trommsdorff (1805), Vogel (1814), Jonas (1828), Hornemann (1828, 1829), Kressler (1832), and Posselt (1843) noted the quantity of elements such as iodine and bromine. However, we do not give their data in full, since the analytical techniques used by them are antiquated. Furthermore, for a long time the subject of investigation was the same sponge, usually obtained from the market after undergoing a manufacturing process, and such sponges were known under several different names.2 The presence of SiO2 in animals,3 specifically in sponges, was noted for the first time in 1788-1789 by Abilgaard (see O. Muller, 1788-1806) ; somewhat later siliceous spicules were described in some Porifera. Gray (1825) separated sponges with SiO2 spicules from Alcyonaria with CaCO3 spicules, and in 1826 Grant discovered CaCO3 in the spicules of Grantia comfressa. These investigations, then, established the division of sponges into the calcareous and siliceous forms which we mentioned above. 2. Water, Ash, Carbon, Hydrogen, and Nitrogen*

A kind of protein called spongin comprises the greater part of the skeleton of many sponges. In the genus Darwinella the spicules are entirely spongin, while the spicules of the siliceous sponges, containing SiO2 • nH2O, are cemented by this material; in the Hyalospongiae the siliceous spicules are often bound together by SiO2 'nH2O. As a rule the spicules of Calcarea are freely situated in the body of the sponge,5 and they are seldom cemented by CaCO3, Owing to certain peculiarities in structure, particularly of the horny sponges, they are able to retain enormous quantities of water, 20 or 30 times their dry weight. Unfortunately many determinations of water in sponges done in the usual way are suspect, since the data often fail to show the amount of water which is part of the body composition and that which is external in the pores. However, the data given in Table 100 are adequate as primary approximations of the amount of water in sponges. The amount of organic residue in sponges is small and fluctuates from species to species.1" The amount of ash is least in horny sponges and greatest in siliceous 1. A history of the investigation of sponges is given by Uhle (1819) and Arndt (1926, 1929); a bibliography is given by Vosmaer (1928). 2. Spongia marina^ S. usta, S. tosta, S. marina usta, and other names were used in the bath sponge trade. 3. Alcyonium lyncurium [= Tethya aurantium) and Sabella chrysodome. For further synonyms see special works. Some indications of the presence of SiO2 in sponges can be found in the work of Welter (1798) and Schweigger (1819). 4. Besides the analyses given in Tables 100 and 101, partial ones are given by Schulze (1873), Siedler (1896), and Detgen. 5. The organic matter of the Calcarea has not been investigated. iH. For recent determinations of the percentage of spicular material in the dry weight, see Bergmann (1949).

178

Memoir Sears Foundation for Marine Research TABLE 100 WATER, ORGANIC MATTER, AND ASH IN PORIFERA (IN °/0 OF LIVING WEIGHT)

ORGANISM

H2O

Demospongiae Tetraxonida Chondrosia reniforms Tethya aurantium (=lyncurium) Stellttta wagneri . . . . Suberites massa

84.0

Suberites dommculus

Cliona hixoni Cornacuspongida Irdnia (j=Hircima) sp 11 'Hippospongta equina" var. elastica* sp Desmacidon fruticosus Aftcrociona prolifera Calcispongiae Sycandra raphanus

.

.

.

.

74.53 77.5 82.2 85.5 78.6 73.23 77.50 93.0

Organic matter

Ash

11.33 13.67 8.00 10.0 7.10 11.79

4.67 11.80 14.50 7.80 4.40 9.61

7.8

14.9

83.8 94.1 86.13

12.0 —

5.46

91.1 83.0

— 17.0

— —

90.15

4.2

3.61

• Hifipotpongia equina is regarded by Burton as a variety of Spongia

6.24

Author

Krukenberg, 1881-1882

Putter, 1914 Krukenberg, 1881-1882 Cotte, 1901 Putter, 1908 Lendenfeld, 1886 Putter, 1908 Allemand-Martin, 1921 Conn. State Exper. Sta., 1890 Bertrand, 1903 Bergmann and Johnson, 1933 (Long Island Sound) Putter, 1908

offidnaUs.

species, especially in the deepwater Hexactinellida and calcareous sponges. The ratio between organic matter and ash in the dry residue fluctuates from 1/10 to x / 2 of the average organic matter of the siliceous sponges, according to the data of Clarke and Wheeler (1922) and many others.6 Determinations of carbon and nitrogen in sponges are rare and probably incorrect. Besides those in Table 101, Stary and Andratschke (1925) determined nitrogen in sponges. The carbon content of the organic ashless residue of Suberites domunculus reaches 52.53°/0, and nitrogen is 7-95°/o' Hence if we exclude the analyses of spongin,7 we see that there are almost no determinations of nitrogen in entire sponges. 3, Class Demospongiae, Order Cornacuspongida

All the earlier analyses of sponges, commonly called bath sponge, common sponge, or sea sponge (Spongia marina, usta, and so forth), probably refer to species of Spongia. 6. Moore, Edie, Whitley, Dakin (1912), and Vogel (1814). Delenk (unpublished work cited in Pax and Arndt, 1937) found up to 7.3 °/0 ash in "Hippospongia." 7. The organic matter of Spongia contains 16.15 */o nitrogen, Irdnia 9.2 °/0 (spongin); see Stary and Andratschke (1925), Posselt (1843), Croockewit (i843~a, b), Maly (1880), Krukenberg (1881-1882), Penneder (1881), Hammer (i9o6-a), and Lavoisier. See also Zalacostas (1888), whose earlier work showed the carbon, nitrogen, and hydrogen in spongin.

Chemical Composition of Marine Organisms

179

Their ability to retain a large amount of water was demonstrated in several early analyses. Besides the investigators previously mentioned, Hatchett (1799), Fourcroy and Vauquelin (1811), Muhry and Wiggers (1834), Thomson (1843), and Haen demonstrated qualitatively the presence of the marine salts of magnesium, calcium, sodium, chlorine, sulfate, and then phosphorus, iron, aluminum, and silicon.8 But there are few quantitative analyses that satisfy modern requirements, for in all the analyses it is doubtful whether the investigators were able to eliminate contaminants. In 1878 Torre and Bomboletti published analyses of various sponges, Ircinia, Suberites, Geodia, and Raspailia, but these analyses need to be repeated at the present time. More modern quantitative analyses of Cornacuspongida have been done by Clarke and Wheeler (1922), but these experiments are incomplete, since they concern chiefly skeletal composition (see Table 102). Presumably Ircinia contains more calcium than silicon, a fact which requires some explanation. It is generally known that Porifera catch foreign bodies easily and are extremely difficult to clean preparatory to analysis, but in Ircinia this is further complicated by the fact that the sponge constructs its skeleton by agglutinating silt particles, so that in comparing its composition with that of other sponges one must take this into consideration. We obviously cannot call Ircinia and Spongia officinalis calcareous,

TABLE 101 CARBON AND NIRTOGEN IN PORIFERA (IN % OF DRY WEIGHT) ORGANISM

Demospongiae Tetraxonida Geodia gigas . . . Suberites domunculus. Suberites massa .

C

N

Author

20.64

8.41 — 8.41

Torre and Bomboletti, 1878 Cotte, 1901 Torre and Bomboletti, 1878

7.41 8.41 8.41 8.41

Moore (see Tressler, 1923) Conn. State Exper. St., 1890 Posselt, 1843* Croockewit, 1843-a, 1843-b

—

7.40

Moore (see Tressler, 1923)

— — —

8.41 8.41 8.41

Torre and Bomboletti, 1878 „

.

Cornacuspongida Spongia (=Euspongia) sp.

Spongia offtcinalis (var. tur.t) Hircinia tipica (probably a synonym of Ircinia strobi/ina) Haliclona (= Reniera) flava Raspai/ia typica . . .

Remarks

„

„

Recalculated as dry matter (Adriatic Sea) Air-dried 13.9 H2O

„

Coarse spongin of sponges. 8. See Traxler (1894) for analyses of freshwater sponges. *3

180

Memoir Sears Foundation for Marine Research TABLE COMPOSITION OF CORNACU-

ORGANISM

Si02

Ircinia strobilina ( — tipica) Ircinia campana var turrita . Callyspongia vaginalis (= Spinosella sororia var. crispa) Haliclona ( = Reniera) f l a v a . . . . . . . . Esperiopsis ouatsinoensis Chondrocladia alaskcnsis * Gtlliodts grandis . * Phaktltia grandis . . » , , . , * * * * Halichondria panicta

68.56 2.27 40.53 70.85 92.45 93.35 88.28 94.69 87.93

CaO

MgO

4.75 79.64 36.85 4.67 3.15 2.21 1.30 0.79 2.75

2.76 6.37 3.42 3.06 1.34 1.00 1.45 0.35 1.69

P20s 4.91 2.71 9.08 1.60 0.81 0.54 1.03 0.71 0.20

as do Clarke and Wheeler (1922). Certainly these sponges have more calcium than silicate in the ash, but on the other hand there is very little ash. According to the data of these same investigators, some other typical horny sponges, namely Spongia of fidnalis, S. agaricina, "Hippospongia equina?\ "//." caniculata and Aplysina hirsuta, contain up to 97 °/0 organic residue in the dry matter, or only i °/0 ash in the living sponge. According to the analyses of Torre and Bomboletti (1878), the sponges of the Adriatic Sea contain an unusually large amount of iron.9 In the Cornacuspongida, SiO2, the chief compound of the ash, occurs in varying amounts—from i to 95 °/0. Kahane (1935) found 98.3 and 98.2 °/0 SiO2 in the dry matter of the spicules of Ephydatia fluviatilis.™ It is interesting to note the relationship between the amount of silicate in sponges and their systematic position. Minchin (1910) showed that in the genera Haliclona and Spongia the changes in the skeletons occur by reduction of siliceous spicules, the latter disappearing in Spongia. Thus, if we place the analyses of these sponges in evolutionary order, we arrive at a chemical expression of the evolution of the series (see Table 103). On the basis of this example we would expect to find that in other cases, similar to the Cornacuspongida, the amount of silicon would also be characteristic of species. On the one hand species can be distinguished which are poor in silicon (horny sponges, such

TABLE 103 SiO, IN A GENETIC SERIES OF SPONGES (IN »/o OF DRY MATTER) ORGANISM

SiO2

Spongia officinalis

Author

1.31

„

.

.

. Clarke and Wheeler, 1922

Callyspongia vaginatis (=Spinoselia sororia) . Haliclonaj)cul ata arbuscula

3.08 31.93

.

. .

. .

. .

Haliclona (=Reniera)

37.32

.

.

.

. Torre and Bomboletti, 1*878

flava

9. This is probably due to contamination, especially in the littoral zone. See the section on algae. 10. The composition of the inorganic part of Aplysillidae has not been determined.

F*A

+ A1.03

6.14

9.11 10.13 5.98 2.45 2.84 6.52 3.59 7.36

Chemical Composition of Marine Organisms

18

102 SPONGIDA (IN •/. OF ASH)

NasO

KjO

SOj

Cl

Ash in »/• dry matter

Locality

Author

4.6 —

0.77 —

2.04 ?

4.91 —

55.46 —

Adriatic Bermuda

Torre and Bomboletti, 1878 Clarke and Wheeler, 1922

5.69 —

1.17 —

3.44 ?

5.39 —

52.88 —

Adriatic Alaska

Torre and Bomboletti, 1*878 Clarke and Wheeler, 1922

— — -

— — —

1.37 ? 0.09

— — —

— — —

Gulf of Maine, U.S.A. . . Northeast of Cape Cod, U.S. A. Alaska

I w .

I w .

I w

I w

as the Spongiidae); on the other hand there are the species rich in silicon (as in those species of Haliclona formerly referred to Reniera). There are no systematic data on other elements. Moore (see Tressler, 1923), in one analysis of a sponge from the family Spongiidae, found i. 17 °/0 P2O6, x -^4 °/o K2O, and 1.41 °/0 SiO2 in the air-dried matter. Precise quantitative data for alkaline and alkaline earth elements in Cornacuspongida are lacking; the earlier analyses indicated above cannot be considered, since the marine salts and other foreign bodies were not excluded. On elements found more rarely in Porifera, see further. 4.

Tetraxonida These are typical siliceous organisms. Their skeletons are spicules of SiO2- nH2O and are well preserved in sedimentary rock. The Tetraxonida in fact contain up to 65 °/0 SiO2 in the dry residue and up to 95 °/0 in the ash. The amount of other elements is only i to 2 °/0. Biitschli (1901), investigating the spicules of Geodia placenta (Tetraxonida), demonstrated the presence of other elements, as did Schulze (1873), Ebner (1887), and others. Gorshkova and Terentieva did analyses of well cleaned spicules of Geodia baretti from the Gulf of Kola ; they found that the spicules lacked alkaline earth metals but did contain alkali metals. Clarke and Wheeler (1922) performed analyses of the dry residue of Geodia mesotriaena. These analyses are essentially in agreement, all the spicules analyzed containing alkali, chloride, and sulfate. Samoilov (1911) suggested that the presence of alkali in the spicules of sponges was the cause of the alkali metals, opal, and so forth11 in the siliceous sediments. 5. Class Hyalospongiae (= Hexactinellidae) Stock (1904) found neither calcium nor magnesium in Monorhafhis chuni, but he mentioned the presence of potassium and sodium; however, other species (Table 105) contain alkaline earths. Some Hexactinellida are the richest in silicon of all the sponges. 11. Diatom silt contains 5-6 °/0 NaCl or more. 13*

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TABLE

COMPOSITION OF TETRAXONIDA

ORGANISM

SiO,

CiO

MgO

P,O,

FejO, + AljO,

Na,O

Suberites dmamctdut Svkritumuu Suberitn tuberea Gtodiagigat Geodia metotnama vvr. pachana Geodia baretti* Gt,&a baretti* Geodia placenta Tttitla travata

87.32 15-31 96.25 70.35 98.08 94.55 94.90 92.42 91.74

— 6.53 0.43 3.37 0.44 none . trace 1.19

— 7.21 0.72 1.75 0.57 trace „ 0.16 0.82

0.23 4.28 0.64 1.35 trace — — 0.64

— 6.76 1.61 4.45 0.32 0.19 0.22 trace 4.97

— 16.7 7.95 — 0.3 0.62 0.84 -

* There was a heating loss of 4.52, 3.91, and 5.97•/, in the preparation of the spicules for analysis.

The spicules of SiO2 • nH2O form a homogeneous skeleton that is almost devoid of organic matter and alkaline earth metals; this is also true of some Tetraxonida, particularly Lithistidae. At depths where they are found, only SiO2 skeletons can resist the solvent action of sea water. Hexactinellida contain a smaller amount of alkaline earth metals than Tetraxonida. 6. Aberrant Siliceous Sponges

In regard to other siliceous sponges, one found near Porto Santo and described by Kirkpatrick in 1910-1911 under the name of Merita normanii had a siliceous skeleton in one layer of the body and a calcareous one in another, the latter consisting

TABLE 105 COMPOSITION OF HEXACTINELLIDA (IN °/0 OF ASH RESIDUE)

ORGANISM Pheronema grayi Bathydorus uncifer Euplectella speciosa Monorhaphis fAww* Hyalonema thomsoni

SiQ2

CaQ

Mg0

p^

Fe2Oa+ A^0a ^Q

J^Q

^

Locality

Author

0.03

Iceland

Clarke and Wheeler, 1922

90.70 4.53

trace trace 4.24

—

94.64 3.45

0.60

0.00

1.30

—

—

trace Galapagos Is.

99.18

0.25

0.00

0.00

0.36

—

0.00

86.1

—

—

—

trace

— '

97.6

—

—

—

— D

"

3.8

—

• The amount of water in the spicules was 10.1 /Q* Cl = trace.

Philippine Is. Stock, 1904

—

Kahane, 1935

Chemical Composition of Marine Organisms

183

104 (IN «/o OF ASH RESIDUE)

K,0

3.38 0.81 0.25 0,59 0.63

so, 2.72 8.56 0.51 4.64 0.32

0.54

Cl

Ash

3.56 21.40

16.25 26.3

6.87

71.15

Author

Locality

Adriatic Alaska . . Adriatic . . . , . South California, U.S.A. Gulf of Kola

« . . .

Mediterranean Buzzards Bay, Mass., U.S.A. .

. Cotte, 1901 . Torre and Bomboletti, 1878 Clarke and Wheeler, 1922 . Torre and Bomboletti, 1878 . Clarke and Wheeler, 1922 Gorshkova, 1925 Samoilov and" Terentieva, 1925 . Butschli, 1901 * Clarke and Wheeler, 1922

of crystals of calcite, according to Prior; this sponge belongs to the Monaxonida. Another, an Australian sponge, Collosclerophora arenacea, described by Dendy (1917), has spicules that are sacks containing a jelly-like material of SiO2 • nH2O gel. The absence of analyses leads to difficulties in interpretation; some investigators expressed the opinion that the liquid part of the spicules may contain other substances besides the gel of SiO2- nH2O, such as urates, according to Bidder (1925). So the question of whether or not these sponges really contain silicic acid gel remains unsolved. 7. On the Form of SiO2 in Sponges and Silicon Exchange in the Sea The spicules of siliceous sponges, besides containing SiO2 • nH2O, have a thin outer layer of organic matter and a similar one in the axis cylinder. All investigators agree that the spicules contain hydrated SiO2 in an amorphous state. On the basis of the specific gravity of the spicule material (2.04), Thoulet (1884, 1890), and later other investigators, assumed it to be opal, SiO2 - nH2O. Analyses showed that the water content fluctuates from 5 to 13 %, and a comparison of the water content with that of silicon, assuming the analyses to be correct, shows that the SiO2 of the spicules is in different degrees of hydration in different sponges. Opals are amorphous and contain amounts of water varying from o.o to 35 °/o; when the amount of water falls to 7 °/0, which corresponds to the formula 4 (SiO2)-H2O, the opals become hard. In some natural opals there is a more or less constant amount of water. According to V. I. Vernadsky (1934), the existence of double refraction and the characteristic crystalline skeletal growth, as in the spicules observed in Hexactinellida, are indications of the transition of SiO2 into a crystalline state, into quartz. He considers opals to be aggregates of the smallest particles of hydrated SinO2n-i(OH2)nH2O. The SiO2 found by Penard and others in the siliceous Foraminifera is probably opal also. Amorphous silica, as has been indicated, also occurs in the sheaths of diatoms.

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But the form occurring in Silicoflagellata, Radiolaria, Heliozoa, and in some other Protozoa is unknown,12 and the form of silicon in the tissues of plants, such as Gramineae, Cyperaceae, and Equisetaceae, is not clearly understood. The SiO 2 -nH 2 O compounds in the nodes of bamboo and in sugar cane are opals, the so-called tabasheer (Si02.H20). The spicules of siliceous sponges usually contain from 5 to 13 °/o water, the highest degree of hydration of SiO2 in the spicules occurring in the species of Collosclerophora, if Dendy's (1917) observations are correct, the minimum in the Tetraxonida.13 There are some indications that gradations in the degree of hydration may be of systematic importance. Art example that provides confirmation is the interesting observation of Vosmaer and Wijsman (1904), who found that the peripheral parts and the axial cylinder of the spicules of Tethya aurantium (Donatia lyncurium) have different properties ; the SiO2 of the axial cylinder could be dissolved more readily in HF than that of the peripheral material of the spicules, and undoubtedly the solubility in HF depends on the amount of water of hydration. Biitschli (1901) observed something analogous in the spicules of sponges, and Schroder (1901-1903) discovered the same phenomenon in the siliceous skeletons of Radiolaria. From the different degrees of hydration of SiO2 in spicules of different species one may conclude that spicules of Hexactinellida contain more water than those of Tetraxonida; in the latter the average amount cor-

TABLE 106 AVERAGE WATER OR HEATING LOSS IN THE SILICEOUS SPICULES OF SPONGES (IN o/0) SPONGE

Demospongiae Tetraxonida Suberites suberea Pachymatisma johnstoni , Stelletta (^Anthastra) communis Theonella swinhoei Vetulina stalactites Corallistes masoni Siphonidium ramosum G^w/ftf placenta

HjO

7.34 7.16 ,6.61 6.53 6.27 6.23 6.10 5.97

Hyalospongiae Poliopogon amadou Monorhaphis chum Hexactinellida (?) (needle-shaped) . Hexactinellida (star-shaped) .

7.16 10.8 13.18 12.86

Formula

Author

4 (SiOJ • H2O „ „ „ „ „ „ w

„ 3 (SiO2) • H2O 2 (SiO2) - H2O „

. . . . . . . .

.

,

.

. . . . . .

. . . . . . . . . . .

. . . . . . . . . . . , . . , ,

Sollas, 1885 „ „ „ „ » » „ „ „ „ fl Butschli, 1901 Schulze, 1873 Stock, 1904 Thoulet, 1884

12. Also in the "spicules" of some Mollusca, the Oncidiadeae, and in Bacillus siliceus and in rare cases of other organisms not mentioned here. 13. Also where quartz could be shown to exist.

Chemical Composition of Marine Organisms

185

responds closely to the formula 5(SiO2)-H2O, while in the former the composition is closer to 4(SiO 2 )-H 2 O, even though more water may be present. The dehydration of silica gels is the basis of the formation of siliceous spicules. A certain proportion of silicon is received by sponges from diatoms; it has been observed that the oscula of modern sponges may be filled with diatoms, and similar observations have been made on paleontological material. With respect to SiO2 • nH2O organisms, it is remarkable that they always do the same work; wherever life meets this substance or hydrates of aluminosilicates, a dehydration of silicic acid gels may be observed, the result of this process being the precipitation of SiO2 with a small amount of H2O ; organisms then use the precipitated substance in the form of skeletal or other supporting tissue. This process is general and cases occur throughout the whole of living nature. The organisms which are concentrating silicon at the present time are those found chiefly at the lowest phases of development of the animal and vegetable kingdoms, representing the primitive classes of organisms ;14 all other cases of large quantities of this element in the tissues are questionable, as for example in Alcyonaria and Corallinaceae. Siliceous organisms Plants

Animals

Bacteria Algae Diatomeae Pteridophyta Equisetaceae Angiospermae Monocotyledones Gramineae Cyperaceae

Protozoa Heliozoa Silicoflagellata Infusoria Radiolaria Foraminifera Porifera Demospongiae Hyalospongiae

In all of these organisms a physiological system of exchange of silicon has been created as a result of the action of colloidal solutions containing SiO2 - nH2O, so that at the end of this process the highly dehydrated SiO2 becomes precipitated in the form of opal and other substances in the skeletal and other tissues of organisms. On land, in our own time, an analogous geochemical process exists on a large scale, especially in tropical regions where high temperature and moisture bring about a rapid transition of SiO2 from massive rocks into soil in the form of SiO2 gels, from whence it enters in abundance into plants such as Bambusa, Saccharina officinalis, and numerous cereals in which the isolation of SiO2 • nH2O occurs. In the ash ofEquisetum, particularly, large quantities of SiO2 are found. Let us also take note of the peculiar process of silica extraction from aluminosilicate 14. Labbl (i933-a, b) has recently described siliceous spicules in a mollusk of the Oncidiadeae. Michio Kono (1933) found up to 88 % SiO, in the ash of skeletons of the insects Pulinnaria horii and Cerococcus murata.

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Memoir Sears Foundation for Marine Research

particles by diatoms. Through the activity of diatoms, nature compensates for decaying rocks by the formation of some new rocks in the form of opal and so forth. The breakdown of kaolin particles in clay is accompanied by the liberation of heat; their splitting occurs in land soils with the help of bacteria and possibly other Protozoa and plants. The participation of bacteria in the concentration of SiO2 has become evident only recently with the demonstration of the existence of siliceous bacteria, Bacillus siliceus (Brussoff, 1933). Formation of laterites occurs on a large scale in the tropics and is possibly connected with the life and activity of organisms.15 Organisms that take part in the exchange of silicon belong to ancient groups. Among plants, the siliceous function, characterized by a concentration of silicon by the organisms and by their participation in the formation of rock, is preserved in the primitive monocotyledons, in cereals, in sedges and others. Among animals the siliceous function does not occur above the Porifera. In higher animals only the physiological significance of this element has been preserved, with the element present in small amounts. Thus we find only limited silicon metabolism in the tissues of the higher organisms. In the opinion of Samoilov (1923), Cayeux (1916), and others the siliceous organism, or the siliceous function of living matter, is the most primitive. However, although the siliceous function really belongs to organisms of the most primitive groups, that does not mean that it is more ancient than the calcium function, phosphate function, or other geochemical functions of living matter. One can say only that the siliceous function developed no further in the formation of higher organisms in the process of evolution, whereas the calcium and phosphate functions did retain their significance in higher organisms. Although the evolution of forms of siliceous organisms ceased at the level of sponges among animals and at the level of cereals among plants, the possibility of the appearance of new siliceous forms in the course of further development of organisms is not excluded.

TABLE 107 COMPOSITION OF PORIFERA

COMPOUNDS

Skeletonless SiO 2 -nH 2 O gel + spongin SiO 2 -nH 2 O (opal) with or without spongin

ORGANISMS

Halisarcidae Collosclerophora (?) Demospongiae (Cornacuspongida, Tetraxonida); Hyalospongiae SiO 2 -nH 2 O (crystalline) Hyalospongiae (?) SiO 2 -nH 2 O +CaCO 3 (calcite) . . . . Merlia (Cornacuspongida) CaCO3 + MgCO3 (calcite) Calcispongiae CaCO3 (aragonite) Jstrosclera willeyana; fossil sponges (?) Spongin (in the supporting tissues, spicules) . Cornacuspongida 15. See Vernadsky, 1934.

Chemical Composition of Marine Organisms

187

Since siliceous skeletons are better preserved than those which are primarily calcareous or phosphate, we cannot prove the antiquity of the siliceous cycle in living matter by reference to earlier discoveries of siliceous spicules of sponges, skeletons of Radiolaria, and other organisms, in the most ancient rocks. It is probable that diverse geochemical functions of living matter existed simultaneously, for among modern representatives of ancient types of organisms we find concentrators of all the common elements. Thus we find calcium, iron, manganese, sulfur, phosphate and other geochemical functions, as well as siliceous, developing along different lines in the course of the evolution of organisms. 8. Calcarea Calcarea, which contain spicules of calcite with a considerable amount of MgCO3, appear in the Devonian and Carboniferous sedimentary rocks considerably later than the siliceous forms of the Cambrian and Silurian. The composition of calcareous sponges in general may be described only on the basis of three more or less detailed analyses, since all other analyses are qualitative and few in number. Ever since Grant (1826) established the presence of CaCO3 in the spicules of certain sponges, these organisms have been classified in a separate group. The CaCOg in their spicules is present in crystalline form (see Haeckel, 1872); Sollas (1886-1887), Ebner (1887), and Rauff (1893) supposed that the crystals of CaCOg were calcite. Kelly (1901) observed the same in various Calcarea, as did Btitschli (1908) in Leucandra aspersa. Calcite has been found consistently by Meigen (1901) in Petrostroma sp. and by Schmidt (1924) in Leucandra, Leuconia, and other species. Minchin (1898) described the development of spicules in various species of Clathrina; CaCOg was found in an amorphous state in embryonic spicules, which phenomenon is probably a general characteristic of Calcarea.18 The Calcarea are magnesium-calcium organisms, depending on the amount of calcium and magnesium carbonates. There is great diversity in the amount of MgCO3 in sponges, from 4.0 to 14.0%. Fox and Ramage (1931) made an important observation concerning Clathrina when they discovered a strong strontium line in a spectroscopic analysis of the ash of this sponge ; this element apparently occurs in the form of SrCO3. Other observations, unsystematized as yet, indicate that we still know very little about the composition of Calcarea. In an aberrant form, Astrosclera willeyana. Lister (1900) found a skeleton consisting of crystals of aragonite and not calcite, as is common for Calcarea; the presence of aragonite in the spicules of this sponge was verified later by Hutchinson (1902) and Schmidt (1924). Since we would expect this form to contain less MgCOg than other Calcarea containing calcite, the following assumptions may be made : i) Among the Calcarea existing at present there are others to be found containing aragonite, and 2) there is every reason to assume the past existence of species of sponges 16. Maas (1904) observed the development of one of the Calcarea, Sycandra setosa, in a medium without CaCO,. The spicules consisted of organic matter only and were deformed.

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Memoir Sears Foundation for Marine Research TABLE 108 COMPOSITION OF CALCAREA (IN °/o OF ASH RESIDUE)

ORGANISM

CaCOj

Fe20s + MgCO, AlgC^ SiOa

86.76 6.84 Leucandra aspersa Scypha lingua (= Grantia ciliata)* 84.92 4.61 Leucilla carteri var. homoraphis* 84.96 14.10

0.26 — 10.47 0.94

CaSO4 Locality

Author

1.97 Mediterranean Butschli, 1908 0.00 Woods Hole, Clarke and Wheeler, Mass., U.S.A. 1922 0.00 Puerto Rico

* CagPA = (?).

with aragonite skeletons, for example among the Pharetronidae. Pavlova describes a fossil pharetronid which existed from the Devonian to the Tertiary that has aragonite rays well preserved.17 The Receptaculidae and Archaeocyathinae, Paleozoic fossils closely related to sponges, possessed a calcareous skeleton, but these organisms have not been investigated in any detail. Nothing is known of the composition of the skeletonless sponges, the Halisarcidae and Oscarellidae. It is premature to speak of the quantities of other common elements, such as sodium, potassium, and silicon. Fox and Ramage (1931) found up to 0.005 °/o lithium in Clathrina. The presence of traces of strontium, barium, lithium, phosphorus, and so forth in the tissues of magnesium-calcium organisms has an important significance in the formation of crystals of CaCO3. We shall return to this subject later (see Ebner [1887], Minchin [1910]). 9. Heavy Metals and Other Elements All determinations of metals in sponges are not only isolated but are mostly qualitative. Furthermore, the possibility of contamination complicates the development of an adequate conception of the distribution of metals in various groups of sponges. IRON. The first observations of iron in the sponge were made by Laugier (i 810), and the element was qualitatively determined by Schneider (1922) in many species, namely Thenea muricata, Ephydatia fluviatilis, Sycon raphanus, and others. As a rule it becomes localized in the intercellular matter. The spicules of Thenea contain iron. MacMunn (1886) isolated a pigment from sponges18 which contained iron and which he called histohematin; similar pigments have been isolated by other investigators. Individual determinations of iron were done by Harnack (1896), Haen, and others. 17. It might be well to mention that Merita normanii and Astrosdera wilUyana, both containing spicules of aragonite and formerly classified with the Pharetronidae, are grouped at the present time with other families} it is even doubtful whether they should be classified with the sponges (see Weltner, 1909, on Merlia normanii); the genus Pharetrones is isolated and its systematic position is not clear, which increases the need for a thorough study of the composition of these organisms. In some of them calcite spicules are cemented by CaCO3. 18. In the species of Halichondria, H.panicea, H.alba, MyxUla. [= Halichondria] incrustans; Hymeniacidon albescent, Halina [= Dercitus'} bucklandi, Halidona (= Rentera) rosea, and Suberites wilsoni.

Chemical Composition of Marine Organisms

189

Halfer found o.ooi °/0 iron and traces of manganese in the dry matter of a sponge from Cuba. Robin (1935) f°un(i i.5i°/o iron *n the main skeletal tissues of Spongia officinalis var. hamakis and 0.43 °/0 in S. zimocca irregularis. The peripheral skeletal parts of these organisms contained 0.141 and o.i6i°/o iron respectively. The author has shown the relationship between the amount of iron and the age of sponges. Quantitative determinations of iron are given in part in Tables 102, 104, and 105. Cotte (1903) determined iron in Tethya aurantium (= lyncurium\ and other species ; Legerlotz (see Arndt, 1924) analyzed the freshwater sponge, Spongilla lacustris for the element; Fox and Ramage (1931) found iron in Clathrina; Phillips (1922) found 0.0075% *n the dry matter of an unknown sponge. The presence of iron in the Porifera was known as far back as Geoffroy (i 706). Although a considerable amount of the element is indicated in Porifera, especially in view of the presence of iron in the pigment of sponges (see footnote 4 on page 436), there have been no systematic quantitative determinations of iron in these organisms. I. and W. Noddack (1939) gave data on heavy metals and other elements in Halichondria sp. (in % °f dry matter): Ti V Cr Mo Mn Fe Co

0.00083 0.0030 0.00002 0.00002 0.0058 0.25 0.000005

Ni Cu Ag Au Zn Cd Ga

0.0022 0.0034 0.0001 0.000001 0.015 0.00011 0.00002

Ge Sn Pb As Sb Bi

0.00003 0.00017 0.00055 0.0005 0.000008 0.00006

A relatively high amount of gold is notable. The quantity of other elements is higher than those in sea water but lower in general than those in other invertebrates. MANGANESE. This element has been qualitatively detected by many investigators, for example by Clarke and Wheeler (1922); Harnack (1896) found the element in Euspongidae, Fox and Ramage (1931) in Clathrina and others. Cotte (1903) did a special study of manganese in sponges. He found the element in Dysidea fragilis (= Spongelia pallescens elastica massa) and Tethya aurantium (= lyncurium). In the dry matter of Haliclona (= Reniera) simulans there was 0.0097 °/o manganese and in Suberites domunculus 0.0032%; the gemmule of the latter sponge contained up to 0.02 % manganese, which is several times more than in other tissues of S. domunculus. Cotte (1903) related the presence of manganese in the gemmule of sponges to its catalytic properties. Phillips (1922) found 0.0113% in an unknown sponge, which is more than the amount in other marine organisms analyzed. COPPER. Determinations of copper, done in the last century on Spongia, require verification.19 Ragazzini (1835) f°un(i i.o$°/0 copper in the ash I Herberger (1935) 19. Bath sponge, Greek sponge, and so forth. Ulex's (1865) data on copper in sponges are of doubtful value, as Lossen (1865) showed.

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found traces of this element; Ulex (1865) found o.oi °/o *n l g of ash! Lehmann (1895) found 0.00088 % in the dry matter. Fox and Ramage (1931) found the element spectroscopically in Clathrina; Phillips (1922) found 0.00065 °/o *n an unknown sponge, and Bertrand (1903) found 5 X io~ 4 % in dry Choanites (= Ficulina) ficus. ZINC. One of the few analyses for this element was done by Phillips (1922), who found 0.0047 °/o *n the dry matter of a loggerhead sponge from the Tortugas. OTHER METALS. Of the other metals, aluminum is found consistently (see Struve X [ 835]> who found 1.77% A1?O3 in the ash of Spongilla lacustris). The element has been determined only qualitatively in many other species. According to Bertrand (i943-a, c), the dry matter of Choanites (= Ficulina) ficus contains 1.3 X io~ 4 °/ 0 molybdenum and 1.7 x io"4°/0 vanadium. IODINE. This element was found for the first time in sponges by Davy (i 8 i4-a,b) and then by Fyfe (1819) in a preparation of Spongia usta marina; it was found also by Vogel (1816), Gobel (1821), Happ (1822), Straub (1820), Hermbstaedt (1827, 1828), Sommer (1834), Sarphati (1837), Pasquier (1843), Peyer (1925) ; see also Smith, 1913, SPONGES AS FERTILIZER. The first quantitavie determinations were done by Stratingh (1823), who found 2 oz. 3 g iodine in 5 troy pounds of sponge (Spongia and "Hippospongia")™ This amount was considerable, and soon iodine determination in sponges attracted the attention of many investigators. All the following determinations concern the Cornacuspongida (see Table 109). Peyer (1925) found iodine in freshwater sponges.21 In 1895 Hundeshagen concluded that in a number of tropical sponges of the Cornacuspongida the iodine content is even higher than that in seaweeds. He determined the percentage of iodine in the iodo-organic compounds of the skeletal matter,22 called iodospongin, with the following results: Verongia (= LuffTaria) cauliformis Aplysina compress a Calfyspongia (= Perongia) plicifera

8—10 °/0 9-10 10 or more.

He also found iodine in other tropical sponges from Africa and Australia. But he found less of the element in the tropical Spongia, S. usitatis, in Euchalina, Chalinopsis, and Aplysina aerophoba** from the Mediterranean and Adriatic seas. The amount of iodine in the sponge is related to the amount of spongin, which contains i o to 15 % iodospongin, representing 3—5-di-iodotyrosin and dibromotyrosin. Ackermann and Miiller (1941) showed that the so-called di-iodotyrosin in sponges is a mixture of diiodotyrosin and dibromotyrosin in the ratio 1:5. 20. Davy stated that these results were erroneous. Sarphati (1837) demonstrated the presence of iodine in Haliclona (= Spongia) oculala. 21. Spongilla locusta and Ephydatia flwviaiilis. 22. Hornemann (1828, 1829), Sommer (1834), and others indicated previously that iodine is bound with the organic matter of the sponges. 2 H. Probably identical with S. officmalis.

Chemical Composition of Marine Organisms

191

Ordinarily siliceous sponges are poor in iodine (see Cameron's [1914] determinations, for example). All Calcarea are also poor in this element. Sponges rich in iodine belong to the Aplysinidae, Spongiidae, and other families of the Cornacuspongida. The distribution of iodine among the species of Porifera reminds us of the distribution of the element in algae (the only plants which concentrate halogens) and in Alcyonaria. In all three classes of organisms we find different degrees of iodine enrichment in different genera and species, and in all three classes we find iodine organisms which concentrate the element up to several percent. Thus there is a peculiar irregularity in the distribution of the element in the species of these groups. Organisms standing higher in the evolutionary scale contain iodo-organic and other halogen compounds, but only in specialized tissues where they play an important role.

TABLE 109 IODINE IN SPONGES (IN «/0 OF DRY WEIGHT) ORGANISM

Demospongiae Cornacuspongida Spongia sp. (?)

"Hippospongia" sp. (?) . . . Halidona (=Reniera) rufescens Myxilla parasitica . Mycale (=Espere/la) adhaerans Esperiopsis quatsinoensis Raspailia abyssorum Phakellia ventilabrum . Tragosia infundibiliformis . Microciona prolifera Tetraxonida Suberites domunculus Geodia miil/eri Geodia sp Hyalospongiae dphrocallistes whiteavesianus . Rhabdocalyptus dowlingi . , Bathydorus dawsonii , . . * Amount of iodine in charred sponges.

Author

Locality

c. 1.0* 1.8*

Herberger, 1835 Sommer and Preuss, 1837 Heyl, 1847 Bleyer, 1926 Fellenberg, 1923 Herberger, 1836

0.22 0.295 0.387 0.85* 0.012 Canada (Pacific) 0.01 „ , 0.015 „ „ 0.027 , „

»

. . . . . . . . .

n

Cameron, 1914

0.153 Brattholmen, near Bergen, Closs, 1931 0.0135 Norway 0.007 „ „ „ „ 0.3 Long Island Sound, U.S.A. Bergmann and Johnson, 1933 Cotte, 1901 0.001 0.0038 Brattholmen, near Bergen, Closs, 1931 0.0037 Norway 0.019 Canada (Pacific) 0.014 0.009

Cameron, 1914

192

Memoir Sears Foundation for Marine Research TABLE no IODINE IN THE SPONGIN OF THE SKELETON OF SPONGES (IN «/0)

ORGANISM

I

Author

Spongia sp „ „ „

1.8 1.9 1.6 0.767

Sommer and Preuss, 1837 Croockewit, 1843-a, 1843-b Harnack, 1896 Sugimoto, 1928

"Hippospongia equina"

1.46

Clancey, 1926

In freshwater sponges there is much less iodine. Qualitatively iodine has been indicated in these organisms by Peyer (1925) and Arndt (1926, 1929). Scott (1906) and Wheeler and Mendel (1909-1910) showed the amount of iodine in the iodo-organic matter of the sponges, 3—5-di-iodotyrosin, Oswald (1911) found that only 15.7% of the total iodine of the sponge occurs as this compound; the remainder, less labile, has not been studied.

TABLE in IODINE IN IODOSPONGIN (IN »/o)

ORGANISM

I

Author

Spongia officinalis

4.86 1.5

Rosenfeld, 1901 Harnack, 1898

BROMINE. Qualitative indications of bromine in sponges (Spongia and others) are found in the work of Jonas (1828), Hermbstaedt (1827, 1828), Pasquier (1843), an^ Nadler (1866); Hundeshagen (1895) found i to 2 °/o in the iodospongin of tropical sponges, probably Aplysina compressa, Verongia (= Lujfaria) cauliformis and Callyspongia (= Verongia) plicifera. Quantitative determinations of bromine were begun in the middle of the last century: Demospongiae Cornacuspongida Spongia sp

the maximum amount found in invertebrates. Vernon (1895) indeed gave very small figures (0.50%) for the dry residue of the medusa Rhizostoma pulmo. Mobius (i882) 3 gave 97.94 to 97-9O°/o as the amount of water in Aureltia aurita^ but Lowndes (1942), who has given the amount as 95.56 °/o *n this organism, has probably obtained more accurate results. Krukenberg (1881 — 1882) found 95-79°/o water on the average in medusae. Teissier (1926) arrived at the same results for water in mature organisms while observing changes in the water content from the first developmental stages of the medusa Chrysaora to its adult form (see Table 114). Krukenberg's (1881 — 1882) figures were 96.3 °/o water in an adult Chrysaora. Both the water absorption and the amount of salt increase with the medusa's growth, and the same tendency towards increase in amount of water in more mature individuals is shown in Hatai's (1917) data on the medusa Cassiopea. Meyer (1914) found a high water content of 98.22 °/0 in medusae from the Baltic, which value agrees with that of Vibrans for material from the same region. Bateman (1932), comparing different results of analyses of dry residue, considers that the amount of water in medusae is high, and Meyer (1914) found but °- I 5°/o dry residue in Phacellophora camtschatica. In general we may conclude that actinians contain about 85 °/0 water, marine medusae 95 to 96 °/o water. The very high estimate of Gortner (1930) who found 99.8 °/0 is certainly incorrect. However, Aurellia aurita from the more dilute waters of the Baltic is seen to be richer in water (98.22 to 2. From Phillips' (1922) data on ten Alcyonaria, figures for the amount of water may be calculated. 3. Ladenburg's analysis. H

196

Memoir Sears Foundation for Marine Research TABLE 113 WATER IN COELENTERATA (IN •/• OF LIVING MATTER) No.of determinations

ORGANISM

Hydrozoa (Hydroids) Tubularia larynx Ahyonium digitatum Thuiaria (= Sertu/aria) cufressina

Hao

Organic matter

39.05 82.2

— —

93.25

Sarsia mirabilis Aequorea aequorta

58

96.65 96.45

Aequarea aequorea (large) Aequorea aequorea (small) jiequorea coeruleiceni

5 28

96.56*« — 96.77 — 0.81 96.43

Phialidium gregarturn Haliitaura cellularia

65 5

96.71 96.55

~ Mean, Hydromedusae Scyphozoa (normal marine localities) Chrysaora hyposcella

Locality

Author

Weigelt, 1891

39.65 8.47

""

97

2

Hydrozoa (Medusae)

Ash

— 0.85

» » — 2.94 Japanese Sea

— —

— —

—

—

W

W

2

96.00

— 2.85 Japanese Sea

Cyanea capillata Aurellia aurita

96.47 97.92

0.68 2.1

2.85 —

2

95.34

4.66

—

2 9

—

2.22

6 » » Rhizostoma pulmo (= cuvieri)

97.22 96.17 95.45 94.14 95.39

— —

— —

1.6

3.0

Rhizostoma sp.

95.97

—

Mean, Scyphomedusae

96.07

Scyphozoa (partially enclosed seas) Aurellia aurita

»

»

»

W

»

»

tr

— 0.74

» » » » Cassiopea xamachana

w

96.59

Dactylometra panfica

»

w

Koizumi and Hosoi, 1936 Puget Sound, U.S.A. Hyman, 1940

96.30 96.41

»

»

Puget Sound, U.S.A. Hyman, 1940 — Norris (in 2.70 Hyman, 1940) Hyman, 1940 —

»

»

»

98.22

—

w

Maine, U.S.A.

Baltic

u

^

1881-1882 1 eissier, inoc ly/o Koizumi and Hosoi, 1936

T*_: — .•

T

w

w

J l_ Liadenburg, 1882 (see M5bius, 1882) Krukenberg, 1881-1882 Weigelt, 1891 Hyman, 1938 Y-»I »ii» i f\r\r\ rhillips, ly/z Hatai, 1917 Krukenberg, TT

2.76 Pacific

—

»

i

.

•

1 f\ 1 "1

1881-1882

Pentegov, et al., 1928

Meyer, 1914

Chemical Composition of Marine Organisms ORGANISM

No. of determinations

Aurellia aurita Rhixostoma pulmo Anthozoa-Actiniaria Ammonia sulcata Actinia equina Actinia mesembryanthemum Cert anthus membranaceus Sagartia troglodytes Anthea cereus Heliactis be His

Organic matter

H20

Locality

Author

Baltic Black Sea

Vibrans, 1873 Sevastopol Biol. Sta.

98.36 99.28

1.7

—

87.2 87.00

9.53

3.27 Bay of Naples

83.2 87.71 76.84 87.56 2 _ 89.99

Mean, Actiniaria

Ash

Putter, 1908 Unpublished data Krukenberg, 1881-1882

Gulf of Kola

15.85

1.75

11.58 20.88 10.68

1.71 2.28 1.59 2.71

197

Weigelt, 1891

85.64

*H Large Aequorca vary from 96.54 to 96.6o°/0 H2O, small at least from 96.58 to 97.o8*/0 H2O. The difference in the means is statistically significant and presumably parallels the difference between the water contents of the large Halistaura and the smaller Sarsia and Phialidium from the same locality.

98-36%) than is the same species from normal oceanic water. Dunham (1942) further found 99.0 to 99.3% in Craspedacusta from truly fresh water. According to Frdmy (1855), Weigelt (1891), and Clarke, the dry residue of some Coelenterata contains considerable mineral matter or ash, reaching 55 % in Madreporaria and Hydrocorallina and 35 to 40% in Alcyonaria; even in skeletonless forms such as Velella^ it reaches 46,8 °/o of the dry matter. In the experiments of Haurowitz and Waelsch (1926), about 4.5 kg of Velella spirans remained after 100 kg was dried. Nitrogen determinations refer almost exclusively to individual compounds isolated from the skeletal organic matter of Alcyonaria and others (see Krukenberg [1881-1882], Drechsel [1896]); seldom does one find a nitrogen analysis for the whole organism. Mohr (1937) found 25.35 g nitrogen in 29.5 kg fresh Cyanea capillata, i. e., about 0.103 °/o- The tissues of Cyanea contain protein. According to our

TABLE 114 WATER, ORGANIC MATTER, ASH, AND PHOSPHORUS IN THE MEDUSA CHRTSAORA HTPOSCELLA DURING THE GROWTH PERIOD (IN °/0 OF LIVING MATTER) STAGES

planula . 2-4 days ] scyphistoma . . . . adult scyphistoma .

.

. ( . { ( . . . .

Hj-O 64.9 66.3 67.5 71.0 94.5 96.3

Ash

Organic matter

. , . . . . . .

