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50 Years of Ocean Discovery: National Science Foundation 1950—2000
eminent scientists and chemists of their times have made significant contributions to understanding the chemistry of the oceans. Among them, during the 1600s and 1700s, were Robert Boyle and his "Observations and Experiment About the Saltness of the Sea" (1674), "which, in the opinion of several (modern) writers, established him as the founder of the science that is now referred to as chemical oceanography" (Wallace, 1974, p. 1). Others from those years included Edmund Halley, Count Luigi Ferdinando Marsigili, Antoine Lavoisier, and Joseph Louis Gay-Lussac. From the late 1700s through the 1800s, Alexander Marcet, Johann Forchhammer, and William Dittmar undertook painstaking analyses of seawater, which provided the heralded "Marcet' s Principle," or the constancy of ratios of several major ions in seawater. Wallace (1974, p. 121) states, "Dittmar's report on the chemistry of the 77 water samples of the 'Challenger' expedition represents the most extensive seawater analysis performed before or since." The importance of knowing the density of seawater drove a significant part of chemical oceanography during the period of 1900 to 1950 to focus on salinity measurements or surrogates, mainly chlorinity, and to affirm the constancy of the ratios of the major ions of seawater. In addition, measurements of nutrients, dissolved oxygen, and the components of the carbonate system and alkalinity were pursued. It was this combination of understanding biological systems, refining and confirming the chlorinity-salinity-density relationships, and the beginnings of the understanding of distinctive chemical compositions for distinguishing water masses that characterized chemical studies of the oceans at that time.
During the 1920s, analytical methods for nutrient substances—mainly compounds of nitrogen and phosphorus— began to appear and to be improved. Individuals such as Atkins, Harvey, and Cooper and the organizing activities of the International Council for the Exploration of the Sea were important in this effort. Harvey's (1928) book The Biological Chemistry and Physics of Seawater captures chemical oceanography of the time as it was involved with biological productivity.
Overlapping in this time frame, in the 1930s, V.M. Goldschmidt, the renowned geochemist, and his school conducted their research on crustal abundances and ionic potential classifications. Goldschmidt and his group also initiated their studies of the mass balances and geochemical cycles of elements, including the oceans in their research (e.g., Goldschmidt, 1933, 1937). Also during this time Buch of Finland and others initiated studies of the physical chemistry of carbon dioxide in seawater. Wattenberg on the Meteor expedition drew attention to the fact that some areas of the ocean were supersaturated while others were undersaturated with respect to calcium carbonate.
Elizabeth Noble Shor, in her historical account of the Scripps Institution of Oceanography, quotes Norris Rakestraw: "One of the most striking observations of marine biology is the fact that some parts of the ocean are fertile while other parts are quite barren. There must be chemical factors which determine fertility, and an explanation of this was perhaps the first serious question which oceanographers asked the chemist. In the year 1930 there were probably no more than a dozen professional chemists in the world who were actively interested in the ocean, and practically every one of them was trying to answer this question" (Shor, 1978, p. 321).
The first chemical laboratory at the Scripps Institution of Oceanography was founded by Erik G. Moberg in 1930 (Shor, 1978). This was the beginning of a tradition of excellence in chemical oceanography and marine chemistry that continues to the present. Further north on the U.S. West Coast, Thomas G. Thompson at the University of Washington labored to improve the analyses of seawater during the 1920s to 1940s. People from those times who should know (NAS, 1971a) described Thompson's laboratory as follows: "For some years this laboratory was the most productive center for chemical oceanography in the United States." (p. 10) Beginning in the 1930s, chemical work began at the Woods Hole Oceanographic Institution (WHOI) with the efforts of Redfield, Seiwell, and Rakestraw, who also conducted research on the questions of the interaction of the biology and chemistry of the sea. Rakestraw later moved to the Scripps Institution of Oceanography.
J.P. Riley (1965) notes that as early as 1935 to 1937, fluorimeteric determinations of uranium in seawater coupled with other observations of the low concentrations of radium in seawater, led to the observation that uranium and radium-226 were in disequilibrium in seawater. The explanatory hypothesis was removal of thorium-230 from the water and its incorporation into sediments.
By 1940, the complexion of chemical oceanography had changed notably. Marine geology, or the geological aspects of oceanography, had been developing through the previous decades, and it had become quite evident that the chemistry of seawater was fundamentally involved in sedimentation phenomena.
Another major division appeared—marine geochemistry— concerned not merely with the use of chemistry to solve geological problems, but also with the part the ocean plays in the broad, general weathering cycles. Since most of the chemical elements have been found in seawater. the chemist is provided with an endless number of problems concerning the source, speciation, function, and significance of these elements and their interactions." (NAS, a, Chapter 1, pp. 10-11).
The World War II years provided a focus for further understanding salinity and the major chemical components contributing to salinity because of its relationship to sound transmission in the sea. At the Woods Hole Oceanographic Institution, Alfred C. Redfield and his former graduate student at Harvard University, Bostwick H. Ketchum, conducted extensive research on antifouling paints with great