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Development of the Chlorinity Salinit.Pdf THE DEVELOPMENT OF THE CHLORINITY/SALINITY CONCEPT IN OCEANOGRAPHY FURTHER TITLES IN THIS SERIES 1 J.L. MERO THE MINERAL RESOURCES OF THE SEA 2 L.M. FOMIN THE DYNAMIC METHOD IN OCEANOGRAPHY 3 E.J.F. WOOD MICROBIOLOGY OF OCEANS AND ESTUARIES 4 G.NEUMANN OCEAN CURRENTS 5 N.G. JERLOV OPTICAL OCEANOGRAPHY 6 V.VACQU1ER GEOMAGNETISM IN MARINE GEOLOGY Elsevier Oceanography Series, 7 THE DEVELOPMENT OF THE CHLORINITY/SALINITY CONCEPT IN OCEANOGRAPHY WILLIAM J. WALLACE Department of Physical Sciences, Sun Diego University, San Diego, Calic, U.S.A. ELSEVIER SCIENTIFIC PUBLISHING COMPANY Amsterdam - London -New York 2974 ELSEVIER SCIENTIFIC PUBLISHING COMPANY 335 Jan van Galenstraat P.O. Box 21 1, Amsterdam, The Netherlands AMERICAN ELSEVIER PUBLISHING COMPANY, INC. 52 Vanderbilt Avenue New York, New York 11017 Library of Congress Card Number: 72-97440 ISBN 0-444-41I 18-6 With 3 illustrations and 49 tables. Copyright @ 1974 by Elsevier Scientific Publishing Company, Amsterdam All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or other- wise, without the prior written permission of the publisher, Elsevier Scientific Publishing Company, Jan van Galenstraat 335, Amsterdam Printed in The Netherlands To Joseph W MacQuade, Jr. a~fellow laborer in the same vineyards This Page Intentionally Left Blank PREFACE In 1899 a group known as the Swedish Hydrographic Commission pre- vailed upon the King of Sweden to convene a meeting of the world’s oceano- graphers to discuss problems vexing sea study at that time. Foremost amongst these was the density problem. The density of sea water is a func- tion of temperature, salinity and pressure and is, in itself, calculated from known relationships of these three parameters used largely in connection with geostrophic computations.But the problem at that time was specifically that of salinity (and chlorinity) determination. There didn’t seem to be any question about the validity of the theory that the ratio of the major ionic constituents in sea water was a constant. “Normal science is predicated on the assumption that the scientific community knows what the world is like” (T.S. Kuhn, The Structure of Scientific Revolutions, Phoenix, Chicago, 1964). To determine salinity the (S%d/(Cl%d ratio was best used, since chlorine is the most abundant ion in sea water and is rapidly, accurately and easily determined. There was, however, definite question as to the value of the coefficient (of chlorine) obtained [ (S%o)/(Cl%o) = k = coefficient of chlorine)]. Forchhammer, the accepted originator of the coefficient of chlorine (as well as the term “salinity”) had arrived at 1.812 in 1865. Dittmar, analyzing the 77 water samples of the HMS “Challenger” expedition, has arrived at a coefficient of 1.8058. Of particular concern was the fact that there was no actual accepted definition of salinity per se but only as a determined quan- tity (i.e., as by the chlorine determination and use of a coefficient). In other words the accepted paradigm was in a state of crisis. There was need of some definition. The situation was not one of radical change or scientific revolution. No scientific theory is ever discarded unless there is another alternate, and there was in 1899 no other available. The situation was rather that of normal scientific activity; namely, the bringing of theory and fact into closer agreement. The scientist charged by the 1899 conference to resolve the problem was Martin Knudsen. By 1902 his group had a gravimetric definition of salinity, a coefficient of chlorine, an equation relating the two (S%O = 1.805 Cl%o + 0.030), and the famous Hydrographical Tables as well. Years ago when 1 first encountered the Knudsen equation, as it is most often called, I wondered about the use of the constant 0.030. It was imme- VIII PREFACE diately bothersome to me since it violated the notion that the equation was one of state which it was supposed to be, as well as the fact that it made the ratio of ions (or S%O to Cl%o) upon which the equation is based not con- stant. A lengthy study of all of the endeavors of Knudsen and his team disclosed the fact that Knudsen was well aware of these problems. What Knudsen said and the questions he raised in the lengthy published reports people did not read. Only the Hydrographical Tables were ever read and used. But the marine community was primarily looking for standardization - so everyone could play the game with the same rules. Man’s ideas about the physical world have changed with time. Not only have specific theories replaced others only to be themselves replaced, but some fundamental concepts also seem to have changed. Lucretius, for exam- ple, would have said that nothing happens without a material or physical