.

.

—

.

. 34.4 . — . . . 25.8 . — . — .

,

.

.

.

.

.

-

—

2.3

— . . . 3.2

. . . .

— —

p —

.

0.33

. . . . , .

0.27 —

.

.

.

—

—

«4*

19 8

Memoir Sears Foundation for Marine Research TABLE 115

WATER, ORGANIC MATTER, ASH, AND NITROGEN IN THE MEDUSA CASS10PEA (IN «/f OF LIVING MATTER).

H20

.

.

94.18 9407

.

93.86 93.88

. . . > . .

N

Ash

Organic matter

9433 94.08

XAMACHANA

2.96 3.13

2 77

. 2.80

5.82

293

3.00

6.14 6.12

- - 0.132

-

.

. .

. - . 0.200 . , .0.196

analyses, the dry matter of Cyanea arctica from the Gulf of Kola contains 0.634% nitrogen, or about 2.5 °/o i*1 the ashless matter. Zeynek and Dimter (1935) investigated the composition of 130 kg of the jelly-like organic substance in the medusa Rhizostoma pulmo; they found a fair amount of sulfur, and they considered the substance to be protein because of the quantity of amino acids. Thus Cyanea, Rhizostoma, and many other medusae apparently differ in composition from Siphonophora such as Vellella spirans, in which, according to Haurowitz and Waelsch (1926), the organic skeletal matter contains a quantity of chitin ; according to Henze (i9o8-b), the skeletal matter of this organism contains 8 °/0 nitrogen and the chitinous material isolated from it, 6.3 °/o nitrogen. Among the invertebrates, Hydromedusae, Campanulariae, Siphonophora, as well as Scyphozoa and Ctenophora, contain the smallest amount of nitrogen, about o. i to

TABLE 116 NITROGEN IN COELENTERATA (IN »/o OF LIVING AND DRY MATTER)

No. of determinations

ORGANISM

Tubularia larynx Sertularia cupressina Aurcilia aurita . »

»

-

-

»

-

Alcyonium digitatum Pcnnatula sp. Cassiopca xamachana »

Antipathcs abies Rhizostoma sp. . Actinia cquina . 2 Hcliactis bcllis .

Unpublished material.

-

. *

- 2 - 2

-

-

.

. 3

-

- 2

-

Living matter

2.22 0.73 0.06 — 1.23 — — — — 0.1 1.39

Dry matter

. . . . . . . . . . .

. . . . . . .

. ,. ,. . . , .

. . . . . .

. 3.66 . 7.41 . 2.1 . 3.97 . 6.78 . 5.76 . 2.36 - 3.0 . 13.71

Author

. . . . . . . . .

- 10.450* - 9.91 .

. . . . . . . . .

. . . . . . . . .

. .

Weigelt, 1891 Vibrans, 1873 Weigelt, 1891 Delff, 1912 Mayer, 1914 Hatai, 1917 Allen, 1930 Pentegov, et al., 1928 Weieelt, 1891

Chemical Composition of Marine Organisms

igg

0.2 % of the living matter, or i to 3 °/0 of the dry matter. Younger medusae contain somewhat more nitrogen than older ones. If the material in the tissues of medusae and in the bladder of Ctenophora consists basically of protein, as is apparently the case, perhaps it is present as a glucoprotein. The presence of chitin together with the protein in these organisms has not yet been proved. The soft tissues of Actinaria (Octocorallia, and especially the Alcyonaria, Gorgonacea, Antipatharia, and Pennatulacea) consist of diverse scleroproteins, such as cornein and gorgonin, which contain about 16 % nitrogen. Fox (1926) indicates that the "peat" which is used in Japan as a fertilizer, consisting of the dried actinian Cereus pedunculatus, contains 4.6 % nitrogen and i % P2O5. Among the Octocorallia, as well as some of the Gorgonacea, Alcyonaria, and Pennatulacea, there are those with organic matter in the skeleton; out of this scleroTABLE 117 CHLORINE IN MEDUSAE (IN •/• OF BODY FLUIDS)

ORGANISM

Jequorea aequorea (= Rhizostoma pulmo (= Chrysaora hyposcella . Cassiopea pofypoides . Aurellia aurita

No. of analyses

forskalia) cuvim) , . . . . . .

2 2

Cl

Author

2.0164 1.8300 2.059 2.2980 5.638*

Krukenberg, 1881-1882 „ „ „ „ „ „ Vibrans, 1873

• In the ash.

protein is formed the homogeneous skeleton of some Gorgonacea, such as Holaxonia. The skeletons of Antipatharia (Hexacorallia) contain protein, as do those of Alcyonaria, and the skeletons of fossil Graptolitoidea contain chitin.1H Dictionema fiabelliferum forms the black clayey shales of the Baltic countries, the organic matter of these shales containing about 3 °/0 nitrogen, which indicates indirectly their animal origin; the presence of chitin in them has been shown by chemical analysis. In Actinia equina the carbon is 5.83 °/0 of the live weight and 43.6 % of the dry weight. There are no other data on this element, except for some given by Teissier (1926) and the author. The composition of salt solutions in the tissues of medusae attracted the attention of investigators long before Krukenberg (1881—1882) and Macallum (1903) formulated the question of the influence of marine salt solutions on the composition of the fluids of these organisms. Laugier (1810), and much later Duval (1925), found the same salts in medusae as are found in sea water. Krukenberg (1881—1882) made a number of observations on the chlorine in various medusae and of the sea water in which they live, with the result that there was always more of this element in the organisms than in the water; this observation was confirmed by later investigations. i H. The Graptolites are now commonly regarded as being related to the Hemichordata rather than to the coelenterates.

2OO

Memoir Sears Foundation for Marine Research

Macallum (1903) formulated the concept of ionic equilibrium in the tissues of medusae as well as other animals, and he tried to reconstruct the history of the development of marine invertebrates from a study of their body fluids.4 In these analyses, the close relationship of the tissue fluids of the medusa to sea water was shown. The mineral residue from the solid matter of the medusa differs in composition from that of the solutions of the body. There are several analyses of entire medusae, and the divergence of the analyses can be explained to a certain extent by the varying degrees of separation of the organisms from sea water. Since the investigators did not always take special precautions, their analyses should be regarded as preliminary. From Table n y a it follows that medusae contain more potassium and to some extent more chlorine than sea water, but less sulfate and usually less magnesium. In the ash of Veletta spirant, Haurowitz and Waelsch (1926) found iron, aluminum, calcium, magnesium, sodium, potassium, and halogens (regarding phosphorus, see observations by Teissier [1926], given in Table 114); the sulfur content is relatively large. Haurowitz and Waelsch (1926), when investigating the gonads of Rhizostoma pulmoy found phosphorus, nitrogen, sodium, potassium, copper, magnesium, iron, and

TABLE 117 A COMPOSITION OF MEDUSAE (IN »/0 OF LIVING MATTER) ORGANISM Cyanea arctica . Aurellia flavidula. Sea water (Canso) . . . Aequorea coerulescens , Cyanea capill ata . Dactylometra pacifica . Sea water (Asamushi) . . Catylorhiza sp. (umbrella) , Catylorhiza sp. (manubrium) . Sea water (Mediterranean)

Na

K

Ca

Mg

Cl

so,

Sum of

ions

Author

0.89926 0.068935 0.034863 0.10221 1.6242 0.11349 2.9029 Macallum, 1903 0.92877 0.04810 0.03841 0.10981 1.7231 0.12245 2.9716 w 0.91898 0.03350 0.03533 0.11085 1.6543 0.18931 2.9422

1.01

0.092

0.0385

0.118

1.90

0.182

3.34

0.98

0.061

0.0385

0.117

1.94

0.087

3.22

0.98

0.068

0.0369

0.111

1.93

0.105

3.23

0.98

0.0355

0.0387

0.119

1.78

0.208

3.16

100*

4.63

3.86

11.6

1.66

100*

4.87

3.81

13.6

1.62

100*

3.57

4.16

12.1

1.83

• Sodium is taken as IOO.

— —

w

Koizumi and

Hosoi, 1936 »

!n

„

n

Johnston, 1939

—

4. He gives the amount of alkali, iron, phosphorus, bromine in the tissue fluids of Aurellia and Cyanea.

9)

n

Chemical Composition of Marine Organisms

201

TABLE 118 COMPOSITION OF HYDROIDS AND MEDUSAE (IN °/0 OF ASH) ORGANISM

No. of analyses PaO5 K2O

Tubularia larynx . Sertularia cupressina Aurellia aurita . . Aurellia aurita* . .

1 2 2 1

1.42 3.23 0.52 0.18

trace 2.21 trace 11.9

CaO

MgO Na2O

SO4

SiO2

5.95 10.85 2.11 0.38

— — — 3.27

— — — 0.83

— — — — — — 2.18 56.38

— — — 37.08

Cl

Ash

Author

65.36 Weigelt, 1891 41.07 80.47 62.94 Vibrans, 1873

• Baltic.

a large amount of sulfur in various extracts from this species; the last named element is apparently in organic combination. The high sulfur content is common to many marine organisms. For Actinaria there are fewer chemical data. Javillier and Crdmieu (1928) found o. 16 °/o phosphorus in the living matter of Sagartia parasitica. According to our data, Actinia equina from the Gulf of Kola contains 0.18 °/o phosphorus in the living matter (i-43 °/o in the dry matter) and 0.25% sulfur in the living matter (i-95°/o *n the dry matter). Needham (1931) analyzed various components of Anthea rustica for phosphorus, while Kreps, Borsuk and Verzhbinskaia determined the same element in the muscles of Cyanea arctica. Actinia equina and Metridium dianthus. On heavy metals, halogens, and so forth in Actinaria, see further. 3.

Hydrocorallina

Of the modern Hydrozoa, the Hydrocorallina have hard calcareous skeletons, and the analyses which have been done concern only the skeletons of these organisms. Among other Coelenterata, Hatchett (1799) analyzed species of Miltepora, in whose skeletons he found CaCO3. Silliman (1846) gave a series of quantitative analyses of corals, among which were species of Hydrocorallina; these analyses showed a predominance of CaCO3 in the skeletons of Hydrocorallina. Later investigations were often limited to determinations of calcium and magnesium, in Millefora and Distichopora. The inorganic part of Hydrocorallina skeletons consists almost entirely of CaCO3 with a small amount of MgCO3, phosphate, and possibly sulfate. Only Millefora braziliensis contains 2.14% MgCO3, according to Lenox (see Branner, 1901), all the rest containing less than i °/0- Damour's (1851) analyses of the fossil species of Millefora showed 8.5i°/o MgCO3,5 and Butschli (1908) showed qualitatively the small amount of magnesium in the skeleton of Millefora alcicornis. Corresponding to the small amount of magnesium, Sorby (1879) found crystals of aragonite in the skeletons of Hydrocorallina; Kelly's (1900) observations do not contradict these data, although in some cases she mistook aragonite for conchite (see Chapter XX). Aragonite was 5. Which should be attributed to metamorphism.

2O2

Memoir Sears Foundation for Marine Research TABLE 119 COMPOSITION OF HYDROCORALLINA (IN % OF ASH RESIDUE)

ORGANISM Milleporina Millepora alcicomis

^0,+

CaCO, MgCO, P2O6 FejOj

SSiOz

CaSO4 Locality

Author

98.22 0.95

trace 0.11

0.24

0.48

Clarke and Wheeler, 1922

99.63 0.22 trace 0.07 97.45 trace (0.27) trace

0.02 —

0.06 —

— 0.09

— 1.80

0.07

0.03

2.14

Millepora cervicornis* 87.32 8.50 0.23 0.55 Millepora tortuosa 94.23 — (1.20) trace Millepora sp. 95.86 0.41 — —

0.63 — —

— — —

Bermuda

94.39 0.97 Millepora braziliensis 96.77 1.28 93.80 2.08

Stylasterina Distichopora mtida Distichopora coccinea Distichopora sulcata

— — trace 0.06 —

Tortugas, Fla., U.S.A. Bermuda Gulf Stream, Atlantic Bermuda Brazil

98.22 0.24

trace 0.21

0.11

1.22

Micronesia

98.43 0.26 98.56 0.26

trace 0.07 trace 0.05

0.09 0.07

1.15 1.06

Sea Islands Cuba

Sharpies, 1871 Hdgbom, 1894 Clarke and Wheeler, 1922 Lenox (see Branner, 1901) Damour, 1851 Silliman, 1846f Hdgbom, 1894 Clarke and Wheeler, 1922

* Analysis of a fossilized specimen, which contains alkali and organic matter. f Silliman's analysis shows the organic matter -j- H2O to be 4.570/0; under PaO6 is indicated the total phosphate.

found in Millepora^ Distichopora^ and Stylaster roseus by Meigen (1901), and his results were confirmed by Schmidt (1924). The aragonite content of this group of Coelenterata is not an isolated fact, for closely related to them are the extinct Devonian Stromatoporida, whose skeletons, according to Nicholson (i 892), originally contained not calcite (which is now found in their fossil skeletons) but aragonite.6 The presence of aragonite in the modern and extinct Tubufaria is highly probable, for among the Hydrozoa of the past, as well as among some Calcarea (Porifera), there were species whose skeletons contained aragonite.7 The quantity of elements other than calcium and magnesium in the ash of modern Hydrocorallina has not been studied systematically. 4.

Hexacorallia

As in the Hydrozoa, some species of Hexacorallia (the madreporarian corals proper) have a calcareous skeleton, while others, the Actinaria, of whose composition 6. We found indications of the presence of aragonite in the skeletons of fossil invertebrates in sediments at least as old as the Cretaceous, as Vernadsky has indicated. 7. See material on Archaeocyathina and Graptolithida. The latter were plankton organisms, and aragonite was probably present in the skeleton.

Chemical Composition of Marine Organisms

203

we spoke previously, do not. Some of them, Sphenopus, Parazoanthis, Palythoa, and Isozoantus, have an agglutinated skeleton which consists of foreign matter such as sand, spicules of sponges, Foraminifera, and so forth. The investigation of madreporarian corals has been limited to analyses of skeletons, chiefly the calcium and magnesium content; Hatchett (1799) and many others have contributed qualitative data, but Merat-Guillot (1797) and Silliman (1846) gave the first quantitative analyses of these skeletons. More modern analyses were done by Clarke and Wheeler, 1922 (see Table 120). Klement (1895) found up to 0.4 °/o MgCO3 in Stylophora digitata. Skeletons of Hexacorallia are poor in magnesium also, and according to the data at our disposal, they do not differ in general from the composition of the skeletons of Hydrocorallina.8 We have demonstrated for Bryozoa and other marine invertebrates the relationship between the form of the skeleton and the habitat. This is particularly true of Hexacorallia, Madrepora pulchra, and other corals, which have only a few branches in regions of clear water and many in muddy waters; in still water the organisms lack long branches, in deep water they are long and numerous, and in tidal regions they are compact, as in sponges (see Jones, 1867). Hosoi (1935), w^° studied the exchange between sea water and the tissues of sea anemones, found the following (in °/a): Cribrina sp. . Metridium dianthus Diadamene sp.

HaO

Ca

76.3 79.3 78.7

0.0298 (0.1237 in dry matter) 0.0291 (0.1441 „ „ 0.0265 (0.1241 „ . „

There was somewhat less calcium in the tissues than in sea water (see Skeats' [1903] and Meyer's [1914] determinations of CaCO3). Of all the Coelenterata, the Hydrozoa and the Madreporaria are those in which we find for the first time in invertebrates a vast process of aragonite formation in the tissues.9 The form of aragonite is less stable in inorganic nature than that of the more common calcite, and its occurrence therefore raises the question as to the causes of the stability of aragonite in the skeletons of Coelenterata and other organisms. Since the formation of aragonite is related to the ionic concentration, temperature, pH, and the medium of the tissues in which aragonite is precipitated, the processes of formation must be different for calcite or for other modifications of CaCO3. It is highly desirable to know the composition of the skeletons of the extinct species, whether Hexacorallia, Tetracoralla, or others, since some of them may be ancestors of modern species. Certainly the majority of the fossil forms contained ara8. Pax (1914) observed different degrees of incrustation, consisting of sand, particles of skeletons of other invertebrates, [and so forth, in the species of Zoontharia which do not possess any other skeleton. The species Palythoa liscia, P. spkaerimorpha and P. seyschellarum are rich in CaCO,. The amount of CaCO3 in the incrustations of the skeletons has been morphologically determined to be more than 50 °/0. The species Palythoa braunsi is poor in CaCO,. Palythoa gregorii does not contain CaCO,. 9. Aragonite has been noted in the Chlorophyceae and a few sponges.

204

Memoir Sears Foundation for Marine Research TABLE 120 COMPOSITION OF HEXACORALLIA (IN »/0 OF ASH RESIDUE)

ft%'3

MgCOg

PA

Balanophyllia floridana 98.05

1.11

trace

0.74

0.10

Paracyathus dtfilipii Dendrophyllia cornucopia D. profunda

. 98.32

0.87

trace

0.37

0.44 0.00

99.35 99.47

0.43 0.12

trace trace

0.12 0.07

0.10 0.34

Favia fragum . Eusmilia aspera Cladocera arbuscula Agaricia purpurea Dasmosmilia lymani

99.20 99.50 . 99.50 99.35 . 98.71

0.39 trace 0.46 trace 0.11 trace 0.61 0.00 0.63 trace

0.12 0.04 0.08 0.00 0.28

0.29 0.00 0.31 0.04 0.21

0.17

99.42

0.37

trace

0.12

0.09

(?)

98.61 99.41

0.43 0.37 0.76 0.33 0.54

trace trace trace trace trace

0.55 0.15 0.14 0.11 0.26

0.41 0.07 0.04 0.06 0.22

(?) (?) (?) (?) (?)

0.45 trace 99.21 0.73 0.00 99.39 0.57 trace — (0.91) 93.56 94.55 — (1.05)

0.06 0.04 0.04

0.00 0.02 0.00 — —

(?)

(?) — — —

—

—

ORGANISM

CaCOs

Flabellum alabastrum F. pavonium var. paripavoninum . Flabellum sp. . . . Madracis decactis . Madracis kauaiensis . Deltocyathus italicus . Acropora cervicornis . Maendra clivosa . M. labyrinthiformis Maendra phrygia , Pocillopora caespitosa . Pocillopora elongata . Pocillopora damicomit Pocillopora ligulata Pocillopora grandit Turbinaria brassica Corallium sp. (?) .

99.06 99.50 98.98 99.49

93.60 94.66 93.85

— — (1.90) — (0.55) — (0.55)

— (1.45) — — 92.75 (1.50) — 97.57 0.59 (?) 0.59

95.0

—

Coelaria daedalia . Heliastraea aperta

96.52

0.32 0.88

Symphyllia harttii . Porites verrillii Porites clavaria

93.44 96.28 99.49

0.52 0.42 0.37

Porites astreoides . Porites fur cata

99.56 99.95

0.40 0.82

—

—

S>Og

— — 1.25 —

Author

CaSO4 Locality

(?)

(?)

(?)

? (?)

— —

Clarke and Wheeler, 1922

S. of Key West, Fla., < U.S.A.

9>

Near Bahama Islands Tortugas, Florida, < U.S.A. 40°06'50"N, 70°34'15"W Near Bahama Islands Hawaii China Sea Bermuda Hawaii 18°30'N, 63°31'W Bahama Is.

9»

9,

„

„

9>

9>

99

9>

9>

9>

9>

9>

„

„

9>

9>

„

„ 9>

9>

9>

9>

9>

9>

9»

Silliman, 1846*

(?)

Panama

Schaller(Ckrke and Wheeler,

— —

Abyssinia Brazil

Nichols, 1906 Lenox (Branner,1901)

1922)

0.07

0.05

trace

0.22 0.09 0.10

0.05 0.03 0.91 0.04 (?)

Bahama Is.

trace trace

0.02 0.11

0.02 0.12

Florida, U.S.A.

—

9>

(?) (?)

9» 9>

Clarke and Wheeler, 1922 \

\

Chemical Composition of Marine Organisms ORGANISM

CaCO, MgCO8 P2O6

Porites favosa . Porites fragosa Porites cylindrica Porites limosa , Porites sp.§

. 95.84 . 93.88

. 94.81 . 94.41 - 93.1

— — — — —

(2.05) (1.56) (0.95) (0.90) (1.48)

Al*08 + Fe^Oj

SiO2

CaSO4 Locality

— — — — —

0.10

(?)

Orbicella annul aris

99.38 0.59

0.00

0.03

0.00

(?)

Muss a dipsacea

99.71

trace 0.05

0.15

(?)

Muss a harttii .

96.66 0.54

Desmophyllum ingens

99.21 0.59

trace 0.06

0.14

(?)

Siderastrea radians Siderastrea sp.

99.27 0.48 99.35 0.42

trace 0.12 (?) trace

0.13 0.23

W

Oculina diffusa

99.47

trace 0.05

0.07

(?)

0.20

0.21

—

—

rt

'

Orbicella cavernosa

Oculina sp. . . Madrepora prolifera Madrepora prolifera (M.muricata) . Madrepora palmata (M. muricata var. palmata) . . .

. 95.94

0.09

0.41

—

. 96.20 0.36 — . 95.09 — (0.30) . 99.38 0.14 .94.81

-

0.2

(0.74)

-

Madrepora plantiginea 94.88 - (0.71) Madrepora spicifera (M. armata). . . 92.81 - (0.6) Astraea cellulosa . . — 0.542 — — Astraea orion 4strata sp. f

96.47

94.51

— —

0.12

— —

trace 0.07

(0.80) — (0.86) —

Author

Silliman, 1846*

— 0.62 — 99.13 0.77 0.00 0.00

rt

205

Bermuda Bahama Is.

Hogbom, 1894 Clarke and Wheeler, 1922

Tortugas, Fla., U.S.A. Reef Golding Cay Brazil Lenox (Branner, 1901) Chile Clarke and Wheeler, 1922 Florida, U.S.A. „ Bermuda Eakins (Clarke and Wheeler, 1922) Tortugas, Clarke and Fla., U.S.A. Wheeler, 1922 Hogbom, 1894 Silliman, 1846* Bahama Is.

Clarke and Wheeler, 1922

Gulf Stream Silliman, 1846* (Atlantic)

Forchhammer, 1852 Silliman, 1846*

* Silliman's results cannot be recalculated and are given in their original form. In all analyses, organic matter and water are included. Under P2O6 are included phosphates and SiO2. Silliman indicates the presence of fluorine, but no direct determinations were made. All these analyses are outdated. § Three analyses. t Five analyses.

gonite. According to some investigators, the fossil Tabulata, closely related to Hexacorallia, possessed aragonite skeletons, but according to others they had skeletons of calcite. The question still remains unsettled, but it could be solved by modern physico-

206

Memoir Sears Foundation for Marine Research

chemical methods, although a direct analysis of the crystalline structure of the skeletons is impossible by reason of the process of mineralization, which changes aragonite into more stable calcite. As a rule, it is because of this mineralization that we do not find aragonite in the fossil skeletons of invertebrates lower than chalk in the organogenic sediments. But certain extinct species of Hexacorallia probably contained calcite also; this is probably true of Turbinolidae. Furthermore it would be interesting to determine the MgCO3 content of these organisms. In conclusion we might point out that a more detailed study of the chemical composition of skeletons of fossil organisms and a comparison of their composition with those of modern organisms would be valuable. 5.

Octocorallia

With the amount of organic matter in these corals being higher than in others, one is reminded of the sponges. On the basis of the amount of mineral residue in various Alcyonaria, the families, or species within families, may be arranged in a definite order, but it remains for the future to show whether or not this has some systematic, and therefore genetic, significance. Continuing the comparison of the chemical structure of the skeletons of Alcyonaria with those of the Porifera (Calcarea), let us note that the skeletons of Alcyonaria also have much in common morphologically with those of Porifera. The spicule composition is similar to that of the magnesium-calcium sponges, but the spicules do differ in organic matter (see Fttrth [1903], M6rner [1907, 1908, 1913^], Henze [i9o8-b], and others; compare the composition of the organic matter of Gorgoniidae and Pennatulidae). The spicules of these organisms may be organic, may be partly calcified, or may be homogeneous with CaCO3. It was some time before the attention of investigators was directed to the considerable magnesium content of the skeletons of Alcyonaria as compared with other Coelenterata. In the early analyses only the presence of CaCO3, and rarely phosphate, was observed (see Merat-Guillot [1797], Hatchett [1799] and Fourcroy and Vauquelin [i8n]10). In 1786—1787 Morozzo and in 1814 Vogel demonstrated the presence of magnesium in Corallium rubrum. Vogel (1814) found up to 7 °/o MgCO3 in Corallium^ and Witting (1832) found 6°/ 0 in the same species. Then in the 1850*5 it was established that, since Alcyonaria were organisms whose skeletons contain a large amount of MgCO3, they could take part in the formation of dolomites. Subsequently an even greater interest in the composition of Alcyonaria skeletons has arisen as a result of the idea expressed by Clark (1911), and well developed in the publications of Clarke and Wheeler (1922), concerning the dependence of the MgCO3 content on the temperature of the habitat. Most of the analyses of Alcyonaria show from 6 to 17 °/0 MgCO3 in the mineral skeleton, Heliopora being an exception with only 0.35 %. Morphologically Heliofora, with their external tube-like skeletons, differ from all other Alcyonaria, thus making 10. See also Krukenberg (1881-1882) and others. Jolly gives an analysis of red coral (according to Quinton, 1904) with 0.376% MgCO»(?); see analyses quoted by Kunz.

Chemical Composition of Marine Organisms

207

TABLE 121 COMPOSITION OF OCTOCORALLIA (IN •/. OF ASH RESIDUE)

ORGANISM

MgC03 P2O6 FejOs SiO2 CaSO4 Locality 98.93 0.35 trace 0.07 0.15 0.50 Philippine Is.

CaCO,

Heliopora cerulea . „

95.54 84.61 12.23

„

Tubipora pur pure a Tubipora musica .

—

Cora/Hum elatior. .

86.57

CoraI Hum rubrum

88.84 90.18 91.45 55.0

n

n

n

»

- (0 -

w

w

»

w

—

3.83 11.56

(\\ atrace

0.57

1.40

—

—

—

0.40

9.18 (0.72) 6.27 3.80 - (4-8)

-

—

—

—

—

9.32 2.13

—

—

—

Pennatula aculeata , 85.62

7.71 3.12

Pennatula sp. .

—

(48.9)*

—

— 2.49 85.0 Gorgonia subfruticosa . 79.84 13.43 0.47 w

w

85.76

Gorgonia acerosa « w

»

"

*

• •

0.15 0.00

13.39

0.44

-

1-01 1.70 —

—

0.85 — 0.28 0.55 —

—

81.45 12.52

3.64 0.22 0.22

79.48 13.29

2.87

0.24 0.04

Gorgonia citrina\ .

85.29

13.43 0.22

—

—

Gorgonia flabellum Gorgonia sp. (?) *

86.04 88.83

13.12 9.29

0.44 0.45

— —

— —

Alcyonium carneum

84.50

6.66 5.19

trace 1.50

Alcyonium palmatum - 88.42 9.63 (1.02) 3.23 — Alcyonium digitatum * (46.65) — Alcyonium rigidum 10.50 (spicules) \ * / — — trace 0.15 13.79 Plexaurella grandtflora 85.61

—

Author

Clarke and Wheeler, 1922 Silliman, 1846 Clarke and 1.19 Singapore Wheeler, 1922 Forchhammer, r» — 1852 Japan Clarke and 1.32 Wheeler, 1922 1.26 Mediterranean Butschli, 1908 Vogel, 1816 0.5 Witting, 1832 — Merat-Guillot, — 1797 — Mediterranean Nichols, 1906 Forchhammer, 1852 Clarke and 0.84 Banquereau Wheeler, 1922 Fr&ny, 1855 44°47'N, — 56°33'W Delff, 1912 Stavanger — Fiji Clarke and 5.43 Wheeler, 1922 — Tortugas, Fla., Phillips, 1922 U.S.A. Clarke and 1.95 Bahamas Wheeler, 1922 4.08 South Florida, w w U.S.A. Tortugas, Fla., Phillips, 1922 — U.S.A. „ » » — 1.43 Sea of Okhotsk Vinogradov, 1933 Newfoundland, Clarke and 2.15 Wheeler, 1922 Canada 0.93 Mediterranean Butschli, 1908 Weigelt, 1891 •?

Samoa — 0.45 trace Australia

Phillips, 1922

Clarke and Wheeler, 1922 (continued next pagt)

2 o8

Memoir Sears Foundation for Marine Research

ORGANISM

CaC03

MgCO3 P2O5

Plexaurella dichotoma — 2.11 — Plexaurella sp. . . 86.75 12.08 0.15 PlexaurelLa homomalla Plexaurella flexuosa . Pseudoplexaura crassa Eunecia roussiani , . Eunecia crassa . , Eunecia tourneforti , Muricea humilis . . Muricea echinata .

86.29 80.87 86.71 86.76 87.27 — 84.47

12.01 16.90 12.12 11.45 11.46 2.78 12.64

A120S + Fc2O3 SiO2

— —

— —

— —

0.04 — 0.35 — 0.19 — 0.12 — 0.09 — — — 0.54 0.07

— — — — — — 0.50

— — — — — — 1.73

0.06

0.11

2.93

. 83.79 12.28 0.83

Paramuricea borealis . 85.11

8.03

1.43

0.30

0.44

Paragorpa arborea . 88.04

9.05

0.56

0.03

0.15

Xiphigorgia anceps

. 80.96

13.04

1.96

0.07

0.14

„ „

. 84.91

13.23 0.26

—

—

Rhipidogorgiaflabellum Leptogorgia rigida

83.38 12.64

1.09

0.28

0.21

80.75 13.19 . 75.36 14.13

2.80 7.95

0.07 0.21

0.24 0.28

13.71 8.27 0.03 15.73 8.57 0.26

0.09 0.34

Leptogorgia pulchra . 74.99 Phyllogorgia quercifolia 72.99 Tsis hippuris .

.

,

—

—

85.13

13.21 0.13

—

Pleurocoralliumjohnsom 93.87 Primnoa reseda . . 90.39

6.03 (0.1) 6.18 0.83

— 0.88

Lepidisis caryophyllia.

6.92 trace 0.05

Briarium asbestianum

—

92.24

Ctenocella pectinata . 81.44 • In the dry residue. a See Murray and Renaxd, 1891.

6.36

CaSO4 Locality

15.65 0.88

0.13

Author

Nichols, 1906 Tortugas, Fla., Phillips, 1922 U.S.A. „ „ „ » Bahamas Brazil

Lower California 4.69 Grand Banks (Atlantic) 2.17 Nova Scotia, Canada 3.83 South Florida, U.S.A. — Tortugas, Fla., U.S.A. 2.40 Bermuda 2.95 Bahamas 2.07 California, U.S.A. 2.91 2.11 Brazil

» » * Nichols, 1906 Clarke and Wheeler, 1922

Clarke and Wheeler, 1922 Phillips, 1922 Clarke and Wheeler, 1922

„ Clarke and Wheeler, 1922 — — Forchhammer, 1852 — — Tortugas, Fla., Phillips, 1922 U.S.A. trace — Canary Islands Anderson0 0.13 1.59 Nova Scotia, Clarke and Canada Wheeler, 1922 0.11 0.68 38°53'N, 69°23'30"W 0.21 1.69 Australia

j In Phillips analyses, Ca3PgOB is shown under P2O6.

it possible to trace a connection between Heliofora and the extinct Paleozoic Tabulata. According to Meigen (1901), the skeleton of Heliofora is constructed with crystals of aragonite, as are those of Hexacorallia and Hydrocorallina; the skeletons of other

Chemical Composition of Marine Organisms

209

kinds of Alcyonaria, among them Tubipora, contain calcite crystals, as shown by the numerous analyses of various species by Sorby (1879), Kelly (1900), Meigen (1901), Btitschli (I9O8),11 and Schmidt (1924). Thus, by analogy one can assume the existence of aragonite skeletons in the extinct species that are closely related to Heliopora, for example Tabulata. Returning to the chemical composition of the magnesium-calcium Alcyonaria (see Table 121), we note rather large fluctuations of MgCO3 in the skeletons, from 6 to I7°/ 0 . On the one hand, as shown by Clarke and Wheeler (1922), there is a large amount of MgCO3 in skeletons of Alcyonaria living in warm seas; on the other hand, species from cold regions contain but little MgCO3. Hence, the amount of magnesium in these organisms is a function of the temperature of the habitat, and, as noted before, this is true of some other organisms with magnesium-calcium skeletons, and the relationship holds also with regard to the skeletons of all Echinodermata. Thus there is established a general relationship between temperature zones of marine organisms and their chemical composition, just as similar zoning has been established for terrestrial organisms. Data given in Table 122 show the dependence of magnesium content of the Alcyonaria skeletons on habitat temperature, and it will be seen that the observed deviations from this dependence are few. Species living in the Arctic and Antarctic oceans contain an average of 6 to 12 % MgCO3, those of the tropics and subtropics up to 17 °/0, with others containing intermediate amounts. Undoubtedly common and regular changes in the chemical composition of the skeletons of all Alcyonaria bring about some common morphological changes in the species of a given area. For example, an increase in the concentration of calcium in the water increases the calcium deposited in the skeleton of Coelenterata (see Tixier-Durivault's experiments with Alcyonium palmatum, 1940). We will return to this question in a more general way when discussing the Echinodermata.12 Hatchett (1799) observed noticeable amounts of phosphorus in Gorgonia^ and Silliman (1846), Frdmy (1855), Valenciennes and Frdmy (i855-a; in Pennatula) and Schmidt-Nielsen observed this element in Alcyonaria. Clarke and Wheeler (1922) usually found around 0.5 °/o ^2^5 *n *he dry matter, but in species of the Leptogorgiae and Phyllogorgiae they found up to 8 °/0 Ca3P2O8 in the ash, which they regarded as worthy of attention. For the most part the phosphorus occurs bound with protein and with other organic matter. Significant in itself is the fact that there is a high phosphorus content, but in order to confirm its significance as a characteristic of a given species or genus, the number of observations should be increased. The relatively high magnesium content in these species corresponds to the higher phosphorus. The reports of a relatively low amount of sulfur in Alcyonaria, or even its absence, as observed by Frdmy (1855), are erroneous, because in many cases the investigators zi. Butschli (1908) found high magnesium in Tubipora musica, in which respect this species differs from Heliopora. 12. For instance, Clarke and Wheeler (1922) point out that in the compact forms of the skeletons of Alcyonaria, for example Coralbum, there is less magnesium.

21 o

Memoir Sears Foundation for Marine Research TABLE 122

MgCO, IN THE SKELETONS OF ALCYONARIA IN RELATION TO THEIR HABITAT (IN % OF ASH)

Locality

Author

42°15'N 130°55'E

Japanese Sea

Vinogradov, 1933 Clarke and Wheeler, 1922

ORGANISM

MgCO8 Latitude

Primnoa resedaeformis var. pacifica .

9.29

Longitude

Primnoa reseda

.

6.18

42°16'N

63°15'W

Nova Scotia

Alcyonium carneum Paragorgia arborea Pennatula acuUata Paramuricea borealis *

, . . .

6.66 9.05 7.71 8.03

45°irN 43°N* 44°47'N —

55°51'W 62°W 56°35'W —

Lepidisis caryophyllia .

.

6.92

38°13'N

69021'W

Rhipidogorgia flabcllum . Tubipora musica ,

. 12.64 . 3.83

32°N —

— —

Corallium rubrum .

. . . . .

6.27 3.80 9.18 9.32 2.13

— — — — —

— — — — —

Alcyonium pal mata TTsis hippuris .

,

9.63 6.36

— —

— —

Corallium elatior .

. 11.56

33°N

—

Gorgonia acerosa . *

Pleurocorallium johnsoni . Gorgonia citrina .

. 12.52 . 13.29 . 6.03 . 13.43

25°5'N 23°3'N 25°45'N 25°N*

Gorgonia acerosa . Plexaurella sp. (?) . . Eunecia crassa , Eunecia roussiani . Plexaurella homomalla Pseudoplexaura crassa Briarium asbestianum . Gorgonia flab e Hum JCiphigorgia anceps Plexaurella dichotoma . PUxauraflexuosa. Rhipidogorgia flabellum .

. 13.39 . 12.08 11.46 . 11.45 - 12.01 - 12.12 * 13.21 . 13.12 . 13.23 - 14.12 . 16.90 . 13.19

Newfoundland Nova Scotia Atlantic Grand Banks, Atlantic Nantucket, Mass., U.S.A. Bermuda Mediterranean (?) Forchhammer, 1852 Vogel, 1816 w Witting, 1832 „ Butschli, 1908 99 „ Nichols, 1906 Forchhammer, 99 1852 Butschli, 1908 ^^^^__ Forchhammer, 1852 Japan Clarke and Wheeler, 1922 Bahamas Florida Canary Islands Anderson f Tortugas, Fla., Phillips, 1922 U.S.A.

99

99

99

99

99

99

99

99

99

99

•

-

*

'

w w

n

„ „ „ „ w

w w

n

— — 20°12'W —

— — — — — — — — — — _ —

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

w

w

99

w

I

I

99

99

99

99

99

n

99

99

99

99

w

w

I n 99 w

Bahamas

Clarke and Wheeler, 1922

Chemical Composition of Marine Organisms ORGANISM Leptogorgia pulchra .

. 13.71

Plexaurella dichotoma . Funecia tourneforti Leptogorgia rigida

. . .

Xiphigorgia anceps Muricea echinata * Gorgonia subfruticosa . Plexaurella grandiflora Akyonium rigidum Ctenocella pectinata

. 13.04 . 12.28 . 13.43 . 13.79 . 10.50 . 15.65

23°30'N 22°52'N 18°S 13°S* 12°S* 10°S*

178°W* — 178°W* —

- 12.64 . 15.73 . 12.23

8°S* 3°50'S 1°20'N

— 32°25'W 103°50'E

Muricea humilis . Phyllogorgia quercifolia Tubipora purpurea

MgC03

*

2.11 2.78 14.13

Latitude 24°36'N

Longitude

—

25°N*

— — —

— 22°52'N

— —

Locality

211 Author

Lower California Clarke and Wheeler, 1922 Bahamas Nichols, 1906 w » » Cape San Lucas Clarke and Wheeler, 1922 Florida, U.S.A. » » Cape San Lucas » » Fiji r> rt Brazil » » Samoa Phillips, 1922 Torres Strait Clarke and Wheeler, 1922 Brazil >» » »

w

Singapore

»

t See Murray and Renard, 1891.

* Approximate.

resorted to burning the organism, which leads to loss of sulfur. Other determinations of sulfur in the skeletal organic matter of Alcyonaria were done by Cook (i 905), Morner (i9i3-b), and Henze. There are no systematic analyses for alkali. Statements of the high silicon in Coelenterata are based on errors,13 for there are no siliceous Coelenterata. The silicon content of Alcyonaria is small; actually the amount does not exceed o. I °/o of the dry matter. 6. Heavy Metals and Other Elements In spite of the absence of more complete analyses, which may be partly explained by the difficulty in getting material, we know that the amount of all heavy metals in these organisms is considerably higher than that in sea water. More recent data on the composition of Coelenterata, chiefly those of heavy metals (in °/o °f dry matter), have been obtained by spectrographic analysis by I. and W. Noddack (1939) for Cyanea capillata and Metridium dianthus i Ti

C. capillata . M. dianthus

. .

. 0.0006 . 0.00073 Ni

C. capillata . M. dianthus .

. 0.003 . 0.0023 Th

C. capillata M. dianthus

. 3xlO-« . 3xlO-«

V

Cr

Mo

Mn

Fe

Co

0.0005 0.0040

0.00013

0.0002 0.0018

0.0006 0.0055

0.015 0.062

0.0007 0.00017

Cu

0.0068 0.0032

Ag

0.00038 0.0006

Ge

Sn

0.00022 0.00007

0.0032 0.0015

Au

7xlO~7 7xlO~7

Pb 0.0027 0.0043

Zn

Cd

Ga

0.155 0.140

0.0011

0.00006 0.00004

0.00004

As

Sb

Bi

0.0050 0.0009

0.000016 0.000023

0.00004 0.000016

13. See Haixne (1849) on the SiO, in Leiopathes glaberrima*

is

212

Memoir Sears Foundation for Marine Research

Thus, for the first time we have data on the amounts of chromium, molybdenum, silver, gold, cadmium, gallium, thorium, germanium, antimony and bismuth in Coelenterata. IRON. Data on this element are found in some of the analyses which we quoted above. The observations of Laugier (1810), Witting (1832), Schneider (1888, 1922), and Macallum (1903) are qualitative. MacMunn (1886) isolated a pigment from Actinia that contained iron, namely actiniochrom,14 which in his estimation is closely related to hemoglobin, and Macallum (1903) determined the iron in the fluid from Aurellia and Cyanea. Vogel (1816) suggested that the coloring of Corallium rubrum depends on the presence of iron; on the other hand, Hooper (1908) found no iron in the white coral. The systematic determinations of iron by Phillips (1922) are given in Table 123. MANGANESE. Determinations of this element are almost all qualitative. Pichard (1898) showed manganese to be present in medusae, while Fox and Ramage (1931) demonstrated the presence of manganese, iron, and copper in the medusa Cosmetira. Phillips (1922) gave a series of determinations for manganese (see Table 123). The manganese content fluctuates from n x io"4 to n X io~ 6 °/ 0 of the live weight. ZINC. For this element there are more definite quantitative data. In general there is less zinc in the Coelenterata than in Crustacea, Mollusca and some other invertebrates, while the amount of zinc in Coelenterata is many times larger than that of copper, just as in all other invertebrates. COPPER. Copper has been detected by many investigators (see Ulex, 1865); it is present in Coelenterata in smaller amounts than in other invertebrates, especially in those containing haemocyanin. Thus, of all the heavy metals, iron, and to some extent zinc, predominate in Coelenterata.

TABLE 123 IRON AND MANGANESE IN COELENTERATA (IN «/0 OF DRY MATTER)

Fc

ORGANISM

P lex aura homomalla . , P lex aura flexuosa Gorgoniumf l a b e l l u m. . Pseudoplexaura crassa . Eunicea crassa Eunicea rissoa Eriarium sp Xiphigorgonia anceps . Gorgonia acerosa Cassiopea xamachana , Pleurobrachia pileus . ,

. . .

.

. . .

.

0.0105 0.0215 0.016 0.0215 0.0130 0.0170 0.0180 0.0160 0.030 0.0008 0.005

Mn

Author

0.00080

Phillips, 1922

0.0006

0.00095

0.0011

0.00030 0.00040 0.00070 0.0005

14. Sec the more recent work of Roche (1936-3, b), Dhe're', and others on this pigment.

Cooper, 1939

Chemical Composition of Marine Organisms

213

TABLE 124 ZINC AND COPPER IN COELENTERATA (IN •/„ OF DRY MATTER)

ORGANISM

Zn

Pocill0pora sp Actinosa metridium Medusa sp. , Ant hea cereus , Physalia sp.

—

,

Plexaura homomalla . Plexauraflexuosa. Gorgonium fiabellwn , Pseudoplexaura crassa Eunecia crassa Eunecia rissoa . . . Briariwn sp Xiphigorgonia anceps . Gorgonia acerosa * Cassiopea xamachana ,

*

+ * *

.




»

»

r>

»

»

»

»

»

r>

rt

Uli 1865"

• In the living matter.

OTHER METALS.IS Forchhammer (1865) found about 0.0002% lead and traces of silver in Podllopora alacornis. Fox and Ramage (1931) indicate strong lines of lead in a spectral analysis of the ash of Cosmetira pilosella. We have shown the presence of titanium and lead in the axial skeleton of a coral Primnoa resedaeformis var. pacifica from the Japanese Sea. The ratio Co/Ni is approximately the same as in sea water, with no enrichment in cobalt. Bertrand (1943^, c) found 7 X io"6°/o molybdenum and 2.3 x io~ 4 °/ 0 vanadium in the dry matter of Anemonia sulcata. RARE EARTHS. The known qualitative data on the presence of rare earths refer mainly to the Alcyonaria. Crookes (1883), indicating the presence of yttrium in Gorgonacea, wrote as follows: "Gorgonia of the species Melitoea and Mussa sinuosa undoubtedly remove from sea water not merely lime but also yttria, and other recent corals Pocillopora damicornis and Symphyllia close to the yttria-secreting Mussa, separate samaria from sea water." Chernik attempted determinations of rare earths in several species and mentions the presence of these elements, but he gives no further information.16 ALKALINE AND ALKALINE EARTH METALS. Fox and Ramage (1931) detected lithium qualitatively in Cosmetira, but on the presence of rubidium and cesium we 15. Taylor mentions the presence of vanadium in Actinia, making no reference. The remark was probably made by mistake. 16. Personal communication.

•s'

214

Memoir Sears Foundation for Marine Research TABLE 125 BORON IN THE SKELETAL MATTER OF COELENTERATA (IN % OF DRY MATTER), FROM GOLDSCHMIDT AND PETERS, 1932

ORGANISM

Hexacorallia Lophohelia anthophyllides . Amfhihelia oculata Herpetolitha Umax Dendrophyllia ramae Pachyseris va/enciennense . Porites c/avaria

B

.

.

, 0.03 0.03 0.015 0.003 0.015 0.015

B

Octocorallia hidella hfotensis Pennatula phosphorea Tubipora purpurea Corallium rubrum

.

,

,

0.0015 * 0.0003 0.015 0.015

have only general statements. The presence of strontium in corals has been mentioned many times, but there are no quantitative data except those mentioned below. Vogel (1816) found this element in corals and other marine organisms, and Dieulafait (1877) found it in various calcareous marine organisms. Moretti, in 1813, indicated the presence of the element in various madreporarian corals; Fox and Ramage (1931) observed strong strontium lines in medusae. These analyses, then, indicate a general distribution of strontium in marine organisms with calcareous skeletons as well as in the skeletonless forms, such as medusae. We have demonstrated the presence of strontium in one Gorgonia^ and Noll (1934) found the following amounts of strontium in corals: Porites clavaria (Florida), 0.42 °/0 of the ash; Corallium rubrum (Sicily), o.i 7 °/0; Millepora alcicornis (Florida), 0.43 °/o- Regarding the distribution of strontium in invertebrates, see the section on Mollusca.2H A single observation on barium is given by Forchhammer (see Dittmar, 1884), who found this element in one Alcyonaria. BORON. Goldschmidt and Peters (1932) found o.ooi to o.i°/ 0 boron in the skeletal matter of various contemporary corals. In the fossil Paleozoic corals there was less of the element, 0.005 to o-°50/o- Goldschmidt and Peters (1932) point out that the reef-forming corals contain more boron than other corals. Igelsrud, Thompson and Zwicker (1938) found 0.187% boron in the dry matter of Hydrocorallina of the Philippine Islands. GALLIUM. We detected this element in Primnoa resedaeformis vzr.pacifica of the Japanese Sea. ARGON IN SIPHONOPHORA. In the pneumatocysts of Physalia the composition of the gas is nearly the same as that of air; Quatrefages (1854) found 17.78 °/0 oxygen, the remainder being nitrogen and carbon dioxide. Schloesing and Richard (1896) found 15.1 °/o oxygen, 83.2% nitrogen, as well as argon, the amount of which was equal to that in air, 1.18 °/0 by volume. Determinations of argon in various organisms have shown that as a rule the amount of this element, or the ratio N/Ar, does not 2H. Tsuchiya (1948) found 2.9% SrO in fresh coral, 1.97% >n oW bleached coral, and 0.87 °/0 in calcareous algae.

