AN ABSTRACT OF THE THESIS OF WILLIAM JOHN WALLACE, JR. for the Ph. D. (Name) (Degree) in GENERAL SCIENCE presented on April 7,1971 (Major) (Date) Title: THE DEVELOPMENT OF THE CHLORINITY-SALINITY CONCEPT INOCEANOGRAM Redacted for Privacy Abstract approved: Vert J. Moris This study traces the historical foundations of the concept of constant ionic proportionality and the equation (Salinity[S°700] = 1.805 Chlorinity [C1700] + 0.030) which has been in general use in ocean- ography since 1902 until 1969 and which is based upon this constancy, The notion that the constituents present in sea water exist in constant proportions was first clearly stated by Marcet in 1819.The germ of the idea may be found, however, in the worksof Bergmann in the late eighteenth century and implied in other works.Maury, in the mid-nineteenth century, popularized the concept and Forchhammer, in 1865, strengthened this idea by quantifying it and introducing the use of the "coefficient" of chlorine to determine salinity,Although he determined a slightly different value for the coefficient, Dittmar regarded his analysis of the sea water samples from the Challenger expedition as a vindication of Forchhammer's work.Knudsen, Forch and Sorensen, in 1902 gave a lengthy gravimetric definition for salinity based on the analysis of nine water samples.As this proce- dural definition was in practice too time-consuming to perform, the above equation was presented which relates the determination of salinity to that of chlorinity.The work of Knudsen, Forch and Sorensen, and that of Dittmar before them, wasaccepted as demonstrating the constancy of ionic proportionality, and the equation was a cornerstone of chemical oceanographyfrom 1902 to 1958. In 1958 a number of oceanographers began to criticize the equation and its underlying concept of constancy and to call for a redefinition of salinity.In 1969 a change in definition was formally recommended. This study supports such a redefinition on the basis that the historical evidence indicates that no one has ever demonstrated that the constitu- ents of sea water exist in constant proportion, that the number and types of sea water samples available to Knudsen,;Forch and Sorensen were not representative of the open ocean,and that these workers, themselves, believed the definition they gave to be only a temporary one. ®1971 William John Wallace, Jr. ALL RIGHTS RESERVED The Development of the Chlorinity-Salinity Concept in Oceanography by William John Wallace, Jr. A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy June 1971 APPROVED: Redacted for Privac Associate Professor eneral Scienc/ in chge of major Redacted for Privacy Chairman of Department of General Science Redacted for Privacy Dean of Graduate School Date thesis is presented May 7, 1971 Typed by Mary Jo Stratton for William John Wallace, Jr. ACKNOWLEDGEMENTS A thesis of this type probably necessitates more assistance from others than most dissertations.Although it would be very difficult to mention all those who have been of help since it was begun, 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 University of Chicago for their comments on Robert Boyle and the silver nitrate test, as well as Dr. John Lyman of the U. S. Fish and Wildlife Service, Dr. Francis A. Richards of the University of Washington, and Dr. Dayton E. Carritt of Massachusetts Institute of Technology for their comments early in the study.Dr. Edward D. Goldberg of the Scripps Institution of Oceanography and John P. Riley of the University of Liverpool were of much assistance in biblio- graphic questions. Dr. Jorgen Pindborg, Dean of the University of Copenhagen Dental 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 dissertation involved the use of many libraries.The friendly assistance afforded 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, and even faculty privileges at no cost, was tremendous.Mrs. Marion Minnick and the staff of the Oregon State University interlibrary loan department cheerfully helped to supply a large volume of photocopies and microfilms of original references. I would like to offer a special vote of thanks to Miss Audrey Lee Krueger for her kindness in the deciphering and transposal of the first good draft from handwritten scrawl to typed copy.Dr. Thomas H. Foote was most generous with his assistance in