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Alfonso Mucci Department of Earth and Planetary Sciences EPSC-542 Department of Earth and Planetary Sciences EPSC-542 Chemical Oceanography Tuesday and Thursday: 11:35AM-12:55PM FDA-348 Alfonso Mucci [email protected] Frank Dawson Adams (FDA) - 201 Teaching Assistant Pascle Daoust ([email protected]) FDA-349 2/66 EPSC-542 Chemical Oceanography Course outline Week Subject 1 Introduction -organization (course description and schedule), books, evaluation scheme. 2 History of chemical oceanography The ocean as a stratified body of water Origin and evolution of the early ocean 2/3 Seawater composition -Definition of salinity/chlorinity and concept of constant relative proportions -Determination of salinity -Salinity distribution in the ocean -Validity of the law of constant relative proportions 3 Properties of water -Isotopic composition -Anomalous physical properties of water -The structure of liquid water -Influence of solutes on the structure of water 4 The behaviour of electrolytes and non-electrolytes in solution -Electrostriction -Speciation and ion-pairing 4/5 Minor elements -Concept of residence time -Distribution of minor elements in the ocean 3/66 Course outline (continued) 6 Micronutrient elements -Phosphate and the phosphorus cycle -Nitrogen and the nitrogen cycle -The ocean's internal cycle -The horizontal segregation of elements in the deep-sea 7/8 Dissolved gases -Solubility of gases in seawater -The rate of gas exchange between the atmosphere and ocean -Disequilibrium between the atmosphere and ocean -Dissolved oxygen distribution in the ocean 9/10 CO2 and the carbonate system -The chemistry of the CO2-H2O system -pH measurements in seawater -Buffer capacity of seawater -The solubility and distribution of carbonate minerals in marine sediments 11/12 Deep-sea sediments -Origin of deep-sea sediments (e.g weathering, transport, authigenic and biogenic production) -Components of deep-sea sediments (e.g. clays, carbonates, evaporites, silicates, phosphates) -Sedimentation rate -Sediment diagenesis 13 Organic matter in the marine environment -Origin and composition of DOC and POC -Humic acids and substances -The carbon cycle 4/66 Method of Evaluation: Mid-term 30% (February 27, 2020, to be confirmed) Problem sets 20% Final 50% (final examination period, in dept.) McGill University values academic integrity. Therefore all students must understand the meaning and consequences of cheating, plagiarism and other academic offences under the Code of Student Conduct and Disciplinary Procedures (see www.mcgill.ca/integrity for more information). L'université McGill attache une haute importance à l'honnêteté académique. Il incombe par conséquent à tous les étudiants de comprendre ce que l'on entend par tricherie, plagiat et autres infractions académiques, ainsi que les conséquences que peuvent avoir de telles actions, selon le Code de conduite de l'étudiant et des procédures disciplinaires (pour de plus amples renseignements, veuillez consulter le site www.mcgill.ca/integrity). In accord with McGill University’s Charter of Students’ Rights, students in this course have the right to submit in English or in French any written work that is to be graded. http://eps.mcgill.ca/~courses/c542/ 5/66 Reference books: Bianchi T.S. (2007) Biogeochemistry of Estuaries, Oxford University Press, New York, 706 pp. Broecker, W.M. (1974) Chemical Oceanography, Harcourt Brace Jovanovich, New York, 214pp. Broecker, W.M. and Peng, T-H. (1982) Tracers in The Sea, Eldigio Press, Palisades, New York, 690 pp. Chester, R. (1990) Marine Geochemistry, Unwin Hyman, London, 698pp. Dietrich, G., Kalle, K., Krauss, W. and Siedler, G. (1980) General Oceanography, Translated from German by S. and H. Ulrich Roll, John Wiley & Sons, New York, 626pp. Horne, R.A. (1969) Marine Chemistry, Wiley-Interscience, New York, 568 pp. Millero, F.J. and Sohn, M.L. (1992) Chemical Oceanography, Taylor & Francis Group, CRC Press Millero, F.J. (2013) Chemical Oceanography, 4thEdition, CRC Press, Boca Raton, 469pp Millero, F.J. (2001) The Physical Chemistry of Natural Waters, Wiley-Interscience, Pilson, M.E. (1998) An Introduction to the Chemistry of the Sea, Prentice Hall, N.J., 431pp. Riley, J.P. and Chester, R. (1971) Introduction to Marine Chemistry, Academic Press, New York, 465pp. Riley, J.P. and Skirrow, G. (1965) Chemical Oceanography, V. 1, 2, Academic Press, London Riley, J.P. and Skirrow, G. (1975) Chemical Oceanography, V. 1, 2, 3 & 4, Academic Press, London. Riley, J.P. and Chester, R. (1976) Chemical Oceanography, V. 5 & 6, (1978) V. 7, (1983) V. 8, Academic Press, London Schulz H.D. and Zabel M. (2006) Marine Geochemistry, 2nd Edition, Springer, New York, 574 pp. Stumm, W. and Morgan, J.J. (1981) Aquatic Chemistry, John Wiley & Sons, New York, 780pp. 6/66 Chemical Oceanography Frank J. Millero Fourth Edition http://eps.mcgill.ca/~courses/c542/ 7/66 8/66 Chemical Oceanography? or phosphate Marine Chemistry? nitrate silicate 9/66 The Earth ~12,756 km in diameter at the equator 10/66 11/66 World Oceans Map The Blue Planet 12/66 Continents and oceans as percentages of the total world surface