Chemical Composition of Marine Organisms

215

differ from that in air (see Hackspill, Rollet and Nicloux, I926).17 But in the swim bladders of fish from a depth of 1,385m, for example Synaphobranchus, there is up to 8o°/0 oxygen, with the ratio N/Ar in the bladder being different from that of air; there was i.94°/ 0 argon, a larger amount than in air. Jacobs (1932), in analyses of gases in the bladder of the siphonophore Stephanomia bijuga of the Mediterranean Sea, found that the gas contained on the average 10.9% oxygen and 2.1 °/0 CO2. The remainder was nitrogen and argon. After the pneumatocyst was emptied, the gas glands at the bottom of this organ formed new gas, which consisted of 4.7 °/o oxygen, 2.5% CO2, and nitrogen + argon. 7. Halogens, Arsenic, and Radioactive Elements As opposed to other Coelenterata, Alcyonaria are organisms which concentrate halogens, particularly iodine and bromine, these being present in the form of halogenorganic compounds. In this respect the Alcyonaria are closely related to the Cornacuspongida, which possess identical iodo-organic complex compounds. At the present time the Alcyonaria are the only known concentrators of bromine, the amount in Alcyonaria surpassing that of iodine by several multiples of ten. Other bromine organisms have not yet been discovered, although there are probably some among other iodine organisms, algae and sponges. In 1825 Balard was the first to find iodine in Gorgonia^ and several years later Sarphati (1837) found it in Gorgonia flabellum as well as in Flustra foliacea (polyzoan). Silliman (1846) found 14 % chlorine, 35.0% bromine, and 13 °/0 iodine in the insoluble part of the ash of Gorgonia antipathes. Iodine was found qualitatively by many others, including Witting (1832), who found it in Corallium rubrum (see also Rossum and Balard). But the systematic study of iodine in Alcyonaria began with the work of Drechsel (1896), who found 7.49% in the skeletal matter of Gorgonia cavolini\ the iodine was bound with the organic matter of the skeleton and was described as iodogorgonic acid, with its properties closely related to the di-iodotyrosin of the sponges. Later Henze (1907) and others repeated these investigations with other species of

TABLE 126 IODINE IN ALCYONARIA AND OTHER OCTOCORALLIA (IN •/» OF DRY MATTER) ORGANISM

Corallium rubrum Paramuricea placomus Alcyonium digitatum Caligorgia (?) sp. (skeletal matter) . Caligorgia (?) sp. (whole coral)

I

.

.

0.00044 0.0398 0.0022 . 0.099 0.057

Locality

Author

Mediterranean Bergen, Norway

Fellenberg, 1924 Gloss, 1931 „ „ Cameron, 1915-a „ „

Canada (Pacific) „ „

17. The determinations done on yeast by Pictet, Scherrer and Heifer (1925) are erroneous.

2 16

Memoir Sears Foundation for Marine Research

Alcyonaria. The most complete picture of the iodine, bromine and chlorine in the skeletal matter of Alcyonaria was given by Morner (1907). Taking into account the fact that Alcyonaria and other Octocorallia lose up to 80 °/0 of their water in drying, one may calculate that in the living matter the iodine fluctuates between io"2 and io"4°/0, which is the same order of magnitude as that of the algae and sponges. The amount of halogen in Octocorallia is typical of individual species. Closs (1931) found 0.0124% iodine in the living matter of Paramuricea placomus; in the solid parts of Alcyonium digitatum he found 0.00078 °/0 iodine in the living matter and 0.0046 °/o i*1 the dry matter; in the fluids of the body he found 0.000031 °/0 (wet) and 0.00065 °/o (dry)- From this it follows that iodine in Alcyonaria is concentrated in the supporting parts. There is a relatively large amount of information on the iodine and bromine in the skeletal matter of these organisms. The iodine and bromine contents in the skeletal matter of various families and species show certain differences. For example, all the species of Plexaura and Eunecia

TABLE 127 HALOGENS IN ORGANIC COMBINATION IN ALCYONARIA (IN % OF DRY MATTER)

ORGANISM

No. of analyses

Gorgoniidae Gorgonia cavolini Gorgonia verrucosa Gorgonia graminea Gorgonia citrina Gorgonia acerosa Gorgonia flabellum Gorgonia setosa Xiphigorgia anceps Other Gorgoniidae 12

I

Br

Cl

Author

5.49—7.79 6.92 5.58 1.17 0.79-1.7

1.98 1.62 1.3

0.16 0.17 0.12

0.61-0.82

0.04

0.80-1.15 0.70—0.77 0.96-1.58 0.02-0.62

0.89 0.23 0.37-2.61

0.18 0.17 0.1

Drechsel, 1896; Mfirner, 1907 Mfirner, 1907 » » Sugimoto, 1928 Mfirner, 1907; Mendel, 1901; Sugimoto, 1928 Mendel, 1901; Sugimoto, 1928 Mfirner, 1907 M6rner, 1907; Sugimoto, 1928

none

0.43

0.68 0.42-0.73 0.04-0.16 0.09-0.86

Antipathidae Cirripathes spiralis 5.45 drachnopathes ericoides 6.14 Other Antipathidae 6 0.02-2.43 Gorgonellidae Plexauridae

0.12-2.21 27 0.11-2.63

0.38-1.53 0.66-1.98 0.96-4.2

Isididae Pennatulidae

2 1.58-2.03 11 trace-0.2

0.74 0.09-1.89

0.1 0.08-0.13

Alcyoniidae Primnoidae

2 0.05-0.15 2 0.05-0.12

2.94-3.76

0.07-0.08

Morner, 1907 Mfirner, 1907; Allen, 1930 Mfirner, 1907 Mfirner, 1907; Sugimoto, 1928; Cook, 1905; Mendel, 1901 M6rner, 1907 Mendel, 1901; M6rner, 1907; Cook, 1905; and others Mfirner, 1907

Chemical Composition of Marine Organisms

217

(Plexauridae) are characterized by more or less equal quantities of iodine (about i % of the skeletal dry matter), with the amount of bromine two to three times greater than that of iodine; on the other hand, species of the family Gorgoniae contain more iodine than bromine, the amount of iodine in some species being atypical, reaching 7 °/0 in Gorgonia cavolini and G. graminea. Leftogorgia contains little iodine and five or ten times more bromine; the family Pennatulidae contains little iodine and a relatively large amount of bromine. The distinctive iodine and bromine content of the species of these three families gives us reason to think that this characteristic is closely related to the entire organization of these Alcyonaria. At the Vernadsky Laboratory for Geochemical Problems, Simorin, with specimens from the Gulf of Kola, found 1.35 x io"10/0 bromine in the living matter of the hydroid, Sertularia pumila, and 9 x io~ 3 °/o bromine in an actinian, Chondr actinia digitata^ which is close to the amount of this element in sea water. Virey found iodine in medusae, and Fyfe (1819) and Stratingh (i 823) found the element in madreporarian corals. Halogens are accumulated in the cornein of Antipatharia. Although quantitative determinations of iodine and bromine in Hexacorallia are few, the amount of these elements in them is considerably less than in Alcyonaria. In medusae and actinians there is about io~ 4 °/o iodine in the dry matter, with bromine sometimes higher, a fact which drew the attention of Sarphati (1837) to Rhizostoma and Cyanea. Adolph and Whang (1932) showed that there is 0.00013 °/0 iodine *n ^c dry matter of Aurellia. Neufeld (1936) determined bromine in various Coelenterata as follows (in % of dry matter) : Aequorea aequorea (- forskaKa) (Hydrozoa) Aurellia flavidula (Scyphozoa) Metridium marginatus (Actinaria) PleurobraMa sp. (Ctenophora) Caligorgia (?) sp. (whole organism) Caligorgia (?) sp. (skeleton)

0.1135 0.1925 0.0355 0.189 0.354 0.876

A calculation of the bromine in percent of living weight in these Coelenterata indicates that it is somewhat higher in medusae than in sea water, but actinians do not concentrate bromine and contain the same amount as is found in sea water:

Aequorea aequorea (= forskalid) Aurellia flavidula Metridium marginata

.

-

-

Br (»/o living matter)

H20 (*/•)

0.0062 0.0121 0.0034

94.6 93.7 90.7

Macallum (1903) noted the presence of bromine in Aurellia and Cyanea; Haurowitz and Waelsch (1926) found bromine, iodine, and possibly fluorine, in Velella spirans. Drechsel's (1896) iodogorgonic acid, on closer investigation by Wheeler and Jamieson (1905), Henze (1907), and Sugimoto (1928), proved to be 3—5-di-iodo-

218

Memoir Sears Foundation for Marine Research TABLE 128 IODINE IN HYDROZOA, ACTINIARIA, AND HEXACORALLIA (IN «/0 OF DRY MATTER)

ORGANISM

Medusae Obelia longissima . Aequorea aequorea Aurellia flavtdula '. Aurellia flavidula* ,

I

.

,

Locality

0.013

0.000 0.000 5xlO- 5

Canada (Pacific)

Author

.

-

.

-

Cameron, 1914

M a l l u m , 1903

Actiniaria Metridium margmatum Bolocera (?) sp. . » » *

0.000114* 0.000261*

Near Bergen, Norway

Cameron, 1914 Lunde and Madsen Closs, 1931

Hexacorallia, et al. Acropora varia .

0.00025

Mediterranean!

Fellenberg, 1924

0.000

Canada (Pacific)

.

.

«

* In the living matter. f Wilke-Ddrfurt (1928) indicates the absence of this species in the Mediterranean Sea.

tyrosin, while Morner (1913^) showed that the bromo-organic compound which he isolated from Primnoa is 3—5-dibromotyrosin. It is quite likely that other compounds of iodine, bromine and chlorine exist in skeletal matter.811 There are no quantitative determinations of fluorine, but Silliman (1846), on the basis of recalculation of data rather than by direct analyses, stated that there is fluorine in Hexacorallia. Fluorine has been indicated qualitatively in the skeletons of Hexacorallia by Sharpies (1871), Forchhammer (1852), and others. ARSENIC. Bertrand (1903) found 1.5 x 10'*% in the dry matter of the actinian Chitonactis richardL Shtenberg (1939) found i ^ y m g in loog of dry matter of a hydromedusa from the Sea of Azov. RADIOACTIVE ELEMENTS. Allen (1930) noted a weak radioactivity, less than that of sea water, in Antipathes abies. 8. Ctenophora Ctenophora, classified with the Coelenterata, are pelagic skeletonless organisms with organic supporting parts. According to Vernon (1895), t*1686 organisms contain 3 H. Roche and Lafon (1948; see also Lafon and Mayol, 1948, as well as Fromageot, Jutisz, Lafon and Roche, 1948) have given a number of new analyses of the iodine content of gorgonians in which they find the range to be from 0.06 °/0 in Euplexaura purpuraviolacea to 9.3 °/0 in Eunicella verrucosa referred to dry organic matter. They claim both mono-iodotyrosin and di-iodotyrosin are present; in the case of E. verrutosa, 7.3 °/0 mono-iodotyrosin and 12.65 °/0 di-iodotyrosin are recorded, while 5.25 °/e of the unhalogenated amino acid is said to have been present. The interpretation of these results is rendered somewhat doubtful by the fact that they studiously avoid mention of the existence of bromine compounds. It is also curious that no one appears to have considered the possible existence of brom-iodotyrosin in these forms (see Low, 1951).

Chemical Composition of Marine Organisms

219

a large amount of water; their dry residue is 0.60% (in Beroe ovata) or even 0,24% (in Cestus veneris\ but this is doubtful. Cameron (1914), attempting to determine iodine in Pleurobrachia^ found less than o.ooo n°/ 0 in the dry matter. Needham, Needham, Baldwin and Yudkin (1932), in data on the phosphate of Pleurobrachia pileus, gave o.ooi i °/0 in the living matter. Cooper (1939) found i.34°/0 nitrogen, 0.23% phosphorus and 0.0050% iron in the dry matter of Pleurobrachia f ileus. The ratio Fe/P was 0.02 in P. pileus; in other Ctenophora the ratios are as follows: Bolina infundibulum> 0.038, and Beroe cucumis^ 0.013-0.017.

Chapter IX Elementary Composition of Bryozoa

B

RYOZOA are widely distributed in the seas, and those with calcareous skeletons participate in the formation of polyzoan reefs. According to their morphological characteristics, there are two subclasses of Bryozoa, namely Entoprocta and Ectoprocta. The Entoprocta are often regarded as being related to the lower worms and as having little affinity with the Ectoprocta, which are of primary interest in the present work. These Bryozoa, which are usually marine, although one important group inhabits fresh water, possess an organic chitinous skeleton. There is a great variety of species that contains different amounts of calcium and magnesium carbonates. Calcium carbonate, discovered in many species of Bryozoa in the beginning of the last century, was later described by a number of investigators, such as Nitsche (1871), Sorby (1879), et al. Some Bryozoa live in both brackish and salt water with resultant differences in chemical composition. The amount of water in Bryozoa is dependent on the degree of development of the mineral skeleton, and the total amount of nitrogen is related to the amount of chitin. The dry residue is composed chiefly of chitin and carbonates, the calcium and magnesium carbonates impregnating the middle layer of the chitinous skeleton, namely the ectocyst. Loppens (i92o-b) has pointed out that the ratio of chitin to ash residue varies in different species according to the conditions of the habitat. Thus, members of a species living in the littoral zone of the sea contain more CaCO3, and consequently less chitin, than other individuals of the same species living in the open sea.1 Furthermore, the more solid littoral forms are bush-like while forms from the open sea are filmy. According to Loppens (i92o-b), there is 44% CaCO3 in the marine form of Membranipora membranipora but up to 88.9% in the littoral Membranipora membranipora f. erecta from brackish waters. In the open sea he observed that Lepralia foliacea contains 64.5 % CaCO3) the littoral form 98.8 °/0. Deepwater species of Bryozoa, x . Plumatella repens does not contain CaCO,, although it lives in fresh water. In certain species, the CaCOs content is rather stable. Undoubtedly the degree of incrustation of CaCO, has systematic significance.

22O

Chemical Composition of Marine Organisms

221

TABLE 129 WATER, ASH RESIDUE, AND NITROGEN IN BRYOZOA (IN % OF LIVING MATTER)

ORGANISM Ahyonidium gelatinosum

Flustra foliacea

* „

. -

. . . . . . - . .

. . . . . . .

Membranipora membranipora . Pectinate/^ sp

.

.

Water

Ash

N

Author

94.93 95.20 97.63

0.27 — 0.92

— — 0.10

Loppens, 1920-b

80.0 84.0

— —

—

87.22

1.32

89.74 99.58

1.12

— present

— —

Weigelt, 1920 » >» Loppens, 1920-b » » Morse, 193o"

such as Mucronella variolosa, are even richer in calcium. Loppens (i92O-b) also pointed out that the precipitation of CaCO3 in Bryozoa occurs more rapidly in the specimens from the deep and quiet parts of the sea. In skeletons of Bryozoa there is present not only CaCO3, as the majority of investigators supposed, but up to 11.08 °/o MgCO3, and therefore it is important to examine the differences in CaCO3 and MgCO3 in the various forms. Clarke and Wheeler (1922) observed that in some species of Bryozoa the external characteristics changed with an increase in MgCO3. Species similar to the heavy corals contained up to 6 °/0 MgCO3 while the less compact species with a fine fern-like structure contained up to ii °/o MgCO3, or more if the possibility of occasional contamination by diatoms and sand be considered.

TABLE 130 THE RELATION OF CaCO, IN BRYOZOA TO HABITAT (IN % OF DRY MATTER), FROM LOPPENS,

ORGANISM

CaCO3

Chitin

Flustra foliacea

58.07 65.12 60.00

41.93 34.88 40.00 48.5 66.6 48.75 31.66 56.0 13.55 35.5 37.4 2.9 2.0 3.0 1.47

Membranipora pilosa (erect form) Membranipora pilosa (creeping form) Membranipora membranipora (marine)

. .

51.5 33.4 51.21

.

68.34 44.0

Membranipora membranipora f. erecta (littoral) • • Lepralia foliacea (marine) Lepralia foliacea (fluvial) Lepralia foliacea (erect form) Cellaria fistulosa Cellepora pumilosa Mucronella vario/osa (deepwater marine) . . . .

86.45 64.5 62.6 97.4 98.0 97.0 98.55

.

.

.

222

Memoir Sears Foundation for Marine Research TABLE COMPOSITION OF BRYOZOA

CaCO,

ORGANISM

Schizoporella unicornis Microporella grisea Celiepora incrassata . , , Flustra membranacea truneat a Flustra foliacea , . , . Lepralia pallasiana Lepralia rosterigera . . . Lepralia sp Holoporella albirostris Frondipora verrucosa Frondipora reticulata . . Amathia spira/is Catenicella margaritacea Bugula turrita Bugula neritina Eschara foliacea »

r»

* * * . , * .

.


i

r»

,

.

.

.

i

-

i

*

i

*

i

+

p

— — — —

MgCO,

CaaP208

CaS04

0.63 4.58 1.11 6.07 6,94 1.23 5.62

trace trace 0.24 trace 0.32

1.32 1.40 1,45 1.76

2.80

5.02 2.59 0.17

0.27 trace

1.45

trace trace

1.54 2.83

0.43 1.58 2.68

2.07 4.76 8.47

0.596

9.57 8.96 10.19 11.08 2.71 0.146

0.445 0.352

3.99 0.0 5.35

* S1O2 together with saod.

On the whole, as seen in Table 131, the MgCO3 in the skeletons of these organisms varies rather a good deal, from traces up to 11 °/0; in skeletons of other invertebrates a similar range of MgCO3 content is not found so often. When the MgCO3 varies considerably, as in Bryozoa, there is a wide morphological variability. There may be a relationship between the amount of MgCO3 in the skeleton and the form of Bryozoa. It is interesting to note that in species with high MgCO3 content, e. g., Bugula turita and B. neritina, the phosphorus is increased to 2.68 °/0 Ca3P2O8 in the ash, while usually in the Bryozoa there are but traces of this element, as was shown by Hatchett (1799). Weigelt found that in Alcyonidium gelatinosum the dry matter contained 1.69 °/0 P2O5 and i.48 °/0 CaO, whereas in Flustra foliacea there was 0.89 °/o P2O6 and 21.08% CaO. Lewis (1926) however, investigating the fossil form Bolopora undosa, near Cardiff, North Wales, discovered that the skeleton contained phosphate. Oakley (i 934) described another occurrence of phosphate in the form of dahllite in the remains of the Silurian Bryozoa Favositel/a interpuncta (from Gotland) and other specimens of

Chemical Composition of Marine Organisms

223

i3i (IN •/» OF ASH RESIDUE) *V>8 +

Al^Oj

SiO2

1.31 0.39 0.12 0.20 4.82 — 0.15 0.41 1.58 0.59 0-72 — — 0.50 2.25 1.54 0,34 —

1.77 2.66 0.18 0.20 4.82 — 5.52 0.38 2.58 0.59 1.42 — — 1.15 16.71* 12.94* 0.31 —

Locality

Author

Vineyard Sound, Mass., U.S.A. . Florida, U.S.A Australia North Grand Banks (Atlantic) . Alaska California, U.S.A Gloucester, Mass., U.S.A. . . Florida, U.S.A Naples Florida, U.S.A Naples

.

Near Cape Hatteras, U.S.A.. Australia Georges Banks (Atlantic) , Florida, U.S.A Naples

.

.

.

.

Bermuda — Gulf of Kola

. ,

Clarke and Wheeler, 1922 „ ^ w n I I I n I w w Nichols, 1906 Clarke and Wheeler, 1922 Kamm (see Clarke and Wheeler, 1922) Schwager (see Walther, 1885) Kamm (see Clarke and Wheeler, 1922) „ „ „ Forchhammer, 1852 Kamm (see Clarke and Wheeler, 1922) Clarke and Wheeler, 1922 „ „ Schwager (see Walther, 1885) Forchhammer, 1852 Nichols, 1906 Vinogradov and Borovik-Romanova, 1935 Nichols, 1906

the family Ceramoporidae (CeramoporelLa, Favositella squammata^ and so forth). It is possible that the phosphate is secondary and replaces CaCO3, but the possibility of phosphate concentration by these organisms during their lifetime is not excluded. It is possible also that Bryozoa with phosphate skeletons have existed in the past. The possibility that the genus Eugula as a whole may contain more phosphate than other recent Bryozoa also requires investigation. According to Sorby's (1879) analyses, CaCO3 in Bryozoa is found in the form of an inseparable mixture of aragonite and calcite (see Cornish and Kendall, 1888). But more recent analyses by Kelly (1900), Meigen (1901), Schmidt (1924), and others (for Crisia eburnea, Eugula neritina and Flustra foliacea] indicate only the presence of calcite. The composition of the matrix of the jelly-like forms of Bryozoa, such as Akyonidium^ is not known. There is little information on the amount of other elements in Bryozoa, and hence it is not known whether iron and copper are physiologically important in these organisms.

224

Memoir Sears Foundation for Marine Research

Iron has been indicated qualitatively in Polyzoa. A brief note by Elmhirst and Paul (1921) mentions the discovery of copper in the ash of Membranifora membranacea; Phillips (1922) found 0.0007 °/o copper in an undetermined Bryozoa, as well as 0.0042 % zinc, 0.0098 °/0 iron, and 0.00081 % manganese in the dry matter. Bertrand found 3.36 X io~ 3 °/ 0 copper, 1.36 X io" 2 % molybdenum (1943-^, and 1.68 X io~ s % vanadium (1943^) in the dry matter of Plumatella fungosa. These are the only analyses which have been done up to the present time. Forchhammer (1852) found 0.002 °/0 lead in the dry matter of Heterofora abrotanoides. Chlorine was easily detected in these organisms; iodine was discovered by Sarphati (1837) in Flustra foliacea, and Cameron (1914) found 0.016% in the dry matter of Eugula flabellata. Of the alkaline elements, potassium was found in traces. According to our analyses, there is 0.2 °/0 strontium in the ash of undetermined marine Bryozoa, and Borovik-Romanova (1939) found that the ash of the polyzoan Retefora cellulosa contains 0.2 % barium.

Chapter X

Elementary Composition of Brachiopoda I. Inarticulate (Calcium-Phosphate Brachiopoda) \ LTHOUGH fossil Brachiopoda werefirstfound in the Cambrian layers, the ap-/A. pearance of these astonishing animals, a few of which have been preserved almost unaltered (for example, Lingula1), will probably be found to have occurred much earlier. Many species of Inarticulata and Articulata had a period of great expansion at some time in the past, and it is important to remember that Inarticulata reached a climax in the Cambrian and Silurian and then sharply declined in the Mesozoic. Representatives of Lingulidae and Craniidae are still living, e. g. Lingula anatina. Lingula, Obollela^ Obolus, and other Inarticulata possessed shells of proteinous organic matter impregnated with phosphate in layers,2 but indications of the presence of chitin in them have not been proved. The bivalve ecardinate shells of these Brachiopoda (Lingula, Obollela, Obolus, and others) are often found well preserved in large numbers in the sediments, especially in those of Cambrian-Silurian origin. Phosphorites, which owe their origin partly to these Brachiopoda, are found over the whole of the earth, occurring chiefly in CambrianSilurian layers, although they have been found in other sediments in many parts of Sweden, the United States, and other countries. Rocks built by these organisms are enriched with phosphorus, and direct analysis of the shells of fossil Brachiopoda shows high phosphorus. In 1854 Hunt and Logan found up to 50 °/0 Ca3 (POJg *n the fossil Lingula, and from that time on important research has been done in this field. The connection between the occurrence of 1. These animals are often found in pre-Cambrian layers [sic]. 2. There were also horny Brachiopoda, without mineral inclusions.

22$

226

Memoir Sears Foundation for Marine Research TABLE 132 COMPOSITION OF SHELLS OF FOSSIL BRACHIOPODA (IN «/„ OF ASH)

ORGANISM

8 CaSO4

Locality

Author

0.00

0.99

trace

Scarborough

Clarke and Wheeler, 1922

0.32 9.72

trace 0.62

0.13 trace

7.644 4.455 1.349 high

— — — —

England(?) Vineyard Sound, Mass., U.S.A. Mediterranean Forchhammer, 1852 North Sea ? ? Butschli, 1908

— —, — —

99

99

99

99

99

99

99

99

99

99

99

Chemical Composition of Marine Organisms

237

TABLE 139 COMPOSITION OF PHOSPHATE TUBES OF POLYCHAETA (IN % OF DRY RESIDUE)

ORGANISM

CaO

MgO

P2O6

Onuphis tubicola

3.40

9.73

Onuphis conchylega 22.7

Organic matter and water Locality

Fe2Oa

SiO2

SO3

21.58

—

—

—

62.55

Naples

—

7.5

—

—

—

53.10

Leodice polybranchia 5.12

4.40

6.43

2.33

28.05 6.06

46.91

Gulf of Kola

Hyalinacia artifex

5.35

8.57

20.72 0.07

0.2

3.47

61.83

5.24

8.17

20.32 0.01

0.24

4.33

61.41

Author

Schmiedeberg, 1882 Vinogradov, 1935

Marthas Vineyard, Clarke and Mass., Wheeler, 1922 U.S.A.

analogy with other skeletal formations in invertebrates, indicates the presence of calcite. However, the cases of low magnesium, and one indication of the presence of aragonite, should be noted. Claims of the presence of traces of fluorine in the tubes of Vermes are without much value because it is not indicated whether these observations refer to phosphate, magnesium-calcium or other tubes. 3. Heavy Metals Iron can be detected easily in the ash of all organs and tissues of Vermes. It was discovered in the ash of the earthworm by Hiinefeld (1839), then in the blood ; later it was detected qualitatively many times in these animals (see Schneider, 1888, 1922). For qualitative determinations of iron and lists of iron organisms, see Dorff (1934). Some quantitative data on this element in worms are given in Table 137. Mutscheller (1935) f°und from 2.3 x io"3 to 4.5 x io~ 3 % iron in the dry matter of the organs of Bonellia viridis. Cooper (1939) found 9.24% nitrogen, 0.945% phosphorus, and 0.042 % iron in the dry matter of Sagitta elegans. The ratio Fe/P was 0.045 *n *kis species and 1.28 in Sagitta setosa? Harrison (1940) repeated these investigations and found, in an average of ten analyses of Sagitta setosa, 9.26% dry matter, 0.921% phosphorus, and 0.091 % iron (in the dry matter) ; in Sagitta elegans he found 10.9 % dry matter, 1.20% phosphorus, and 0.055% ^ron- The ratio Fe/P in the first case is about o.i, in the second 0.046. According to Griffiths (i892-c), Warburg (1914), and many others, there is up to 0.5 % iron in the red pigment of some worms, the iron being bound in an organic complex. The blood of many Vermes is red,6 and the presence of erythrocruorin and its derivatives in their blood and tissues proved to be a widespread phenomenon. In 5. The Sagitta setosa specimens were old. Possibly this is erroneous. 6. The first observations were made by Swammerdam (1758).

238

Memoir Sears Foundation for Marine Research

some species the erythrocruorin occurs not only in the blood plasma but also in the blood corpuscles. Its properties are similar to, but not entirely the same as, those of the haemoglobin of the higher animals. In 1861 Rollet discovered so-called haemoglobin in the blood of earthworms, and these observations were continued by Nawrocki (1867), Kobayashi (1927-1928), and others. Later Lankester (1871) systematically investigated the blood of different species, finding the pigment in many of them (see also Krukenberg [1881-1882], Halliburton [1891]). It has been found in numerous Chaetopoda, Gephyrea, Nemertini, and others. Svedberg (1933) called the haemoglobin of invertebrates erythrocruorin. A detailed study of erythrocruorin was done by Redfield and Florkin (1931) on Urechis caupo\ see also Quatrefages (1846), Winterstein (1909), Jordan and Schwarz (1920), Vies (1923), Barcroft (1928), Fisher and MacGinitie (i928-a, b), Lingen and Hogben (1928), Dolk and Paauw (1929), Borden (1930), Baumberger and Michaelis (1931), and Fox (1932); see also Chapter XIX. Besides erythrocruorin, other iron blood pigments were found in some Vermes. The blood of Sabella is green, and Lankester (1868) isolated chlorocruorin, a pigment containing iron, from the blood of these organisms. Investigations of this pigment by Warburg (1914) in Spirographis spallanzanii, by Roche (1936-^, and especially by Fox (1932), showed that the pigment is an analogue of haemoglobin. In the blood of Sipunculus nudus^ Krukenberg (1881—1882) discovered a peculiar pigment called haemerythrin, which also contains iron (see Marrian, 1927). Finally, MacMunn (1886) demonstrated the presence of derivatives of haemoglobin, the haemoporphyrins, in the tissues of Luminous, and Zieliriska (1913) made an analogous discovery in Eisenia. Thus, in the blood of Vermes there is a whole series of pigments which contain iron and which are closely related to haemoglobin and its derivatives. The diverse living conditions of the worms create a great diversity in the composition of the respiratory pigments of the blood. Neither copper nor other metals have been found in the respiratory pigments of these organisms.7 While iron-bearing pigments are significant as carriers of oxygen, it is still unknown whether this is true of the pigments under discussion. Many carry oxygen effectively only under special conditions and can play a functional role solely when the partial pressure of oxygen is low. Manganese, copper and zinc are found in considerably smaller quantities in Vermes than in Mollusca, Crustacea, or even Coelenterata. The majority of determinations are qualitative; the investigators usually say only that these elements are found in traces, and they refer to terrestrial rather than to marine species. Determinations of manganese by Bertrand, traces of copper by Dubois (1900), and traces of zinc by Delezenne (1919), are known for a leech, Hirudo officinalis. In the tubes of the annelid, Serpula sp., 0.090% manganese was found by Vinogradov (1938). 7. The pigment of Bondlia viridis proved to be a derivative of chlorophyll (dioxy-meso-pyrrochlorine) and contained no metal (see Dhere and Fontaine [1932], Lederer [1939], and others).

Chemical Composition of Marine Organisms

239

The only systematic qualitative determinations were done on 19 Polychaeta by Fox and Ramage (1931). Although a concentration of manganese was never found, the possibility of such a concentration still exists, as was shown by the investigations of Berkeley (i922-a) on the distribution of this element in Mesochaetopterus taylori and Chaetopterus variopedatus: Mesochaetofterus taylori

Tubes as a whole Tubes, anterior part . . . . Tubes, middle part Tubes, posterior part . . . . Tissues of body, anterior part . . Tissues of body, middle part . . Tissues of body, posterior part. . Chaetopterus variopedatus Tubes, inner layer Tubes, outer layer

No. of analyses

«/, Mn

«/, Ash

4 2 2 2 2 1 2

0.029 0.0047 0.0102 0.0338 0.0063 0.015 0.0016

— 47.8 48.3 0.129 — — —

2 1

0.0444 0.0219

26.61 47.48

Manganese was not found in the tubes of Sabellidas and Spiochaetopterus. For copper there are qualitative analyses by Muttkowski (i92i-a) and Zanda (i924).8 Mutscheller (193$) obtained the following results from his investigations of the organs of Bonellia viridis; he gives data for copper, manganese, and iron in percent of the dry matter: Cu

Proboscis Intestines

Body without intestines

2.65xlQ-* 3.81 x 10~*

4.41 X 10~*

Mn

3.1 xlO' 8 6.2xlQ-«

8.2x10"'

Our statement as to the small amount of manganese, copper, and zinc is possibly incorrect, since there is a lack of quantitative data. In regard to the other metals, according to Fox and Ramage (1931) nickel was found in five species of Polychaeta out of 19 investigated, cobalt less frequently. Based on a number of analyses, Myxicola infundibulum contained 0.002 °/0 cobalt and from o.oi to 0.08 °/0 nickel in the dry matter, Aphrodite aculeata 0.0025 % cobalt and 0.003 % nickel, Audouinia tentaculata up to 0.0014 % nickel, Arenicola up to 0.0008 % nickel, Spirographis spallanzanii up to 0.0008 % nickel; a certain variation was observed in the amount of nickel according to the place of collection. Maliuga (1946), reporting on Arenicola marina from the Gulf of Kola, gave the following figures: 9.5 x io~*°/ 0 cobalt in the ash, or $.$ x io~ 4 °/o in the dry matter and 2 x io~*°/ 0 in the living matter; 1.8 X io~ s °/o nickel in the ash, or i.i x io~ 8 °/ 0 in the dry matter and 3.9 x io~*°/ 0 in the living matter. 8. An old determination of copper in Eutora, which requires verification, was done by Ulex (1865), who found 0.027 °/o in the ash.

240

Memoir Sears Foundation for Marine Research

Silver and lead were found in Vermes by Fox and Ramage (1931), silver occurring only in Owenia fusiformis, Mellina palmata, Myxicola^ and Sabellaria alveolata and lead only irregularly in Lumbricus, Aphrodite, and Spirographis. The presence of lithium; rubidium, and strontium was shown qualitatively; the Polychaeta Mellina, Notomastus latericius, Arenicola, and Aphrodite contained up to 0.0008 % lithium in the dry matter; rubidium was detected only in Myxicola and Notomastus, in which there was 0.00014 % of the dry matter; strontium was detected in the calcareous tubes of Polychaeta. Fox and Ramage (1931) determined this element qualitatively in 17 Polychaeta,9 and they were unable to find it in only Nephthys and Notomastus. In Protula there was 0.002 °/0 strontium. Yamamura (1934) gave data on the composition of Limnodrilus sp. (Oligochaeta) and Nereis japonicus (Polychaeta) and showed the amount of some rare elements in these organisms (in °/0 of dry matter): H,O

8.110 Limnodrilus sp. N. japonicus . 85.0

Ash

Ca

7.65 3.67

0.50 2.43

Zn As Al s Fe P 0.158 0.345 0.043 0.692 0.036 0.0013 0.00032 0.408 0.019 0.550 0.032 0.0000 0.00087 1.00

Mg

Webb (1937) determined rare elements in Lineus longissimus (Nemertea) and Nephthys sp. (Polychaeta) (in °/0 of total ash cations): Sr

L. longissimus Nephthys sp.

Ba

B

Al

Cr

Mn

Fe

Cu

Zn

Cd

Sn

Pb

0.015 0.005 0.05 0.15 0.07 0.15 0.8 0.05 1.0 0.002 0.02 — 0.05 — 0.1 — 0.06 0.005 1.0 0.03 1.0 — — 0.03

4. Nonmetallic Elements Iodine occurs in all marine Vermes. On the basis of isolated determinations by Cameron (1915^) for almost 20 different worms collected near Nanaimo, Canada (see Table 140), there is io~ 2 to io"s°/0 iodine in the dry matter, or more. A particularly large amount was found in the tubes of Sabella, Bispira, Diopatra, Chaetopterus, and Thelepus. These tubes are known to be organic, possibly keratin or chitin, with low ash. According to Cameron (1915^), the dry matter of Bispira polymorpha contains 16 % ash> while the amount of iodine in these tubes reaches 0.65 % (cf. horny sponges). Furthermore, different layers of the tubes contain different amounts of the element, more being present in the inner layers. It is also of interest to examine the iodo-organic compounds of the tubes. Apparently the horny tubes with protein, keratin, such as those of Sabella and Bispira, are the richest in iodine. On the other hand, tubes which consist of substances such as onuphin, chitin, and so forth10 are poor in the element 9. Sthenelais boa. Nereis cuMfera, Nephttys sp., Owenia fusiformis, Audouinia tentaculata, Amphitrite ed

w

rt

Weigelt, 1891 Meyer, 1914 Moore, Whitley and Adams, 1913 Mathews, 1897 Wetzel, 1907 Russo, 1926 Ephrussi and Rapkine, 1928 Putter, 1908 McClendon, 1909 Koizumi, 1935 w

w

w

w

McClendon, 1909 Koizumi, 1935

* In percent of dry matter.

dermata is considered to be approximate, because the existing data are not satisfactory. Griffiths (i 905) gives analyses for the muscles of Uraster and Echinus and Hilger (1875) for the body wall of Holothuria, in which he showed the amount of alkali. According to Bialaszewicz (1926), potassium predominates in the eggs of Echinodermata, whereas Page (1927^) claims that differences in the potassium and sodium of the eggs are not so great. Koizumi (1935) gives an analysis of the skin and muscles of Caudina chilensis in percent of living matter (cf. Hilger's [1875] analyses5): Na

Skin

Longitudinal muscle

0.69 0.44

K 0.31 0.54

Ca

Mg

2.16 0.72

0.44 0.20

ci 0.99 0.43

SO4

1.84 1.25

C03

3.66 1.02

5. Lindemann (1899) gives the amount of water and ash in the skin of Stichopus regatis, Holothuria lubulosa, and Cucumaria syraktuane. Huarachi (1942) gives an analysis of Sphaerechinus escuUntus\ see also Krogh (1939)-

248

Memoir Sears Foundation for Marine Research TABLE 143 NITROGEN IN ECHINODERMATA (IN °/o)

ORGANISM

Dry matter

2.23

6.81 3.86 5.45 5.32—5.65

Asterias glacialis

— —

Asterias rubens Asterias forbesi

. 1.76—1.87

Asteracanthion rubens »

»

.

.

.

6.37 4.63 1.96 7.23 1.30 2.86 0.45 1.15 10.7

1.21 0.92

.

•

Hippasterias phrygiana * Ophiothrix fragilis Ophiopholis acut eata Spatangus purpureus . , , Echinus esculent us var. depressus Paracentrotus sp.* Paracentrotus sp.* Strogylocentrotus lividus .

Author

Living matter

— —

0.41 1.31

.

— — — — —

Sempolowski, 1889 Marchand, 1866 Delff, 1912 Hutchinson, Setlow amd Brooks, 1946 Weigelt, 1891 » » Vibrans, 1873 Meyer, 1914 Weigelt, 1891 »

»

Meyer, 1914 » » Ephrussi and Rapkine, 1928 Russo, 1926 Wetzel, 1907

8.6 7.2

* Eggs.

Note the low potassium in the muscle of Holothuria (Na/K = i) compared with that of other invertebrates; these observations should be verified. Myers (1920) found 0.053 % CaO and 3.2 % NaCl in the blood of Pisaster ochraceus> 0.056 % CaO and 3.2% NaCl in the blood of Picnopodia helianthoides> and 0.068% CaO and 3.1% NaCl in Strongylocentrotus franciscanus. Pora (i936-c) found 3.378 % NaCl, 0.0488 % potassium, and o.i 156 % CaO in the blood of male Paracentrotus lividus^ and 3.334 % NaCl, 0.0497% potassium, and 0.0914% calcium in the females. Sex differences in TABLE 144 COMPOSITION OF EGGS OF ECHINODERMATA (IN % OF LIVING MATTER)

Ash

ORGANISM a

Arbacia sp. Arbacia pustulosa Strongylocentrotus lividus . Paracentrotus lividus jfsterias sp. Arbacia punctulata . Strongylocentrotus lividus]

Na

K

Ca

0.231 0.434 0.338 2.0 1 39 0.042 0.456 0.029 . 2.14 — — — . 1.33 0.014 0.536 0.040 ?0 0.690 0.772 0.169 — . 0.4 — — — — — — -

a So4 = 0.00008; Fe = 0.00048; Cl = 0.0332.

Mg

P04

Author

0.796 0.114 0.024 0.840 — 0.310 0.044 0.684 0.240 0.388

— —

Page, 1927-a Bialaszewicz,1926 Wetzel, 1907 Bialaszewicz, 1 926 Page, 1927-a — McClendon, 1909 2.86* Matthews, 1928

present Pantin, 1931

* Phosphorus in percent of dry matter.

-j- Sperm.

Chemical Composition of Marine Organisms

249

blood composition are small and irregular, which evidently stems from the fact that Echinodermata have an open blood system. The amount of chlorine is equal to that of the medium (see chapter on fluids of invertebrates) ; the comparative analyses of haemolymph given in Table 327 show more detail. To these observations should be added those of Pantin (1931) on echinoderm eggs, as follows (grams per liter): Na . K . Ca . Mg

Arbacia

Asterias

6.1 11.5 8.9 21.1

23-24 32 7.0 9.9

Cl . SO4 P04

Arbacia

Asterias

0.88 0.0023 4.3

5.3

Most of the ash residue of Echinodermata consists of calcium carbonates, followed by magnesium carbonates, which compounds form the skeletons of these organisms. But in the soft parts of Echinodermata, so far as one can see from isolated analyses, magnesium predominates over calcium. Since these elements occur in the eggs in equal amounts, the amount of calcium evidently increases as development proceeds. Ephrussi and Rapkine (1928) found 1.5% as^ *n t^ie dry matter of the fertilized egg of Strongylocentrotus lividus, 9.1 °/0 after 12 hours, and 16.8 °/0 after 40 hours (see also Schiicking, 1903). In mature Echinodermata the composition of the ash residue reflects primarily the composition of the skeleton. The distribution of phosphorus in these organisms can be presented somewhat more completely than that of most other elements. In whole organisms there is an average of about i °/0 P2O5 in the dry matter, and in muscles, and especially in eggs, P2O5 forms more than half of the ash (see Table 145). Javillier and Cr^mieu (1928) found 0.384% phosphorus in the dry matter of Synapta inhaerens. Needham and Needham (1930) observed an increase in phosphorus with the development of echinoderm eggs (in °/0 of dry matter): Dendraster excentricus

Unfertilized egg Gastrula Pluteus

Patiria mini ata

Unfertilized egg Bipinnaria

0.694 0.880 0.95 0.694 0.615

Phosphorus is also found in the form of various phosphoro-organic compounds and as phosphates of alkaline and other metals.6 The ratio between different forms of phosphorus in the tissues of Echinodermata is more or less stable, and from the point of view of evolution it is of great interest to study these ratios in different species of Echinodermata and other organisms. This has been done by Needham (1931), Bertolo 6. See Verzhbinskaia, Borsuk and Kreps (1935) on phosphorus compounds in the muscles of Holothuria.

250

Memoir Sears Foundation for Marine Research TABLE 145

**

COMPOSITION OF ECHINODERMATA (IN % OF DRY MATTER)

ORGANISM

CaO

wisterias glacialis Asterias sp.* Asterias rubens . Asterias for best

.

99

99

99

99

Ash in dry matter

1 46 21.66 0.89 0982 21.04 0.88 0.184 3.154 47.05 47.44 25.98 1.02 0.29 — . * 23.63 1.03 0.049 — —

6.50 1.63 0.89 Hippasterias phrygiana — Echinus esculentusvur. depressus — Spatangus purpureus . — Ophiothrix fragilis 0.55 Ophiopholus aculeatus . — Asteracanthion rubens .

Cl

36.96 19.53 26.77 22.58 37.72 12.88 37.40 —

6.13 — 1.35 1.37 — — — 0.65 — 0.79 0.46 5.34f 0.36 0.20 7.67f 0.32 0.36 3.59f — 0.33 — — 0.88 —

34.37 45.16 60.04 51.73 85.31 93.13 82.64 —

Author Sempolowski, 1889 Marchand, 1866

Delff, 1912

Hutchinson, Setlow

and Brooks, 1946 Vibrans, 1873

Weigelt, 1891

Meyer, 1914 99

99

99

99

99

99

Weigelt, 1891 Unpublished^

* Na20-z.oz %; MgO-i.9i •/.; SO3-i.o8 «/0. f As NaCl. § Unpublished material of the Vernadsky Laboratory for Geochemical Problems.

(1912), Robertson and Wasteneys (1913), Kreps, and by Fr£nkel and Jellinek (1927-^ for both phosphorus and sulfur. In the skeletons of Echinodermata the presence of phosphates is always noted (see Table 146 and subsequent tables). Compared to other invertebrates, Echinodermata do not contain an exceptional amount of sulfur (see Tables 144, 146). Silberstein (1934) found 0.8927% in the dry matter of the tissues of the sea urchin and 0.2673 °/o in the shell, including spines.1" Lindemann (1899) gives the amount of sulfur in the body wall of Stichopus and other Holothuria (see also Kossel and Edebacher, 1915). The amount of silicon in Echinodermata is insignificantly small. 3. Composition of the Skeletons, Particularly of Echinoidea The first attempt to determine the chemical composition of the mineral part of echinoderm skeletons was made by Valentin (1842), who performed analyses on the ambulacral plates, shell, and spines of the sea-urchin. Besides CaCO3, about 1.0% MgCO3 was found. However, more modern analyses indicate that these results for MgCO3 are incorrect, because we know now that skeletons of all Echinodermata contain considerably more. It is probable that the data given by Schurig (1906) on Phormosoma sp. (Echinoidea) are also quite inaccurate.7 i H. Hutchinson, Setlow and Brooks (1946) indicate 0.87 »/0 of the dry matter or 0.29 '/0 of the living matter to be sulfur in Asterias forbesi. 7. He found 57.7% CaaP2Oe in the dry matter of this species I

Chemical Composition of Marine Organisms

251

Besides CaCO3 and MgCO3 in the skeletons of Echinoidea, as in other Echinodermata, there are phosphates and sulfates, possibly CaSO4, the total of which is usually not more than i % of the ash. The amount of strontium and barium varies from o.oi to 0.5%, as seen in Table 157. Skeletons also contain alkalies, but it is not clear whether they enter into the composition of the mineral skeleton or are present in the organic parts. However, most of the skeleton is composed of CaCO3. The MgCO3 in different species varies from 5 to 15 % of the ash residue. The numerous qualitative determinations of calcium from the skeletons of Echinoidea, mentioned in almost all works of biologists who have studied the histology of echinoderm skeletons, are not given here. Clark (1911), investigating Crinoidea, showed that the skeletons of species from warm waters are richer in MgCO3) and from data collected recently, especially in the work of Clarke and Wheeler (1922), this regularity can be traced for the skeletons of many other invertebrates; in regard to Alcyonaria, we have already mentioned the relationship between the amount of MgCO3 and the temperature of the habitat. The skeletons of all Echinoidea which live in the Arctic or Antarctic regions at low temperatures, or which live in more or less deep places in more moderate latitudes, contain, as a rule, a smaller amount of MgCO3J about 5 to 7 °/0, whereas tropical and subtropical species contain up to 15 °/0; we have seen this relationship in the magnesium-calcium skeletons of Alcyonaria and other organisms, and it also holds for the rest of the Echinodermata classes. Thus the ratio MgCO3/CaCO3 in the skeletons of Echinodermata, Alcyonaria, and other organisms, varies regularly as the habitat of a species varies from Poles to Equator, or vice versa. External differences also occur in the skeleton, sometimes being present in all organisms of one class; for example, there is a greater compactness in the skeletons of the more tropical species of Crinoidea. Differences in morphological characteristics are also analogous to those observed in plants and animals on land, this being known as geographical variability. Undoubtedly there are changes in the chemical composition of the organisms along with morphological changes. However, no systematic attempts have been made to study the morphology of Echinoidea and other organisms in relation to the chemical composition of the skeleton, but it seems to us that in this way we can clarify the mechanism of greatest influence which the action of the medium has on organisms with a common habitat. This influence is widely distributed, forming zones in which marine organisms have common characteristics of chemical composition. Now let us turn to an examination of the chemical composition of the skeletons of different species of Echinoidea. Clarke and Wheeler (1922) found that the spines, chewing apparatus, and shell of the same species of Echinoidea contain different amounts of MgCO3 ; Samoilov and Terentieva (1925) got the same results. The spines, on the periphery of the skeleton, contain less MgCO3, with the smaller spines richer in MgCO3 than the larger ones. The main body of the skeleton, especially the inter-

252

Memoir Sears Foundation for Marine Research TABLE COMPOSITION OF SKELETAL PARTS OF ECHINOIDEA

ORGANISM

Comments

CaCOs

93.28 93.13

Strongylocentrotus drobachiensis Strongylocentrotus fragilis , Strongylocentrotus franciscanus Echinarachnius parma „ . . M Echinarachnius excentrica Encope califomica Encope micropora . Lyt echinus anamesus , Lyt echinus a/bus , Tetrapygus niger . Tetrocidaris of finis . Heterocentrotus mammillatus . Clypeaster testudinarius Echinus af finis Echinus esculentus Echinometra lucunter AleHit a sexiesperforatus . . jfrbacia pustulosa * Paracentrotus Hindus Prionocidaris (= Phyllacanthus)

, .