the proofing of the multilith masters of this- thesis. In closing, I would like to thank the members of my committee and especially my major professor, Dr, Robert J. Morris, who waded through a number of often barely legible drafts of this weighty tome and in whose hands the thesis improved measurably. TABLE OF CONTENTS Pa e I.THE VIEWS OF ANTIQUITY ON SALT AND SEA WATER 1 Water Analysis Prior to Boyle 1 Solution Analysis Prior to Boyle 23 The Late Seventeenth Century 30 IL ROBERT BOYLE 33 III.THE BEGINNINGS OF THE SYSTEMATIC STUDY OF THE SEA--HALLEY AND MARSILLI 55 Halley 58 Marsilli 63 IV. FOUNDATIONS OF SYSTEMATIC MINERAL AND SEA WATER ANALYSES 71 Gionetti 76 Lavoisier 78 Bergman 87 V. SEA WATER ANALYSIS AND THE PRECIPITATION METHOD 100 Murray 112 Marcet 128 Usiglio 148 VI. CONSTANT PROPORTIONALITY OF CONSTITUENTS 159 Gay-Lussac 165 Maury 183 VII.THE COEFFICIENT 191 Roux 208 H. M. S. Challenger 212 Dittmar 218 Page VIII.THE EQUATION 237 IX.CONCLUSIONS AND EPILOGUE 262 BIBLIOGRAPHY 284 APPENDICES Appendix I 312 Appendix II 314 Appendix III 318 Appendix IV 330 Appendix V 344 Appendix VI 347 Appendix VII 354 Appendix VIII 357 Appendix IX 359 LIST OF TABLES Table Page 1 The results of the analysis of sea water by Lavoisier, 81 2 The results of Lavoisier, Macquer and Sage for the analysis of water from the Dead Sea. 83 3 The results of the analysis of sea water by Bergman. 95 4 The results of the analysis of Baltic Sea water according to Heinrich Link. 106 5 The results of the analysis of Baltic Sea water by J. F. Pfaff. 107 6 The results of analyses by Bouillon- Lagrange and Vogel for sea water from tne English Channel, Atlantic Ocean and Mediterranean Sea. 110 7 The results of a sea water analysis by Murray according to the method of Lavoisier. 115 8 Conversion of the results by Murray given in Table 7. 116 9 Results of a sea water analysis by Murray based on an evaporation and crystallization method. 116 10 Results of the analysis by Murray of sea water with the assumption that the sulphate exists as sulphate of magnesia. 123 11 The results of sea water analysis by Murray using the indirect method. 123 12 The results of Murray's sea water analysis assuming that the constituent Table Page acids and bases combined as in evaporation mode. 124 13 The results of Murray's sea water analysis with the assumption the lime existed as muriate. 125 14 The results of Murrya's sea water analysis with the assumption that the sulphuric acid existed as sulphate of soda. 125 15 The results of Marcet's analysis of Dead Sea water. 130 16 Marcet's interpretation of the salts contained in Dead Sea water. 131 17 The analysis results by Marcet of sea water from the North Atlantic given as acids and bases. 134 18 Marcet's inferred state of combination of the results of Table 17. 135 19 The corrected values for Table 18, after drying. 135 20 The results of sea water analysis by Friedman Gobel. 140 21 The inferred state of composition of acids and bases of Table 20. 141 22 The analysis of sea water by Ernst von Bibra. 142 23 The analysis of Mediterranean sea water by G. Laurens. 144 24 The analysis of sea water by Darondeau. 145 25 The analysis of North Sea water by G. Clemm. 146 Table Page. 26 J. Usiglio's analysis of Mediterranean Sea water. 149 27 The analysis by Usiglio of three sea water samples partially evaporated to different specific gravities. 152 28 The analysis of Usiglio of sea water samples partially evaporated to varying specific gravities. 155 29 The composition of sea water (1965). 161 30 Density and salt content values by Gay-Lussac for a series of locations between Rio De Janeiro and France. 169 31 The salt content of sea water given by Maury. 185 32 The composition of sea water in the different parts of the ocean between N. 51°1-1/2' and 55°32'; and longitude 12°6' and 15°59' by Forchhammer. 197 33 The composition of sea water from the Red Sea, and from different depths in the Baltic, by Forchhammer. 199 34 Results of analysis of Atlantic Ocean water by Vincent. 207 35 Comparison of values of Dittmar and Forchhammer for components of sea water analysis. 222 36 Dittmar's inferred representation for the salt content of sea water. 223 37 Report of the composition of ocean water from the Challenger Expedition by Dittmar. 224 Table Page 38 Schmelk's analysis of water from the Norwegian Sea.