area Earth = 510 million km2 Oceans = 362 million km2 or ~71% of Earth’s surface = 1.37 billion km3 = 1.37 x 1021 liters = 1.40 x 1024 g = 98% of the water on the Earth’s surface. From: P.J. Wyllie (1976) The Way the Earth Works 13/66 Elevation map of the Earth Darker blues are deeper water in the ocean (average depth = 3800 m) Greens are lower elevation on land (average elevation = 880 m) 14/66 15/66 Hypsographic curve of the Earth’s surface Everest = 8850 m Continental slope Continental rise Abyssal plains Trenches Mariana Trench = 11000 m 16/66 Distribution of land masses on Earth Today, 65% of the continents are found in the Northern Hemisphere From: P.J. Wyllie (1976) The Way the Earth Works 17/66 The ocean floor revealed Continental shelf Continental slope Continental rise 25% of the continental Mid-ocean ridges crust (or 11% of the Earth’s surface) is cover ~25% of the Abyssal plain Earth’s surface presently covered by whereas mountain ranges water. cover only ~10%. 18/66 Mid-ocean ridges Mid-ocean ridges cover ~25% of the Earth’s surface 19/66 The Ocean as a chemical system 20/66 The Ocean as a Chemical System 21/66 History of Chemical Oceanography 1627-1691 / Robert Boyle (Often considered the founder of modern chemistry and scientific oceanography, but best known for his law on the relationship between gas pressure and volume, i.e., P1V1 = P2V2 at constant T.) 1670 - “Observations and Experiments on the Saltness of the Sea” Introduced the use of AgNO3 to test for the “saltness” of natural waters. He believed sea salts to be residues of leaching from land by rivers. Attempted to determine the total salt content of seawater by evaporation … but concluded that measurements of specific gravity provided a more accurate measure of seawater salt content. 22/66 History of Chemical Oceanography 1635-1703/ Robert Hooke (Best know for his law of elasticity, inventor of the air pump and watch balance spring) In 1655, he became Robert Boyle’s assistant. Observed that the density of seawater in the English Channel increases with depth, which he attributed to an increase in salinity but … 23/66 History of Chemical Oceanography 1743-1794/ Antoine Lavoisier (French chemist best known for proving the law of conservation of mass and identifying the elements that make up water, i.e., oxygen and hydrogen) 1776 – First analysis of seawater following its slow evaporation (~70%), during which he observed the precipitation of calcium carbonate and calcium sulfate. Upon further evaporation, NaCl was precipitated, followed by MgCl2 and MgSO4. He was then left with an unidentifiable residue. 24/66 History of Chemical Oceanography 1778-1850/Joseph Louis Gay-Lussac (French chemist, best known for his two laws relating the behavior of ideal gases: stoichiometry of reacting gases and the relationship between gas pressure and temperature, i.e., P1/T1 = P2/T2 at constant V). 1817 – He used titrimetry to develop simple and accurate methods to determine salt concentrations in seawater and concluded that these were constant everywhere in the open ocean, as published in “Note sur la Salure de l’Océan Atlantique.” 25/66 History of Chemical Oceanography 1778-1820/ John Murray (Scottish chemist) Using the evaporative procedure of Lavoisier, he demonstrated that the precipitates were far from being pure salts. He proposed that seawater was made up of individual “acids and bases” and elaborated a number of gravimetric methods for the determination of individual ions. Precipitated sulfate with BaCl2 BaSO4 Precipitated calcium as an oxalate (CaC2O4) and converted it to sulfate (CaSO4) for weighing. 1818 – Published a paper entitled “An analysis of sea-water; with observations on the analysis of salt-brines” 26/66 History of Chemical Oceanography 1770-1822/ Alexander Marcet (Physician and animal chemist) Using Murray’s procedures, he analyzed 70 seawater samples collected in the Mediterranean and in the Atlantic . In 1819, he presented a paper to the Royal Society in which he suggested that they contained the same ingredients, bearing very nearly the same proportions to each other, and that their concentration differ only as to the total amount of their salt content. 27/66 History of Chemical Oceanography 1794-1865/ Johann Georg Forchhammer (Ph.D. Polytechnical Institute, Copenhagen) Repeated previous studies on several hundred samples collected over a 20-year period (1843-1863) by seafaring men from different parts of the world. He analyzed for Ca, Mg, Cl, SO4 and, in some cases, K. He confirmed that the relative proportion of these ions was almost the same in all the samples. As a geologist, he was mostly interested in the fate of inorganic materials brought to the sea by rivers. He attributed their removal from seawater to the action of organisms, as skeletal components. More importantly, he concluded that the quantity of different elements in seawater is not proportional to the quantity of elements that river water delivers into the sea but is inversely proportional to the facility with which the elements in seawater are made insoluble by organisms or chemical reactions.
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