, .

. . , . . Large spines «

.

.

.

Shell .

.

.

. . . ,

.

.

.

baculosa

Shell . „ * * Shell „

. ,

.

.

-

92.83 88.44 95.06 92.39 92.13 89.90 79.94 82.36 77.91 91.73 90.52 89.35 86.42 91.29 88.96 89.64 83.87 85.02 90.08 89.40 89.33

AJ.O.+ Fe203

MgCO3

6.36 5.99 5.44 6.95 3.24 6.59 6.13 8.80 10.38 13.79 7.44 7.38 6.27 9.30 12.26 8.41 5.41 8.84 11.56 11.91 7.72 8.53 10.67

trace trace 0.28 1.06 0.48 0.12 trace trace 0.48 trace trace trace trace trace trace 0.08 1.85 trace

~

ambulacral plates, contains the largest amount of MgCO3; the chewing apparatus of Echinoidea is rich in MgCO3. No regularity in the distribution of phosphates and sulfates is observed in the skeleton of Echinoidea and other Echinodermata; phosphates form not more than i °/0, while up to 5 °/0 of the total is sulfate, usually calculated as CaSO4. The skeletons of Echinodermata, and Alcyonaria, as we have seen, give the highest figures for sulfate. However, the mineralogical character of the sulfate is unknown. Neither anhydride nor gypsum has been found in these organisms by optical methods or otherwise. The question now arises as to whether or not the SO4 could be formed from the organic matter of the skeleton. The organic basis of the skeleton, called chondrin in Holothuria, is protein and contains a good deal of sulfur. Hessel (1826), who was the first to observe crystals of calcite in the skeletons of the fossil Echinodermata, thought that they were formed as a result of mineralization. However, in 1841 Haidinger showed that in the modern representatives of Echino-

0.36* 0.37

0.81 0.29 5.20 0.98 3.51 0.18 0.32 0.16 0.14 0.14 2.38 0.37 0.39

"

Chemical Composition of Marine Organisms

253

146 (IN °/o OF ASH RESIDUE)

SiOa

CaSO4

Locality

Author

trace 0.13 — 0.32 — 0.15 — 3.99 2.87 9.93 0.05 0.33 0.12 0.02 0.16 3.25 0.04 0.13

trace 0.38 1.45 2,42 1.28 0.46 1.74 1.30 0.49 trace 0.73 0.66 2.56 1.07 1.16 trace trace 1.40 2.22

North Sea Greenland Barents Sea Southern California, U.S.A. California, U.S.A New England, U.S.A Bering Sea „ „ Galapagos Lower California California, U.S.A Patagonia Peru Florida, U.S.A Tuamotu Southern Japan Cape Hatteras, U.S.A Mediterranean British West Indies

Schmelck, 1901 Clarke and Wheeler, 1922 Samoilov and Terentieva, 1925 Clarke and Wheeler, 1922 Terentieva, 1932 Clarke and Wheeler, 1922 Terentieva, 1932

"• 13

— -

l.oO

2.20 2.07 —

„

„

Bay of Naples Sicily Red Sea

„

„

,

*

.

,

.

Clarke and Wheeler, 1922 Salkover (see Clarke and Wheeler, 1922) Clarke and Wheeler, 1922 „ „ „ „ Salkover (see Clarke and Wheeler, 1922) „ w Biitschli, 1908 Kamm (see Clarke and Wheeler, 1922) *

.

.

„

„

„

Terentieva, 1932

H

T)

„

dermata the inorganic part of the skeleton contains calcite crystals ;8 this was confirmed in the work of Kelly (1900), Meigen (1901), Butschli (1908), and others. The optic properties of skeletons were examined in detail by many investigators, more recently by Schmidt (1924), and in all of the skeletons calcite crystals were distributed in a definite way in different parts of the skeleton. Thus the optic axis of the ambulacral and interambulacral plates of Echinoidea regulata lies meridianally, while in Echinoidea irregulata and in some species of the genus Echinometra it is perpendicular. The optic axis of the spines coincides with the direction of the spine. Schmidt (1924) found that the optic axes sometimes go in different directions in the spicules of Holothuria having the same form. All this is important in genetic studies, for the directing action of calcite crystallization on the formation of the skeleton, and of the whole body, is evidently destroyed in the process of evolution, although not entirely in some cases (see Schmidt, 1924). However, to dwell further on this interesting topic would lead us far afield, so we will return later to these questions, 8. Biocrystals. The whole skeleton is a rhombohedral crystal system.

254

Memoir Sears Foundation for Marine Research TABLE 147

MgC03 IN THE SKELETAL PARTS OF ECHINODERMATA IN RELATION TO THE TEMPERATURE OF THE HABITAT 160

UO

120

100

80

60

40

20

0

20

40

60

80

lOg,

20

I 0

>60

10

l O

70

60

4(

40

2C

20 0

C

2(

20

4C

40

O

e

160

4.

• 140

5 to

7

7 to 10

10 to 15 120 100

80"

60

«0

20

0

20

40

60

60

100

120

140

160

160

160

Composition of the Skeletons of Crinoidea

Most analyses of crinoid skeletons were done by Clarke and Wheeler (1922), and it has been found that the composition of these organisms is of the same magnesiumcalcium type. The amount of MgCO3 in the skeletons of modern Crinoidea varies from 7.28 to 13.37 %59 depending on the habitat of the species; this was first shown in 1911 by A. H. Clark (see Tables 147 and 149). MgCO3 is easily extracted from the skeletons of Crinoidea by weak acids. CaCO3 is present in the form of calcite (see Meigen [1901], Schmidt [1924]). Parallel with the analyses of modern Crinoidea, Clarke and Wheeler (1922) investigated the skeletons of fossil forms, ten different species being taken from different parts of Europe and America from the lower Silurian to Eocene. With the exception of one species, Triassic Encrinus liliiformis from Germany, which contained 20.23 °/0 MgCO3, there was from 0.80 to 2.56% MgCO3, which is considerably lower than in modern Crinoidea. Likewise, Samoilov and Pustovalov found little MgCO3, from 2.14 to 3.17 %, in the stalks of Crinoidea from marl and limestone of the Serpukhovski formation of Tver.10 Consequently, two hypotheses are possible: i) The skeletons of 9. Tcrcnticva (1932), on the basis of one set of determinations of MgCOa, supposed that there was more in the arms and less in the disk (see analyses of Clarke and Wheeler, 1922). 10. The rock in which the fossils were found contained up to 42.24% MgCOa.

Chemical Composition of Marine Organisms

255

extinct Crinoidea, and perhaps of Echinodermata in general, contained little MgCO3,n or 2) MgCO3 was removed from the skeletons of dead Crinoidea by solution during metamorphism, especially since the solubility of MgCO3 in the skeletons is high. Both processes can take place during metamorphism of magnesium-calcium skeletal remains—a decrease in MgCO3, as for example in Crinoidea, and an increase in MgCO3, as in fossil calcareous algae. Although the problem of the evolution of the composition of skeletons and the changes in the biogenal migration of MgCO3 is of considerable scientific and practical significance, it still remains unsolved; much more research is required. 5. Composition of the Skeletons of Asteroidea The skeletons of Asteroidea are also of the magnesium-calcium type (calcite). In all the known analyses, chiefly qualitative, the amount of alkaline and of other elements is indicated, with the quantitative determinations still referring to the same elements

TABLE 148 MgCO8 IN DIFFERENT PARTS OF THE SKELETONS OF ECHINOIDEA (IN °/0 OF ASH RESIDUE)

ORGANISM

Tetrocidaris affinis . Heterocentrotus mammillatus Strongylocentrotus drobachiensis franciscanus Paracentrotus /ividus . Sphaerechinus granularis . Prionocidaris (= Phyllacanthus) bacu/osa. Arbacia pustu/osa Cidaris thouarsii Echinarachnius parma . excentrica .

Shell

9.30

12.26

Dental ^ Spines-, pyramid white red

_

_

_

12.27 8.32 9.86

Interam- Ambubulacral lacral ,^Spines—s plate plate large small

_

_

4.63*

—

—

—

—

—

—

—

2.68*

—

6.89

7.78

—

—

—

—

—

—

8.53

6.69 —

—

—

—

2.92*

8.60

8.26 —

—

—

—

5.16* —

10.67 7.72 —

— — 7.85 — 9.5 —

— — — 5.98 8.53 — — — 4.82* — — 10.11 6.14 3.72 6.16

6.13 8.80

5.86 — — —

7.78 4.97 3.24

The dimensions are not indicated. n. Modern Crinoidea contain the smallest amount of MgCOj-y.28 %.

Author

Clarke a n d

Wheeler, 1922

Samoilov and Terentieva, 1925 3.75 Terentieva, 1932

—

256

Memoir Sears Foundation for Marine Research TABLE 149 COMPOSITION OF SKELETAL PARTS OF CRINOIDEA (IN °/0 OF ASH RESIDUE)

ORGANISM Heliometra glacialis var. maxima .

ALO.4CaC08 MgC03 Ca3P*08 Fe2Os SiOa —

7.28

—

9.50 10.34

— —

a Metacrinus rotundus

88.50

Ptilocrinus pinnatus . Florometra asperrima . Psathyrometra fragilis . . . . Pentametrocrinus japonicus . Capillaster multiradiata . Pachylometra patula Catoptometra ophiura Hypalocrinus naresianus . Parametra granulata . Craspedometra anceps . . . . Pilometra mulleri . Hathrometra dentata

88.48

7.91 0.29

89.45

9.44 0.58

87.77

9.25 trace

87.34

10.15 1.12

86.32

85.81

12.69 trace 12.20 1.11

86.46

—

—

Author

Locality

Northern Japanese Sea Gulf of Kola South Japan

Palmer (Clarke and Wheeler, 1922) — Terentieva, 1932 — Palmer (Clarke and — — Wheeler, 1922) 1.31 2.01 British Columbia Clarke and Wheeler, 1922 0.48 0.05 Pacific (near Washw »» ington,U.S.A.) „ „ 1.41 1.57 Yezo Strait, Japan —

0.91 0.48 Omai Saki Light,

w

«

„ „

„ „

w

»

»

»>

»1

»

«

w

11.68 0.86

Japan 0.78 0.21 Philippines 0.74 0.14 Philippines (near Balabac) 0.95 0.05 » „

89.66

10.16 trace

0.10 0.08

t>

87.86

11.08 trace

0.59 0.47

»

86.93 87.94

12.34 0.27 11.13 0.48

0.22 0.24 Tinakta Island 0.24 0.21 Sydney Harbor,

„

„

83.47

9.36 0.88

0.56

5.73 Marthas Vineyard,

»

n

87.16 10.09 trace 87.96 11.69 trace 88.20 11.69 trace 88.27 11.42 trace 88.13 11.62 trace 87.58 11.96 trace 87.51 11.77 0.27

0.33 0.30 0.08 0.21 0.21 0.29 0.43

0.42 0.05 0.03 M „ 0.10 „ 0.04 0.17 w 0.02 Rio de Janeiro,

w

»»

83.13

13.74 0.64

0.51 0.54

91.55

7.86 trace

Anthomttra adriani 91.05 Zygometra microdiscus 85.48

8.23 trace 13.37 0.48

Bythocrinus robustus Crinometra concinna Isocrinus decor us* . Isocrinus dtcorus\ . Endoxocrinus parr a* Endoxocrinus parra\ Tropiometra picta . Tropiometra carinataP . Promachocrinus kerguelensis

0.57

Australia

Mass., U.S.A. Gulf of Mexico Cuba

Brazil Tobago, B.W.I.

0.02 Antarctic,

Gaussberg

0.44 0.28 a 0.62 0.05 New Guinea, Aru Islands

«

»

» »»

n

n

n

«

w

» «

w

Kamm (Clarke and Wheeler, 1922) Clarke and Wheeler, 1922

«

»

Chemical Composition of Marine Organisms ORGANISM

A1203+ CaC03 MgCO3 Ca3P2O8 FeaO3 SiO2

Zygometra microdiscus — — — — — Chlorometra rugosa 89.80 9.87 trace 0.27 0.06 Heterometra quinduflicata . . See Craspedometra anceps Perissometra patula * Stalk. t Arms.

Locality

257

Author

A. H. Clark, 1911 Lesser Sund, Rott Clarke and Wheeler, 1922 A.H.Clark, 1911

See Pachylometra patuia

„

„

a CaSO4 = 2.30. p CaSO4= 1.44.

—magnesium, calcium, SO4 and P2O5. As a rule the amount of MgCO3 is greater in species from warm regions of the ocean (see Table 147). Schmelck's (1901) data on magnesium for species of Asteroidea of northern waters differ somewhat from those of other investigators, the results for magnesium in all invertebrates investigated by him being higher than the average results of other workers. The amount of MgCO3 varies in different parts of the skeleton of Asteroidea with a similar regularity to that found in other Echinodermata; the interambulacral plates are richest in this substance, with somewhat less in the ambulacral plates and considerably less in the arms.

6. Composition of the Skeletons of Ophiuroidea The skeletons of Echinodermata are characterized by: i) A variation in the amount of MgCO3 depending on the temperature of the habitat, and 2) a smaller amount of MgCO3 in the peripheral parts of the skeleton, rays, and so forth; this holds also for the skeletons of Ophiuroidea. Rays in the same species of different ages, differing in thickness, do not differ in amount of MgCO3, 7. Form of CaCO3 and MgCO3 in the Echinoderm Skeleton CaCO3 is found in the skeletons of all Echinodermata in the form of calcite,12 But in what form does MgCO3 occur in the skeletons of Echinoidea—as free MgCO3, as magnesite, or as dolomite ? On the basis of thermal analyses of the mineral part of echinoderm skeletons, in particular the disk of Ophiopleura borealis^ Samoilov (1923) concluded that MgCO3 is present in the form of dolomite, which opinion was also held by Linck (1912). Terentieva (1932) recently approached this question with a somewhat different method when she compared the solubility of skeletons in i °/0 acetic acid with that of the corresponding minerals; she came to the conclusion that 12. All extinct fossil Echinodermata, such as Cystoidea and Blastoidea, contain calcite; see Cayeux (1916) and others. In some skeletons, such as those of the Crinoidea from the Silurian to the Jurassic, there is usually low MgCOa, not more than 2.5 °/0. Whether this is the result of metamorphism, or was actually a condition of the living organisms, has not been settled.

258

Memoir Sears Foundation for Marine Research TABLE COMPOSITION OF SKELETAL PARTS OF

CaCO,

ORGANISM Asterias vulgaris Asterias tanneri\ . Asterias forbesi . Asterias acervata borealis Asterias linckii f. robusta Asterina minuta Asterina miniata . . Asterina pectinifera Leptasterias compta . . Benthopecten spinosus Luidia clathrata Acanthaster planci Linckia guildingii , , Linckia laevigata . Ctenodiscus crispatus . Ctenodiscus procurator Ctenodiscus australis Odonaster hispidus Plutonaster agassizii . Pont aster tenuispinus . Astropecten articulatus Astropecten americanus . Astropecten andromeda , Orthasterias tanneri Urasterias linckii Phataria bifascialis . Phataria pyr amidata Or taster occidentalis Marthasterias glacialis . Culcita novaeguinea Coscinasterias calamaria Arcaster tenuispinus . . w

»

.

Hippasterias phrygiana

.

.

. . .

.

.

.

.

.

.

.

.

.

. , .

, , ,

. , . ,

..

.

. , , , . .

. .

.

.

.

.

.

.

.

.

,

91.06

, . 87.44 . . 88.19 . . 87.39 , . 88.01 86.77 . . 88.06 82.51 86.57 . . 86.42 , , 86.77 , , 85.99 , . 83.42 . . 85.63 . , 88.48 . . 87.52 , . 80.78 - . 87.16 - . 89.18 . . 89.34 . . 85.08 . . 87.93 . . 78.67 . , 86.41 . . 88.25 . . 71.28 , . 81.82 . , 80.04 . . 85.99 , , 82.27 . 85.29 . . 88.46 - 87.92 . . 87.97

MgCO,

7.79 10.28 8.24 9.60 9.46 12.53 11.24 12.05 10.27 9.88 12.13 13.33 14.31 9.32 8.78 11.16 10.51 10.58 9.09 8.86 13.02 10.11 10.42 10.69 8.91 13.56 13.52 13.76 8.29 14.35 11.22 11.18 10.29 8.77

CVA

0.21 0.57 0.78 trace 0.58 trace 0.40 trace 0.45 0.29 0.36 0.21 trace trace 0.73 trace trace 0.08 — 0.15 trace trace trace trace trace trace trace trace trace trace trace trace trace —

AJjOj-f Fe.O.

0.3 0.70 0.78 2.19 — 0.70 0.27 2.44 0.77 0.94 0.42 0.20 0.26 2.64 0.22 1.32 7.66 0.12 0.18 0.45 0.23 0.33 0.45* 1.88 2.84 11.04 1.86 3.99 2.90 0.92 3.49 0.36* 0.66* —

• Clarke and Wheeler's material was determined by Austin H. Clark so that the 'nomenclature that they give is retained} nevertheless t F«»0,.

MgCO3 is present in a very soluble form, but not as magnesite or dolomite. The solubility of MgCO3 in Echinodermata proved to be greater than the solubility of the MgCO3 of Lithothamnium (see Chapter II, Section n). The disks and rays of Ophiopholis and Ophiura sarsii were both investigated.

Chemical Composition of Marine Organisms

259

150 ASTEROIDEA (IN % OF ASH RESIDUE)

Si02

CaS04

Locality

Author

0.64 1.01 0.17 0.82 — 0.70 0.03 0.71 1.94 2.47 0.32 0-27 0.24 0.70 0.39 trace 1.05 0.62 0.35 0.31 0.24 0.29 8.66 1.02 0.00 2.06 1.06 0.06 0.41 0.15 0.00 trace trace —

— — 1.84 trace 1.95 — — 2.29 — — — ~ 1.77 1.71 1.40 trace trace 1.44 0.20 0.89 1.43 1.34 1.01 trace trace 2.06 1.74 2.15 2.41 2.31 trace — 1.13 3.26

Eastport, Maine, U.S.A. . . . 35°43'N, 73°52'W Vineyard Sound, Mass., U.S.A. . Nova Scotia, Canada , . . , White Sea British West Indies . . . . California, U.S.A Otaru, Japan 40°17'N,69051'W 39°15'N,68°08'W Charleston, S. Carolina, U.S.A. . Palmyra Is British West Indies . , . . „ „ „ . , . . Newfoundland, Canada . . . Chile Patagonia Marthas Vineyard, Mass., U.S.A. „ „ „ Hatteras, U.S.A Western Florida, U.S.A. . . . Marthas Vineyard, Mass., U.S.A. 61°4rN,3°19'E Hatteras, U.S.A Nova Scotia, Canada , San Lucas, Lower California . . „ „ „ , • • California, U.S.A Azores East India N e w Zealand 61°41'N, 3°19'E 63°10'N, 5°25'E Arctic Ocean

Clarke and Wheeler, 1922 „ Kamm (see Clarke and Wheeler, 1922) Salkover (see Clarke and Wheeler, 1922) Samoilov and Terentieva, 1925 Kamm (see Clarke and Wheeler, 1922) Clarke and Wheeler, 1922 Salkover (see Clarke and Wheeler, 1922) Clarke and Wheeler, 1922 „ „ Kamm (see Clarke and Wheeler, 1922) Salkover (see Clarke and Wheeler, 1922) Kamm (see Clarke and Wheeler, 1922) Salkover (see Clarke and Wheeler, 1922) „ „ „ „ Kamm (see Clarke and Wheeler, 1922) „ „ „ w Salkover (see Clarke and Wheeler, 1922) „ Schmelck, 1901 „ w „ „ » Salkover (see Clarke and Wheeler, 1922) „ „ „ „ w „ w „ w w w Schmelck, 1901 Terentieva, 1932

Arterial tanneri seems to appear again later in the table as Orthastfrias tanntri.

8. Composition of Skeletal Parts (Spicules) of Holothuria In the dermal cover, which forms a kind of sack to retain the inner organs of Holothuria, mineral inclusions or spicules of diverse forms which have systematic significance are present in many species. As mentioned previously, the optic properties 18

260

Memoir Sears Foundation for Marine Research TABLE 151 MgC03 IN DIFFERENT PARTS OF SKELETONS OF ASTEROIDEA (IN % OF ASH RESIDUE), FROM TERENTIEVA, 1932

ORGANISM

dsterias rubens . Crossaster papposus . SoLaster endeca . Ctenodiscus crisfatus

Chewing apparatus

7.57

Interambulacral plates

8.90 9.87 9.83

Ambulacral plates

6.85 9.86 9.97 8.94

Small spines

2.30

Large spines

2.16

Spines

1.75 8.78

of the spicules could also serve as a distinguishing characteristic of certain genera. The spicules consist of calcite crystals (see Biitschli, 1908), and in general their chemical composition does not differ from the composition of skeletons of other Echinodermata ; Biitschli (1908) also showed the presence of large amounts of MgCO3 in the spicules. Qualitatively, the calcareous character of the spicules was shown by many investigators such as Merker (1921), Panning (1931), and others. Woodland, investigating the

TABLE COMPOSITION OF SKELETAL PARTS OF ORGANISM

CaCO,

MgCOs

P8O6

Gorgonocephalus arcticus

86.60

9.53

0.64

87.08

9.31

Gorgonocephalus caryi Gorgonocephalus eucnemis Ophiogfypha sarsii Ophiogfypha lymani Ophioglypha lutkeni Ophioderma cinerum Ophiomyxa flaccida „ Ophiocoma pumila Ophiocoma aethiops Ophiocoma erinaceus Ophiothrix angulata Ophiophotis aculeata japonic a Ophiomusium lymani Ophiocamax fasciculata Ophionereis eurybrachiplax Astrophyton sp.* t Together with SiOr * This species is supposed to be a more southern form.

84.36 88.44 87.65 89.50 86.34 85.09 81.02 79.37 84.44 92.12 86.83 87.24 91.16 92.70 91.30 85.53 89.67

9.66 8.39 9.84 8.24 10.19 14.08 14.56 14.95 12.97 7.04 12.05 11.68 8.01 6.61 7.62 13.38 9.11

—

1.14 trace 0.74 trace trace 0.18 trace trace 0.14 trace trace (?) (?) trace trace trace trace

A1A +

Fe2O,

0.84

-

1.17 2.92 0.62 2.26 3.47 0.11 0.70 0.85 0.47f 0.73 1.12 0.77 0.44 0.69 1.08 1.09 0.31

Chemical Composition of Marine Organisms

261

optic properties of the spicules of Holothuria larva, auricularia, assumed that they consist of SiO2> but this is improbable. Schmidt (1924) thinks that the spicules of the auricularia are comparable to those known to contain strontium and that the double refraction of SrSO4 might have been unobserved, since it is less marked than in calcite (see Bert and Blanchard, 1885).

9. Heavy Met ah IRON. There is n X io~ 2 % in the living matter of echinoderm tissues and organs. Schneider (1888), Fox and Ramage (1931), and others detected this element in qualitative analyses of all tissues and organs, skeletons and fluids; the determinations by Clarke and Wheeler (1922) refer to the skeletal parts of Echinodermata (see Tables 149 to 155). Quantitative determinations of iron in Echinodermata are scattered (see Warburg, 1914). Concentrations of iron in the tissues of some Holothuria have been observed, especially in those which swallow silt, such as Molpadidae. Oya and Shimada (1933) found the following amounts of aluminium and iron (in °/0) in Stichofus jafonicus which contained 94.25% water:

152 OPHIUROIDEA (IN '/• OF ASH RESIDUE)

SiOjj

2.39 1.76 0.25 1.15 0.00 0.00 0.24 0.16 0.66 0.11 0.00 0.31 0.39 0.00 0.00 0.00 trace

C»S04

(?)

3.61 1.91 trace (?) trace trace 0.30 3.56 4.17 1.98 trace trace

(?) (?)

trace trace trace 0.85

Locality

Author

Cape Cod, Mass., U.S.A. . . Gulf of Kola Alaska Japan 39°32'30"N, 72°21'W . . . Chile California, U.S.A Puerto Rico British West Indies . . . .

Kamm (see Clarke and Wheeler, 1922) Terentieva, 1932 Kamm (see Clarke and Wheeler, 1922) Salkover (see Clarke and Wheeler, 1922) Kamm (see Clarke and Wheeler, 1922) Salkover (see Clarke and Wheeler, 1922) „ „ Kamm (see Clarke and Wheeler, 1922) „ „ w

Gulf of California Hawaii Ouba . . . . Unalaska Galapagos Caribbean Japan North Sea

Salkover (see Clarke „ « „ „ „ „ „ „ „ „ » „ „ „ „ „ „ Schmelck, 1901

.

.

.

.

.

.

.

.

H

.

.

and Wheeler, 1922) « » » „ * n „ « » n „ » « „ „ „

18«

262

Memoir Sears Foundation for Marine Research Al in living matter Fe , „ „

. , 0.0044 . . 0.00042

Al in dry matter . Fe „ , „ .

. -

. 0.07626 . 0.00730

The iron of the tissues is partly bound with various pigments, the physiological role and chemical composition of which have not yet been clarified. Foettinger in 1880 extracted a red pigment from the cells present in the fluid of the ambulacral system of Ophiactis sirens; he supposed that this was haemoglobin, and that the substance, which contained iron, was a respiratory pigment, a viewpoint which was much criticized

TABLE 153 MgCOj IN DIFFERENT PARTS OF THE SKELETONS OF OPHIUROIDEA (IN °/0 OF ASH RESIDUE)

ORGANISM

Disk

Rays

Ophiopleura borea Us Ophiura sarsii . Ophiopholis aculeata Gorgonocephalus arcticus

10.10 12.08

8.62

8.94 9.20

10.63

—

Rays 5 mm diam.

Rays i mm diam.

— —

— —

9.57

9.96

Author

Samoilov and Terentieva, 1925 Terentieva, 1932 99 9» 99

at first. Later Howell (i885-a, b) found a similar pigment in Holothuria (Cucumaria ?) which also contained iron and which was closely related to haemoglobin in its properties. He made the suggestion that haemoglobin is widely distributed among marine organisms, which Lankester criticized. MacMunn (1886) isolated haematoporphyrin from the tissues of Asterias rubens and did likewise with a number of other pigments from the tissues of Echinodermata, including echinochrome, which, according to Griffiths, contains 3 °/o iron- Considerably later the echinochrome of Arbacia punctulata was investigated by Cannan (1927). However, the respiratory significance of the ironTABLE 154 COMPOSITION OF SKELETAL PARTS OF HOLOTHURIOIDEA (IN % OF ASH RESIDUE)

Holothuria sp. Holothuria floridana^ Stichopus regalis , Cucumaria frondosa . Trochostoma intermedium , 99

PA SiO2 CaSO4 Locality . 78.96 12.10 0.96 0.57 1.04* ? . 83.29 13.84 trace 0.15 2.38 Puerto Rico CaC03

ORGANISM

.

' CaS04 -I- * H20.

.

.

MgCO,

. 81.54 8.10 — — 2.09 . Ash residue of body about 4t 99

99

99

99

99

99

99

99

„ „

$ Al^-H Fe203 = 0.34.

24t 18t

? North Sea

California, U.S.A. Bering Sea

Author

Hilger, 1875 Clarke and Wheeler, 1922 Butschli, 1908 Clarke and Wheeler, 1922 99

99

f See original data for more details.

Chemical Composition of Marine Organisms

263

bearing pigments of Echinodermata has not yet been demonstrated, although numerous indications of the presence of colored pigment cells (blood corpuscles) in the coelomic fluids of Echinodermata have confirmed indirectly the significance of these pigments in respiration. In recent years, publications have appeared which apparently solve this problem more positively. Van der Lingen and Hogben (1928), studying the properties of a pigment from the blood corpuscles of the perivisceral fluid of Cucumaria frankenfeldi, came to the conclusion that it is related to a series of haemoglobin pigments. Kawamoto (1928) supposed analogous pigments of Caudina chilensis to be haemoglobin, which have a typical dissociation curve for the system Hb + O2. Kobayashi (1932), on the basis of his observations, also came to the conclusion that Caudina chilensis and Molpadia rorefz.ii contain a red pigment closely related to the haemoglobin of vertebrates. Vies supposed the pigment from the haemolymph of Cucumaria and other Holothuria to be haemoglobin.13 All these pigments contain iron. Thus there are grounds for the belief that iron in Echinodermata, at least in a certain type of pigment, is connected with porphyrin metabolism and has to do with respiration. We will return later to the subject of the presence of iron in various invertebrate pigments, but here we wish to point out the presence of iron-bearing respiratory

TABLE 155 IRON AND MANGANESE IN ECHINODERMATA (IN °/o OF DRY MATTER) ORGANISM

Toxopneustes sp Mellita sp Cfypeaster sp „ Diadema sp Astrofecten sp Pentaceras sp Holothuria bermudiana . Holothuria bermudiana* Holothuria bermudiana . Holothuria bermudiana* Stichopus mdbii Stichopus regalis jlsteracanthion rubens . . Jsterias rubens * Inner organs.

* . .

. , ,

, . ,

.

.

.

Fe

Mn

Author

0.13 0.00075 0.0160 0.018 0.014 0.016 0.0145 0.0036 0.0155 0.0285 0.0010 0.0890 — — present 0.1288§

0.00034 0.0025 0.0028 0.0018 0.00077 0.00158 0.00143 0.00081

Phillips, 1922

trace trace trace 0.0011 0.000040f 0.000094f

Phillips, 1917

present

Phillips, 1918 Bertrand and Medigreceanu, 1913 » » » » Vibrans, 1873 Marchand, 1866

f In percent of living matter.

§ Together with manganese..

13. See Shintaro Ogawa (1927) on the respiratory pigment of Caudina ckilensis, and see Chapter XIX on the composition of blood. See also Crescitelli (1945) on the respiratory pigment of Cucumaria miniataznd Molpadia intermedia.

264

Memoir Sears Foundation for Marine Research

pigments (erythrocruorin) and the absence of copper-bearing respiratory pigments (haemocyanin) in Echinodermata. MANGANESE. Determinations of this element in Echinodermata have been haphazard, with the exception of the series of analyses by Phillips (1922), which show a small amount of the element. In all Echinodermata of the Barents Sea we invariably found manganese, but concentrations of this element have not been found in these animals. ZINC. Zinc is always found, the amount in the tissues being several times larger, as a rule, than the amount of copper, as in other invertebrates such as Coelenterata in which copper does not have an important physiological role in the respiratory pigment. COPPER. Ulex (1865) and Marchand (1866) demonstrated the presence of copper TABLE 156 COPPER AND ZINC IN ECHINODERMATA (IN «/o OF DRY MATTER) ORGANISM

Comments

Toxopneustes sp Mellita sp Clypeaster sp „ Diadema sp Astropecten sp Pentaceras sp Holothuria bermudiana

Stichopus mobii Stichopus regalis Echinus esculentus „ „ Asterias rubens „ „ Asterias (Marthasterias) glacialis. Asterias oreacea Asterias sp. (gelb) Petaria nuniaba Strongylocentrotus puperatus . . Paracentrotus lividus Cucumaria lefevrei * In percent of living matter.

Inner organs * „ „

.

.

.

Cu

Zn

0.00080 0.00160 0.00130 0.0011 0.00105 0.00145 0.0018 0.0006

0.0023 0.0021 0.00135 0.0017 0.0003 0.0046 0.0028 0.0017

0.00055 trace 0.0020 0.0045 0.00283* trace — 0.00245* (0.057)? 0.0023 0.00047 0.000271 0.000227 0.000199 0.000168

0.0032 0.0180 0.00544 — — — present — — — — 0.00207 0.00157 0.0019 0.00021

3 2 3 . 2 Without skeleton 0.00013 0.00053

Author

— —

Phillips, 1922

„

„

Phillips, 1917 Phillips, 1918 Dubois, 1900 » » Delezenne, 1919 Dubois, 1900 Ulex, 1865 Marchand, 1866 Bertrand, 1943-c Severy, 1923

Bertrand, 1943-c »»

w

Chemical Composition of Marine Organisms

265

in Asterias rubens, and recent data show the order of magnitude of this element in Echinodermata (see Table 156). We note that the relatively large quantities of copper which occur in Mollusca, for example, do not appear in echinoderms, and that the copper content is smaller than that of zinc, all of which indicates that copper does not participate in the formation of respiratory pigments in Echinodermata. But the role of copper in these organisms has not been studied in much detail. Glaser (1923) performed some interesting experiments on copper in Arbacia eggs ; in i cm3 of eggs there was an average of o.oi 6 mg; in i cm3 of fertilized eggs there was 0.174 mg; and in i cm3 of shell, 0.02 mg. The eggs extract copper from sea

TABLE 157 STRONTIUM AND BARIUM IN THE SKELETONS OF ECHINODERMATA (IN °/0 OF ASH RESIDUE) ORGANISM

Sr

Ba

Author

Ophiopleura borea/is . wisterias linckii Asterias rubens . . . . Strongylocentrotus Jrobachiensis

0.05* 0.05* 0.15 0.15 0.05* 0.2 0.2

0.5* 0.5*

Potapenko, 1925

Ophiopholis aculeata . Gorgonocephalus eucnemis .

present present 0.5* present present

Vinogradov and Borovik-Romanova, 1935 »

»

W

w

»»

w

w

w

Potapenko, 1925 Vinogradov and Borovik-Romanova, 1935

* Maximum.

water, the copper then being concentrated in the pigment layer. In the opinion of the investigator, copper influences the processes of fertilization, being connected with lipoid metabolism.2" VANADIUM. Phillips (1918), in analyzing the ash of the holothurian Stichopus mobii from Tortugas, found up to 0.123% vanadium in the dry matter, besides the usual amounts of copper, iron, and manganese. Until the present time vanadium has not been found in comparable quantities in any other marine invertebrate except the ascidians (see following), in spite of special determinations. We worked on Stichopus japonicus var. armatus, which material was collected in 1900 and was preserved in alcohol; vanadium was spectroscopically found in traces. In Holothuria, such as Cucumaria frondosa, Molpadia affinis, and others from the Barents Sea, vanadium could not be detected in i g of ash. We have also done analyses of trepang from a Vladivostok market; these are Holothuria that are first dried and then treated in a special way for consumption as food by the Chinese and Japanese people. Vanadium was present only in traces. Bertrand (1943^, c) found the following amounts of molybdenum and vanadium in Holothuria and other Echinodermata (in °/0 of dry matter): i H. Rothschild and Tuft (1949) have recently indicated the importance of copper and zinc in the physiology of Echinus sperm.

266

Memoir Sears Foundation for Marine Research TABLE RARE ELEMENTS IN ECHINODERMATA

Cr

ORGANISM

Comments

Ti

V

Stichopus tremulus . Brissopsis lyrifera . dsterias rubens .

Shell . . .

0.00043 0.00048 0.0005

0.0057 0.0005 0.0009

dsterias rubens* Afarthasterias glacialis* Ophiocomina nigre* Paracentrotus Hindus* . Paracentrotus Hindus* . Echinus esculentus* . Cucumaria frondosa

Disk, arms , Ovary . . Coelomic fluid

ORGANISM .

dsterias rubens* Afarthasterias gtaciatis* Ophiocomina nigra* Paracentrotus Hindus* . Paracentrotus Hindus* . Echinus esculentus* . Cucumaria frondosa

Disk, arms Ovary Coelomic fluid

Mo

Mn

0.00026 IxlO'5 0.00024

0.0037 0.053 0.019

. i ^^~

0.003 0.010 0.03 0.008

— —

— —

Ge

Sn

3xlO- 5 7xlO-5 3xlO- 5

0.0006 0.00016

0.003

— —

— —

0.00026 3x10-' 0.00017 0.00011 0.003

Shell

9xlO2xlO-6 2xlO~6

—

— — —

Cd

Stichopus tremulus Brissopsis lyrifera dsterias rubens .

5

— — Th

Ca

3xlO- 7 IxlO'7 3xlO-7

5xlO- 6 7xlO~6 7xlO~5

0.00072

0.08

0.003 0.003

0.08

* The investigators have calculated the results of the spectroscopic analyses in an unusual way, as percent of weight of ash cations.

Cucumaria lefevrei

.

wisterias (Marthasterias) glacialis Paracentrotus lividus

v

Mo

0.0001 0.0003 0.00008

0.00023 0.00011 0.00011

Thus any concentration of vanadium in Holothuria is a rare phenomenon. Possibly the element is restricted to certain species of the genus Stichopus and a few other genera, just as vanadium occurs only in certain species of Ascidia. Regarding the significance of the occurrence of this element in Holothuria from the point of view of systematics and geochemistry, see Chapter XVII, Tunicata. In general, those Echinodermata (except for Asteroidea) which have no well developed liver do not concentrate heavy metals, a condition which suggests the Vermes to us.

Chemical Composition of Marine Organisms

267

158 (IN •/„ OF DRY WEIGHT) Fe

CO

Ni

Cu

Ag

Au

Zn

Author

0.041

0.00012 0.0002 0.00009 0.0003 —

0.0038 0.00021 0.0024 0.0004 —

0.0057 0.0018 0.0018 — 0.03 0.01 0.04 0.003 0.003 0.008

0.00026 0.00015 0.00038 — — — — — —

2.4 xlO~ 6 7 xlO- 7 3 xlO- 6 — — — — —

0.014 0.0065 0.016 — — — — — — -,—

LandW.Noddack, 1939

0.057 0.03

— 0.08 0.05 0.25 0.05 — — — Pb

— — — — —

— — — — — 0.000067

0.0002

As

Sb

0.0021 0.0005 0.0015

0.0002 0.0008 0.0004

0.005

—

Bt 5

2.4xlO1.8x10-* 1 xlO- 5 — — — — — —

Sr 5

2.7xlO~ 3 xlO- 6 3 xlO' 6 — — — — — —

— —

—

»

»

n

n

r»

r»

r»

»

w

w Maliuga, 1939, 1941 Webb, 1937 n

«

y»

y»

T»

J1

»

n

Maliuga, 1939, 1941

Ba

— — —

— — —

0.8 0.6 1.0 0.05 0.1 0.1

0.003 0.004 — — — —

I. and W. Noddack, 1939

0.15 0.03 0.08 0.01 0.03 0.03 —

Maliuga, 1939, 1941 Webb, 1937 LandW.Noddack, 1939 Webb, 1937 „ „ „ „ Maliuga, 1939, 1941

io. Other Metals STRONTIUM AND BARIUM. We have always found strontium spectroscopically in the skeletons of Echinodermata, as did Fox and Ramage (1931). And in our work with Borovik-Romanova the presence of barium was always noted in the skeletons of Cucumaria frond os ay Ophiopholis aculeata^ and others. As a rule, strontium predominated. The quantitative data on these two elements are summarized in Table 157. Webb (1937), observing barium also, found 0.004 and 0.003 °/0 (of dry matter) in Marthasterias and in Asterias rubens. The magnesium-calcium skeletons of Echinodermata apparently contain from 0.005 to °-5°/o strontium and somewhat less barium, probably in the form of carbonates. The fact that up to 0.5% strontium is present in the skeletons of invertebrates should attract the attention of geochemists. TITANIUM. This element was always detected in qualitative spectroscopic investi-

268

Memoir Sears Foundation for Marine Research

gations done in our laboratory. Kaminskaia (1937) found i X io~ 4 °/ 0 in the living matter of Ophiofholis aculeata. Webb (1937) and I. and W. Noddack (1939) did a series of spectroscopic determinations of rare chemical elements in a number of Echinodermata (see Table 158). The majority of elements occur in amounts that are less than in other invertebrates, such as Vermes, Mollusca, and Crustacea. Holothuria contain more vanadium and lead. It is interesting that the ratio Co/Ni is close to that in sea water, while in the external parts of Brissopsis the ratio is somewhat larger. RADIUM. In the Vernadsky Laboratory for Geochemical Problems, K. Kunasheva (1944) determined radium in the following Echinodermata from the Gulf of Kola (in °/o of living matter) : Jsterias rubens

(1938)

3.7 X lO'13

Cucumaria frondosa Strongylocentrotus drobachiensis

(1938) (1938) (1938)

3 X 10~13 4.9xlO~ 1 3 6.1X10- 13

„

(1938)

3.9xlO- l s

The amount of radium in Echinodermata is the lowest among the invertebrates and is close to that of fish and other vertebrates. 11. Nonmetallic Elements BORON. In Echinodermata this element was detected for the first time by Bertrand and Agulhon (1913); in Strongylocentrotus lividus (inner organs), Asterias rubens^ and Asterias glacialis there were i to 2 mg in 100 gof dry matter. Later Goldschmidt and Peters (1932) found o.oi °/o B2O3 in the skeleton of Echinus esculentus. In our laboratory T. Glebovitch (1941) found the following amounts of boron (in °/o) in Echinodermata from the Barents Sea: Organism

Dry matter

Living matter

Ophiura sarsii Asterias rubens Cucumaria frondosa Echinus Strongylocentrotus Ophiopholis aculeata Gorgonocephalus sp

5.53xlO~ a 3.76 xlO" 3 5.67xlO~ 3 5.13 x l O ~ 3 3.55X 10~3 3.72 X 10~3

1.66xlO~ 3 4.76 x l O ~ 4 1.24X 10~3 9.61 X 10~4 1 54x 10~3 1.12xlO~ 3

IODINE. This element was first detected in Asterias rubens by Sarphati (1837), and somewhat later it was quantitatively determined by Marchand (1866) in the same organism. However, further study of the distribution of this element in marine organisms refers least of all to echinoderms. The order of magnitude of iodine in Echinodermata, n x io~ 4 °/ 0 , is fairly well known and is similar to that of all other marine organisms, with the exception of the iodine concentrators. Lunde, B6e and

Chemical Composition of Marine Organisms

269

TABLE 159 IODINE IN ECHINODERMATA (IN »/„)

ORGANISM

Living matter Dry matter

wisterias rubens wisterias forrei

. . . .

.

Asterias glacialis . » » Pentagonaster granu/aris.

.

— 0.000046

0.046 —

0.000129 0.000111 0.00153

0.000739

\j»\j\j\j i *«*

Stichopus californensis* , Stichopus calif or nensis^ Strongylocentrotus drobachiensis * Strongylocentrotus drobachiensis f Strongylocentrotus drobachiensis purple* var. . Picnopodia helianthoides . Holothuria sp. * Inner organs.

0.000338 0.000155

— —

— — — —

0.002 0.0025 0.02 0.003

— — —

0.049 0.000 0.0006

Locality

Author

La Jolla, California, U.S.A.

Marchand, 1866 Lunde, Boe and Closs, 1930

Oslo "Fjord

Closs, 1931

?

99

11

99

99

99

99

99

Lunde and Boe.

1931

Canada (Pacific)

Cameron, 1914

»

?J

99

99

99

99

99

«

9)

71

99

9»

99

99

99

»

99

»

99

99

China Sea

Adolph and

Whang, 1932

f Gonads.

§ Body wall.

99

Closs (1930) have studied in detail the distribution of iodine in separate organs of Echinodermata, and they found that there is a particularly large amount of this element in the intestines. Lunde showed that the contents of the intestines of Mesothura intestinalis had about 0.0022 °/0, while the intestines themselves contained 0,0012 °/o of the fresh matter. This indicates that Holothuria utilize food containing much iodine, algae, and so forth. Iodine occurs in a water-insoluble form in Echinodermata, in an organic compound in the body wall of Holothuria. For example, from the body wall of Asterias

TABLE 160 IODINE IN DIFFERENT ORGANS OF ECHINODERMATA (IN °/o OF LIVING MATTER)

ORGANISM Muscle

Asterias glacialis Stichopus regalis

Liver

Ovary

Stomach

Body Fluids

0.000126

0.0000117 0.0000081 0.0000053 0.00027 0.000066 0.000106 0.0000117 0.0000102 — 0.00033 0.000097

0.000003 0.000003

Intestines

— —

Author

Closs, 1931 Lunde and Bde, 1931

0.002722 Closs, 1931 0.002455

270

Memoir Sears Foundation for Marine Research TABLE 161 BROMINE IN ECHINODERMATA (IN °/0 OF LIVING MATTER)

So/aster endeca Cucumaria frondosa Gorgonocephalus arcficus HeKometra glacialis

.

.

.

.

0.0080 0.0066 0.0059 0.0063

Strongylocentrotus drdbachiensis dsterias rubcns Ctenodiscus crisfatus Ophiura sarsii

.

.

0.0042 0.0040 0.0022 0.0015

glacialis one can extract 37.2% with alcohol, 3.3% w^h chloroform, and none with water; in alkali and acid, 59.6% of the total iodine went into solution. Lunde, B6e and Closs (1930) showed in numerous analyses that echinoderms of the Pacific Coast of America are poorer in iodine than those of the Norwegian Coast, which also holds in the case of fish from the same areas; Asteriasforrei from La Jolla contained 0.000046 % iodine while Asterias glacialis from the Norwegian Coast contained 0.00012 9% *n the fresh matter. Possibly the enrichment of iodine in the Norwegian organisms has a more general character (see Algae). These phenomena might be explained by the composition and abundant development of plankton (chiefly phytoplankton) on which many invertebrates and fish feed. BROMINE. Marchand (1866) found 0.007 °/o *n the dry matter of Asterias rubens, but the first systematic determinations of this element in Echinodermata were done in our laboratory by A. M. Simorin. The organisms, collected from different parts of the Gulf of Kola, showed no accumulation of bromine (see Table 161). ARSENIC. The only determinations of arsenic in Echinodermata were done by Bertrand (1903), who found 3.7 X io~ fl °/o in the dry matter of Stichofus regalis, 1.5 X io~ 6 °/ 0 in Strongylocentrotus drdbachiensis, and 7 x io~ 6 °/ 0 in Pedicellaster sexradiatus, i. e., on the average less than the amount of iodine. FLUORINE. Available determinations are qualitative and unreliable.