cause. Or, in other words, one only attained true knowledge when all things came to pass without the intervention of the gods. Modern science, however, says that everything happens unless there is a reason for it not to happen (i.e., the conservation laws). What I have tried to do in this book is trace man’s ideas about the sea’s saltness from antiquity to the present time and show with the salinity/ chlorinity concept something of the way science operates. In so doing this work also becomes, at least until 1902, a rather detailed history of marine chemistry. The study of science as well as its history and historiography are fascinat- ing. It is, I think, unfortunate that it is generally only those who are engaged in these studies that tend to see science as a human activity ~~ probably the most human of activities. I would hope that works such as this one help indicate this. ACKNOWLEDGEMENTS A work of this type probably necessitates more assistance from others than most. Although it would be very difficult to mention all those who have been of help since it was begun seven years ago, it would be remiss not to cite a number of these people. I would like to thank Dr. Marie Boas Hall of the Imperial College of Science and Technology in London, and Dr. Allen G. Debus of the Univer- sity of Chicago for their comments on Robert Boyle and the silver nitrate test. Dr. Edward D. Goldberg of the Scripps Institution of Oceanography and John P. Riley of the University of Liverpool were of much assistance in early bibliographic questions. Dr. Jorgen Pindborg, Dean of the University of Copenhagen Dental PREFACE IX School not only was most helpful with translations from the Danish but also in supplying at least one especially important paper by Forchhammer from the University’s library. Dr. Robert Stadler of Heidelberg was of particular assistance in the identification of compounds from German papers on sea water analysis written in the first half of the nineteenth century. This treatise involved the use of many libraries. The friendly assistance afforded, for example, by the great Widner Library of Harvard as well as the Library of the Museum of Comparative Zoology with the granting of visiting scholar status which involved desk and office space, complete admittance to the stacks, as well as faculty privileges at no cost, was tremendous. In closing, 1 would like to thank Dr. Robert J. Morris, who waded through a number of often barely legible drafts of this weighty tome and in whose hands the book improved measurably, and 1 would like to offer a special vote of thanks to Miss Audrey Lee Krueger for her kindness in the decipher- ing and transposal of the first good draft from handwritten scrawl to typed copy. My good friend Dr. Thomas H. Foote, of the Evergreen State College in Olympia, Washington, was most generous with support, comments and his assistance in the reading and proofing of the final draft. This Page Intentionally Left Blank CONTENTS PREFACE VII CHAPTER 1. THE VIEWS OF ANTIQUITY ON SALT AND SEA WATER 1 Water analysis prior to Boyte 1 Solution analysis prior to Boyle 11 The late seventeenth century 14 CHAPTER 2. ROBERT BOYLE 17 CHAPTER 3. THE BEGINNINGS OF THE SYSTEMATIC STUDY OF THE SEA: HALLEY AND MARSILLI 31 Halley 32 Marsilli 34 CHAPTER 4. FOUNDATIONS OF SYSTEMATIC MINERAL AND SEA WATER ANALYSES 39 Gionetti 41 Lav o isie r 43 Bergman 47 CHAPTER 5. SEA WATER ANALYSIS AND THE PRECIPITATION METHOD 53 Murray 60 Marcet 69 Usiglio 80 CHAPTER 6. CONSTANT PROPORTIONALITY OF CONSTITUENTS 87 Gay-Lussac 90 Maury 99 CHAPTER 7. THE COEFFICIENT 105 Roux 116 H.M.S. Challenger 118 Dittmar 121 CHAPTER 8. THE EQUATION 135 CHAPTER 9. CONCLUSIONS AND EPILOGUE 151 XI1 CONTENTS APPENDICES I (Observations on natural waters suggested by Robert Boyle) 165 II (Sampling devices) 166 111 (Specific gravities of sea waters by Alexander Marcet) 168 1V (The silver nitrate test) 179 V (Forchhammer’s analysis schemes) 182 VI (The results of the sea water analyses of Georg Forchhammer) 184 VII (Results of the sea water analyses from the Challenger Expedition by William Dittmar) 189 VIIl (The method used by Hercules Tbrnoe) 191 IX (The recommendations of the Joint Panel of the Equation of State of Sea Water, published by UNESCO in 1962) 191 NOTES 193 BIBLIOGRAPHY 209 INDEX 22 1 CHAPTER 1 THE VIEWS OF ANTIQUITY ON SALT AND SEA WATER WATER ANALYSIS PRIOR TO BOYLE In 1674 the famous English chemist and natural philosopher Robert Boyle (1 627- 1691) published a treatise entitled Observations and Experiments on the Saltness of the Sea. This was an extraordinary work which in the opinion of several (modern) writers established him as the founder of the science that is now referred to as chemical oceanography (258*, p.5; 284*, p.
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