Chapter XV Elementary Composition of Mollusca i. General Remarks

T

HE MOLLUSCA, widely distributed in the seas, constitute one of the largest groups of invertebrates. The soft parts of many of these organisms are eaten by numerous marine predators, such as fish and echinoderms, and man takes an enormous number of oysters and other mollusks for food and other purposes.1 Since many kinds of limestone are formed from mollusk shells, and since many shell fragments are found in various sediments, often as the principal fossil forms, the study of the elementary composition of Mollusca was dictated by both scientific and practical needs. However, in spite of the fact that oysters were used for food long before the beginning of the modern era,2 and although the participation of shells in the formation of rock was known even to Roman scientists, the study of the composition of Mollusca is still not well developed. Nevertheless, in comparison with other invertebrates, the greatest amount of the most varied data has been collected on Mollusca. One could repeat for this group all that was said about the analyses of algae, except that the majority of these analyses are even less complete. While the quantitative analyses for heavy metals, copper, manganese and iron, and to some extent zinc, are better than in algae, those for the majority of other elements are few and often scattered. For the more common elements, such as magnesium, sodium, silicon, and many others, in the soft parts of Mollusca, quantitative data are almost absent. Studies of the composition of mollusk shells have usually been limited to calcium, phosphorus, sulfur, magnesium, and water. But even these investigations, with rare exceptions (see Clarke and Wheeler, 1922), were done unsystematically or were limited i. See Tressler (1923).

2

- Even in prehistoric times man used mollusks for food.

271

272

Memoir Sears Foundation for Marine Research

to two or three species. Actually the shell composition is more complicated and less uniform than is apparent at first glance, for the presence of other elements, even in small amounts, is characteristic of individual species and should be brought to the attention of geochemists and palaeontologists. Then there are the investigations of blood and other fluids of Mollusca, as well as recent investigations of the composition of the eggs, the latter having been done in connection with questions of genetic origin. The first investigations of the composition of these organisms were done at the end of the eighteenth century, when the work of Merat-Guillot (i 797), Hatchett (i799)> John (1818), Vauquelin, and others on shell composition appeared. In the early and middle nineteenth century, interest in these studies grew, first on the part of mineralogists (Forchhammer [1852], BischofF [1847]) anc^ then °f biologists and chemists in connection with the discovery of copper in the blood of Mollusca (see Bizio [1834], Harless [i 847], and others). Investigations of this kind started in a number of countries, such as the United States and France, relative to public health, particularly in connection with cases of poisoning by oysters and other Mollusca. The diversity of information on the chemical composition of Mollusca as a result of the different approaches does not obscure the peculiarities in different species and other groups of Mollusca, which we will try to show in some detail. 2. Water ^ Organic Matter^ and Ash In a large majority of cases, the determinations of water in Mollusca only give an idea of the average amount. These analyses refer to the amount of water in the whole organism, including the shell, or to soft parts with fluids of tissues and other parts, such as those of the mantle cavity of Lamellibranchiata, or to the soft parts without fluids, or to the fluids alone, or to the shells alone. In addition, there are determinations of water in separate organs, such as muscles, for example the podium of Lamellibranchiata. The variations in the amount of water observed in certain species of Mollusca are partly explained by the fact that the investigators sometimes did analyses of soft parts plus fluids, in other cases without fluids. Frequently the method of preparation of the material is not described. Depending on whether or not the fluids were included, the total amount of water varied greatly. In Ostrea edulis there was 80.30% water without the fluids of the mantle cavity, but when they were included there was 87%; likewise in My a arenaria—79.38 and 85.82% water respectively. Our own determinations of water in a large number of Mytilus edulis have shown that these variations can reach 15 % of the initial weight. Further data can be obtained in the works of Ryder (1882), Greshoff (1903), and Bosz (1910), on Loligo javanica. Octopus fansiao, and others. Atwater (1892) has studied in detail the amounts of water and other substances in Mollusca, and Buxton (1923) has determined the amount in Mollusca and other invertebrates. Additional data are given in Table 168. From the data of many investigators, the percentage of water may be calculated

Chemical Composition of Marine Organisms

273

indirectly from the amount of dry residue (see Vernon [1895], Konig [1903], Petersen and Boysen-Jensen [i9n]j 3 Bertrand and Vladesco [1923], Wang-Tai-Si [1928], Santos and Ascalon [1931], Riesser and Hansen [1933], and Silberstein [1934])Known also are analyses of different food products prepared from Mollusca, but we will not dwell on those here.4

TABLE 162 WATER AND ASH IN THE BODY OF MOLLUSCA (IN °/o OF LIVING MATTER)

ORGANISM

Comments

Water

Lamellibranchiata Ostrea edulis

„ Ostrea imbricata Crassostrea virginica 41 „ „ „

.

„

.

80.38 77.0 80.69* 82.03 80.09 80.89 80.50 78.7 82.2 87.36f 83.0§ 86.4 . 80.30 87.5

— 82.50 84.50

Crassostrea gigas

Localitv

2.69 1.79 2.37 — Ostend — 2.08 2.04 2.2 2.03 2.5 2.13 1.19 U.S.A. —

87.5 87.3

Crassostrea circumpicta Crassostrea laperousii

Ash

,

87.97 82.69 83.11 84.27

2.9 2.21 U.S.A. (Atlantic) 2.29 New England, U.S.A. 1.36 Chesapeake Bay, U.S.A. 0.57 Philippines 2.62 Cape Basargin, U.S.S.R. 4.64 Philippines 1.71 Japan

Author

Payen, 1865 Mobius, 1877 Konig, 1879 Stutzer, 1882 Sempolowski, 1889 Weigelt, 1891 Balland, 1898-a Cox (see Ortonetal., 1924) Voit,1892(?) Griffiths, 1905 Henseval, 1903 Albu and Neuberg, 1906 Atwater, 1892 Peterson and Elvehjem, 1928 Lindow, Elvehjem, and Peterson, 1929 Hindman and Goodrich, 1917 Taylor, 1925-b Hunter and Harrison, 1928

Valenzuela, 1928 Pentegov, Georgievski, and Mentov, 1928 Etorma, 1928 Yoshimura and Nishida, 1930 (continued next page}

3. Often the weight of the dry residue of organisms is based on specimens fixed in alcohol, formalin, and other preservatives; this can lead to erroneous results. 4. See Beythien (1901), Konig (1903), Henseval (1903), Bell (1937), Ludwig, and Stern; see also the large bibliography on oysters given by Stevenson (1894) and MacDonald (1921).

274

Memoir Sears Foundation for Marine Research

ORGANISM

Comments

Water

Crassostrea gigas

Year-old ?

82.55

82.90 82.09 77.66 84.14 84.73 85.61 82.93 82.20 75.74f » n 82.2 80.40 86.50 » » 86.37 » » 82.25 » » 84.03 Mytilus dunkeri 78.67 » » Cardium tdule . 78.67 92.0 » » Mesodesma glabrata 86.11 78.0 Pecten jacobaeus Pecten irradiatus . 2 . . - . 80.32 84.50 Afya arenana 83.46 » » 79.51 » » 81.0 4 . . . . 85.91 » » 78.89 Venus mercenaria . 2 . . . . 84.56 74.44-t » » Cyrena gigantea 85.04 Tapes striatus . 84.23 Teltina incerta 86.42 Tridacna curningii . 80.06 Area granosa . 79.61 Pinna tnriata . 80.89 Circe gibba 85.79 » » • » » » » * » » » » * » » » » Mytilus edulis .

Mactra solida (Turbo iittoraiis) Anodonta sp. . Gastropoda Cerithium vertagus S trombus canarium n

»

Littorina litterea .

Year-old $ Year-old ? Year-old »

>»

Nucella lafillus . >» >» Pate/la athletica . . Patella vu/gata . Scaphander lignarius Sphaerostoma hombergii Lamellibranchiata Crassostrca commercialis Crassostrca gigas Crassostrea virginica . Mytilus edulis . Ostrea lurida Pecten fumatus . Cephalopoda Loligo bleekeri .

>»

>»

*

w

>»

*

» »

.

•

.

. •

,

-

H

P

*

*

,

, •

*

.

, •

McCance and Masters, 1937 „ w w M „

^

*

• • • . . . * * '

Australia Pacific Coast, U.S.A. East Coast, U.S.A Australia Pacific Coast, U.S.A. Australia

*

^

„

„

^

^

^

*

n

M

n

*

>»

>»

>»

>»

>»

>»

»>

»>

+

, *

* '

,

-

.

.

.

.

w

w

„

»

w

McCance and Shackleton, 1937 >» >» >» >» McCance and Masters, 1937 M » n n McCance and Shackleton, 1937 » » » >» >» Clements and Hutchinson, 1939 Nilson and Coulson, 1939 „ Clements and Hutchinson, 1939 Nilson and Coulson, 1939 Clements and Hutchinson, 1939 Kamachi, 1936

290

Memoir Sears Foundation for Marine Research

these elements decrease. According to Krogh (1934), calcium from the water enters into the tissues of Mollusca to a considerable extent (see Galtsoff, 1938). The liver and intestines, and the mantle and gills to some extent, show a higher calcium content, with a Ca/Mg ratio > i. In the blood of Mollusca there is always more calcium than magnesium. The blood of Mytilus edulis and other Mollusca contains an amount of calcium and magnesium close to that in sea water. Pora (1936-6) showed that the calcium, potassium and other elements in the blood of Mollusca relative to sex differences are more regular than in Echinodermata. McCance and Shackleton (1937) have divided the Mollusca into three groups according to the amount of magnesium in the organism. The first group (Aeolidia, Mytilus, and Ostrea) contains less magnesium than the surrounding medium ; the second group (Pecten maximus, Cardium edule, Buccinum undatum, Aplysia, and Sphaerostoma) contains magnesium in an amount close to that in sea water; while the third group (Archidoris, Jorunna, Littorina, and probably many others) concentrates magnesium. When the tissues under the skin of Archidoris are treated with acid, bubbles form from dissolving spicules of amorphous CaCO3.1H Calcium is found in the liver as amorphous carbonate, in ionic form, and as calcium organic compounds. When some of the shell is destroyed, as in Helix pomatia, the calcium from the liver (and from the kidneys as well according to Sioli, 1934) is utilized for restoration of the CaCO3 (see Dotterweich and Eltzner [1935] on Anodonta). Sioli (i 934) believes that calcium goes into the blood with protein and P2O5, with which it is partially bound in the liver; there it remains and becomes fixed by the organic matter in the liver. The CaCO3 removed from the blood in the formation of shells is apparently a secretory product. All the above mentioned investigators give data on calcium, ash and P2O5 in various organs of freshwater Mollusca. 7. Phosphorus, Sulfur, and Chlorine The amount of phosphorus in the tissues of Mollusca is known to be high, but due to some irregularities in different analyses, there have been some mistaken ideas as to the amount of sulfur in Mollusca.15 Usually P2O5 forms 33 to 50% of the ash residue of the tissues, or approximately i % phosphorus in the dry matter or 0.2 % in the living matter. Mollusca usually contain no less sulfur than phosphorus, while in some organs and tissues the amount of sulfur is sometimes considerably higher than that of phosphorus. For data on phosphorus and sulfur, in addition to those following, see Tables 173 and 174. Riesser (1928), studying the distribution of phosphorus in the tissues of Mollusca in great detail, concluded that the quantities of different types of phosphorus compounds in the muscles of Gastropoda are subject to a certain regularity, according to the phylogenetic relationship. Sioli (1934), determining phosphorus in various organs of Helix, XH. Odum (i95i-b) has confirmed that the spicules of Archidoris are amorphous CaCOa. 15. For determinations of sulfur in ash, see Griffiths; the results are low.

Chemical Composition of Marine Organisms

291

TABLE 174 COMPOSITION OF VARIOUS ORGANS OF MOLLUSCA (IN % OF LIVING MATTER) ORGANISM

Ash

Cardium edule

podium

,

,

mantle . , muscle* . , intestines and liver. . ,

Pecten maximus podium

.

,

— 0.51

* Two analyses.

Cl

—

0.0155

— 0.61 0.18 0.180 0.117 — 0.388 0.269 0.078 0.090

— —

— —

0.0175 — 0.005 —

— 0.241 0.302 0.145 0.094 — — — — — 0.21 0.24 —

—

Author

McCance and Shipp, 1933

0.081 —

0.052 0.104

—

—

— — Taylor, 1925-b 0.0009 — McCance and

0.026 0.038 0.054 0.118 0.041

0.063 0.078 0.111 0.080 0.093

— — — — —

— — — — —

0.0018 0.0058 0.0017 0.0112 0.0155

0.425 0.375 0.265 0.346 0.415 0.277 1.266 0.304 0.342 0.390 0.168 0.460

— — —

— — —

0.0178 — 0.0187 — 0.0288 —

))

»

0.438 0.473 0.550 0.507

—

—

0.0336

—

»

»

1.38

— 0.612 0.148

0.742 0.424 0.566 0.726 0.351

0.387 0.283 0.143 0.262 0.305

— — — — —

Shipp, 1933

»» » » » »

« » » i> »

>»

»

M

»

-—

—

0.2

0.2

—

—

—

—

—

—

-—

0.6

0.8

—

—

—

—

-— —

— —

— —

0.8 0.6

0.4 0.1

— —

_ _

— —

— —

— —

— —

— —

0.4 1.0

0.4 0.2

— —

— —

— —

— —

»

— —

1.0 1.3

0.3 0.2

— —

— —_

— —

— —

»»

— 0.26

0.4 1.26

0.4 0.01

— muscle . . — — liver . — Lottia gigantea — muscle . , — Lima* agrestis . 3.1 0.072 Mytilus edulis .

Fe

Mg

—

Ischnochiton conspicuus

muscle

Ca

K

0.305 0.041 0.093

mantle . . -— muscle . , — gonads * . — gills . . . — intestines . . — Littorina littoralis podium , . — mantle . . — gonads . . — intestines and liver . . — Haliotis sp. muscle . . —

liver . . . Tivela stultorum muscle . . liver Cryptochiton sp. muscle . . liver

Na

Albrecht, 1920-21, 1923-b »i

» »»

»»

99

— _ — — 0.301 0.033 0.013 0.078 Bezold, 1857 9)

. 2.4 0.144 0.906 0.013 0.070 0.360 0.010 0.005 0.110 Griffiths, 1905 (continued next page) 2O

2g2

Memoir Sears Foundation for Marine Research

ORGANISM

Ash

Na

K

Ca

Mg

Mytilus edulis . — 0.290 1.315 0.090 0.023 . 2.22 —

w

Anodonta sp.

muscle

—

—

P

S

—

—

_0.17

0.43

Fe

Cl

0.0058 — —

—

Author

McCanceand Shipp, 1933 Taylor, 1925-b

,

. 1.8 0.110 0.677 0.115 0.054 0.267 0.008 0.004 0.083 Griffiths,

My a arenaria

muscle . . 1 . 2 Octopus sp. muscle . , 1 . 4 Sepia officinalis muscle . . 1 . 3 eggs . . . _

Hemifusus tuba

0.031 0.470 0.007 0.037 0.179 0.005 0.003 0.055

1905

0.080 0.558 0.008 0.034 0.197 0.006 0.005 0.073 0.060 0.526 0.006 0.031 0.219 0.005 0.005 0.065 0.009 0.034 0.012 0.007 0.337 — — 1.71 Bialaszewicz,

eggsf . . . 1.920.71650.046 eggs'* . . . 2.01 0.691 0.028 eggsP . . . 3.420.688 0.048 Poluta brasiliensis eggs , . . 4.08 1.340 — Penus mercenaria

1928

0.01110.053 0.01740.0264 — 0.029 0.057 0.019 0.047 — 0.302 0.058 0.024 0.056 —

1.003 Kumon, 1933 1.033 0.9178 „

0.054

2.07

—

—

0.087

—

Roffo and

Correa, 1927

muscle . . 1.460.205 0.311 0.038 0.048 0.153 0.225 0.0 0.322 Meigs, 1915 Ostrea edulis . — 0.650 0.258 0.185 0.041 — — 0.006 — McCanceand Crassostrea

virginica .

, 2.76 —

Patella vu/garis ovary .

testis . mantle podium liver .

t

. .

Primary stage.

,

1.7 —

— — — —

—

—

—

0.33

—

—

Shipp, 1933

Taylor, 1925-b — — 0.089 0.246 0.112 0.315 0.0012 — Coulson, 1935-a 0.36 0.273 0.057 0.070 — — 0.014 — Jones, McCance and Shackleton, 1935 0.448 0.326 0.129 0.072 — — 0.006 — 11 11 0.562 0.340 0.097 0.097 — — 0.046 — 11 11 0.416 0.243 0.104 0.076 — — 0.069 — 11 11 0.466 0.888 0.346 0.108 — — 0.051 — 11 11 a Middle stage.

0.13

P Final stage.

found the maximum amount in the liver. Suzuki, et al. (1912) found 2.85% *n the dry matter of the cephalopod Ommatostrephes. Traces of phosphorus are present in the egg whites of Cephalopoda; more details on the distribution of this element in various compounds in the developing egg and embryo of Sepia are given by Needham (1931) and others. Meyerhof (1911), Eggleton and Eggleton (1928), Needham and his collaborators (i932-a, i932-b), Baldwin (1933), Suzuki,16 Kreps, and many others have studied the 16. Suzuki (1934) worked on Octopus octopodia.

Chemical Composition of Marine Organisms

293

types of compounds in which phosphorus occurs in the tissues of Mollusca and other invertebrates. In particular, great interest was shown in the question of the distribution of arginine-phosphorate and creatine-phosphorate in the tissues of animals; this was studied from the phylogenetic point of view. Numerous observations show that creatinephosphorate is found mostly in the tissues of vertebrates, with arginine-phosphorate in the tissues of invertebrates. A number of separate determinations of phosphorus in Mollusca might also be mentioned; these appear in the works of Drost (1886), Balland (i898-a), Wetzel (1907), and Duval (1925). There is about 0.4 °/0 sulfur in the living matter of Mollusca, or i °/0 of the dry matter, with sulfur predominating somewhat over phosphorus. But the distribution of sulfur and its compounds in the tissues of Mollusca has not been studied to the same extent as has been phosphorus. Sulfur is found in the form of sulfo-protein (in various organic compounds, especially taurin) and as SO4. Masters and McCance (1939) found the following amounts of sulfur in Mollusca (in °/0 of fresh matter) : Cardium edule Mytilus edulis Pecten sp. (?)

0.286 0.326 0.342

0,401 0.265

Buccinum undatum Busycon sp. .

The ratio N/S is close to 7, while in vertebrates it is about 14. The considerable amount of sulfur in Mollusca, particularly in the marine species, was known long ago. Figuier (1840) noted the presence of sulfur in organic compounds of the tissues of Helicidae. Valenciennes and Fr6my (i855-b) showed that the muscles of Mollusca, especially Cephalopoda, contain a considerable amount of taurin

TABLE 175 COMPOSITION OF MOLLUSCA (IN °/0 OF DRY MATTER)

MgO

ORGANISM

Comments

CaO

Haliotis sp Haliotis (fulgent)

Gonads

0.1079 0.3259 0.48 0.32

SiO2

—

— — Tivela stultorum „ 0.63 0.47 ^ Cryptochiton sp. „ 1.08 0.32 -— Ischnochiton sp. „ 1.00 0.30 Octopus sp 0.1683 0.5297 — Yenm sp 0.7819 0.3988 — Helix sp 1.3202 2.7673 —— 5.06 Helix pomatia . * Liver 2.066 — 1.16 . . Kidneys — — 0.706 . . Mantle — Foot

7.19

Fe2O3

—

—

0.47 0.66 2.56 1.20 — — — — -— —

1.71 2.16 1.92 1.55 — — —

— — —

Ash

Author

— —

Takamatsu, 1936 Albrecht, 1923-a1

—

Takamatsu, 1936

16.12 Sioli, 1934 7.425 24.67

* Albrecht's data differ widely from those of other investigators. 20*

294

Memoir Sears Foundation for Marine Research

(C2H4NH2HSO3); Fr6d6ricq (iSyS-a) and Krukenberg (1881-1882) isolated this substance from Cephalopoda and other Mollusca; Schmidt (1845), Kelly (1904), Mendel (1904), Henze (1904), Jansen (1913, 1914)3 Daniel (1920, 1921), Daniel and Doran (1926), Morizawa (1926), Suzuki (1934), and many others showed the wide distribution of taurin in the tissues of Mollusca. The amount of taurin, and of organic sulfur in general, and the total sulfur of the organism, are interdependent. As seen in Tables 174 and 176, the largest amount of sulfur occurs in the muscular tissue of Cephalopoda. Berkeley (i922-a) and others showed the presence of sulfur in the chondrin of the stylet (an appendage of the stomach) in Schizotherus nuttalli) Saxidomus giganteus^ and other mollusks. A peculiar case of sulfur concentration is noted in the presence of free sulfuric acid in the salivary glands of some Gastropoda. Bodeker (see Troschel, 1854), in an analysis of the secretions of such glands from Dolium galea of the Mediterranean Sea (donated by Troschel), found 2.7% free H2SO4. Preyer (1866) found 4.88% free H2SO4 in a similar secretion, TABLE 176 PHOSPHORUS AND SULFUR IN MOLLUSCA (IN °/0)

ORGANISM

Gastropoda Haliatis sp. . Helix sp. Murex sp. . Lamellibranchiata Card mm edule * 99

99

Crassostrea virginica Mya arenaria . Mytilus edulis , Ostrea edulis Pecten irradiatus Pecten jacobaeus Pinna sp.* . Venus mercenaria Cephalopoda Loligo sp.f , Octopus ocellatus Octopus sp. . Sepia officinal is . Sepia sp. * Average.

living matter

dry matter

0.0460 0.0254

0.125 0.0473 0.1333 0.2064 —

0.582

0.2064

1.0576

0.0325 0.1720 0.1453 — 0.1096 0.1432 —

—

—

—

living matter

dry matter

— 0.1397 —

— 0.7197 —

— —

— —

—

0.3200 0.224 0.2378 0.2619 0.236 0.0963

1.4000 1.1000 1.6879 1.8912 0.996 1.7099

0.7998

0.3560

1.6440

— 0.67 — — —

— — — — 0.3855

— 1.60 — — 2.1865

0.7095 1.0105

—

—

f Muscle.

Author

Riesser and Hansen, 1933 Silberstein, 1934 Riesser and Hansen, 1933 Javillier and Cr&nieu, 1928 Riesser and Hansen, 1933 Atwater, 1892 99

99

Silberstein, 1934 99

99

Atwater, 1892 Silberstein, 1934 Riesser and Hansen, 1933 Atwater, 1892 Riesser and Hansen, 1933 Kawai, 1928 Riesser and Hansen, 1933 Silberstein, 1934"

Chemical Composition of Marine Organisms

295

while DeLuca and Panceri (i867-a,b), and then Panceri (1869), found from 3.3 to 4.5%; but Maly (1880) found only 0.98 %. In many other Mollusca the contents of the salivary glands are very acid, but what causes this acidity is not always known.17 There are few direct analyses for chlorine, which is present in amounts from 0.2 to 0.7 % *n the living weight of the tissues ; many prefer to express chlorine as NaCl. Any determinations of chlorine in the blood and other fluids of Mollusca were done in connection with the study of osmotic relationships of the tissues of various marine invertebrates (see Krukenberg [1881-1882], Frdddricq [1884], Duval [1925], Thomas [1929], and others. The chlorine in the blood of Patella^ Mytilus and others is almost the same as in the sea. For example, in the blood, Myers (1920) found the following (g/1): Organism

Salt residue

CaO

NaCl

Saxidomus nutalli Schizotherus nutalli Cryptochiton stelleri Haliotis rufescens

28.0 32.9 — 23.7

3.07 1.93 0.66 0.74

— 31.9 30.9 31.30

He found considerably less in the organs and other tissues. When the medium is diluted and its chlorine content decreased there is an accompanying decrease of chlorine in the blood and muscles (see Table 173). 8. Silicon On the basis of numerous analyses (see Table 172), one can conclude that silicon occurs in very small quantities in the organs. Likewise in the shells there is little silicon, since almost 99% is CaCO3. Turek (1933), who also gives data on organic matter, nitrogen, and water in mollusk shells, found an average of o.i to 0.2% SiO2. Since there are relatively few existing analyses, and since these do not include all species, undoubtedly new facts will be discovered in the future. Noteworthy is the increase in silicon in the eggs of Hemifusus tuba during development (see Table 174). In the body of Oncidiidae (gastropod), Labbd (1933-*) observed spicules of small dimensions, which Stantschinsky assumed to be CaCO3. With H2SO4 + HF, Labbd (1933-*) showed that the spicules consist of SiO2 and possibly a small amount of protein. Oncidiella celtica, weighing 0.37 g, contained 0.04 g SiO2) or about io°/ 0 . Labbd also found SiO2 insertions or spicules in the species Oncidiella patellddes (Oncidium leopoldi), Oncidiella maculata (spicules 30 to 60 mm long), Oncidium griseum (O. astride), Oncidium straelenii, and others. Thus the whole genus Oncidium is siliceous and participates in intensive silicon metabolism. Kahane (1935), receiving these siliceous mollusks from Labbd, did a detailed analysis and concluded that the SiO2 is present chiefly in the form of amorphous silica 17. Possibly HC1.

296

Memoir Sears Foundation for Marine Research

(he gives a Debye-gram), although some of the SiO2 apparently occurs in the spicules as silicate. The ratio of amorphous silica to the silicon of the silicates is seen from the following data: Organism

Oncidium durum

„

SiO2 + silicate (°/»of dry matter)

SiO2 (°/0 of SiO2 + silicate)

0.61

84.7

0-17

„

Paraperonia gondwana

64.5

1.13

Oncidiella celtica

59.0

6.9

55.1

3.56 6.13 4-13

65.1 70.3 71.2

1-81 5.25

73.5 80.0

6.46

„ „ „

Oncidiella celtica (without intestines)

60.5

3.86

70.5

Particles of sand and hard SiO2, and similar material, penetrate into the liver of these mollusks with the food; here the particles undergo a change, forming silicolites (pieces of SiO2 of a certain form), which in turn become divided into particles that are carried into the tissues by special cells. Thus they form spicules of different forms in the skin of various species of Oncidiidae which consist of sacs containing the particles. The amount of SiO2 (silicolite) in the liver, according to Kahane's (1935) analyses, is as follows (in % of the liver): Scaphis viridis Paraperonia fidjiemis . . Paraperonia gondwana . . Paraperonia gondwana * .

0.25 , 0.62 . 0 . 8.65

Peronia peronia Oncidium planatum . Scaphis punctata

.

.

,

2.87 11.3 0

The phylogenesis of Oncidiidae is complicated; according to Joyeux-Laffuie (1882), Oncidiella celtica, primarily a marine form, lived on land and then returned to life in the sea.2H 9. Composition of Shells; Other Skeletal Formations The shells of Mollusca, particularly Lamellibranchiata and Gastropoda, play a considerable role in the formation of rock, some limestones being composed entirely of shells of Lamellibranchiata. The destruction of rock by Mollusca, which is done by drilling or by dissolving the rock,18 is also geochemically significant. Even in ancient times the calcareous nature of shells was suspected, and in 1718 Reaumur suggested this to be the case. But it was not until the end of the eighteenth 2 H. For the occurrence of silicate in radulae, see page 317. r8. For example, in Litkopkisa, Clcruagella and Saxicava. Calcareous rock, and possibly even quartz, are drilled by Mollusca (see Fox, 1936).

Chemical Composition of Marine Organisms

297

century that the first quantitative analyses appeared, thus establishing the fact that the shells of Mollusca contain 85 to 95 °/o CaCO3, or even more. Analyses of the shells are found in the publications of many naturalists of that time, such as Humboldt (1793), Merat-Guillot (1797), Hatchett (1799), Fourcroy and Vauquelin (1811), John (1814), Rouelle (cited by Diderot, ed. 1875), and Bernard, the analyses referring chiefly to the shells of Ostrea edulis and then to those of Helicidae. The largest number of qualitative analyses were done by Hatchett (1799). At the same time the mineralogical character of the CaCO3 in the shells was made known. In 1808 Bournon found differences in the shell structure of Gastropoda and Lamellibranchiata, and on the basis of the specific gravity of the pieces of shells he concluded that they probably consisted of calcite. However, Brewster (1836, 1837 ; see L. Horner) showed from a study of the optic properties that the inner mother-of-pearl layer of some shells consists of another type of crystalline CaCO3, aragonite. Necker (1839), Noggerath (1849), Sorby (1879), and many other investigators later proved that both modifications of CaCO3) calcite and aragonite, are present, sometimes separately but more often together.19 The material for the shells is secreted by the epithelium of the mantle, and according to the modern viewpoint, the calcium bicarbonate in the blood is changed into fairly insoluble crystalline calcium carbonate, thus forming the basis of the shell formation, leading to the precipitation of CaCO3. Besides calcite and aragonite, amorphous CaCO3 and vaterite have been found in the shells; the stability of these forms under natural conditions increases from amorphous CaCO3 -* vaterite -* aragonite -* calcite. Thus very ancient fossil shells usually consist of secondary calcite.20 Under certain conditions aragonite changes into calcite, which can be identified by the lack of regularity in the distribution of the CaCO3 crystals in the layers which have undergone metamorphism. The shell construction is rather complex, but it is not our problem to describe in detail its fine structure. Therefore we will confine our remarks to those chief characteristics of its structure which will illustrate further the connection of shell composition with detailed structure. The shells of Lamellibranchiata usually possess three layers : the outer epidermal layer consists of conchiolin, a scleroprotein ; the middle layer is formed of CaCO3 crystals, often in the form of prisms, which accounts for the term "prismatic layer1'; then there is the third inner mother-of-pearl layer. But in Gastropoda the epidermal layer is less developed, while the mother-of-pearl layer is often lacking; the porcelain-like layer which corresponds to the prismatic layer of many Lamellibranchiata is much more complicated in construction and is further divisible into several more thin layers. The layers consist of crystals of CaCO3 interspersed with organic matter, the prisms, plates, and other aggregations of CaCO3 crystals being oriented towards the 19. See the lists of shells given by Sorby (1879), Kelly (1900), and Biitschli (1908). 20. As a rule, shells found lower than the chalk sediments contain calcite. There are a few exceptions.

298

Memoir Sears Foundation for Marine Research

surface of the shell at a certain angle, thus forming a thin characteristic structure. The outer layer of CaCO3, often prismatic and sometimes consisting of plates, contains calcite crystals as a rule, while the inner mother-of-pearl layer contains aragonite. But variations occur in some species, as in Haliotidae shells, where the outer layer consists of aragonite, the inner one calcite. The shells of Gastropoda which do not possess a mother-of-pearl layer often consist of aragonite only, as do those of some Lamellibranchiata such as most of the Homomyaria, and all freshwater forms, including not only the Unionidae but Congeria and Dreissensia; in our opinion the zoologists who proposed the transfer of these organisms from the Anisomyaria into the Homomyaria were correct. There are also those shells which consist of calcite only, as in many of the Anisomyaria (Aviculidae, Ostreidae, and Argonauta); and then there are those with an outer layer of calcite, the next of aragonite, and the inner layer of calcite, as in some Pectinidae. The layer consisting of calcite crystals differs from that of aragonite in optic properties and otherwise. These layers are packed tightly together but they do not become intermixed. In studying the structure of the shells, especially the thin structural layers, many attempts have been made to establish the mineralogical character of the CaCO3 crystals21 with the help of diverse methods such as determination of specific gravity of shell fragments, Meigen reactions, and refraction. A large number of observations were made by Carpenter (1844, 1847), Sorby (1879), Tullberg (1881), Cornish and Kendall (1888), Mayer (1889), Appellof (1893), Ke% (19°°)> Meigen (1901), Biedermann (1902), and others. As soon as x-ray analysis came into existence it was applied to the study of the structure of shells. By this method Tsutsumi (1928, 1929) showed that the outer layer of Pinna shells consists of calcite, the inner of aragonite, this corresponding with previous observations; the axes of the calcite crystals are perpendicular to the surface. Rama-Swamy (1934) studied the structure of the mother-of-pearl layers of many shells (Pinctada vulgaris. Nautilus, and others) and they always consisted of aragonite. Galibourg and Ryziger (1926) showed the presence of aragonite in pearls by x-ray analysis (see Rinne, 1924); and Mayer (1931) found vaterite, a third kind of CaCO3, in some shells. Oldham (1908, 1929), Orton and Amirthalingam (1926), Prenant (i928-b), Ahrberg (1935), Tsuboi and Hirata, and Raub gave data on the detailed structure of the mineral parts of various mollusk shells. However, in spite of these abundant observations, the main work has not been done; the fine structure of the shells has not been examined mineralogically in relation to the systematic position of the Mollusca and the chemical composition of their shells. Schmidt's (1924) monograph gave a more or less complete summary of information on optic properties of the shells. But Boggild (1930), in his great work on the structure of shells, studied the problem more closely along the lines mentioned. He tried to arrange his observations of mineralogical properties according to the systematic divisions of Mollusca, and consequently individual observations were brought into a certain order, 21. See Nilakantan (1935) on anisotropy in the shells.

Chemical Composition of Marine Organisms

399

thus permitting one to draw more general conclusions. On the basis of this information one can conclude that the majority of freshwater forms have an aragonite skeleton. Among the Lamellibranchiata, the shells of Anisomyaria are partly or entirely calcite, those of Homomyaria aragonite. In the shells of Gastropoda aragonite is more characteristic, although many of them contain calcite and aragonite together. Needless to say there are exceptions. Later we will tackle this subject in greater detail, devoting a separate chapter to it. In the works mentioned above, the chemical properties of shells were not compared. The CaCO, was often determined from the amount of CO« that was liberated when the shells were dissolved in acid, and this method was particularly helpful in the discovery of conchiolin. The amount in mollusk shells varies from traces to 5 %,22 and as seen from subsequent data, there is more in the shells of Lamellibranchiata than in Gastropoda. We will see further that the amount of conchiolin is greater in species living in the sea and in slightly saline waters than in those from fresh water; in less saline marine basins the shells are smaller and contain less CaCO3. Let us now return to mineral composition. Besides CaCO3, traces of phosphate and sulfate, which play an important role in the crystallization of CaCO3 in biological systems, were indicated a long time ago; strontium, barium, iodine, bromine, and fluorine were also found. But the observations on the amount of MgCO3 are of special importance. Evidently Forchhammer (1852) was the first to determine MgCO3 quantitatively in a number of mollusk shells, although there were earlier qualitative indications of the presence of magnesium by John (1814), Figuier (1840), and Vauquelin. The attention of Forchhammer (i 852) and others was directed toward the origin of dolomites and the participation of organisms in their formation; later Btitschli (1908) compared the amount of magnesium in the prismatic layer of mollusk shells with that in the mother-of-pearl layer of the same organisms. MgCO3, being isomorphic with calcite, becomes precipitated with it, and, as we have just seen, shells of different species contain different calcite-aragonite ratios in the various layers, while other shells consist of calcite or of aragonite exclusively. It is natural, therefore, to look for calcite in shells rich in magnesium, and hence to find a large amount of magnesium in Mollusca with calcite shells. In aragonite shells one would expect an insignificant amount of this element. Some mollusk shells, which are ordinarily light in color, turn various dark shades. Kessel (i936-b), investigating this coloring, found that the calcareous layers of the shells of Buccinum, Natica, Aporrhais^ Spirula and Macoma contain filaments of a dark substance, apparently basically hydroxides, carbonates, and sulfides of iron ; sulfur was present also in these particles. Kessel supposes that they are iron semisulfides, partticularly in the shells of dead organisms, and in his opinion, iron penetrates the shells O

6

22. On the structure of conchiolin, see Kost (1853), Fiirth (1903), and Wetzel. More recent data are presented by Friza (1932); conchiolin is a protein and contains about i °/0 sulfur. On nitrogen in shells, see the section pertaining to that element.

3 oo

Memoir Sears Foundation for Marine Research

from the sea water and becomes precipitated with the participation of organic matter containing sulfur. However, we do not support this theory. Iron and manganese in the shells have been shown by Carazzi (1897), Bradley (1907^), and Butkevich (1928), and we have frequently observed the same. Possibly a biochemical accumulation of iron takes place, with the participation of bacteria, algae and diatoms which concentrate iron. The ionic iron in sea water is very small in comparison with the total iron. Thompson and Wilson (1935) found from 0.003 to 0.007 °/0 manganese in various shells from Puget Sound.

TABLE 177 COMPOSITION OF MOLLUSK SHELLS (IN % OF MINERAL RESIDUE) Organic matter in fresh shell

ORGANISM

Mytilus eduKs* Lophyrus occidentalis Fissure/la graeca Turbo sp. Pivipara sp. 99

99

Erronea caurica Bulgaria sp. Auricula sp. Limnaea stagna/is Arim empiricorum Limax cinereo Cepaea nemora/is Pila werneri Pi/a sp. Dentalium vulgaris Pecten varius Solenomya togata Anodonta sp. Nautilus pompilius Ommatostrephes sp. Loligo vulgaris Sepia officinalis Sepia sp. f Spirula spirula Argonauta argo Ampullaria sp. 99

99

a CaSO4 = 1.54.

CaCO3

MgCO,

—

97.50

0.57

0.69 0.43 1.10 2.20 91.84 0.17 0.58 1.54 0.28 0.71 1.93 1.36 0.47 0.937 0.21 0.65 10.35 2.31 3.07 90.32 79.30 6.99 93.0 4.52 4.21 1.24 1.33

99.42 99.43 99.72 99.20 85.06 99.88 99.73 99.87 99.93 99.11 99.59 99.70 99.92 99.29 99.51 99.41 99.70 99.87 99.68

0.20 0.17 0.15

trace 8.30 0.0323

0.019 trace trace

0.322 0.267 0.0089

trace 0.147

0.169 0.346 0.087 0.010 0.058 trace 3.135 58.398 38.121 99.61 0.332 88.7 1.7* 99.48 0.152 96.09 3.380 trace 99.89 99.50 0.165 t CaSo4 = 0.76.

P*05 —

0.0099 0.0044 0.0 0.002 0.0 0.0013 trace 0.0015 trace 0.0085 0.0

0.0093 0.0 0.0136 0.0049 0.0058 0.0 0.0012 0.0017 3.668 1.402 0.0118 0.02 0.0195 0.028 0.0 trace

A1Z03 + F«Z03

0.34

SiO2

Author

0.11

Thomas (see Field, 1922) Turek, 1933

0.034 0.18 0.083 0.066 0.0046 0.12 0.00058 0.048 0.27 6.35 0.0018 0.072 0.0014 0.45 0.00048 0.10 0.00038 0.045 0.0051 0.187 0.00098 0.114 0.0020 0.222 0.0018 0.050 0.0097 0.51 0.0055 0.30 0.0012 0.212 0.0084 0.133 0.0179 0.051 0.0043 0.167 0.3216 92.96 — 0.93 0.0021 — 0.46 0.10 0.0049 0.369 0.0068 0.430 0.0038 0.041 0.0052 0.294

99

99

91

99

99

99

99

«

99

99

91

99

99

91

99

91

99

99

99

9)

99

99

19

99

99

99

99

99

99

99

99

99

99

99

99

99

»

T9

91

99

99

99

Hooper,1908 Turek, 1933

* Together with alkali.

99

99

99

99

11

11

Chemical Composition of Marine Organisms

301

10. Composition of Shells of Cephalopoda Modern Cephalopoda usually possess only an inner shell, which is greatly reduced and often contains no lime; only a single representative of the modern Tetrabranchiata, Nautilus, has an outer shell. Chemical analyses of the shells and of other homologous formations in Cephalopoda are known for the following modern genera: Sepia, Spirula, Nautilus and Argonauta. But the shells of the last named are not homologous to the shells of other Mollusca and are found only in the female; as we will see later, shells of Argonauta have a chemical composition that is different from all other shells and analogous formations in Cephalopoda. In general the shells of Cephalopoda contain more organic matter than do those of Lamellibranchiata and Gastropoda, with the so-called os sepia™ having been an object of investigation more so than others. Merat-Guillot (1797), Hatchett (1799), Neumann, and Fourcroy, in the beginning of the last century, found that the mineral part consists chiefly of CaCO3 and traces of phosphates; John (1818) analyzed the inner part and outer layers of os sepia separately and found traces of iron and magnesium; Forchhammer (1852) found 0.41 °/0 MgCO3. Karsten erroneously supposed that os sepia consisted of calcium phosphate. More complete analyses have been given by Butschli (1908) and by Clarke and Wheeler (1922). The data on magnesium do not always agree, but the causes of these variations are not clearly known. Sorby (1879) showed that all shells and other skeletal parts of Cephalopoda consist of aragonite, although aragonite skeletons, as a rule, contain only traces of MgCO3. Appellof (1893), Meigen (1901), Butschli (1908), Rinne (1924), and Boggild (1930) confirmed these observations. According to Butschli (1908), another representative of the Dibranchiata, Spirula peronii, whose shell also consists of aragonite, contains a maximum of 0.5 °/0 MgCO3. Boggild (1930) concluded that the shells of all Spiriophoridae are made of aragonite. The shell of Argonauta argo does not possess a mother-of-pearl layer, and according to the closely-coinciding analyses of three investigators it contains about 6.0 °/0 MgCO3. Kelly (1900), Meigen (1901), Butschli (1908), and Mayer (1932) showed that the CaCO3 in the shell of this mollusk is in the form of calcite crystals.24 This is the only instance where such a large amount of MgCO3 is found in a cephalopod shell. However, it is not homologous to the shells of other Mollusca, since it originates from the epithelium of the pseudopodium rather than from the mantle. These species, according to Butschli (1908), contain considerable amounts of phosphate, which is not apparent from the data of other investigators. The shells of Nautilus pompilius have two layers, the inner one being mother-ofpearl ; the partitions of the shell consist of the latter substance exclusively and, according to Kelly (1900), contain only CaCO3. The MgCO3 in the shells of Nautilus pompilius, from all known analyses, is very low, about o.i °/0. The investigations of Beche (1853), Sorby (1879), Appellof (1893), Kelly (1900), Meigen (1901), Butschli (1908), Schmidt 23. Of sepia is the name of the shell of Sepia, which is formed by enlargement of the cavity of the siphon. 24. In fossil Argonauta as well, only calcite was found.

302

Memoir Sears Foundation for Marine Research

(1924), Rinne (1924), Boggild (1930), Mayer (1932), Greiss, and others established without a doubt that the CaCO3 in the shells of this organism occurs in the form of aragonite. According to Boggild (1930), aragonite is present in the fossil Nautiloidea, Nautilus imferialis^ N.pompilius, Aturia^ Eosteroti^ and Eutrephoceras dekayi, while the shells of Orthoceratidae, such as the fossil Orthoceras annulatum^ are exceptional in that they contain calcite and aragonite together (see also Appellof [1893] on Nautilus umbilialis). The shells of Cephalopoda contain some soluble salt, which can be related to the relatively large amount of organic matter in these shells. Deecke (1923) showed that there is 0.53 % alkali, with 1.09 % water-soluble salt, in the shells of modern Nautilus. It is of interest to note that there was 0.59% soluble salt and 0.54% alkali in the fossil forms such as Liassic Eelemnitus ekngatus (Lehrti); in the same species from chalk (Rtigen) there was 1.68 % K2O. In the shell of Eelemnitus davatus there was 3.12 °/0 alkali. These observations indicate how far we are from knowing the whole story of the shell composition of Cephalopoda. What was the mineralogical and chemical composition of extinct cephalopod shells, particularly of ammonites and belemnites-? The shells of ammonites have many characteristics in common with the shells of modern Nautilus \ e. g., the mother-of-pearl layer is greatly developed in these organisms. It is probable that the shells of extinct ammonites, Ammonoidea and Nautiloidea, contained aragonite and were poor in MgCO3. Mayer (1932) found aragonite in the shells of the fossil ammonites Amalthaeus cestatus and Harpoceros opolinum\ Cornish and Kendall (1888)

TABLE 178 COMPOSITION OF THE SHELLS OF CEPHALOPODA (IN % OF ASH RESIDUE)

ORGANISM

Ash

CaCO3 MgCO3Ca3P2O8CaSO4 SiO2

Nautilus pompilius 94.63 99.5

trace

—

97.73 99.66 0.17

—

0.17 —

—

—

Argonauta argo

93.14

—

—

0.09

0.13

Sepia offidnalis

97.88 89.93 5.37 3.24 1.46 95.50 96.58 0.13 2.50 0.69

— —

— —

Sepia sp.

97.03 98.32

Spirula peronii

96.74 95.75 0.48 3.39 0.38

„

„

„

„

—

—

—

0.16 0.118

93.76 6.02

—

—

0.19

Fe203+ A12O3 Locality

—

0.15

—

0.401

—

—

—

—

1.62

trace

—

0.00

0.06

—

—

Author

Mindanao, Clarke and Philippine Is. Wheeler, 1922

Biitschli, 1908

High Seas, Pacific

Forchhammer, 1850 Clarke and Wheeler, 1922

Butschli, 1908

Forchhammer, 1850 Tawi, Clarke and Philippine Is. Wheeler, 1922 Butschli, 1908

Chemical Composition of Marine Organisms

303

concluded that most ammonite shells were aragonite, although they did find species containing calcite.25 Modern species of Spiru/ay which are closely related to them, contain aragonite, as do all the other modern Dibranchiata except Argonauta argo. Nevertheless, Cesaro (1898), in studying optic and other properties of the skeletal remains of Belemnitus mucronatus, came to the conclusion that they consisted of calcite. Cornish and Kendall (1888) and others consider the rostrum of belemnites, which originates from the borders of the mantle, to be calcite, while the phragmacone of Astractites, a projection of the shell which included air chambers, is probably aragonite according to Boggild (1930). Grandjean (1910), on the basis of his analyses of fossil shells of Ammonoidea and Belemnoidea, especially the wall of the siphons, considers that the mineral part of the siphons consists of phosphate. The siphon of Oxynoticeras guibalianum, without the rest of the shell, contained (in °/o): Ca3(PO4)2 84.0, CaCO3 9.5, Residue 6.5. Thus the shells and other skeletal parts of Cephalopoda are very diverse in composition. In a small amount of material we found three or four shells of different composition :26 first, those of aragonite, the most common at the present time, which were probably distributed widely in the past, with a small amount of MgCO3 ; second, calcite shells, such as those in Argonauta^ with high MgCO3 content, quite different from the common calcite shells of other Mollusca; third, calcite shells, which probably existed in the past, with a relatively small amount of MgCO3, similar to the shells of other Mollusca; fourth, shells apd skeletal parts of Cephalopoda containing calcite and aragonite together. Possibly in certain cephalopods some skeletal parts consist of aragonite, others of calcite or phosphate. Besides the above-mentioned elements in cephalopod shells, o. 103% sulfur was found in os sepia by Silberstein (1934). Nautilus has jaws containing CaCO3, which compound has also been found in the otoliths of Cephalopoda. 11. Composition of Shells of Lamellibranchiata The shells of some ancient Lamellibranchiata, especially those from the families Ostreidae (Ostrea, Gryphea, Exogyra, and others) and Pectinidae (Pleuromyida, Panophaeida, and others), participated in the formation of rock. More than any others, Lamellibranchiata shells have been examined by geologists and chemists, observations and experiments having been done as far back as the fifteenth century, at which time it was known that they contained lime. Later investigations of their composition appeared at the end of the eighteenth and beginning of the nineteenth centuries, but 25. In the fossil ammonites, especially the most ancient ones, calcite was frequently discovered by Meigen (1901), for example in Pakinsonia sp., apparently a Jurassic form. This could be explained by metamorphism, the transformation of aragonite into calcite. Cornish and Kendall (1888) found calcite in Aptycki, where it could be secondary; compare with the results of Cayeux (1916) and Boggild (1930). 26. There is a parallel diversity in morphological skeletal units: the rostrum of the belemnites, the phragmacone, the outer shell of the Argonauta, and so forth.

304

Memoir Sears Foundation for Marine Research TABLE 179 COMPOSITION OF THE SHELLS OF OSTREA EDULIS (IN % OF ASH RESIDUE)

CaC03

98.6 97.65 96.54 97.0

MgC03

QS

0.312 0.9125

1.2* 0.520f 0.058 0.09

trace

A1203+ Fe203

Si02

CaS04

Author

—

trace 1.456

Buchholz and Brandes, 1817 Serres and Figuier, 1847 Chatin and Miintz, 1895

.

trace

0.0719* 0.03

a

0.813 —

2.0

M6bius, 1877

t Ca3P2o8. a 0.9 %H2S04.

• Ca3P2Og; contains 0.5 °/0 organic matter. * Fe203.

at the present time these data are only of historical interest; some of these analyses, given in Table 179, were done by Merat-Guillot (1797), Hatchett (1799), How (1866), Monas, Kolt, and others. Most of the data refer to the shells of Ostrea edulisy which were collected from different parts of America and Europe, and therefore we will begin our discussion of the chemical composition of Lamellibranchiata shells with an examination of Ostrea edulis. From the data in Table 179 one can see that the largest part of the shell of this species consists of CaCO3 and that there is an average of about 0.5% MgCO3 (see also the less complete analyses of Forchhammer [1852], Schlossberger [1854—1856], How [1866], Weigelt [1878], and Turner); CaCO3 is found in the form of calcite in these shells as well as in other Ostreidae, such as Gryphea (see Rose [1858], Sorby [1879], Tullberg [1881], and Meigen [1901]). The frequent occurrence of these shells in sediments and their participation in rock formation might be explained by the solidity of the shells, which consist entirely of calcite. Therefore, the paleontologists should introduce corresponding corrections into their statements as to the exceptional geological role of Ostreidae. In the shells of Ostrea the amount of MgCO3, which is relatively high on the whole, usually varies somewhat, but it is not always possible to correlate these variations

TABLE 180 COMPOSITION OF THE SHELLS OF CRASSOSTREA VIRGINICA (IN °/Q)

Al Ca Cu Fe Mgo Mn P2OB

.

.

,

. . .

. . .

. . . .

sir?) . . ,

,

0.044 38.80 0.0025 0.09 0.189 0.009 0.073 0.58

Zn , . Cl . . F As CO, .* ^^^2 H2O + organic matter N

0.0009 0.0035 not found »

»

41.96 1.79 0.196

Chemical Composition of Marine Organisms

305

to conditions in the water and similar factors. Substances other than MgCO3 in the shells have been studied but little. The only more or less complete analysis of the shells of Crassostrea virginicay done in 1922 by the U. S. Bureau of Chemistry for the U. S. Bureau of Fisheries, was published by Tressler, 1923 (see Table 180). In the shells of other Lamellibranchiata the amount of CaCO3 varies from 97.0 to 99.9 °/0, the organic matter from o.i to 4.0 °/0 (compare with the Gastropoda). The earlier data (by Merat-Guillot [1797], Serres and Figuier [1847], Schlossberger [1854 -1856], Ulex [1865], Weigelt [1878], Kelly [1900], Vater [1901], Silliman [see Butschli, 1908], and Essner [cited by Boutan, 1923]) and those appearing later (Butschli [1908], Delff [1912], Clarke and Wheeler [1922]) are essentially in agreement (see Lazarevski [1933] for analyses of the shell of Margaritana). The amount of CaCO3 and conchiolin in shells of different ages was studied by many investigators, but no definite conclusions were reached. Embryonic or very young shells are poor in CaCO3; according to Delff (1912) there is more CaCO3 in the older than in the younger shells of Mytilus edulis. But Loppens (i 92O-a), on the basis of analyses of conchiolin, found that the amount of CaCO3 decreases somewhat with the growth of the shell.27 According to Loppens (i92O-a), Pelseneer (i92O-a), and others, the ratio CaCO3/conchiolin in the shells of Lamellibranchiata varies in relation to the medium.28 Thus, the shells of My ft/us edulis from the sea contained an average of 3.86 °/0 conchiolin and 96.14% CaCO33 a specimen from a river 2.60% conchiolin and 97.40% CaCO3. Trahms (1939) found that the shell of Mytilus edulis from well-freshened regions of the Baltic Sea contains only 50 % CaCO3 and 50 % conchiolin.29 Analyses of various Lamellibranchiata shells,30 given in Table 181, show that magnesium, phosphorus, sulfur, iron, strontium, and barium are present. The shells of Pectinidae contain a larger amount of magnesium most consistently; they are followed by Placuna orbicularis. Pinna, and Modiola, although there are only isolated analyses.31 In these organisms CaCO3 occurs as calcite, which sometimes predominates. Calcite was found in the shells of Pecten by Sorby (1879), Cornish and Kendall (1888), Meigen (1901), Schmidt (1924), and Bray (1944). Pinna has an outer prismatic layer of calcite, and the thickness of this layer determines the amount of MgCO3 in the whole shell. Biitschli (1908), in determining the MgCO3 in the prismatic layer alone of Pinna japonica, found that it contained 0.92 %. In the mother-of-pearl layer, MgCO3 occurred only in traces. According to Boggild (1930), Modiola (family Anomiidae) has a typical calcite shell (as do Placuna orbicularis and others; see Table 181). Mytilidae contain both layers, one of aragonite and another of calcite. 27. When the shell weighed 5.015 g there was 3.86 % conchiolin in Mytilus edulis, and when the weight was 69 g there was 4.34 °/0. 28. In Table 182 we have given some analyses of freshwater and terrestrial Mollusca for comparison. 29. On the loss of CaCO3 in freshwater Mollusca, see March's work on Anodonta; also Reech. 30. When there is a lack of calcium in the basin, the shells are formed of conchiolin only, as in Unto complanatus. When there is a surplus, massive shells are formed; for example, A nod on t a cygnea incraiata has a thick shell. 31. See Schmidt (1845) on Placuna placenta. Carpenter (1844, 1847) stated that the shell of Placuna contains aragonite.

3 06

Memoir Sears Foundation for Marine Research TABLE 181 COMPOSITION OF THE SHELLS OF LAMELLIBRANCHIATA (IN »/o OF ASH RESIDUE)

ORGANISM

CaCO3

MgCO3P2O6

Pecten diilocatui

98.0

1.0

AV),+

FejO3 SiO2

CaSO4 Locality

trace 0.08

0.32

—

Pecten ventricosus 98.98 0.73

trace 0.15

0.14

—

Pecten hlandicus

trace

—

1.12

97.6

1.28

—

trace 0.15 trace 0.20

-

-

0.30 0.90 0.15 0.93 — -

trace

—

—

—

Pectengroenlandicus 90.00* 0.8

—

—

—

—

Pecten glaber

98.88 trace

—

0.31

—

0.72

Jstarte crenata

99.65 0.0

trace 0.09

0.26

—

98.51 0.58 98.49 0.57

96.7 —

1.28

0.0

98.76 0.35 97.42 0.31

— —

98.7

0.62

—

94.96 0.47 98.95 0.29 Jstarte acuticostata 98.08 0.71

—

„

„

Astarte borealis

—

present trace

0.2 0.15 — 0.81 0.71 0.40 —

—

—

—

0.68

—

CalKsta convexa

0.89 2.57 0.65 0.15 0.25 0.44 0.44 99.62 trace 0.07 0.12 0.19

Ma coma sabulosa

99.47 0.00

— —

trace

0.23

0.30

Meleagrina sp. 93.80 1.42 0.09 1.04 0.39 Venericardia ventricosa . . 99.79 0.00 trace 0.08 0.13 Cardium substriatum . 99.80 trace trace 0.09 0.11 Cardium edule

98.5

0.28 0.13 0.42 0.56 0.35 trace

—

—

—

—

Charlotte Harbor, Fla., U.S.A. Southern Calif., U.S.A. Barents Sea, 71°30/N,47°0/E Bodo „ Gulf of Kola

Author

Clarke and Wheeler, 1922

Samoilov and Terentieva, 1925 Schmelck, 1901 w

w

Samoilov and Terentieva, 1925 Vinogradov and Borovik-Romanova, 1935 Barents Sea, Samoilov and 73°30'N, 68°5'E Terentieva, 1925 Serres and Figuier, 1847 Marthas Vineyard, Clarke and Mass., U.S.A. Wheeler, 1922 Hammerfest Schmelck, 1901 North Sea w w Gulf of Kola Vinogradov and Borovik-Romanova, 1935 Novai'a Zemlya, Samoilov and 74°10'N, 54°24'E Terentieva, 1925 Spitzbergen Schmelck, 1901 Finmarken North Sea Vineyard Sound, Clarke and Mass., U.S.A. Wheeler, 1922 Massachusetts Bay, U.S.A. Ovchinnikov, 1932 34°25'N, Clarke and (Calif.., U.S.A.) Wheeler, 1922 Long Beach, Calif.., U.S.A. Phipson, 1859 Gulf of Kola Vinogradov and Borovik-Romanova, 1935

Chemical Composition of Marine Organisms ORGANISM

A1203+ CaCO3 MgCO3 P2O6 Fe2O3 SiO2

Cardium edule . 98.53 0.02 Doris tuberculatum 99.76 trace

— —

trace 0.04

— 0.09

0.2 —

trace 0.40 0.50 0.00 trace 0.08 0.70 trace 0.08 0.92 — — 1.0 — —

0.36 0.10 0.00 — —

Leda pernula

98.79 0.51

0.25

—

—

Tellina calcarea

98.84 0.71 trace

—

—

Mytilus edulis

99.0* — — — 99.9* — 0.048 — — present trace —

—

99.14

Venus virginea . 99.49 Teredo gigantea * — * Approximate.

Vater, 1901 Serres and Figuier, 1847

— 0.2

98.74 99.82 99.22 93.94 —

_

Author

— —

Nucula expanser Adla mirabilis . Placuna orbicularis Pinna japonica] . Pinna nigra .

Modiola papuana Pectunculus glycemeris *

CaSO4 Locality

— —

99.96 trace — Calyptogena pacifica 99.87 0.00 trace

0.705 —

—

—

trace

—

—

— 0.00

— —

0.41 —

—

307

15°44'N (Alaska) Clarke and Wheeler, 1922 — North Bering Strait — Korea — Luzon, Philippines 2.82 Butschli, 1908 — Red Sea Forchhammer, 1852 0.45 73°65'N, 73°6'E Samoilov and (Kara Sea) Terentieva, 1925 0.45 74°10'N, 54°20'E (Novaia Zemlya) Weigelt, 1891 Fr&ny, 1855 — Gulf of Kola Vinogradov and Borovik-Romanova, 1935 Forchhammer, 1852 Serres and 0.41 Figuier, 1847 0.31 — Indian Ocean Forchhammer, 1852

With Pinna flamulatus.

Among the Lamellibranchiata there are those species of the order Anisomyaria whose shells are either partly or wholly calcite; to the typical calcite group belong the families Aviculidae (Aviculae), Anomiidae and Ostreidae ;32 all other species of this order contain calcite in the outer shell layer and aragonite in the inner. However, the shells of freshwater species in Congeria and Dreissensia (family Dreissensiidae) are exceptions in that the shells contain only aragonite. In Dreissensia^ a mollusk which lives under diverse conditions in both fresh and salt water, there is a variation in the amount of MgCO3. In another order, the Homomyaria, which embraces the majority of Lamelli32. See the analyses in the works of Carpenter (1844, 1847), Rose (1858), Tullberg (1877) and Sorby (1879). BQtschli (1908) found a considerable amount of MgCO9 in AvUula. Cavalca (1949) has recently published x-ray diffraction data. 33. See Cantor and Mayer for analyses of fossil shells of Dreissensia and Arcicardium. 21

3 o8

Memoir Sears Foundation for Marine Research TABLE 182 COMPOSITION OF THE SHELLS OF TERRESTRIAL (Tr) AND FRESHWATER (Fw) MOLLUSCA (IN °/0 OF ASH RESIDUE)

CaCOs MgCOs P205

ORGANISM

Gastropoda Helix nemoralis (Tr) . 95.2 99

99

—

0.9*

A1.0.+ Fe,0, —

SiO,

SO,

Schmidt, 1845 Ddring, 1872 Joy, 1852 Gobley, 1858 Wicke, 1863 Weigelt, 1878 Meyer, 1914 Ddring, 1872 Vinogradov and Borovik-Romanova, 1935 D6ring, 1872

—

99.51 0.052 0.072* 0.041 0.289 — — — — 98.5 — 0.5* — — 92.82 1.02 5.90* — 0.37

99

Helix pomatia (Tr) . 99.98

Helix fruticola var. alba (Tr) . . . . . Helix ericotorum (Tr) Limnaea stagnalis (Fw) Planorbis corneus (Fw) Buliminus detritus (Fw)

Author

97.50 — — — — 99.52 0.082 0.0204*0.0408 0.204 — 0.0 — — — 99.73 0.020 0.0404*0.120 0.1212 99.36 0.091 0.111* 0.0706 0.3955 96.73 — — — — 97.55 — — — — 99.64 0.020 0.040* 0.070 9.172

99

99

Meyer, 1914 99

99

Ddring, 1872

Lamellibranchiata Pisidiumfontinale (Fw) 97.96 0.0963 0.0214* 1.2412 — — Cyclas rivicola (Fw) , 99.84 0.031 0.041* 0.061 0.2142 — Margaritana margaritifera (Fw) . . . 99.71 0.021 0.0530*0.0424 0.01802 —

»

»

»

Anodonta cygnea (Fw)

99.51 99.47 92.37 99.22 0.062 trace 99.8 0.0

Anodonta lenkoranensis var. armenica^ (Fw) 93.82 0.62 Unto pictorum^ (Fw) 97.32 trace M

»

Unto erassum m. ater (Fw). . . . . Dreissensia polymorpha^ (Fw) . . . . . Dreissensia polymorpha var. fltfuiatilis (Fw). Dreissensia polymorpha var. aralensis (Fw) . * Phosphates.

94.32 0.94

0.021 0.55

0.413 —

0.062* 0.041 trace

—

0.07

0.30 0.94 1.04

0.16

94.39 0.94

1.17

94.99 0.46

0.48

— —

— —

0.11 0.28

0.08 1.85

0.51

1.54

Voit, 1860 Schmidt, 1845 Meyer, 1914 0.2266 — Ddring, 1872 trace — John, 1814 Vinogradov and Borovik-Romanova, 1935 1.45 Ovchinnikov, 1932 0.62

0.06

97.11 0.42 97.92 0.50 Together with organic matter.

Deksbach, 1931

Chemical Composition of Marine Organisms

309

branchiata, there are species whose shells contain aragonite; evidently there is a small amount of MgCO3 in this order (see Table 181). Exceptions are to be found, for example, in shells of Rudistes, which contain both calcite and aragonite, and in those of species such as the fossil Hippurites, which contain calcite only. All analyses show the dearth of MgCO3, especially in shells from the family Naiadidae (Unto, Anodonta, Margaritana margantifera^ and so forth) and from the majority of freshwater Mollusca (see Boring, 1872). Carpenter (1844, 1847), Kell7 (1900)3 Meigen (1901), and Schmidt (1924) showed the presence of aragonite in the following Homomyaria also: Teredo^ Pectunculus, Phola, Cyrena, Venus^ Cardium, Chama and Naiadidae; Boggild(i93o) gives a long list. A more detailed comparison of the mineralogical and chemical composition of shells could be made on the basis of a large number of systematic observations. Thus far no regularities in phosphate and sulfate have been noted, the presence of phosphorus and sulfur in the shells often being indicated merely by the words "found in traces/' Silberstein (1934) found 0.245% sulfur in the shell of Pecten jacobaeus, 0.1023% in Mytilus edulis, 0.221 % in Ostrea edulis, and 0.0409 % in os sepia. Gautrelet (1902) found from o.oo to 0.06 % phosphate in the shells. Regarding rare chemical elements in mollusk shells, see the separate sections following. 12. Composition of Shells of Amphineura, Scaphopoda, Pteropoda, and Heteropoda AMPHINEURA. The shell composition of these organisms is not very different from that of other Mollusca. Unfortunately there are few analyses of these organisms. The shells, or spicules, contain a small amount of MgCO3. Cornish and Kendall (1888) and Butschli (1908) found that the CaCO3 in those of Chiton spiniger is aragonite. Schmidt (1924) investigated the spicules of various Amphineura of the order Aplaco-

TABLE 183 COMPOSITION OF THE SHELLS OF AMPHINEURA, SCAPHOPODA, AND PTEROPODA (IN °/o OF ASH RESIDUE)

ORGANISM

Amphineura Mopalia muscosa Chiton spiniger

CaCO3 MgCO3 P2O5

Fe2O3+ A12OS CaSO4 SiO2

Author

98.37 0.45 trace 0.22 0.35 0.61 Santa Barbara, Clarke and Calif., U.S.A. Wheeler, 1922 — trace trace trace trace trace Butschli, 1908

Scaphopoda Dentalium solidum 99.13 0.20 trace 0.27

—

Pteropoda Hyalaea sp.

—

Phosphates.

Locality

97.7

0.61

1.69* —

0.40 Georges Bank Clarke and (Atlantic) Wheeler, 1922 —

Wicke (Keferstein in Bronn, 1866) 21*

3Io

Memoir Sears Foundation for Marine Research

phora (Solenogastres), namely Chaetoderma canadense, Rhofalomenia aglaofhenia, an w- Wicke (1853), Gobley (1858), B. Wicke (1863), Weigelt (1878), Barfurth (1883), and Meyer (1914) limited themselves to determinations of a few common elements in the shells of Helix pomatia and other Helicidae, showing the presence of other elements qualitatively. As we have seen, analyses of marine gastropod shells were done in later years. Usually there is 97.0 to 99.95 °/o CaCO3 in gastropod shells. Next comes organic matter, conchiolin, which is present in traces, although it may be found in amounts as great as 4.0 °/0; this is low in comparison with the conchiolin in Lamellibranchiata (see Table 182). As shown by Loppens (1920), the ratio of CaCO3 and conchiolin depends on the habitat; in investigating the shells of Littorina littorea, Natica alderi, and others he found that gastropods from slightly saline waters contain less conchiolin than those living in the sea and that the CaCO3 is correspondingly somewhat greater. Actually, considerable variation in the amount of conchiolin and mineral residue (CaCO3) is sometimes noted within one species, as was observed by Pelseneer (1920) and others. Thus, 35. See the analysis of Limacina retroversa by Fox and Ramage (1931).

312

Memoir Sears Foundation for Marine Research

the decrease in CaCO3 sometimes depends on the accessibility of the calcium to the organism. Many Helicidae and other terrestrial Mollusca show polymorphic changes in relation to the amount of calcium in the soil,36 and freshwater gastropods, such as Limnaea and Vivipara^ like the terrestrial forms, sometimes suffer from an insufficiency of calcium in pond water (see Clessin, 1877). The magnesium in the shells of marine Gastropoda is not high; it varies from traces to 1.78 %. Compared to Lamellibranchiata, there are fewer species of Gastropoda with shells containing an amount of MgCO3 higher than 0.5 %• Nassa, Tachyrhynchus and Neptunea contain more MgCO3 than is usually present in gastropod shells, but it is not known how regular this phenomenon is. It would be interesting to compare the amount of MgCO3 with the mineralogical character of the CaCO3 of the shells, but at the present time it is almost impossible to do so, because we do not have enough systematic quantitative data on the MgCO3 in gastropod shells (see Table 184). In almost half of the analyses given, magnesium is indicated qualitatively. The majority of Gastropoda in Table 184 possess shells consisting chiefly of aragonite, although there are a few with aragonite and calcite together. Sorby (1879) asserted that all gastropod shells are aragonite, but actually the analyses by many investigators show that species of Gastropoda whose shells contain both modifications of CaCO3, calcite and aragonite, occur rather often and that those with shells which contain calcite alone are found only occasionally. Boggild (1930) considers the shells of the fossil BelLerophon sp. of the Bellorophontidae (normally aragonite) to be calcite. Patellidae and Neritidae have a shell with a beautiful outer calcite layer (cf. Butschli's [i 908] analyses of the shell of Patella vulgaris, which contains a good deal of MgCO3). However, aragonite is more characteristic of the majority of Gastropoda. In some species of Prosobranchia the shells contain aragonite and calcite, for example, species of the families Neritidae, Euompholidae, Fissurellidae and Trochonematidae; among the Cyclobranchia this is true for species of the families Janthinidae, Solariidae, Littorinidae, Muricidae, Purpuridae, Fusiidae, and Capulidae. Often only the amount of CaCO3 is indicated, which is probably erroneous, since MgCO3 was not determined quantitatively. In some cases a noticeable amount of magnesium was found, as by Biitschli (1908), in the shells of Littorina and others. In certain species a modern detailed analysis shows the presence of both aragonite and calcite, whereas before only aragonite was found, as in Murex and Scurria. Only aragonite, or mostly aragonite, was found in Strombus gigas^ Oliva sp. and other Olividae, Natica, Cerithiidae, Buccinidae, Cyclostomata, Cyprea and Trochiidae (for example, Trochus dub. and T. cinerariui) as well as Turbinidae, Bulla, and many others. According to Boggild (1930), all Pulmonata contain aragonite.37 He gives des36. Helix striata var. solidus lives on a calcareous soil and has a thick shell; var. tenuis, with a thin shell, lives on a siliceous soil. 37. Aragonite was found by various investigators in Succinea oblonga, S.patrina, Pupa trumentum, Papilla, Phisa, in

Chemical Composition of Marine Organisms

313

criptions of the shell structures of more than 50 families of Gastropoda, the majority of them with an aragonite shell or with aragonite predominating. According to Kessel (i936-a), Haliotis is an exception in structure, with the calcite layer between two aragonite layers. In the first outer layer of H. tuberculata and H. lamellosa he found grains of crystalline aragonite, and then deeper groups of long calcite crystals. Presumably metamorphism takes place, with the formation of calcite directly from the aragonite of the shell, analogous to the process which occurs in the fossilization of shells. Corresponding to the aragonite character of the majority of gastropod shells, the magnesium content in general is low. Patella vulgata, Purpura lapillus, and Littorina, in whose shells CaCO3 is present as calcite, or as calcite and aragonite together, contain somewhat more MgCO3 (see Table 184). A very important observation was made by Schmidt (1924) concerning the CaCO3 in the spicules of Nudibranchia. Woodland (1907^) reported calcite crystals in the spicules of Doris tuberculata^ but Schmidt noted that the optic properties of the spicules did not coincide with Woodland's observations. From the specific gravity (2.6), small double refraction and Meigen reaction, showing aragonite, he concluded that vaterite rather than calcite is present in the spicules of Doris tuberculata and other Nudibranchia.38 After the spicules were heated or treated with alkali, the vaterite changed into calcite. These investigations were continued by Mayer (1931, 1932), who, starting from the supposition that vaterite occurs in the earliest stage of shell development,39 did an x-ray analysis of the embryonic shell of Paludina vivipara and of the shells of Limnaea ovata. Helix nemoralis, and Buccinum undatum. By comparing these x-rays with those of different combinations of vaterite and aragonite, he established that vaterite predominates in the earliest stage of shell development but partly changes into aragonite as the organism matures. Vaterite is found with aragonite also in Buccinum undatum and other organisms. The analogous process of change from vaterite into calcite has been observed by Dudich (1929) in the carapace of Crustacea (see Chapter XVI). Thus the presence of vaterite in the earliest developmental stage of mineral formations in the shells and other skeletal parts of invertebrates is quite general. Vaterite changes either into aragonite or calcite according to the degree of shell development, a certain concentration of CO2 assisting the change of calcium into calcite and magnesium ions influencing the change to aragonite. We will return to this question in Chapter XX.40 The amounts of phosphorus and sulfur (as phosphate and sulfate), and of some other elements in gastropod shells, are very diverse and are not unrelated to the processes of CaCO3 crystal formation. Prenant (i928-b) has shown the role of phosphates in the different species of Helix, Limnaea, and many others. Rose (1858) erroneously supposed that Helicidae contained calcite. 38. According to the analysis of Benrath, they consisted of calcite only. Rinne (1924)1 Mayer and Weineck (1932), and Odum (i95i-b) find that the spicules of ArcMdoris are actually amorphous CaCO3. 39. Also assumed by Linck (1912). 40. There has been confusion as to the significance of the term vaterite (Johnston, Merwin and Williamson [1916], Gibson, Wyckoff and Merwin [1925]). The usage followed here is that of Mayer and Weineck (1932).

314

Memoir Sears Foundation for Marine Research TABLE 184 COMPOSITION OF SHELLS OF GASTROPODA (IN °/0 OF ASH RESIDUE)

ORGANISM Nassa californic a . tegula . isculpta Tachyrhynchus erosa . Ranella pulchra Turitella gonostoma , Neptunea despecta

MgCOs P205

99.22

0.37 trace 0.13

0.28

96.84 0.44 0.18*0.35

2.19

97.08

1.78 0.10 0.52 0.52

97.0

1.02 0.82* 0.90 0.26

96.60 0.51 trace 0.63 2.26 97.21 —

0.44 trace

1.89 0.26

present —

—

—

98.52 1.17 —

—

—

98.84 0.74 —

—

—

—

—

—

0.486 —

—

Monterey Bay, Calif,, U.S.A. — Magdalena Bay, Calif., U.S.A. — 32°20'30"N (Cortez Bank)« — Avatcha Bay, Kamchatka — Prabas Is., China Sea 0.20 Mulege, Calif., U.S.A. — Gulf of Kola

(Barents Sea)

—

groenlandicum rt

.

—

98.0 —

— — present —

— —

— —

98.56 98.92 97.26 98.14 97.60

0.29 0.38 0.78 0.46 0.79

0.15 0.15 0.31 0.21 0.10

0.52 trace 0.54 trace 0.52

trace 0.36 trace 0.25 trace 0.31 0.135 0.21 trace 0.25

. 99.28 0.41 trace 0.16 0.15

96.35 0.54 — —

present —

—

—

— —

Clarke and Wheeler, 1922

0.45 71°30'N,47°0'E

98'33 0.26 trace 0.43 0.98

— —

Author

Vinogradov and Borovik-Romanova, 1935 0.31 69°38'N,57°21'E Samoilov and Terentieva, 1925 (Barents Sea)

98.35 0.68 trace 0.70 0.10 0.53 North Sea 98.22 0.77 trace 0.51 0.46 0.75 Lofoten

Buccinum undatum

glaciale Purpura lapilius

AL,03+ Fc20s SiO2 CaSO4 Locality

CaCOs

—

0.17 —

Forchhammer, 1852 Schmelck, 1901

Narragansett Bay, Clarke and R.I., U.S.A. Wheeler, 1922 Weigelt, 1891 Gulf of Kola Vinogradov and Borovik-Romanova, 1935 Vardo Schmelck, 1901 Lofoten Hammerfest Vadsoe North Sea Eastport, Maine, U.S.A. Gulf of Kola

Clarke and Wheeler, 1922 Butschli, 1908 Vinogradov and Borovik-Romanova, 1935

Chemical Composition of Marine Organisms ORGANISM Aporrhais occidental'^ Natica duplicate . clausa .

.

0/iva literata Fasciolaria distant. Crepidula onyx Antiplanes perversa . Volumetra alaskana

A1203 Fe203 SiO2 CaSO4 Locality

CaCOs

MgC03P206

98.30

trace trace 0.23

, 99.95 trace trace 0.05 . 98.54 0.84

trace

—

1.32 0.15 0.0 —

. 99.91 0.00 trace 0.04 0.05

— 0.84 —

99.48 0.14 trace 0.04 0.34 — . 99.73 trace trace 0.11 0.16 0.0 . 99.41 trace trace 0.11 0.48

—

. 99.75 trace trace 0.18

0.07

—

0.08

—

97.82 0.20 0.85* 0.4 0.73 99.36 0.24 trace 0.23 0.17

— —

99.90 —

trace trace 0.10 0.00 0.189 — — —

— —

99.70 trace trace 0.21 0.09

—

99.30

Pyrolofusus harpa Carolina longirostris . Plicifusus dirus. Cerithium aluco . teles copium S trombus canarium . gigas

99.84 trace trace 0.08

—

—

—

—

—

—

—

—

—

— 0 — — 0.001 — 0.35 — —

— — —

— — —

99.75 trace Patella vulgata. — Littorina littorea 99.9f Vermetus sp. , — a California, U.S.A.

* CWV

Marthas Vineyard, Mass., U.S.A. Cape Lookout, U.S.A. Barents Sea, 69°30'N, 46°55'E Sarasota, Florida, U.S.A. San Pedro, Calif., U.S.A. Bodega Head, Calif., U.S.A. Unalaska „

315

Author

Clarke and Wheeler, 1922 „ „ Samoilov and Terentieva, 1925 Clarke and Wheeler, 1922 Clarke and Wheeler, 1922 Clarke and Wheeler, 1922

Philippines Sitka Harbor, Alaska Philippines

Forchhammer, 1852 Luzon, Philippines Clarke and Wheeler, 1922 Potyka (G. Rose, 1858) Oesten (G. Rose, 1858) Butschli, 1908

Bermuda f Approximate.

How, 1866

Forchhammer,

1852

precipitation of CaCO3 from solutions in the tissues during formation of the shell. Phosphorus in the shells is seldom higher than o. I °/0.41 The sulfur determined in shells was probably partially bound in conchiolin; Silberstein (1934) found the total to be 0.0412% in Helix shells. Neither gypsum (CaSO 4 «2H 2 O) nor the anhydride have been found. Usually there is about 0.2 °/0 iron. As we have already pointed 41. Miiller did an analysis of the shell of the fossil gastropod, Cyclora minuta, from the Devonian and from other sediments of America, containing phosphorites. He found 22.7-28.0 °/0 P2O6, whereas the rocks contained 0.7711.9%. Muller notes that other species of Cyclora, found in similar sediments, are also rich in phosphorus.

3 16

Memoir Sears Foundation for Marine Research

out, an increase in iron is sometimes related to the growth of Protozoa and algae on the shells. There is very little manganese in gastropod shells. Boring (i 872), doing systematic analyses for manganese in terrestrial Mollusca, showed that the amount of this element varies from n X io~* to n x ic"1 °/o> with the exception of Anodonta, which contains more. Regarding fluorine and other halogens in the shells, see later sections of this chapter. Since the amount of silicon is insignificantly small, cases of high SiO2, for example in Nassa tegula, arouse suspicion as to the purity of the sample taken for analysis. We have pointed out previously the only known case of concentration of SiO2 in Mollusca, namely in Gastropoda. The operculum of Turbo and of Nerita contains aragonite. Traces of manganese, iron and silica were also found. A radula, which is situated in the oral cavity in the form of plates and which serves to grind the food, is present in the majority of gastropods. Most of the data on the composition of the radula are qualitative. Different investigators disagree on numerous points, but the history of this problem was discussed recently by Spek (1921) and then by Pruvot-Fol (1926). Hancock (1845) and Hancock and Embleton (1845) found SiO2 in the radulae of Eolidae, Pholas, Teredo, and Saxicava; they supposed that it is present in the surface layer of the radula. Sollas (1907) also found SiO2, as well as calcium and phosphorus, in the radulae of Patella, Haliotis, Natica, and Helix, the composition of the radula of Helix apparently varying according to the time of year; she considered her analytical observations to be of systematic significance.42 The majority of other investigators, such as Leuckart (1852), Bergh (1853), Kohler (1856), and Troschel (i893),43 supposed that the foundation of the radula is an organic substance which includes calcium, phosphorus, iron, and other elements in various forms; some assume that it is chitin, others keratin. Spek (1921) found no SiO2 in the radulae of Patella, Haliotis, Natica and Buccinum, but there was iron, calcium and phosphorus in consider-

TABLE 185 COMPOSITION OF THE OPERCULUM OF TURBO AND EPIPHRAGM OF HELIX

ORGANISM; part

CiCO^

Organic MgCO3 Ca3P2O8 matter

Operculum Turbo rugosum

.

.

96.55

trace

Epiphragm Helix pomatia . „ . -

. , , , -

94.24 86.75 95.5

— 5.73 0.96 5.63 present —

—

3.45 — 6.42 —

Fe2O3 Author

—

Schlossberger, 1854-1856

trace — Schlossberger, 1854-1856

42. Troschel (1893) attributed systematic significance to the form of the radula: he investigated the radula of Eotis papillosa, Marsenia perspia, and others. Sollas (1907) indicates a large amount of SiO2 in Docoglossa only, with none in other Mollusca. 43. See also Pantin and Rogers (1925) and Bowell (1928).

Chemical Composition of Marine Organisms

^ i7

able quantities. Many investigators have stressed particularly the presence of iron in the radula. As noted earlier, Prenant (igsS-a) attempted to explain the accumulation of this element in the radula of Chiton by the participation of the epithelium in the isolation of iron from the organs. The composition of the radula, as nearly as one can determine from the qualitative and sometimes contradictory data, is basically protein with salts of phosphoric acid, hydroxides of Fe2O3> SiO2 and other compounds. The only quantitative analyses of the ash were done by Jones, McCance and Shackleton (1935), w^° collected radulae of Patella athletica and obtained the following results (in °/0):

SiO. . Fe2O3 CaO . NaCl . KC1 . P2OS . MgO

. . . , . .

CuO . . Total . .

Dry matter

. .

. .

. .

.

* . . . ,

,

8.70 14.3 0.43 0.97 091 094 0.13 0.005 . . 0.004 . , 26.389

Ash

5400 1 62 3 55

t

3 54 047 002 002 . . . 99.58

Besides these substances, strontium, silver, manganese, lithium, and lead were detected spectroscopically. We found that the shell composition of Foraminifera, for example, was similar to that of these skeletal parts, consisting mainly of hydroxides of Fe2O3 and SiO2, but the form of this iron and silicon is not known. Jones, et al. (1935) con~ sider that these elements occur as a compound with the formula ([FeAl]2O3)3 (SiO2)4. In Patella athletica and other Docoglossa (P. vulgaris, P. coerulea, P. lusitanica, and P. pellucida) the radulae contain both iron and silicon ; these observations confirm those of Sollas (1907). All Chitonidae (Craspedochilus cinerus, Chiton olivarius, C. emarginata and C. discrepant) contain much iron and no silicon; Prenant (igsS-a) also found a good deal of iron in Chitonidae. But iron and silicon are absent in the radula of species of Rhipidoglossa (Emarginula fissura and Calliostoma zizyphynum\ in Taenioglossa (Hydrobia jenkinsi, Aporrhais pespelicani. Lacuna vincta, and Littorina littorea\ in Stonoglossa (Buccinum undatum and Nucella lapillus\ in Tectibranchia (Scaphander lignarius and Aplysia punctata\ in Nudibranchia, Doris tormentosa, and others. These data indicate that composition of the radula is variable and probably characteristic of different Mollusca. The epiphragm or cover which serves to close off the entrance of the mouth of the shell is found in many species of Gastropoda. It may be purely organic (protein and horny) or it may contain a certain amount of inorganic salt. Individual analyses show that the inorganic part of the operculum may consist of salts of phosphoric acid, calcium

3i8

Memoir Sears Foundation for Marine Research

carbonate, and perhaps a combination of magnesium and calcium carbonates. Thus the epiphragm of Helix pomatia contains almost 6 °/o calcium phosphate.44 14. Composition of Pearls

Pearls are situated on the inner surface of the shells of some Lamellibranchiata and other Mollusca, and their structure is similar to that of the mother-of-pearl and other layers of shells. They are formed by a secretion of the epidermis. Pearl formation has been explained by some as being due to the presence of parasitic worms in the organism, these having caused a diseased condition leading to pearl formation. According to other hypotheses, pearls originate where there has been some destruction of the unity of the inner layer of the shells because of the presence of foreign bodies, and so forth (see Boutan [1898, 1921], Korschelt [1912], Haas [I931])- Genuine pearls are found chiefly in the species of Meleagrina^ which are widely distributed along the shores of the Pacific and Indian oceans. These are : M. margaritifera^ M. californica, M. margaritifera erythroensis, M. maratlantica^ M. radiata, M, vinesi and M. martensi. Pearls have been found also in Ostrea, Mytilus, Pinna syuamosa, Strombus gigas, Turbinella scolymus, Haliotidae, Nautilus^ and so on. It was known as far back as Reaumur45 that pearls contain a good deal of calcium carbonate, there being an average of about 92 °/o CaCO3 in the pearls of Meleagrina margaritifera. Note the different amounts of water in pearls of Meleagrina margaritifera and Pinna nobilis. We know of no more detailed analyses than those given in Table 186. Some investigators, such as Hessling (1859), Voit (1860), Mabius (1877), Rudler (1885), Harley and Harley (1888), Boutan (1898, 1921), Kunz and Stevenson (1908), Dubois (1909), Haas (1931), and others, in reporting analyses of the mother-of-pearl in shells of Meleagrina and others, indicate only qualitatively the absence of phosphorus, the presence of sulfate, and so forth, in pearls. The CaCO3 in pearls is found either as

TABLE 186 COMPOSITION OF PEARLS (IN %)

ORGANISM

CaCO3

Organic matter

H2O

Volatile matter etc. Locality

Pearls*"

91.72

5.94

2.23

0.11

Meleagrina margaritifera . 91.59 Pinna nobilis . . . . 72.72

3.83 4.21

3.97 23.06

0.81 0.01

Author

England Harley and Harley, 1888 Australia Ceylon — Dubois, 1909 —

*H Average analysis of six pearls: two from Ceylon, two from Australia, and two from Britain. The last two are presumably from Margaritana, the other four from Meleagrina,

44. Qualitative indications of phosphorus are given by Biedermann (1902). 45. At the beginning of the eighteenth century (1718). Actually it was known much earlier, in ancient times.

Chemical Composition of Marine Organisms

319

aragonite or calcite, or both,46 depending on the species. In the genuine pearls of Meleagrina margaritifera, CaCO3 is present as aragonite (see Galibourg and Ryziger, 1926). But according to Schmidt (1924), those found in M. californica contain calcite, Calcite was found also in pearls from Mytilus edulis and others; aragonite pearls are found in Margaritana margaritifera and other Unionidae, freshwater Mollusca in which the entire shell is composed of aragonite. Mixed forms of pearls, containing layers of calcite and aragonite, similar to the structure of the shells of many Mollusca, have been found in Pinna and other organisms. 15. Manganese, Iron, Copper, and Zinc MANGANESE. That the physiological role of this element in plants and terrestrial animals is being studied at the present time is evident in the large body of analytical material concerning the presence of the element in different organisms as well as in their organs and tissues. But we are only at the beginning of a systematic study of the distribution of manganese in many marine invertebrates. The Mollusca happen to be a particularly favorable subject of study, because certain species are typical concentrators of the element, a feature which has helped to attract the attention of investigators to the problem of manganese metabolism in invertebrates. The presence of manganese in Mollusca, sometimes in large quantities, became known rather late. Erman, in 1816, demonstrated the presence of it in the blood of Helix pomatia and others; in 1835 Lavini showed that it was present in the byssus of Pinna nobilis, in the organs of which a considerable concentration of the element was later discovered ; John (1814) and others found manganese in the shells. In 1872 Doring determined manganese qualitatively in many shells of freshwater Mollusca.47 Other qualitative indications are given by Koch. Somewhat later it was detected in marine Mollusca by Krukenberg (1881-1882), Pichard (1898), Griffiths (i892-b), and Boycott and Cameron (i 930). Bradley (i 9oy-a) did a systematic study of the distribution of manganese in the tissues of Unionidae, and later he studied it in various mollusk tissues. Kohn (1898) did histochemical determinations. The latest works of Dubuisson and Heuverswyn (1931) and Waele (1930) are devoted exclusively to the question of the distribution and the physiological role of manganese in the tissues of Mollusca. We have investigated manganese in the shells of marine and freshwater Mollusca, and, as expected, freshwater shells contain more of the element than do those of marine origin (see Table 187). Thus marine limestone probably contains less manganese than does that of freshwater, and consequently we may be able to determine the origin of some limestones which have been doubtful previously. Recent data on manganese in the tissues of Mollusca have been given by Webb (1937). MANGANESE IN CEPHALOPODA. Pichard (1898) found manganese qualitatively in 46. Pearls may be composed of material from any layer of the shell, calcite, aragonite, conchiolin, and so forth. See Shaxby's (1925) x-ray investigations. 47. Margaritana margaritifera, Cyclas rivicola, Buiiminus detritus, and Pisidium fontinale.

3 2o

Memoir Sears Foundation for Marine Research TABLE 187 MANGANESE IN MOLLUSCA (IN

ORGANISM

Ash

Comments

Lamellibranchiata (soft parts) Penus mercenaria — Crassostrea virginica — Pinna japonica (Atrina pectmatd) 3; byssus . 14.1 „ „ 3; hepatopancreas 3.9 „ „ 3; mantle glands 7.13 3; kidneys . . 3.1 3; muscles . . 2.93 Mytilus edulis — Pecten fumatus Pecten maximus Freshwater Unionidae . , Gastropoda (soft parts) Helix aspersa Littorina littorea Purpura lapillus Pleurobranchus plumula Aeolidia papillvsa Archidoris britannica . .

.

- -

Lamellibranchiata (shell) Anodonta cygnea

Dry matter

Locality

Author

0.0043 0.0049

U.S.A.

McHargue, 1927

0.18 0.60 0.18 0.73 —

6xlO- 6 *

Suto, 1938

—

— 5xlO~6* 0.008 — Mixed

Mantle

„

.

•

.

.

-

.

.

,

.

—

0.5424

0.08 0.08 0.06

— — —

0.015 0.04

— —

0.02

—

0.078 0.078

— —

0.07

U.S.A.

0.001 0.002

— —

0.04 0.035 0.001 0.01

— — — —

Unio pictorum Unio tumidus

0.055 0.069

— —

rt

11

r»

Clements and Hutchinson, 1939 „ „ Webb, 1937f McHargue, 1927

Webb, 1937f „

-

Cardium edule Mytilus edulis Afargaritana margaritifera » Pecten islandicus Ostrea sp

rt

I Dnieper Leningrad, Sablino Barents Sea

I

Vinogradov, 1938-c

"

Kazanka River Vinogradov, 1938-c Vorgusa River w Barents Sea Avachinsky Bay, ^ " Kamchatka Dnieper

Chemical Composition of Marine Organisms ORGANISM

Comments

Ash

Gastropoda (shell)

Buccinum undoturn Helix pomatia Neptunea despecta

Dry matter

0.001 0.005 0.002

— — —

321

Locality

Author

Kiev

Vinogradov, 1938-c

* The results are apparently too low. f The author gave his results in terms of the total ash cations.

the os sepia, as did Ranzi (1935) *n SePia officinalis. Then later Bertrand and Medigreceanu (1913) determined the element quantitatively in the body of S. officinalis. But Wang-Tai-Si (1928) did systematic determinations of manganese in numerous Cephalopoda. All cephalopods are poorer in this element than species of other classes of Mollusca (cf. data of Tables 18 8, 189 and 190) ; organs like the liver (hepatopancreas) and kidneys contain relatively smaller amounts of manganese in Cephalopoda when compared with the same organs of Gastropoda and Lamellibranchiata, which are usually richer in heavy metals, as we will see later. Only in the young organisms is there a larger amount of the element. In addition to the parts listed in Table 188, Wang-Tai-Si gave the manganese content of a number of other parts of Sepia, Octopus and Loligo, namely the heart, eye, and arm, but the manganese in these does not differ significantly from the amounts given for those listed in Table 188. However, in the eggs of Sepia officinalis there is a relatively large amount of manganese, up to 0.00175 °/o °f the dry matter, in the shell of the egg 0.00368 %, and in young S. officinalis up to 0.00231 % °f the dry matter; although the ink sac of S. officinalis, together with its contents, contained no manganese, the ink sac of Loligo vulgaris contained 0.00208 °/0 in the dry state. Fox and Ramage (1931) found no manganese in the ink sac of Sepia officinalis, although they detected it in the liver and pancreas of Sepia. MANGANESE IN GASTROPODA. For qualitative determinations of manganese in the

TABLE 188 MANGANESE IN THE ORGANS OF CEPHALOPODA (IN % OF DRY MATTER)

ORGANISM

Sepia officinalis

Sepia officinalis zo

0.341

0.352 0.758 0.138 0.263 0.345 0.192 0.083 0.500 0.075 — — — —

0.048

0.130 0.268 0.041 — — — —

FeP04-o.o5 «/0.

Author Delff, 1912 Wang-Tai-Si, 1928 w

n

>i

»

n

n

n

n

n

n

n

n

n

n

n

n n

n

n

n

»»

n

n

n

n

n

»i

5?

n

n

n

n

it

n

»»

»»

Phillips, 1917 n

n

n

n

n

n

Meyer, 1914 Weigelt, 1878 Wang-Tai-Si, 1928 Dastre and Florescu, 1898 Wang-Tai-Si, 1928 n

n

n

n

Dastre and Florescu, 1898 Bezold, 1857 (?) Wang-Tai-Si, 1928 Berthier, 1846 Meyer, 1914 9)

99

McHargue, 1924 (?) a Fresh water.

334

Memoir Sears Foundation for Marine Research TABLE 198 IRON IN VARIOUS ORGANS OF GASTROPODA (IN % OF DRY MATTER)

ORGANISM

Muscle

Gills

Mantle

Sex glands

Haliotis tuberculata Helix aspersa§ Littorina littorea

— 0.022 0.061

0.016 — —

0.025

0.015

Average,

Kidneys Liver

—

0.022* Wang-Tai-Si, 1928

O.OSlf 0.027 1.691 0.068 0.092 — 0.114 § Terrestrial.

Author

„ „ „ „ McCance and Shipp, 1933 f Hermaphrodites.

Haliotis, Aplysia, Archidoris tuberculata, Aeolidiapapillosa, and the terrestrial Helix aspersa, H.pomatia, and Arion ater\ analyses are found also in Jordan (1925), Petree, and many others. As mentioned previously, Erman (1816) showed a considerable amount of iron in the blood of Planorbis. The order of magnitude of iron in Gastropoda is approximately the same in all species analyzed, but it is notably greater in Gastropoda than in Cephalopoda. The largest variations in iron, related as they are to a diversity in nutrition, occur in terrestrial species of Helicidae and Pulmonata. A relative richness in iron should be noted in Patella vulgata, Trochus crassus, T. ombicalis (all Aspidobranchia), in Purpurea lapillus, and some others. For the first three species, Wang-Tai-Si (1928) observed a complete absence of copper in the organs, including even the liver; the blood pigment of these species has not been studied, but it is probably haemocyanin. A number of Gastropoda whose blood contains copper as haemocyanin (such as Buccinum undatum and Murex trunchulus) have little iron. There is only a small amount of iron in Aplysia, as is the case with other heavy metals ; the blood pigment of this organism has not been studied either. At the present time all of our knowledge about the respiratory pigments in Gastropoda indicates that there is usually only one pigment, haemocyanin, this containing copper and not iron. Species of Planorbis are exceptions. Lankester (1868) discovered that their blood contains a red pigment that is closely related to the haemoglobin of the higher animals, and Erman (1816) has shown54 that this pigment does contain iron. Sorby, and later many others, demonstrated that it differs somewhat from the haemoglobin of the higher animals (see Chapter XIX); it is now classified with the erythrocruorins (red pigments containing iron) found in the blood of other invertebrates, such as Vermes and Crustacea. In the blood of Gastropoda, which contains haemocyanin, iron has usually been found only in traces (see Boussingault [i872-b], Gorup von Besanez [1874-1875], and Gatterer and Philippi [1933]). Haemoglobin-like pigments and derivatives of haemoglobin have been found frequently in the tissues of other Gastropoda, but they have not been found in the blood. Lankester (1871) obtained a pigment of the haemoglobin type from the pharynx muscle of Paludina and Limnaea, while haemocyanin was present in the blood of the former; 54. The red color of the blood of Planorbis comeus was known earlier.

Chemical Composition of Marine Organisms

335

the same haemoglobin-like pigment occurs in the muscles of Littorina. In the liver of Helicidae, Sorby found another pigment, helicorubin, which according to the investigations of Vegezzi (1916), Dh6r£, and others is an iron-bearing porphyrin also. MacMunn (1886) demonstrated the presence of a porphyrin in Arion ater. Dhdrd and Baumeler (1928) supposed that the pigment in the tissues of A. empiricorum actually is a porphyrin but that it differs from the haematoporphyrin of the higher animals; the character of the tissue pigment in other species of Arion and Limax has not been determined. Another pigment which is discussed comes from the shell of Haliotis rufescens, H. gigantea^ and others ; according to Kodzuka (1921) and Dhdrd and Baumeler (1930) it should be classified likewise with the porphyrin bodies formed from the pigments of the liver (bilirubin). Schulze and Becker (1931), working on this pigment from Haliotis californiensis, did not think it was a porphyrin ; in their opinion it is closely related to indigo.55 Just as in Murex, the blood of Haliotis contains haemocyanin. Pigments with iron have been found in Nudibranchia. We have discussed to some extent already the question of iron compounds with organic matter found in the blood and body of Gastropoda. Observations show that iron metabolism in Gastropoda which contain haemocyanin is largely connected with the metabolism of porphyrin derivatives,

TABLE 199 IRON IN THE LIVER AND MUSCLES OF AMPHINEURA AND GASTROPODA (IN % OF DRY MATTER) ORGANISM

No. of analyses

Amphineura Cryptochiton sp hchnochiton sp Gastropoda Patella vulgata Trochus crassus Littorina littorea Purpura lapillus Aplysia punctata

4 2 2 4

Fasciolaria gigantea Cassis sp Strombus gigas Haliotis sp Helix pomatiaa

2 2 2

Helix hortensisa Limax sp.a . * Very high figures.

a Terrestrial.

Muscle

Liver

Author

0.83 0.83

(4.46) (2.91)

Albrecht, 1920-1921, 1923-b*

0.119 0.124 0.058 0.071 0.078 0.062 0.080 0.046 0.144 0.93 (2.07) 0.066f 0.0016§ 0.015 0.018 0.009 0.0024$ 0.015 0.0078

Wang-Tai-Si, 1928

Phillips, 1917

Albrecht, 1920-1921, 1923-b* Barfurth, 1883 Dastre and Florescu, 1898 Wang-Tai-Si, 1928 Dastre and Florescu, 1898 Boussingault, 1872-b

f Average for normal Helix.

55. Lemberg (1931) considers this problem unsolved. See Petree on iron in Haliotis.

§ Exclusive of inner organs.

336

Memoir Sears Foundation for Marine Research

The amount of iron in gastropod shells is usually about o. i % of the ash residue. The large amount found occasionally in the shells is due to a growth which often consists of ferrobacteria concentrating iron. IRON IN LAMELLIBRANCHIATA. The amount of iron in various Lamellibranchiata is somewhat more uniform than was observed for Gastropoda, and on an average it may be somewhat lower. If we exclude the edible oyster and Mytilus edulis, for which there are about 20 determinations of iron, then we have only isolated analyses left, some of which need verification. However, among the Lamellibranchiata it is known that some species are poor in iron while others concentrate the element, particularly in the liver.

TABLE 200 IRON IN LAMELLIBRANCHIATA (IN %)

ORGANISM

Ostrea edulis Ostrea edulis* »

»

Living matter

Comments

—

. *

Crassostrea virginica

Crassostrea angulata Mytilus edulis .

Anomia ephippium . Pectunculus glycemeris Pecten jacobaeus Pecten varius Pecten maximus . Tellina tenuis Tellina crassa Mactra corallina Donax tronchulus Strobicularia piperata Venus verrucosa Venus mercenaria

5 5} gills

4 4

— —

4 2 2 5 4 3 7 3 4

Author

0.0018 0.0365 0.0668

Dastre, 1898 Chatin and Miintz, 1894

— — —

W

W

W

W

— — 0.266 Griffiths, 1905 McCance and Shipp, 1933 0.0060 — — 0.005 0.022 0.120 Wang-Tai-Si, 1928 — — 0.27 Albu and Neuberg, 1906 Peterson and Elvehjem, 1928 0.00314 — — Skinner and Sale, 1931 — 0.016 — Coulson, Remington and Levine, 0.0104t — —

0.0057f 4 0.002 — — 2 — Muscles 0.0058 0.003 »

Dry matter Ash

0.002 0.003 0.006 0.003 0.001 0.009 0.004 0.002 0.001 0.005 0.009 0.001

— — 0.057 0.016 0.34 2.80 0.21 — 0.0036t — — 0.014 0.097 0.21 0.010 0.050 0.017 0.057 0.038 0.197 0.020 0.069 0.015 0.050 0.031 0.185 0.036 0.061 0.020 0.033 0.011 0.026 0.047 0.093 0.045 0.248 0.006 0.028

1932 Galtsoff, 1934 Wang-Tai-Si, 1928 Brandt and Raben, 1919-1922 Delff, 1912 Henriques and Roche, 1927 McCance and Shipp, 1933 Wang-Tai-Si, 1928 Griffiths, 1905 Wang-Tai-Si, 1928

Chemical Composition of Marine Organisms ORGANISM

Comments

Venus mercenaria Tapes decussatus Tapes aureus Dosinia exoleta * Cytherea chione . Cardium edule . 99

99

'

'

-

Mya arenaria . 99

99

-

99

99

'

Lutraria elliptica Sol en siliqua . Anodonta cygnea

.

Anodonta mutabilis .

.

Muscle 4

. . .

4 2 4

*

3

. . .

Muscle

Muscle

2 4

Fresh water

-

Living matter

0.0 0.004 0.01 If O.OlSf 0.002 0.002 0.0039 O.OlSf — — 0.007 0.007f 0.0357f

0.07

Dry matter Ash

0.025 0.072 0.089 0.009 0.016 — 0.113 1.225

Meigs, 1915 Wang-Tai-Si, 1928

0.158 0.415 0.450 0.058 0.075

99

— 0.28 0.120 0.205 —

0.518

—

t

99

99

TJ f)

99

99

99

99

99

99

99

99

99

99

99

99

91

99

99

McCance and Shipp, 1933 Wang-Tai-Si, 1928 Delff, 1912 Griffiths, 1905 Wang-Tai-Si, 1928

— 0.417

— 0.044 0.032 —

* Soft parts without gills.

Author

—

—

337

Butschli, 1908 Meyer, 1914

Maximum.

Iron has been determined qualitatively in the organs and tissues of Lamellibranchiata by many investigators: Pasquier (1819), Schlossberger (1856), Chatin and Muntz (1894, 1895), Bradley (1904), and many others. The liver, and then the kidneys, are richest in iron. Schlossberger (1856), Krukenberg (1882), and later others, showed a large amount of iron in the concretions of the organ of Bojanus, for

TABLE 201 IRON IN VARIOUS ORGANS OF LAMELLIBRANCHIATA (IN '/0 OF DRY MATTER)

ORGANISM

Muscle

0.005 0.006 0.002 0.007 0.003 0.003 0.004 — 0.005 — 0.003 0.0147 0.008 » 99 • " — Cardium norvegicum . Pectunculus glycemeris Mytilus edulis Pecten jacobaeus , Pecten maximus . Crassostrea angulata . Mactra helvetica . Donax tronchulus . So/en siliqua . Mya arenaria Lutraria elliptica Cytherea chione . Cardium edule

Gills

Mantle

0.031 — 0.087 0.017 0.013 0.007 0.008 0.017 0.037 0.038 0.030 0.044 0.009 0.022

0.035 0.033 0.022 0.0075 0.030 0.017 0.027 0.041 0.024 0.050 0.023 0.113 0.015 0.028

Sex organs

0.010 0.010 — 0.03 0.005 0.008 — 0.040 0.018 — 0.018 0.020 —

Kidneys Liver

Author

0.031 0.140 0.097 0.042

Wang-Tai-Si, 1928

— —

—

—

0.051 — 0.138 0.043 — 0.044 — —

—

0.015 0.049 0.050 0.066 0.044 0.017 0.032 — 0.047 0.063

„

99

99

99

„

99

99

99

99

99

99

99

99

99

McCance and Shipp, 1933 Wang-Tai-Si, 1928 „ „ „ „ 99

99

99

99

99

99

99

99

99

99

„

99

99

99

Wang-Tai-Si, 1928 „ 99

99

99

338

Memoir Sears Foundation for Marine Research

example, in Pinna squamosa. On the other hand, the muscles and sex organs are poorest in iron. In the muscular tissue, regardless of whether the blood of the mollusk contains haemocyanin or erythrocruorin, there is always the same amount of iron. A detailed examination of the data on the amount of iron in the organs of Lamellibranchiata shows that in some species an accumulation of iron of ten takes place along with an increase in copper, and sometimes with an increase in manganese. However, in other species with a considerable amount of iron, copper and sometimes manganese are completely absent; in the third group of species, on an average the iron is low while the amount of copper and manganese is higher. In the tissues of Pectunculus glycemeris, Solen siliqua, Mya arenaria, and others there is much iron together with a considerable amount of copper, as in the liver of Solen. At the same time, in the precordial gland of Pectunculus^ Mya, and others there is a good deal of iron (in some cases, as in Mactra, there is an accumulation of manganese). In Pectunculus and Solen the respiratory pigment is erythrocruorin, which contains iron. In Tellina, Wang-Tai-Si (1928) found no copper in the whole organism, but it is known that species of this genus (7\ planata, and others) contain erythrocruorin. Consequently, the connection between the amount of iron in the tissues and the presence of erythrocruorin in the blood of Lamellibranchiata is not sufficiently clear. Sometimes species with blood of haemocyanin, such as Venus, are as rich in iron as species with haemoglobin. Perhaps seasonal influences or other factors are at work here. Species like Dosinia, Venus, Tapes, and Cardium, with relatively high iron, also differ from Solen, Pectunculus, and others by their high amount of copper content. Systematic determinations of iron in the organs of Mollusca whose blood supposedly contains a large amount of erythrocruorin would be of great interest. These are: Area barbata, A. trapezia, A.pixata, A. tetragona, A.inflata, Pectunculus pilla, P.glycemeris, P. violacescens, Solen legumen, Solecurtus stritigillatus, Paramya cardita (aculeata ?), Tellina planata, T. capsa fragilis (Neomenimorpha ?), and probably many others (see Chapter XIX on erythrocruorin in Mollusca). The Anisomyaria (modern marine forms), in contrast to the others, have no species which contain an iron pigment in the blood. These species are typically marine, and by the characteristics of their blood they are closely related to the Cephalopoda.

TABLE 202 IRON IN THE LIVER OF LAMELLIBRANCHIATA (IN '/0 OF DRY MATTER) Liver

ORGANISM

Ostrea edulis Pecten jacobaeus Mytilus edulis . Tivella stultorum* . Lottia gigantea (?)* * Muscles.

. . . . .

. 0.011 . 0.020 . 0.016 . (0.64) —

Rest of body

Author

0.0018 .

0.004 — (1.07) (1.13)

. . . .

.

. . . .

.

. . . .

.

. . . .

Dastr^, 1898 »

»

T»

»>

Albrecht, 1920-1921, 1923-b »

M

»

Chemical Composition of Marine Organisms

339

The iron in Mollusca varies with age and changes with the seasons; this follows from certain observations on Ostrea edulis. The increase in the amount of iron in Ostrea edulis and of copper in other organisms was connected with the appearance of a green color.56 Kohn (1896, 1898) found that the amount of iron in "green oysters1' (French, American and German), varying from 1.8 to 4 mg in six oysters, is not proportional to the color. The concentration of iron, together with manganese and calcium, in the spherules of the pigmented tissues of Anodonta was noted by Dubuisson and Heuverswyn (1931). Mollusks easily extract iron from the medium (see Ranson). COPPER. The presence of copper in organisms was known to the alchemists,57 and in the first decades of the nineteenth century John (i 814), and especially Sarzeau (i 830), demonstrated its presence in various organisms. In marine organisms, particularly Mollusca, copper was found in 1833 in various species by Bizio ; four years later it was obtained by Bouchardat (1837) in Mytilus edulis. These observations were well known in European scientific circles of that time,58 but the works of Bizio, which were of great interest and which have not lost their significance up to the present time, were soon forgotten. However, 47 years later in 1879—1881, following the appearance of a number of new works which showed the wide distribution of copper in organisms, his son, G. Bizio, again published the forgotten work of his father. By this time the discovery of copper in the blood of Cephalopoda and Helix pomatia by Bibra (1846) and Harless (1847) was already known. For a long time this work influenced the direction of investigations on the distribution of copper and its physiological role in animal organisms. In recent years the study of the physiological role of copper has developed due to the work of Fischer and Hilger (1923) and other investigators. The investigation of the biochemistry of copper in Mollusca and other organisms, begun almost 100 years ago, is vigorously pursued at the present time. The discovery of the formula for the porphyrins and the clarification of the connection of porphyrin with copper metabolism showed that the presence of copper in organisms had a broader significance, the result being that scientists from many different fields were drawn to the problem. Here we will confine ourselves to the study of copper in Mollusca, for in Chapter XIX we will return to the respiratory blood pigments of the invertebrates; also, we will examine more closely the distribution of these metal-bearing pigments in different representatives of the invertebrates. From the geochemical point of view this is an important problem because it indicates indirectly the participation of invertebrates in the migration of copper and other elements. Marks (1938), observing the copper toleration of different Mollusca, showed that the amount in these organisms changes with their size and age. In Octopus bimaculatus (Cephalopoda) the amount of copper increases linearly with the weight, i. e., the con56. Some investigators associated the coloring with chlorophyll (the pigment of the diatoms), others with the amount of copper. 57. See Margraf (1768); Hierne (1753) detected copper in plants. 58. On the work of B. Bizio, see Journal de chim. Med. (1833), 10: 102.

23

340

Memoir Sears Foundation for Marine Research

centration of copper remains almost the same. In Haliotis fulgens, H. crackerodia, H. rufescenSj and Helix aspersa, the amount of copper increases with age and the concentration becomes higher in large specimens. In Mytilus californica the amount of copper decreases with age and with increase in size. Marks (1938) placed various Mollusca in sea water with different amounts of copper and observed which organisms could tolerate the strongest concentrations. The most resistant proved to be Paphia staminea var. laciniata^ which lived 30 days with a concentration of i o mg per kg water, while Haliotis fulgent, Astrea undosa, and others died in 3 to 5 days when the copper concentration was o.i mg per kg water. Gaarder (1932) found that even 0.02 mg/1 of water interferes with the development of Astrea. COPPER IN CEPHALOPODA. In 1816 Erman observed a blue color in the blood of Cephalopoda, as in Sepia, and in 1833, B. Bizio showed the presence of copper in the tissues of Sepia officinalis, expressing the opinion that copper is bound with an organic substance. However, as already mentioned, the work of Bizio (1833) was forgotten for about 47 years, and during that period, Bibra (1846) and Harless (1847), being unfamiliar with Bizio's work, discovered copper but no iron in the blood, liver and other organs of Cephalopoda, namely Eledone; these workers also supposed that copper in the blood was bound with a protein. Following the discoveries by Bibra (1846) and Harless (1847), copper was shown qualitatively by Schlossberger (1854-1856, 1857), Gorup von Besanez (1874-1875), and others. Other investigators were drawn to the study of the respiratory blood pigment of Cephalopoda and other Mollusca, and it was shown that this pigment, which contains copper, gives the blood its blue color. Frdddricq (i878-c) was the first to isolate from the blood of invertebrates a pigment con-

TABLE 203 COPPER TOLERATION OF MOLLUSCA, FROM MARKS, 1938 Mg/Cu 2idded to x kg sea water

ORGANISM

O

O.O5

O.1O

0.15

0.20

Survival in days

Acmea scabra var. Kmatula . Fusinus kobelti Astraea undosa . Haliotis fulgins Ischnochiton conspicuus * * , Mytilus californica Mytilus edulis Tcpula vallina . Tegula viridula var. ligulata Paphia staminea var. laciniata * Died at the end of this period.

16* 60

*

*

*

,

.

30 30 60 30 35 60 60 100

—

14* 30

— — 60 60 —

3* 60 5* 3* 60 60 35 15* i \j 25* —

— — 10*

3* 8* 5* 1*

L\J

*J

30 —

2* 17*

— — —

ft* 18* —

O

Chemical Composition of Marine Organisms

341

TABLE 204 COPPER IN MOLLUSCA (IN %)

ORGANISM

Comments

Ostrea e dull 3 maximum minimum green maximum minimum Ostrea lurida Crassostrea virginica maximum minimum average . maximum minimum maximum minimum average . maximum minimum average . maximum minimum average . maximum minimum average . maximum minimum average . maximum minimum average . maximum minimum average , green . Crassostrea virginica n

..... ..... ...... ..... ..... , , .

.

.

.

.

.

.

.

.

.

.

.

-

,

,

.

.

. .

, .

.....

..... ..... 16 . ..... ..... * . ..... 13 . ..... ..... 37 . ..... ..... 14 . ..... ..... 20 . ..... ..... 10 . ..... ..... 13 . ..... ..... 10 . 3.

.

.

. .

.

.

-

.

,

. .

2.

* See Hiltner and Wichmann, 1919.

Living matter

0.1000 0.004 0.330 0.0352 0.0025 0.001240

0.0158 0.0017 0.0081 0.1487 0.002 1.0161 0.0029 0.0073 0.0539 0.0064 0.0225 0.0214 0.0028 0.0098 0.0089 0.0024 0.0119 0.003 0.0006 0.0016 0.0362 0.0016 0.0079 0.0131 0.0008 0.0031 —

—

—

Dry matter

Ash

—

—

Locality

Author

England

Orton, 1924

Kohn, 1898 U.S.A. (Pacific) .

— —

New York, Maryland, U.S. A U.S.A. . . » New York, U.S.A. . . „ . . — [ Connecticut, — U.S.A. . ,

»

»

Nilson and Coulson, 1939 Hiltner and Wichmann, 1919 Elliot" 1915 •"

— [ Maryland, — U.S.A. . , Georgia, New York, Virginia, U.S.A. New York, Black, 1915 Maryland, U.S.A. . . [ New York, Harrison, 1915* Mass., U.S.A. Mass., U.S.A. Feldstein, 1917*

2.72

—

0.0231

0.487

—

New Jersey, U.S.A.

U.S.A. .

Nelson, 1915

Nelson, 1925 McHargue, 1924 (continued next page) 23-

342

Memoir Sears Foundation for Marine Research Comments

ORGANISM

Crassostrea virgmica Crassostrea gigas . Pecten maximus . Pecten fumatus Pecten circularis laquisulcatus Modiola modiola * Aeolidia papillosa Pleurobranchus plwnula . Purpura lapillus . Helix aspersa

Dry matter

0.00313

—

0.001230 — 0.00001

— — —

0.00031 0.00240 Gonads _

. . . . .

jj

»

Mantle

Living matter

_

— —

— —

0.00163 0.0107

Ash

Author

Locality

U.S.A. (Atlantic) — Japan 0.007 England . — Australia U.S.A. (Pacific) 0.008 England . 0.015 „ . 0.02

0.6 0.6

—

"

»

0.0108 ft ftftflj \j.\j\j*j

0.0561

.

Body .

0.0024

—

—

England .

„

,

Inner organs

0.015

—

—

n

—

0.02

u

.

.

.

drchidoris montereyensis

2 . .

.

.

.

*

Archidoris undosa Littorina littorea .

Littorina neritoides Littorina rudis * Lacuna vineta Patella vulgata Patella athletica ,

—

0.00013 0.00059 Podium Gonads, liver

Littorina littoralis

—

0.00156

0.00252 0.00473

Gonads, liver

0.00913

Without radula

—

0.00080 0.00283 0.00177 —

Podium

Podium Gonads, liver

—

0.0102 0.0031 0.0081 0.0081 0.00097 0.00067

»

u

U.S.A. (Pacific) England

—

—

—

0.6

w

w

»

»

»

»

Marks, 1938

U.S.A. (Pacific)

Blood .

.

—

w

Webb, 1937

»

.

w

Webb, 1937 Clements and Hutchinson, 1939 Marks, 1938

—

Helix pomatia drchidoris britannica . .

Nilson and Coulson, 1939

—

*

*

*

*

»

>»

Guillemet and Sigot, 1933 McCance and Masters, 1937 » »» Webb, 1937 McCance and Shackleton, 1937 Marks, 1938 McCance and Shackleton, 1937

Webb, 1937 McCance and Shackleton, 1937

Chemical Composition of Marine Organisms ORGANISM

Comments

Calliostoma zizyphinum ,

Podium » • • Gonads, liver Buccinum undatum Podium Gonads, 11 11 liver Nucella lapillus Podium Gonads, 11 i» liver Scaphander lignarius , Aplysia punctata . Without radula yorruna tormentosa Polypus bimaculatus , jlstrea sp. . Chione undatella . 11 11 Donax gouldii .

.

Ischnochiton conspicuus 11 11 i» 11 Navanax inermis . . . Mytilus edulis . i» i» i» 11 Mytilus obscurus . Pa phi a staminea var. laciniata 11 11 11 11 i» Tegula gallina Tegula viridula viligulata

t

t

T nli on co

Dry

matter

Ash

0.0054 0.0110

.— -—

— —

0.00055 0.0548

— —

— —

— —

— —

—

—

—

—

0.0015 0.0053 0.00050 0.0007

0.00216 — 0.00315 0.0156

,

—

—

0.00434 0.00094 0.00124 0.00041 0.00044 0.00103 0.00097 0.00108 0.00498 0.00017 0.00238 0.0012 —

— — — — — — — — — — — —

0.00021 0.00168

—

0.00018 0.00018 0.00024 0.00061

— — — —

0.00126 0.00012 0.00020 0.00006 0.00007 0.00037 0.00025 0.00028 0.00044 0.00023 0.00037 — 0.00002

0.00144 0.000148 0.00238 0.00203

0.00061 0.00031 0.00032 0.00021 0.00023

.

•11 Tivela crassatellmdes

Venus mercenaria Saxostrea commercialis

Living matter

0.00230 0.00325 0.00593 0.00119 0.00139 0.0016 .— 0.00003 0.0158

— — — — — — —

Locality

343

Author

England . „ . 11

. .

'

'

'

-

11

'

'

11

••

McCance and Shaclcleton, 1937

»

rt

11

11

11

11

w

1>

11

11

U.S.A. (Pacific)

Marks, 1938

11

W

11

w

11

11

»

11

,1

n

11 11

'

'

11

11

W

tt

11

11

11

11

»

11

„ U.S.A. . Australia

. *

U.S.A. (Pacific)

11 11 McHargue, 1924 Clements and Hutchinson, 1939 Marks, 1938

n

"

*

11

11

11

•

-

11

11

11

11

11

11

11

11

•

•

f

11

*

«

U.S.A. . Australia

, .

.

.

11

11

11

11

McHargue, 1924 Clements and Hutchinson, 1939 Bertrand, 1943-c

344

Memoir Sears Foundation for Marine Research

taining copper; he called it haemocyanin. The blood of all Cephalopoda contains haemocyanin, which has an influence on the total amount of copper in the tissues and organs. Subsequently we will examine the distribution of haemocyanin among Mollusca, its chemical properties, the copper content, and so forth. Bibra (1846) and Harless (1847), determining copper in the liver of Eledone, gave 1.12 % in the ash, and Henze (i9Oi-b) and others showed clearly that the liver of Cephalopoda contains the most copper. Henze did a detailed study of copper in the liver of Octopus vulgaris, and he showed that copper occurs in a compound with organic matter which can be extracted by various solvents and which contains up to 0.48 °/0 copper; a nucleoproteid of the hepatopancreas contained 0.96 % of the element. The amount of copper as well as iron in the liver evidently increases during growth. Schmidt-Nielsen and Flood (1926-1928) found 84.5 mg copper in 100 g of dry liver from Architeuthis dux. From the work of Wang-Tai-Si (1928) and Cunningham (1931) we can obtain a reasonably good though still incomplete picture of the distribution of copper in other organs of Cephalopoda; their data are so interesting that we give most of them herewith. Copper was indicated qualitatively by Fox and Ramage (1931) in Loligo forbesii and others. It is present in all organs of Cephalopoda. There is more copper than iron in the liver, and there is a small amount of manganese. Also in the other organs of Cephalopoda copper often predominates. The muscles, with relatively more iron, are poorest in copper. These observations confirm again the physiological significance of iron for organisms with haemocyanin blood. Bibra (1846) and Harless (1847) found copper in the eggs of Eledone, and Dubois found up to 8 X io~ 4 °/o in fresh specimens of Sepia officinalis eggs. According to Wang-Tai-Si (1928), who worked on the eggs of Sepia officinalis, there was up to 2 x io"* % in the fresh material and up to 5 x io"3 % in the ash ; there was no copper in the shell. Ranzi (1935) discovered a considerable amount of copper in the embryo of Sepia officinalis, and Kamachi (1936) found from 1.9 X io~ 3 to 2.9 x icr3 °/o in the

TABLE 205 COPPER IN THE LIVER OF CEPHALOPODA (IN °/0) ORGANISM

Octopus vulgaris Octopus vulgaris 9

France (Atlantic) Wang-Tai-Si, 1928 99

99

99

99

99

99

Lindow, Elvehjem and Peterson, 1929 France (Atlantic) Wang-Tai-Si, 1928 99

99

99

99

JJ

JJ

19

19

19

19

99

99

99

JJ

99

9J

J»

99

99

9J

JJ

99

J>

JJ

99

99

99

99

JJ

99

99

JJ

99

99

99

JJ

JJ

99

JJ

99

jj

99

19

99

99

99

U.S.A. (Pacific) Severy, 1923 France (Atlantic) Wang-Tai-Si, 1928 99

99

19

99

99

9J

JJ

99

99

99

19

99

99

99

19

99

99

JJ

99

19

99

99

J9

99

99

99

99

99

99

99

U.S.A. (Pacific)

Rose and Bodansky, 1920 France (Atlantic) Wang-Tai-Si, 1928

Severy, 1923 Phillips, 1922 Dubois, 1900 Bertrand, 1943-c

354

Memoir Sears Foundation for Marine Research

So/en ensis contains no copper. The blood of Solenidae also contains homologues of haemoglobin as respiratory pigments (see also Chapter XIX). According to a number of analyses (see Table 213), although haemocyanin has been shown to be present in My#, these organisms contain only irregular amounts of copper. Rose and Bodansky (1920) found no copper in Mya, whereas the organisms are always rich in iron. Species similar to Mactra contain copper in the liver only, and the same is true of Donax. They are all rich in iron. In addition to the liver, a relatively large amount of copper has been observed in the mantle and gills of Lamellibranchiata, and it should be noted that there is more copper in the connective tissue of the liver than in the glandular tissues; the opposite is true of zinc. Wang-Tai-Si (1928) gave data showing the enrichment of copper in the precordial glands, for example in Venus and Mytilus. Sometimes a good deal of copper occurs in the siphon of Pecten and Donax. However, future investigations will determine the extent to which one may generalize from these observations. Perhaps at a certain time the supply of copper is shifted from one organ into another in Mollusca. It is interesting that Pectunculus glycemeris^ whose blood contains a respiratory pigment with iron, contains rather a good deal of copper in all its organs. The muscles of Lamellibranchiata contain little copper or none at all. With but few studies having been done on the blood of these organisms, the data on copper are fragmentary. In the majority of cases the blood of these mollusks is quite

TABLE 214 COPPER IN VARIOUS ORGANS OF LAMELLIBRANCHIATA (IN % OF LIVING MATTER)

ORGANISM

Mantle

Muscle

Crassostrea virginica*

0.0036 0.00029 0.00036 0.00069 0.00036 0.0013 0 0 0.00023 0.00104 0.00055 0.00023 0.00052 0 0 0.00025

0.00

»

»

Crassostrea angulata . Mytilus edulis Pecten jacobaeus . Pectunculus glycemeris. Mactra helvetica . Donax tronchulus . Penus -uerrucosa . Penus mercenaria Tapes decussatus . Cytherea chione Cardium edule Mya arenaria Lutraria elliptica Solen siliqua . . .

.

—

0 0.00053 0.00008 0.0000 — 0 0 —

0 0 0

—

— —

Gills — 0

0.00034 — 0.00025 0.00057 0 0 0 0.00077 — 0 0.00001 0 0

Intestines Liver 0.0035 — 0 —

— — — — — — —

— — — — — —

* Analyses by Rose and Bodan:iky (1910); all other analyses by Wang-Tai-Si

0.0007 0.00208 0.00146 0.00132 0.00054 0.00222 0.00075 0.00236 0.00207 0 0.00174 0.00037 0 —

(1928).

Sex

organs

—

0 0.00121 0.0012 — 0.00125 0 — 0.00035

0.00267 0 0 0 0

—

Precordial glands — — — — —

0.00306 0 — 0.00463 — — 0.00119 — 0 — —

Chemical Composition of Marine Organisms

355

TABLE 215 ZINC IN CEPHALOPODA (IN %)

ORGANISM Sepia officinalis

Living Comments matter

Dry

matter

Author

0.0077 0.07727 0.01753 0.01443 0.01172

Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928

,

,

,

.

.

Whole 18 M.\J eggs ^550 Liver

Octopus vulgaris Loligo vulgaris .

.

.

.

.

Whole

0.0013

0.00636 0.00696 0.00532 0.00283

99

99

99

99

colorless, except for species which contain pigments of the haemoglobin type. The amount of copper in the blood is of the same order of magnitude as in Gastropoda. More than half of the copper in the blood of Lamellibranchiata is found in a dialyzed state, whereas more than half of the total iron, zinc and manganese does not become dialyzed. ZINC. Determinations of zinc are all recent. Since the analyses present certain difficulties, there are fewer data for zinc in Mollusca than for manganese and copper. Zinc often predominates over copper in organisms, and in Mollusca and some other invertebrates it is sometimes found in greater quantities than are manganese and iron. The first demonstration of the presence of zinc in Mytilus edulis may be found in the work of Forchhammer (1852). In 1904 the work of Bradley appeared, and then the study of Mendel and Bradley (1905) on zinc in Sycotypus canaliculatus (Busycon canaliculatus"). It was only after World War I that the distribution of zinc in organisms was studied in Mollusca in particular; these investigations were carried on chiefly by Birckner (1919), Delezenne (1919), Hiltner and Wichmann (1919), Bodansky (1920), Phillips (1922), Bertrand and Vladesco (1923), Severy (1923), McHargue (1924), Wang-Tai-Si (1928), and Webb and Fearon (1937). ZINC IN CEPHALOPODA. The determinations are isolated, but in comparion with other Mollusca, the amount of zinc in this group is not exceptionally high. There is somewhat more in the liver of Sepia officinalis and in the eggs of the same species (see Table 215). ZINC IN GASTROPODA. Bradley (1904) found this element in Sycotypus canaliculatus and in other Gastropoda, such as Fulgur carica. Mendel and Bradley (1905) isolated a protein containing 0.7 °/0 zinc and 1.2 % copper from the blood of Sycotypus canaliculatus, and they concluded that the zinc-organic complex, haemosycotypin, can have a respiratory function. But Redfield (1933) has shown recently that haemocyanin is the respiratory pigment in Sycotypus^ and consequently zinc in the organic complex is connected with some other physiological function of Sycotypus. According to Mendel and Bradley (1905), the amount of zinc in the liver of Sycotypus canaliculatus varies from 8.69 to 18.79 % of the ash. Different parts of the liver of Sycotypus contain different *+

356

Memoir Sears Foundation for Marine Research

amounts of zinc; for example, in the ash of the connective tissue of the liver there is 8.49% zinc and 26,5% copper, while in the glandular tissue there is i $.o$Q/t7,inc and 3.11 % copper. Thus it is apparent that the glandular tissue of the liver contains more zinc; it has been supposed that zinc is connected with the glandular tissues and their nucleoprotein metabolism (see Delezenne [i9i9])- BH In other Gastropoda there is a tendency toward localization of zinc in the hepatopancreas. In Table 216 it is seen that zinc is present in Gastropoda in more or less equal quantities. Although the liver of the Pulmonata is somewhat enriched in zinc (cf. the amount of manganese, iron and copper), these organisms contain a relatively small amount of the element. Webb (1937) found 2.5 °/0 in the ash of Purpura lapillus, i °/0

TABLE 216 ZINC IN GASTROPODA (IN %) Living Comments matter

ORGANISM

0.0038 0.00494 99 99 Littorina obtusata , 0.00563 Patella vulgata . 0.00430 0.00389 99 99 Haliotis tuberculata . 0.00515 Haliotis cracker odia . 5 0.002412 Trochus crassus . 0.00653 Trochus ombilicalis . 0.00407 Buccinum undatum . 0.00497 Murex tronchulus * 0.00532 Purpura lapillus 0.00456 Limax maximus 0.00310 Crytochiton stelleri . 17 0.001267 Fasciolaria gigantea . 2; liver — Cassis sp 2 — Strom bus bituberculatus . — Strombus gigas , 2 — 2; liver — 99 » — Fulgur perversus Littorina littorea

Terrestrial species Helix pomatia . 99

99

Helix aspersa 99

99

Helix pisana Arion flaws .

Liver

* •

.

* .

0.00168 — 0.00175 0.0026 0.00093 0.0011

Dry matter

Ash

0.0152 0.02508 0.02514 0.0162 0.01596 0.0244 — 0.02690 0.01805 0.01603 0.01398 0.01603 — — 0.0316 0.00660 0.0055 0.0180 0.0188 0.0308

— 0.1277 0.10076 — 0.08169 0.14550 — 0.11176 0.07077 0.14816 0.05807 0.08623 — — — — — — — —

0.00623 0.0366 0.00969 0.0145 0.00518 0.00545

0.02630 — 0.06738

— 0.02677 0.02006

Author

Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928 99

99

99

9*

99

99

99

99

Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928 Severy, 1923 Wang-Tai-Si, 1928 99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

Severy, 1923 99

99

Phillips, 1917 99

99

99

99

99

99

99

99

99

99

Wang-Tai-Si, 1928 Delezenne, 1919 Wang-Tai-Si, 1928 Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928 9)

99

99

5H. A modern review of the functions of zinc in mammals is given by Vallee and Altschule (1949).

99

Chemical Composition of Marine Organisms

357

TABLE 217 ZINC IN LAMELLIBRANCHIATA (IN %)

No. of

ORGANISM

analyses

Mytilus edulis 99

99

99

99

.

Mytilus calif ornica . Ostrea edulis 99

»

*

Ostrea lurida Crassostrea virginica 99

-

. . . .

153

99

99

99

-

99

-

Crassostrea angulata 99

Penus verrucosa 99

4 2 8 5

. 4

99

A^HHJ mercenaria . A^HHJ kennicotti . Tapes decussatus 99

. *. *.

99

Tapes aureus Cardium edule . 99

»

Cardium norvegicum Cytherea chione . 99

9 9

Pecten jacobaeus 99

•

99

'

Pecten jacobaeus * . Pecten maximus . Pecten varius . Mya arenaria * 99

99

. .

- 2 . 2 ,

. 2 ,

. 2

*

Pectunculus glycemeris , Tellina crassa Tellina tenuis Mactra helvecea , Mactra corallina , Donax tronchulus Scorbicularia piperata , , Dosinia exoleta , Lutraria elliptic a . . . 3 Ensis americanus Unio sp.f * Liver.

•

Living matter

Dry matter

0.0021 0.00413

0.0113 0.02322 0.0106

— 0.0049 0.02010 0.03095 0.006497 0.02598 — —

0.00993 0.05966 0.0033 0.00470 0.00451 0.00051 0.0017 0.00435 0.00450 0.0014 0.00455 0.00383 0.00490 0.00277 0.0086 0.00268

—

0.00586 0.00520 0.00391 0.0077 0.00255 0.00799 0.0157 0.0062 0.00523 0.0174 0.00526 0.0074 0.00946 0.001163

—

Ash —

0.11487

— — —

—

0.11460 0.1458

0.7797

— — —

— 0.1—

0.006(?) 0.4966 0.38296 0.0127 0.02447 0.033450

—

0.0102 0.02539 0.02938 0.0066 0.03255 0.0160 0.01851 0.01660 0.435 0.01605 0.0439 0.04422 0.03138 0.02533

—

—

1.48625

—

0.13234 0.14870

Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928 Delezenne, 1919 Severy, 1923 Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928 Severy, 1923 Bodansky, 1920 Hiltner and Wichmann,1919 Skinner and Sale, 1930 Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928 Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928 99

99

99

99

99

99

»»

ft

— —

Severy, 1923 Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928

—

Bertrand and Vladesco, 1923 Wang-Tai-Si, 1928

0.15329 0.12802 0.07603 0.14094 0.07131

— —

0.08141

—

0.16178 0.10987 0.09540

—

0.01142 0.06424 0.03691 0.02886 0.0546 0.10058 0.04045 0.02338 0.05850

0.02589 0.10948 0.21428 0.09669 0.10744 0.2169 0.08172 0.11918 0.18194

0.0160

— —

—

Author

99

99

99

99

99

99

99

99

Bertrand and Vladesco, 1923 99

99

99

Wang-Tai-Si, 1928 Delezenne, 1919 Wang-Tai-Si, 1928 99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

99

59

99

99

99

99

99

99

99

99

99

99

99

99

99

9*

99

Bodansky, 1920 Wang-Tai-Si, 1928

Severy, 1923 Phillips, 1922

f Fresh water. 24*

358

Memoir Sears Foundation for Marine Research

in Pleurobranchus plumula, and i.5°/o in Aeolidia papillosa. According to Yamamura (1934), Fivipara japonica contained up to 0.0678 °/o z*nc and up to 0.00061 °/0 arsenic. See also Blasius. ZINC IN LAMELLIBRANCHIATA. Since there are somewhat more data for Lamellibranchiata than for Gastropoda, it is possible to study the distribution of zinc in different species. The zinc in at least some species of Lamellibranchiata is considerably higher than in Gastropoda, and it is certainly higher than in Cephalopoda. An exceptional concentration of zinc has been observed in Ostrea, where it occurs in organic complexes. Orton (1924), studying oysters from the shores of the English Channel region, found that the amount of zinc fluctuates from traces to 0.78 °/o> especially in afflicted oysters; usually there is 0.03 to 0.04 °/0, which is greater than the amount of copper. Earlier analyses of oysters were done by Dieulafait, who found up to 0.0139%. Hiltner and Wichmann (1919), investigating more than 150 oysters from different parts of the Atlantic Coast of the United States, always found a large amount of zinc, which varied from o.i 137 to 0.2298 % of the dry matter. Hubbell and Mendel (1927), also observing oysters from the United States, found 0.0286 to 0.0412 °/0; but in Mya arenaria there was only 0.0015 to 0-00221 °/0 zinc. It is of interest to note the data of other investigators who show that in another species of the family Ostreidae, namely Crassostrea angulata^ there are also large amounts of zinc. As a rule all figures for zinc in Ostreidae are high, but possibly oysters living in water that is polluted with copper and zinc salts accumulate these metals. Only a special investigation can probably show how much of those marked variations in zinc can be attributed to such a factor. Certainly Ostrea from different localities, always richer in zinc than any other Mollusca, contain varying amounts of the element. Zinc is present in all organs of Ostrea^ and according to Bodansky (1920), half of it occurs in the form of a metallo-organic compound. In the blood of Mytilus edulis there is also bound zinc in an amount up to 60 %. Zinc distribution in the organs of Ostrea is given in Table 219. Koga's (1934^) determinations of zinc (in %) in different organs of Ostrea are interesting also, since they confirm earlier observations that this element is concentrated particularly in the gills and testicles: Ostrea laperousii

Living matter

Dry matter

Whole Hepatopancreas Mantle Gills Muscles Other tissues

0.006 0.00657 0.0070 0.0134 0.0043 0.0115

0.0410 0.0245 0.00500 0.1002 0.0233 0.0661

The muscles contain the smallest amount of zinc. Bertrand and Vladesco (1923) noted the large quantity in the so-called "bosse de polichinelle" of Pectenjacobaeus, the amount being four to five times more than in other organs of this mollusk. The amount in Mollusca increases with age, although the very young organism, particularly its liver,

Chemical Composition of Marine Organisms

359

is often rich in zinc. Webb and Fearon (1937) found 0.3% in the sex products of Pec fen maximus and 0.6 % *n the mantle. As a result of this survey, we may conclude briefly that various Mollusca react differently in accumulating zinc. Cephalopoda and the majority of Gastropoda contain TABLE 218 ZINC IN CRASSOSTREA VIRGINICA ORGANISM

Fresh matter

Crassostrea virginica maximum . minimum . average (16).

0.1168 0.0133 0.0652

maximum . minimum . average (13).

0.1102 0.0280 0.0658

maximum , minimum , aveiage (31).

0.062 0.0026 0.0200

maximum minimum average maximum minimum average maximum minimum average

0.2298 0.028 0.1153 0.1309

. . (37). . . (14). . (18).

Locality

Author

New York and Maryland

Hiltner and Wichmann, 1919

M

»

»

»

99

Connecticut, Massachusetts, and New Jersey

99

0.0730 0.0089 0.0020

0.441

0.0779 0.0146 0.0383

maximum , minimum > average (13).

0.1220 0.0398 0.0829

maximum . minimum » Crassostrea virginica Mytilus e dull 3

0.1026 0.0224 0.4284 0.0750

99

99

99

99

99

99

99

99

99

99

99

99

99

99

*

Connecticut

.

99

'

Maryland

,

'

Sale, 1914 (see Hiltner and Wichmann, 1919) '

'

*

Elliot, 1915 (see Hiltner and Wichmann, 1919)

,

n.iMQ

New Jersey, Virginia, New York and Maryland

99

99

99

99

99

99

99

99

99

99

99

99

99

99

Black, 1915 (see Hiltner and Wichmann, 1919)

99

99

99

99

99

99

99

99

New York, Connecticut, Massachusetts and other states

Harrison, 1915 (see Hiltner and Wichmann, 1919)

99

99

99

99

99

99

99

99

99

9»

99

99

Massachusetts

USA

99

99

Maryland

99

99

Elliot, 1915 (see Hiltner and Wichmann, 1919)

0.017

maximum . minimum . average (10).

Vtnu r mrrrpnnrtn

AND OTHER MOLLUSCA (IN •/„)

.

•

Feldstein, 1917 (see Hiltner and Wichmann, 1919) -

•

»

. . . .

McHargue, 1924 99 ••

99 M

360

Memoir Sears Foundation for Marine Research

the smallest amounts of zinc, while some Lamellibranchiata are very rich in the element. In general, Mollusca and Crustacea are the richest in zinc and copper when compared with other invertebrates. 16. Other Metals The data on the distribution of copper, zinc, iron, and manganese show that there are various species among these organisms which concentrate certain metals; some species, such as those of the Unionidae, concentrate manganese, others, such as those of Cephalopoda and Ostreidae, concentrate copper or iron and zinc, or all of these elements at once. These data lead one to assume that similar phenomena might be discovered for other elements, and the data given hereafter confirm this assumption. However, although there are hundreds of determinations of copper, zinc, and iron, very little is known about other metals in Mollusca. Forchhammer (1852) was the first to note the presence of rare elements such as silver and lead in these organisms. Although the number of observations on silver in invertebrates is always growing, the order of magnitude of lead in Mollusca and other invertebrates is still not clear. Nickel is not concentrated in these organisms, but concentrations of tin, cadmium, titanium, lithium, boron, lead, molybdenum, gold, silver, aluminum, strontium, barium, and rubidium have been found in Mollusca. Much of this material requires verification, and more quantitative determinations are needed. RARER ALKALINE AND ALKALINE-EARTH METALS. There is relatively little known about the distribution of rubidium and cesium in marine organisms, although the question of their distribution in the sea has attracted the attention of many geochemists up to the present time (see Goldschmidt, Herman, Hauptmann, and Peters, 1933). Sonstadt's (iSyo-b) observations on these two elements in various marine organisms, particularly in the shells of Mollusca, deserve no attention. Ramage (1929) showed by spectroscopy the wide distribution of rubidium in nature, particularly in organisms. Fox and Ramage (1931) gave the first quantitative determinations of rubidium in marine organisms (in °/0) : Loligo forbesii Sepia officinalis drion attr (liver) Archidoris tuberculata (mucus glands) Aeolidia papillwa Helix aspersa (liver)

trace trace 0.002 up to 0.002 0.002 up to 0.002

Regarding Helix aspersa^ they noted that the amount of rubidium in the organs varies according to the region. They did not detect cesium in the Mollusca which they studied. There is about io~ 4 °/ 0 lithium in sea water, and according to our data there is up to n x io~ 3 °/0 in the water of marine silts. Lithium is found in all marine organisms, and it has been shown qualitatively in Mollusca by Ranzi (1929) and Webb (1937).

361

Chemical Composition of Marine Organisms TABLE 219

ZINC IN VARIOUS ORGANS OF AMPHINEURA AND LAMELLIBRANCHIATA (IN »/„ OF LIVING MATTER) *

Intestinal glands Mantle

Other organs

ORGANISM

Muscle

Cryptochiton stelleri Crassostrea virginica Crassostrea angulata

0.00187 0.0003 0.0040 0.0160 0.0237 0.0267 0.0269 0.1074 0.0652 0.3223 0.0312 0.005 0.0043 0.0086 0.0082

Pecten jacobaeus

Gills

Author Severy, 1923 Bodansky, 1920 Bertrand and Vladesco,

»

»

i»

1923 »

Gerard and Meurin (1908) found 0.00012 °/0 in oysters ; according to Fox and Ramage (1931) there is 0.0002 °/0 in the dry matter of the Pecten mantle and 0.00008 °/o *n the liver. In freshwater Anodonta from four localities, lithium was present only in traces or was not detected at all. In Arion, Helix pomatia and Helix aspersa it was discovered qualitatively. Evidently lithium is a common element in Mollusca and other organisms. For earlier indications, see Griffiths (1890-1891) on Anodonta. The wide distribution of strontium and barium in marine organisms is shown in the data that have already been given in earlier chapters. Strontium was found in shells long ago, as shown in the work of Moretti (1813), Vogel (1814), Forchhammer (1852), Dieulafait (1877), and Schmelck (1901). Quantitative spectroscopic determinations of strontium have showed the element to be present not only in the shell but also in the soft parts of Mollusca. Fox and Ramage (1931) investigated 65 samples of ten species of Mollusca and found strontium in all of them. Quantitative data are given in Table 2 20. The strontium in the soft parts of Mollusca is of the same order of magnitude as that in sea water,62 and no great concentration has been found. However, the differences in the amount of strontium in different species, apart from individual variations, are being investigated. Archidoris britannica, without shell, has a high strontium content, while in freshwater Anodonta there is little strontium. In the soft tissues the element was not detected everywhere. In the shell, according to our data, there is less strontium than in various marine Mollusca, the shell usually containing about n x io-1 to n x io"2°/0. Noll (1934), on the basis of his own analyses and earlier observations, found that there is always more strontium in the aragonite limestones than in those of calcite. Although this rule cannot be applied to the shells in a strict sense (for more details see Section 9* in this chapter), it is valid for them along main lines. Some exceptions to this rule deserve special attention. The calcite alga Lithothamnium contains 2 x i o ~ l o / 0 strontium, i.e., similar to the amount in aragonite skeletons of marine organisms rich in strontium. However, the aragonite shell of the freshwater mollusk Anodonta contains but little strontium, and its soft parts contain less than those of other Mollusca. Ap62. According to Desgrez and Meunier (1926), there is 0.0007 % strontium in sea water. Thomas (see Thompson, 1932) found 0.0013 % (^h *9 °/o chlorine). Noll (1934) gave 0.0007 °/o Sr. According to our data there is o.ooi °/0 (with i9°/ 0 chlorine). Odum (i95i-a) finds 0.00081 or 9.23 atoms strontium per 1000 atoms calcium.

362

Memoir Sears Foundation for Marine Research

parently, besides the mineralogical character of the skeleton, the chemical composition and the medium in which the mollusk lives are of some significance.83 Thomas, whose work (unpublished data) is discussed by Thompson and Robinson (1932), has investigated a large number of shells from Borneo, the Philippine Islands, and other localities, and he has found a Sr/Ca ratio close to that of sea water. There is considerably less barium in Mollusca, and it occurs chiefly in the shells. Potapenko (1925), in determining barium spectroscopically in the shells of Astarte borealis, Tellina calcarea^ and Neptunea despecta, found 0.005 to 0.05 °/o- We always

TABLE 220 STRONTIUM IN THE ORGANS AND TISSUES OF MOLLUSCA (IN °/0 OF DRY MATTER) Parts of organisms

ORGANISM

Limacina retroversa . whole podium Aplysia punctata . blood . n Sepia officinalis . n n * ' Haliotis tuberculata . Helix pomatia Helix aspersa Archidvris tuberculata

, .

.

ink sac . shell of eggs podium . sex products . 91

ft

body wall

. , .

. , . . - . . . . , . . , . .

Sr

Author

0.008 0.008 0.004 0.002 0.008 0.008 0.006 0.008 0.0008 0.008

Fox and Ramage, 1931 n n n n n n n n n n n n n n n n n n n n n n n n n n n n » » ft »» ft

Shelb of organisms J. T UtU 11 U*

J/V/rtJ/tt

*M J

Pinna squamosa . Bui I a ampulla Dentalium sp. Mytilus edulis Pecten islandicus . n n Cardium edule Purpura lapillus . Neptunea sp. . Buccinum undatum Helix pomatia"\ , Anodonta cygnea^ Astarte crenata + Artarte borealis . Tellina calcarea . Neptunea despecta t Terrestrial.

1~ V/ll, A J\J I

. calcite predominates 0.04 . aragonite + calcite . 0.2 . aragonite . . . . 0.2 . calcite

.

.

0.2

. .

. aragonite .

-

. 0.5 Of\fi

09 . 0 2

. .

09

09

.

.

,02

.

0.08 Or;

0.05* 005 005 § Fresh water.

63. Fresh water usually contains about io~ 6 o / 0 strontium.

»»

ft

Vinogradov ft Potapenko, Vinogradov

and Borovik-Romanova, 1934 n n » n 1925 and Borovik-Romanova, 1934

ft

n

n

»»

»»

ft

rt

ft

ft

n

n

»

>>

»»

»»

ft

n

n

ft

ft

n

n

ft

Potapenko, 1925 n n rt n

n

n

0

Maximum.

Chemical Composition of Marine Organisms

363

TABLE 221 STRONTIUM AND BARIUM IN MOLLUSCA (IN % OF ASH RESIDUE) ORGANISM

Comments

Helix aspersa . Helix pomatia . Littorina littorea . Purpura lapillus . 99

99

•

Pleurobranchus plumula Aeolidia papillose . Archidoris britannica , 99

91

99

99

Modiola modiola Pecten maximus 99

>»

. '

Pecten islandicus . Mytilus edulis Buccinum undatum Neptunea despecta . Astarte crenata Anodonta cygnea .

.

Soft parts Shell , Soft parts . „ „ . Shell . . * Soft parts . . , Mantle . „ , Body . . , Gonads . >» . Mantle . . Shell . , „ „ „ „

- „

. .

Sr

Ba

Author

0.2

0.25

Webb, 1937* Borovik-Romanova, 1939

0.04 0.04 — 0.80 0.02 2.0 0.1 0.80 0.03 0.02 0.03 — — — — — —

0.02 — Webb, 1937* — „ 0.001-0.005 Borovik-Romanova, 1939 0.004 Webb, 1937* — 0.008 0.006 n

— 0.003 — 0.05 0.001-0.005 0.001 0.002 0.002 0.004 0.03

>»

99

99

99

99

99

99

99

99

99

McCance and Masters, 1937 Webb, 1937* Borovik-Romanova, 1939 McCance and Masters, 1937 99

99

99

99

99

99

19

99

99

99

99

19

99

99

99

99

* Percent of total cations in the ash. Preliminary data.

detected this element in the shells of Mytilus edulis^ Astarte^ and others. The shells and tissues of freshwater and terrestrial Mollusca contain relatively more barium. At the Vernadsky Laboratory, strontium and barium have been redetermined in a number of Mollusca; the results of spectroscopic analyses by Borovik-Romanova (1939) are given in Table 221. Webb (1937) and McCance and Masters (1937) have also produced some results. BORON. A relatively high boron content was found in Mollusca. The data of Bertrand and Agulhon (1913) showed that marine organisms are richer in boron than terrestrial organisms ; Goldschmidt and Peters (1932) gave a number of determinations of boron in shells. Webb (i 937) determined the element spectroscopically; the following percentages of ash were obtained : Helix aspersa, 0.25 ; Littorina littoralis, 0.03 ; Purpura lapillus, 0.03 ; Pleurobranchus plumula, 0.07 ; Aeolidia papillosa, 0.03 ; Archidoris britannica, o.oi ; Modiola modiola, 0.04 ; and the mantle of Pecten maximus, 0.03. Igelsrud, Thompson and Zwicker (1938) found 0.0225% boron in the shell of Conus sp. and 0.0865 °/o ^ the shell of Cyprea. T. Glebovitch (1941) showed chemically that the soft parts of Mytilus edulis from the Barents Sea contain 6.53 X io' 4 °/o in the living matter and 3.27 x io~ 3 °/ 0 in the dry matter; Buccinum undatum contains 3.39 X io"*°/ 0 and

364

Memoir Sears Foundation for Marine Research

its roe 1.89 x io~ 4 or 1.34 x io~ 3 °/ 0 of the dry matter. The order of magnitude of boron in Mollusca and other invertebrates is the same as in sea water. TITANIUM. Titanium has been found recently in Mollusca, but systematic investigations have just begun. Consequently there are few data. Bertrand and Voronca-Spirt (1930) found the element in the soft parts of various mollusks as shown in Table 223. Sh. Kaminskai'a (1937), determining the element in Mytilus and Cardium, obtained 3*5 x io~ 4 °/o in the shell of Mytilus edulis and 2 x io"*°/o in the shell of Pecten islandicus. Evidently titanium is widely distributed in marine organisms, but in very small quantities. Little is known of titanium in the shells, where, according to isolated observations, more should be expected than in the soft parts.

TABLE 222 BORON IN MOLLUSCA (IN °/0 OF DRY MATTER)

ORGANISM Soft parts Helix pomatia . Haliotis tuberculata Pecten jacobaeus Shells Sepia officinalis . Nautilus pompilius * Spirula peronii . Pinna squamosa .

Author

B

. . . . . . . .

.

.

.

.

.

.

0.001 0.0001

Bertrand and Agulhon, 1913 „ „ „ „ » 11 11 11

. . * .

. . . . . . . - . . . .

. 0 0.000545 . 0.00027 . 0.00027 .

.

.

,

Goldschmidt and Peters, 1932

,

.

0.01

,

COBALT AND NICKEL. These metals occur in Mollusca and other invertebrates in quantities 10 to 100 times smaller than do manganese, copper, and zinc. Quantitative data for nickel and cobalt in Mollusca were given for the first time by Bertrand and Micheboeuf (1925^1) and then by Fox and Ramage (1931). Paulais' (1936) recent data on nickel in Mollusca show the relative concentration of nickel in the gills and liver; the muscles contain the least nickel and are also poor in other heavy metals (see Table 225). D. R Maliuga showed that cobalt is of the same order of magnitude as nickel. Cobalt has been systematically determined for the genus Pecten. It is quite evident from these data that nickel is found more frequently than cobalt and in relatively larger quantities. Except for Archidoris, an organism containing more cobalt than other Mollusca and with no nickel in the liver, the ratio Ni/Co is the same as that found in rocks. There is a larger amount of cobalt in mollusk eggs and in the liver of young organisms. LEAD. In the past, investigators have been skeptical about the idea of a universal occurrence of lead in the tissues of animals. But it has become clear recently that there is usually about io~°°/ 0 in the living weight of organisms. Lead was discovered in

Chemical Composition of Marine Organisms

365

TABLE 223 TITANIUM IN MOLLUSCA, WITHOUT SHELLS (IN %), FROM BERTRAND AND VORONCA-SPIRT, 1930 ORGANISM

Living matter

Crassostrea angulata Cardium edule Mytilus edulis Pecten jacobaeus Helix pomatia Helix aspersa

0.0003 0.0003 0.0006 0.00018 0.00006 0.00006

Dry matter

0.00214 0.00205 0.00273 0.00083 0.00036 0.00046

. , .

Mollusca for the first time by Forchhammer in 1845, and considerably later several investigators tried to determine the element quantitatively, but the data did not always agree. Chapman and Linden's (1926) figures are apparently too high. These data should be examined carefully and the lead redetermined. Fox and Ramage (1931) found lead irregularly in the organs of Mollusca ; it was almost always present in the liver of Helix^ Pecten^ and Pinna but not in other Mollusca. GOLD AND SILVER. Gold was once found in the shell of an oyster by Liversidge (1897). Silver was detected by Forchhammer (1852), and all the spectroscopic analyses indicate its presence in organisms (see Zbinden [1930], and others). Fox and Ramage (1931) found up to o.ooi % in Helix aspersa (podium and shell). In the liver of Pecten^ there was 0.005 %• Silver was found also in a secretion of Aplysia, in the liver of Ostrea, in the liver and kidneys of Pinna^ and in the liver and other organs of Sepia and Loligo. On gold and silver in sea water and marine organisms, see Yasuda and others. ALUMINUM. In the shells of oysters aluminum was detected by Bucholz and Brandes (1817), Tressler (1923), and others. However, the majority of determinations of iron have been done without separating iron from the aluminum. Table 228 gives

TABLE 224 NICKEL AND COBALT IN MOLLUSCA, WITHOUT SHELLS (IN «/0 OF DRY MATTER)

ORGANISM Mytilus edulis . Crassostrea sp. . Haliotis sp. . Aplysia sp. . Pinna sp. Aeolidia sp. . Anodonta sp. Archidoris sp. 99

w

Cardium edule .

Co

Comments

Ni

Podium , Liver . Kidneys . Liver .

0.000235 — 0.000174 — none 0.004 trace 0.004 0.006 0.005 — 0.0008

, .

Liver .

2

99

*

*

. . . .

trace none

»»

0.0022

0.0034 0.0031 —

Author

Bertrand and Macheboeuf, 1925-a 99

99

99

Fox and Ramage, 1931 91

99

99

99

99

99

11

99

9>

99

11

11

>9

99

99

99

99

99

99

99

Paulais, 1936

99

366

Memoir Sears Foundation for Marine Research TABLE COBALT AND NICKEL IN VARIOUS PARTS OP

living matter

ORGANISM Mya arenaria Pecten maximus . Pecten tslandicus . Crassostrea angulata Scrobieularta piper at a Cardium edule

, Mytilus edulis Littorina Kttorea . Pleurobranchus plumula . . .

dry matter

6.8xlO-«

1.5x10,-e

Ni Siphon

Ni Whole

Co Whole

living matter

4.5x10-

dry matter

living matter

dry matter

0.0191

0.096

2.1x10 -6 0.0438f 0.240f

2.1 xlO- 4 1.7x10-* _ 0.025*

4.3 xlO- 6 3.3 xlO' 6 — —

1.5x10-* 4.8xlO~ 6 _ —

7 xlO- 4 2.4xlO- 4 0.02« 0.15«

— — — —

$ Nickel was determined in the hepatopancreas and sex organs together.

• Analysis for nickel in the gills and mantle together.

some recent determinations of this element in Mollusca. The order of magnitude of aluminum lies between io"2 and io" 3 % of the dry matter. CADMIUM. Cadmium .was detected for the first time by Fox and Ramage (1931) in spectroscopic analyses of the ash of the liver of Pecten maximus taken from various localities. There was 0.05 to 0.2 °/0 in the dry matter of the liver. Obviously there is a concentration of the element. Webb (1937) determined cadmium in percent of ash as follows : Helix aspersa 0.03, Littorina littorea o.ooi, Purpura lapillus 0.03, Pleurobranchus plumula 0.04, and Archidoris britannica 0.03 (mantle) and o.oi (remainder). TIN. According to Orton (1924), tin is apparently present in Ostrea, but these results are of doubtful value. Webb (1937) found 0.025 % *n Helix pomatia and o.oi 5 % in the ash of Aeolidia papillosa. VANADIUM AND MOLYBDENUM. Qualitatively, vanadium was detected in traces by

TABLE 226 LEAD IN MOLLUSCA (IN »/0), FROM CHAPMAN AND LINDEN, 1926 ORGANISM

No. of analyses

Dry matter

Mytilus edulis Cardium edule Littorina sp Buccinum sp Ostrea edulis Crassostrea angulata.

2 2 2 3 3 5

0.0015 0.00035 0.00126 0.00097

* . . . . .

-

.

0.0144! 0.0078!

~ — —

Chemical Composition of Marine Organisms

225

367

MOLLUSCA (IN MG PER 100 G)

Ni Gills

living matter

Ni Mantle

dry matter

living matter

dry matter

living matter

dry matter

0.0208 0.0148*

0.1475 0.0164 0.0160* —

0.0910 —

0.0234 0.0258

0.0213 — 0.1755*

0.1295 — 1.495*

0.0935 — — ^

0.0170$ 0.10$ 0.0940 0.435 0.301 2.345 — —

0.0133 — —

Ni Podium, sex organs

Ni Hepatopancreas

—

—

0.111 0.1280

—

j- Nickel was determined in the siphon, gills and mantle together.

living matter

Ni Muscle

dry matter

living matter

dry matter

0.0083 0.0054 — — 0.0150 0.1585 —

0.0445 0.0315 — — 0.0725 0.1340 —

0.0037 — — — — — —

0.0200 — — — — — —

—

—

—

—

Author

Paulais, 1936 Maliuga, 1946 Paulais, 1936 „ Maliuga, 1946 Webb, 1937*

a In percent of total cations and anions; the data are preliminary.

Ranzi (1935) in ^e embryo of Sepia officinalis. Webb's (1937) discovery of a considerable quantity of vanadium in Pleurobranchus plumula proved to be erroneous. Bertrand (i943-a, c) found the following amounts of molybdenum and vanadium in Mollusca (in °/0 of dry matter): Mo

3.7 X l O - 4 3.0X 10~5 l.SxlO" 3 2.0 X 10~4 1.1 X 10~4

Helix sp Loligo sp Afytilus edulis Crassostrea sp Patella vulgata

V 5 xlO'5 4 XlO-5

1.2xlO- 4 1.3 xlO- 4 1 xlO- 5

TABLE 227 LEAD IN MOLLUSCA, FROM MORE RECENT DATA (IN °/0) ORGANISM

Comments

Living matter

Ash

Helix aspersa Littorina littorea . Purpura lafillus . Pleurobranchus plumula Aeolidia fa piI I osa Modiola modiola . Pecten maxtmus Ostrea edulis . Buccinum sp. -

Soft parts

— 0.2 — 0.03 — 0.1 — 0.02 — 0.03 — 0.015 — 0.02 5 — 2 xlO1.3xlO- 4

Author

Webb, 1937

Monier-Williams, 1938

368

Memoir Sears Foundation for Marine Research TABLE 228 ALUMINUM IN MOLLUSCA (IN %)

ORGANISM

Comments

Helix aspersa Littorina littoralis . . . . Purpura lapillus . Pleurobranchus plumula , Archidoris britannica . Octopus vu/garis , fivipara japonica . Meretrix meretrix Ommatostrephes sloanipacificus Haliotis japonica .

Soft parts .

*

7»

11

77

11

71

Dry matter

Ash

Author Webb, 1937*

.

.

—•

0.25

—

, ,

. .

— —

0.8 0.1 0.1

• ,

. .

0.0011 0.0085 0.1069 0.0212 0.0533

2 ... 2 . 2 ... 2 ... .

,

„ * 11

„ 11 11

0.2

0.053

Meunier, 1936 Yamamura, 1934 Oya and Shimada, 1933 11

71

11

11

11

11

11

»

* In percent of total cations and anions; the data are preliminary.

17. Nonmetallic Elements IODINE. Qualitative determinations of iodine in these organisms were first done a long time ago. Fyfe (1819) found no iodine in mollusks, but soon Cassola (1822) and Balard (1825) detected the element in Doris, Venus^ and Ostrea edulis, and Sarphati (1837) in Mytilus edulis. Iodine was found to occur in freshwater Mollusca also (see Chatin, iS^ob), but in considerably smaller quantities. Although most of the investigations have been done on Lamellibranchiata, the amount of iodine in Mollusca is now more or less clearly known, there being n x io"5 to n X io"4°/0 iodine in the living matter. These organisms extract some iodine from sea water and get some from their food. According to the experiments of Loubatte (1930), when the organisms are placed in sea water to which iodine has been added they extract it in amounts many times greater than the amount normally available (see also Turchini, 1930). Chevallier demonstrated the presence of iodine in Mollusca qualitatively. In their soft parts there is more iodine than in the shells (calculated in percent of dry matter or ash), but the amount in the shells is very stable. Typically marine species are somewhat richer in iodine than those living in the littoral zones. Nilson and Coulson (1939) gave the following results (in °/0 of living matter) for iodine in oysters of the United States : Crassostrea virginica Crassostrea gigas Ostrea /urida Mya arenaria

4.9xlO~5 3.6x 10~ 5 3.0xlO~5 1 X 10~ 7

Nilson and Coulson, 1939

Clark and Adams, 1929

The only analyses of the distribution of iodine in different organs of Mollusca are found in the work of Cameron (1914), who studied Schizotherus nut alii (results given in °/0 of dry matter) :

Chemical Composition of Marine Organisms

369

TABLE 229 IODINE IN MOLLUSCA, INCLUDING ALL OF THE SOFT PARTS (IN MG PER 100 G)

ORGANISM

Comments

Crassostrea commercialis

.

.

,

0.088

.

In shell

.

0.0043

T1

.

.

.

99

'

99

T

virginica 99

*

Living matter

0.0935

99

angulata , Ostrea lurida . » 99 Paphia sfamine a

.

.

0.00 0.13 0.031

Market 99

Market

,

Pecten sp.* Pecten maximus . Pecten grandis .

„ ,

,

.

Pecten horicius Mytilus edulis Mytilus edulis]

.

.

.

.

.

.

. , .

Mytilus californica Penus mercenaria Solen(*) sp Cardium cor bis jlstarte sulcata VI

V*

Siliqua patula IMyo orenorio. V*

0.116

Vt

Schizotherus nutalli . . Polynices

.

Dry matter

0.60

0.164

0.179

1.059 0.12 0.081

0.137

0.218

0.5048

42.0 0.4368 0.620

0.12

Dermis .

0.816

"

0.693

. .

"

Dermis

236.0

0.6875

9.0

—

New Zealand

Hercus and Roberts, 1927

U.S.A. (Atlantic)

0.03

0.320 0.4042

0.21

Author

1.620

0.034 0.0833 0.022

0.015

Locality

0.24 9.20

France Seattle, U.S.A. 99

Seattle, U.S.A. 99

China Sea U.S.A. (Atlantic) France California, U.S.A. U.S.A. (Atlantic) China Sea Herdla, Norway

California, U.S.A. China Sea

Almquist and Givens, 1935 Tressler and Wells, 1924 Jarvis, 1928 Remington, McClendon, Kolnitz and Gulp, 1930 Coulson, 1934 Hodges and Peterson, 1931 Bourcet, 1899 Lunde, Boe and Closs, 1930 99

99

99

99

99

Jarvis, 1928 Lunde, Boe and Closs, 1930

Adolph and Whang, 1932 Tressler and Wells, 1924 Jarvis, 1928 Bourcet, 1899 Cameron, 1915-a Jarvis, 1928 Tressler and Wells, 1924 Adolph and Whang, 1932 Cameron, 1915-a Lunde and Boe, 1929 Closs, 1931 Jarvis, 1928 Cameron, 1914 Adolph and Whang, 1932 Cameron, 1915-a

dn rm (continued next page)

37° ORGANISM

Memoir Sears Foundation for Marine Research Comments

Saxidomus gigantea . . Dermis Haliotis sp Littorina littorea . Helix pomatia. Terrestrial Helix aspersa Octopus sp Haliotis sp

Living matter

Dry matter

—

9.00

0.0065 — —

0.010 0.86 —

— 0.075 0.032

— —

0.3621

Locality

Author

Cameron, 1915-a Almquist and Givens, 1935 Bourcet, 1899 »»

»

Sandonnini, 1930 Closs, 1931 Jarvis, 1928

* Part of the body. f In the byssus. In all cases in which the byssus, dermis or operculum is analyzed, the material is probably largely schleroprotein.

Shell Cuticle of the foot Muscle of the foot

0.000 0.298 0.000

Heart and kidneys Gonads Gills

(0.02) 0.000 0.000

Cameron's figures for iodine in various invertebrates are somewhat higher than those given by other investigators, and the absence of iodine in the gills might be explained by the lack of sensitivity of the method chosen by the author. Lunde, Boe and Closs (1930) found 0.000073 °/o in ^e fresh matter of Pecten gonads, whereas Turchini (1930) found no iodine in the gonads of Ostrea. Iodine has been found in the shells of mollusk eggs. Plepp (1927) and others determined iodine in the soft parts of freshwater Mollusca; in them there is less of the element (n x io~ fl to n x io~ 6 °/ 0 ) than in marine species. Less noticeable is the difference in the amount of iodine in the shells of marine and freshwater Mollusca, but a difference certainly exists (see Table 229). Investigators note a smaller amount of iodine in fossil or old samples of shells than in those taken directly from living organisms*'(see Mohr [1865], Wilke-Dorfurt [1928], Krafft; see also data on Cyprea tigris in Table 229). According to Fellenberg (1924), some of the iodine in the shells occurs as an organic compound and some as an inorganic compound; in the shell of Ostrea edulis there was i x io~ 6 °/ 0 inorganic iodine and 1.24 x io~ 4 °/ 0 organic. BROMINE. Soon after its discovery, Cassola (1822), Balard (1826) and Sarphati (1837) found this element qualitatively along with iodine in various mollusks. At the same time the investigators noted that there was always more bromine than iodine in Mollusca. Chatin and Miintz (1894) also found more bromine than iodine (0.005%) in the shells of Ostrea. Since that time, 100 years ago, this subject has been abandoned. However, systematic investigations of bromine in Mollusca have been done recently in our Laboratory, and detailed investigations along these lines give promise of much that is new. A. Simorin found 5.84 x io" 3 °/o *n Neptunea despecta and 4.65 x io~ 3 °/ 0 in Pecten islandicus. Neufeld's (1936) data on bromine are given herewith (in °/0 of dry matter) :

Chemical Composition of Marine Organisms

371

TABLE 229 A IODINE IN SHELLS OF MOLLUSCA (IN MG PER 100 G) ORGANISM

Comments

Lamellibranchiata (shells) Ostrea edulis 9 9

•

^

„

•

'

. . .

Ostrea denselamellosa Mytilus edulis . . . 99

•

5

+

3 ,

«

•

.

.

...

91

Cyprina islandica Petricola pholadiformis Tellina baltica Venus verrucosa Venus gallina Mya arenaria Tapes decussatus Cardium edule . . . „ . . . Cardium tuberculatum Donax trunculus Cardita sulcata Dreissensia polymorpha. Anodonta cygnea . Unto pictorum , Unto tamidus . * . Unto crassus . Cephalopoda (shells) Sepia officinalis Octopus sp.* Cyprea tigris Gastropoda (shells) Littorina littorea Buccinum undatum Cerithium vulgatum Murex brandaris Patella scutellaris Pivipara vivipara Helix aspersa

.

Ash

Locality

Author

0.134 3.00 0.45

Mediterranean , Santander, France North Sea, Mediterranean, et al. Pacific . , . Various seas Ostsee . . Atlantic , . . North Sea . .

Fellenberg, 1924 Chatin and Miintz, 1895 Wilke-Ddrfurt, 1928

0.46 0.49 0.70 9.00 0.34 0.16 0.21

0.4

0.13 0.02 White Black . . . .

0.2

. .

Fresh water „ „ „ „ „ „ „ „

3.10 12.00 0.27 0.31

0.1

0.49

0.2 0.4

99 99

99

99

99

99

99

99

99

99

99 99

Gulf of Naples Baltic . . Mediterranean Ostsee . .

. . , ,

*

Gulf of Naples . 99

Adriatic , Rhine , 99

*

99

*

.

.

"

*

Neckar, Botweil

0.045

Mediterranean . . . Indian Ocean

.

North Sea

,

.

'

•

0.02 0.54 1.27 0.73 2.40

99

99

0.11 0.024

99

99

Wilke-Ddrfurt, 1928 99

9?

99

99

Plepp, 1927 99

99

99

99

99

99

99

99

Fellenberg, 1924 Closs, 1931 Wilke-Ddrfurt, 1928

99

99

99

99 99

99

91

99

99

99

99

99

99

9 9

h

99 99

99

99

Mediterranean

0.7

99 99

Plepp, 1927

99

0.02 0.16

—

99

Wilke-D6rfurt, 1928 19

99

99

99

99

99

99

99

99

Plepp, 1927

•

•

.

*

Sandonnini, 1930

* 0.86 in living matter.

*$

3 72

Memoir Sears Foundation for Marine Research Schizotherus nutalK (skin, podium) Mytilus edulis (byssus) Polynices lewisii (opercula)

0.102 0.135 0.382

L. S. Selivanov (1939) was the first to determine bromine in freshwater mollusks (in °/0 of dry matter) : Limnaea stagnalis Vnifara contecta

2.58xlO~° 1.47xlO~ 3

Bromine occurs in the form of a bromo-organic compound in the excretions of the Mediterranean gastropod Murex brandaris and other species of this genus. This substance changes in air, forming a purple coloring matter (Tyrian purple) that was used in ancient times for dying textiles. Friedlander (1909), having collected this pigment from 12,000 samples of Murex brandaris, was able to determine its chemical structure. The pigment proved to be 6-6-di-brom-indigo, which occurs in both skin and shell.64

/\ Br-,

\

CCK

J-NH

/\

/ co--/ v

| L

Br

Purpura brandti and other species of this genus, namely P. haemostoma from the shores of western Syria, P. aperta from the western shores of Mexico, and the widely-distributed species P. lapillus, also contain a pigment in which bromine appears in the form of 6-6-di-bromo-indigo. It should be noted that the presence of analogous pigments in marine animals increases the total amount of bromine. Iodine also occurs partly bound in an organic compound in these organisms. ARSENIC. In all marine Mollusca the amount of arsenic is high, sometimes reaching io~ 3 °/ 0 of the living weight, as seen from Chapman's (1926) data. However, he has given higher figures for arsenic in Mollusca than most other investigators. Hiltner and Wichmann (1919), in a long series of determinations of arsenic in Crassostrea of the United States, have shown that the amount of the element proved to be more or less stable, varying from traces to 0.00015% of the dry matter and averaging about o.oooi °/0. Figures of the same order of magnitude are given by other investigators for the oyster. Orton (1924), when he determined arsenic in oysters from the shores of England, usually found from traces to 4 x io~ 4 °/0 in the fresh matter, with an average of n x io~ 4 °/o, which is somewhat higher than the results of other investigators. In green oysters, the arsenic as well as the copper is much higher. Chapman (1926), observing exceptionally high arsenic in Mytilus edulis, considered that the phenomenon of poisoning by this organism was caused by the presence of large quantities of arsenic. Recent determinations of the element have been done by other workers; Yamamura (1934) found 6.1 to 4.6 X io~ 4 o /o in Fivipara japonica; Luzanski 64. See material on the pigment in Haliolis\ see Vialli (1922) and Dubois on bromine in the purple pigment.

Chemical Composition of Marine Organisms

373

TABLE 230 ARSENIC IN MOLLUSCA, WITHOUT SHELLS (IN »/„)

ORGANISM Ostrea edulis .

.

.

.

Crasssostrea virginica Cra&ostrea angulata . w

w

Mytilus edulis Cardium edule Buccinum sp Littorina littorea Helix hortensis Sepia officinalis Mya arenaria

•

T

No. of analyses

Living matter 0.00041

.

.

,

5

. . , . . . . .

. . . . . . . .

. . . . . . . .

11 4 8 6 6 6 6 2

0.00037 0.0002 0.00011 0.0034 0.0034 0.0068 0.0019 0.0018 0.0021 0.00003 0.0002

Dry matter

— — — — —

0.0049 —

Author

Chapman, 1926 Cox (see Orton, et al., 1924) White, 1933 Hiltner and Wichmann, 1919 Chapman, 1926 » » » » 11 » » » t*

w

»

>»

Bertrand, 1903 White, 1933

(1935) worked on various marine organisms; and Shtenberg (1939), in studies on Mollusca from the shores of the Pacific, found that they contained 0.349 mg/ioog of dry matter. Terrestrial Mollusca are much poorer in the element. FLUORINE. All mollusk shells contain this element. Qualitative determinations of the last century can be found in early works by Nickles (1858), Mohr (1865), Kupffer (1870), and Andree (1909). Carles (igoy-a, b), in an attempt to determine fluorine quantitatively in the shells, found the following amounts (in °/0): Ostrea edulis Mytilus edulis

„

-

Limnaea, Planorbis Helicidae Ostrea edulis

0.012 0.012

0.003

0.003 0.003 0.003 (According to Chatin and Muntz, 1894).

There is more fluorine in the shells of marine Mollusca than in freshwater forms, which is explained by the fact that there is ten times more fluorine in sea water than in freshwater basins (sea, n x i o ~ 4 ; rivers, n x io~ & ). Still more fluorine is found in the shells of fossil Mollusca. Using the microchemical reaction with the zirconium-alizarine indicator, we determined fluorine in various mineral inclusions in the tissues of invertebrates. The mineral inclusions in the skin of Archidoris britannica gave the only positive fluorine reaction in Mollusca. We could not determine the type of the fluorine compounds because of lack of material. The high fluorine in this mollusk has been confirmed by

*(•

374

Memoir Sears Foundation for Marine Research

the analyses of McCance and Masters (1937), who found up to 3.0 °/0 in this organism ; Webb (1937) showed up to 2 °/0 *n the ash of the same species. Thus it is possible that the mineral inclusions (spicules) of this mollusk consist of CaF2, as Fox and Ramage (1931) maintained earlier.85 This should be verified. 65. Woodland (1907-6), Prenant (1928-6), and others found that the spicules of Doris were in the form of the usual spherulites. Upon decalcification of the spicules, no organic matter remained. These investigators supposed the spicules to be calcite. Rinne (cited by Prenant, 1928-6) and Odum (1951-6), using x-rays, found spicules of nudibranchs Doris and ArcMdoris to have an amorphous structure. On the other hand, Mayer and Weineck (1932), also with x-ray, found vaterite and aragonite in some Doris specimens that had been kept in 70 % alcohol.

Chapter XVI

Elementary Composition of Arthropoda i. General Remarks

I

N MODERN seas the Arthropoda are represented mainly by species of Crustacea; there are but few species of all other classes. There is but one living genus of Merostomata, Limulus, and but few marine insects, Halobates* being the only genus that is truly oceanic. The geochemical role of Crustacea and extinct Merostomata, chiefly by participation in the formation of concretions, is considerable. Well known is the fact that the shells of Ostracoda form limestones. Furthermore, planktonic Crustacea, and particularly Trilobita and Merostomata, played a role in the formation of phosphorite sediments (see further). The chemical composition of most Crustacea, as well as the extinct Merostomata and Trilobita (mostly marine organisms), is close to that of Arachnoidea, which adapted themselves to existence on land. The chemical composition of the other classes of Arthropoda, notably the Myriapoda and Insecta, was evolved under the influence of the diverse and complicated conditions of dry land. From a chemical point of view, the Crustacea have been studied more thoroughly than other classes of Arthropoda, such as Insecta or Arachnida. Investigations devoted to the composition of Crustacea, chiefly marine forms,2 have one characteristic in common with the investigations of Mollusca; the main subjects of study have been the composition of the carapace and other parts of the crustacean skeleton as well as that of the blood and the blood pigment. Although the composition of the inner organs and tissues attracted less attention, some data on their composition may be found in the

1. There have been no analyses of marine Insecta. 2. Of the freshwater species, a number of analyses have been done on Potamobius flwuiatilis. [The specific name in genus Potamobius is that given by the author, but there is no certainty as to its validity.]

375

376

Memoir Sears Foundation for Marine Research

numerous physiological investigations of marine Crustacea pertaining to questions of their adaptability to waters with low salinity, or to salt solutions, and the mechanism of osmoregulation, and so forth. Although the chemical composition of Crustacea has interested scientists for some time, there are few satisfactory analyses. The first analyses, done by Merat-Guillot (1797), Chevreul (1820), Gobel (1823), and others, refer to the carapace. These analyses showed a basic difference in the skeletons of most Crustacea when compared with those of other invertebrates ; the former contained a large amount of phosphorus, thus indicating a comparison of the composition of the carapace with that of vertebrate bone. The crustacean carapace and other parts of the skeleton, as well as entire organisms in different orders, show variations in the amounts of calcium, phosphate, and other chemical elements. Thus, in almost every order, and sometimes within smaller taxonomic units, there are marked characteristics of chemical composition. The muscular system of Arthropoda has acquired a refined differentiation, and the salt composition in these tissues reminds us of that in molluscan muscles. The smooth and transverse striated muscles differ in composition. 2. Water) Ash, Nitrogen^ and Chlorine in Crustacea Crustacea contain an average of 70 to 80 % water in the living state, with the amount of ash residue varying considerably between species—from fractions of i °/0 to 50 °/o °r more. In the majority of Crustacea, the high ash with its relatively high phosphorus indicates the important role of these organisms in the exchange of phosphorus in the sea. We will return later to this question. Water, organic matter, and ash residue, representing the mineral part of the skeleton (the carapace of Crustacea), occur in different ratios in different species. In early investigations, analyses of the dry residue and ash from the freshwater crayfish Potamobius fluviatilis* are often given. Even in the work of Geoffroy (1705) there is a determination of water in this species. However, more systematic data were collected later by Bezold (1857), Konig (1879), Krukenberg (1881-1882), Vernon (1895), and others. Of the more recent analyses, most of them refer to separate parts of Crustacea. A number of other analyses, found in the works of Brand (1898), Waksman, Carey and Reuszer (1933), Vinogradov, and others, refer to crustacean plankton, such as Copepoda.4 Planktonic species of Crustacea, including Copepoda, Cladocera, Mysidae, and others, contain less ash than the typically benthonic Crustacea, such as most Decapoda. Crustacea living in littoral or analogous conditions, such as Amphipoda and Isopoda, have a higher ash residue. We will see later that the ash content is related to the struc3. Potamobius astacus. 4. Data referring to prepared crustacean products may be used for comparison of chemical composition, to a certain extent, but we do not give them here. See Konig (1879), Kuo-Hao Lin (1926-*)), and others. On the composition of dried crustacean meal, see Harry, Crabs as Fertiliser\ see also Daniel and McCollum (1931) and Morschner.

Chemical Composition of Marine Organisms

377

ture of the carapace of the crayfish, particularly as regards the degree of calcification. There are hardly any data on Ostracoda, with only indirect indications of their large ash content. If we examine carefully the analyses done on one species by several investigators, we will note that they are very similar, which indicates a certain stability within these units. All analyses of Gammarus locusta are alike; in different specimens of Calanus the amounts of water, ash and nitrogen are alike; analyses of Carcinus moenas are also very uniform. Thus, Carcinus moenas has a characteristic high ash content of up to 40 %, Potamobiu s fluviatilis about 30%, Crangon about 20 %, and plankton My sis 10 to 15 %. Copepoda contain less ash than all the others. It is interesting that the freshwater isopod Asellus aquaticus contains 8o°/ 0 water and 8 % ash while the terrestrial isopod Oniscus marinus contains about 70 % water and more than 10 % ash (cf. Spielmann's determination). It is well to remember that the age as well as the place and time of collection influence the composition of Crustacea. According to our data, Calanus finmarchicus from the White Sea contains from 8.06 to 16.64% as^- ^n small planktonic Crustacea the data for ash content are somewhat high owing to the difficulty of thoroughly removing marine salts from the plankton. We have observed that Calanus from the freshened regions of the White Sea contains less ash residue than the same organism from the open parts of the sea. According to Weismann (1876, 1877, 1879) and Ramult (1930), in their work on Daphnidae, Ceriodaphnia, Scapholeberis, and Simocephalus, the eggs of Crustacea contain the least amount of water, which increases during the development of the fertilized egg. In general, the composition of arthropod eggs is like that of the mollusk and echinoderm eggs. The covering tissue of the eggs is chitin. There is an average of about 2.5 °/o nitrogen in the living matter of Crustacea, or about i o °/0 of the dry matter, the amount being greater in species in which the mineral residue is small; these are chiefly species of Entomostraca. The amount of nitrogen depends first on the total amount of organic matter and second on the amount of chitin. Crustacea contain more of this element than most other marine invertebrates, there being a considerable amount in Copepoda and in other planktonic Crustacea. The high food value of crustacean plankton is widely known. Elsewhere we give data for nitrogen in the flesh and various parts of crustaceans. The distribution of numerous nitrogencontaining compounds in the tissues of some species has been studied by Campbell (1935) and others. One of the chief nitrogen-containing substances in Crustacea is the foundation of the skeleton, chitin (C18H30N2O12), which contains an average of 6 °/0 nitrogen. This substance forms the cuticle of all Arthropoda; in some it forms a thin cover, as in the majority of planktonic arthropods, Copepoda, Arachnoidea, Pantopoda, Tardigrada, and so forth; in others it forms a massive skeleton; and in Crustacea and Coleoptera (Insecta) it is often impregnated with calcium salts, carbonates, phosphates, and so forth. In Crustacea, Insecta, and others, chitin is amalgamated with the intestines and other organs. Furthermore, the chitinous tissue of Crustacea evidently has some

378

Memoir Sears Foundation for Marine Research TABLE 231 WATER AND ASH IN CRUSTACEA AND XIPHOSURA (IN «/0)

ORGANISM

Comments

Branchiopoda Daphnia pulex .

Fresh water 90.67 „ . 8; fresh water — Fresh water — » » 3; fresh water — Fresh water —

Sida hyalina Holopedium gibberurn Leptodora sp. , Bosmina sp. >»

H20 living matter

M

Cirripedia Ba/anus balanoides Copepoda Rhinocalanus gig as Euchaeta sp.* . Euchaeta norvegica Centropages hamatus Calanus finmarchicus

90.78

84.91

n

Limnocalanus sp. . . Anomalocera patersoni » » Eutemora sp.* . - Cyclops sp Mysidaceae My sis flexuosa

.

Fresh . . * • Fresh „

.

Weigelt, 1891 Hensen, 1887

11.85 15.99 —

Delff, 1912 Hensen, 1887 Valenzuela, 1928

79.67 — 83.46 78.44

— — — 6.28

— 23.76 21.69 —

Unpublished material §

77.63 78.00 —

— — —

— — 28.60

Fresh water

Gammarus pulex .

.

„

„

•

»

»

Carinogammarus roeselii . . . . » » • * • • Hyalella knickerbockeri Fresh water

W

— 3.55 1.63

.

water . . * * water „

.

•

»

5.94 10.92 9.3 4.10 6.61 15.40 4.24 5.74

Amphipoda Gammarus locust a .

»

JJ

— — — — — — — —

.

n

0.052 0.60 0.007 0.45 — 4.40f

»

Volk, 1906 Knauthe, 1907

14.16

.

.

18.30 21.5 7.74 11.60 3.30 17.4

Geng, 1925 Meyer, 1914 Birge and Juday, 1922 Morawski, 1897 Birge and Juday, 1922

—

77.79 Inner organs 75.43

„

— — — — — —

— 27.03

Author

Orr" 1933 " Hensen, 1887 Vinogradov, 1930-a » » Vinogradov, 1931 Stiehr, 1922 (see Brandt and Raben, 1919-1922) Birge and Juday, 1922 Brand, 1898 Morawski, 1897 Birge and Juday, 1922 Delff, 1912 Brandt and Raben, 1919-1922 Volk, 1906 Birge and Juday, 1922

93.43 86.70 84.80 85.70

Diaptomta sp. . . . Fresh water Mixed crustacean plankton , »

1.72 -

30.39 64.04 92.00

Calanusf i n m a r c h i c u s *. . . .

»

, Ash , living dry matter matter

73.91

0.25

3.78

14.30

6.18

—

Delff,"l912 Geng, 1925 Meyer, 1914 Geng, 1925 Schumann, 1927 Birge and Juday, 1922

Chemical Composition of Marine Organisms living matter

, Ash . living dry matter matter

80.33

—

75.49 72.03 74.52

2.84 2.55 5.04 1.21

83.06

62.98

4.07 24.00 2.58 —• 1.72 — 12.52 — 9.10

75.48 80.07

1.43 2.49

H2O

ORGANISM Isopoda Gfyptonotus entomon Oniscus murarius . *>

-

99

Armadillium sp. Asellus aquaticus . 99

99

»

9 9

Decapoda Penaeus indicus Penaeus sp. Crangon vulgaris , 99

9 9

•

Comments

.

Fresh water 99

"

' •

99

99

99

99

99

99

99

1

'

Palaemon sp. (?) . Homarus vulgaris .

99

99

*

V

78.8 75.18

Muscle Muscle 99 99

99

99

99

99

'

Homarus americanus 99

99

99

99

99

99

1

'

Eggs

.

.

Outer parts

T

99

Jasus lalandii ,

Nephrops norvegica Potamobius fluviatilis 99

99

99

Soft parts; muscles

„

»

Neptunus pelagicus Carcinus moenas

3 . Eggs

.

99

74.42 79.55 75.00

7.28

— — 1.2

—

0.99

37.74

—

— —

10.15 37.86 6.37 31.34 9.45 32.72 71.12 74.12 9.061 7.02 77.96 1.79 56.4 1.80 — — 73.19

. .

80.37

— —

41.91 49.31 14.5 79.77 10.02 49.53 62.64 16.45 44.02

71.8 70.6

Stomatopoda Xiphosura Limulus pofyphemus

81.1

— —• 19.71

79.66

*

99

Maja verrucosa

70.8 77.31 76.61

76.5 80.51

Muscle Eupagurus bernhardus Paralithodes camtschatica Muscle

27.87

11.80 39.08 10.62 33.36 — — 32.0 80.90 8.0 41.80 80.23 — 7.02 — — (94) 69.61 68.17

Eggs .

71.96

5.94

26.90

49.63

1.97

3.91

379

Author

Delff, 1912 Meyer, 1914 Bezold, 1857 Vinogradov, 1935 Meyer, 1914 Geng, 1925 Spielmann, 1713 Greshoff, 1903 Etorma, 1928 Buttenberg, 1908 Balland, 1898-a Delff, 1912 Weigelt, 1891 Atwater, 1892 Hemala, 1888 Payen, 1854 99

99

Peterson and Elvehjem, j f 1928 Valenzuela, 1928 Balland, 1898-1 Weigelt, 1891 Okuda and Matsui, 1916 Matsui, 1916-b Clements and Hutchinson, 1939 Meyer, 1914 Kubovets, 1931§ Bezold, 1857" Unpublished material^ Wetzel, 1907 Bialaszewicz, 1926 Machida, 1910 Delff, 1912 Schdnborn, 1910 Weigelt, 1891 99

99

Krukenberg, 1881-1882 Greshoff, 1903

* Plankton, predominating form. t Maximum. § From unpublished work of the Vernadsky Laboratory for Geochemical Problems.

380

Memoir Sears Foundation for Marine Research TABLE 232 WATER, ASH AND NITROGEN IN CRUSTACEA (IN °/0 OF DRY MATTER)

ORGANISM

Ligia exotica n

n

Comments

. •