The effects of secular calcium and magnesium concentration changes on the thermodynamics of seawater acid/base chemistry: Implications for Eocene and Cretaceous ocean carbon chemistry and buffering

Global Biogeochemical Cycles

Volumn 29, Issue 5, 2015, Pages 517-533

  Hain, Mathis P ^a   Sigman, Daniel M ^b   Higgins, John A ^b   Haug, Gerald H ^c  

^a UNIVERSITY OF SOUTHAMPTON   (United Kingdom)

^b PRINCETON UNIVERSITY   (United States)

^c GEOLOGICAL INSTITUTE   (Switzerland)

Author keywords

acidification; carbon chemistry; carbon dioxide; ion pairing; seawater buffering; seawater calcium

Indexed keywords

ACIDIFICATION; BUFFERING; CARBON DIOXIDE; CRETACEOUS; EOCENE; ION; SEAWATER; SECULAR VARIATION; THERMODYNAMICS;

EID: 85027936341     PISSN: 08866236     EISSN: 19449224     Source Type: Journal    
DOI: 10.1002/2014GB004986     Document Type: Article

References (99)

1. 2 history, Nat. Geosci., 4, 418-420.
2. Ben-Yaakov, S., and, M. B. Goldhaber, (1973), Influence of sea-water composition on apparent constants of carbonate system, Deep Sea Res., 20 (1), 87-99.
3. Buitenhuis, E. T., H. J. W. de Baar, and, M. J. W. Veldhuis, (1999), Photosynthesis and calcification by Emiliania huxleyi (Prymnesiophyceae) as a function of inorganic carbon species, J. Phycol., 35 (5), 949-959.
4. Campbell, D. M., F. J. Millero, R. Roy, L. Roy, M. Lawson, K. M. Vogel, and, C. P. Moore, (1993), The standard potential for the hydrogen-silver, silver-chloride electrode in synthetic seawater, Mar. Chem., 44 (2-4), 221-233.
5. Clegg, S. L., J. A. Rard, and, K. S. Pitzer, (1994), Thermodynamic properties of 0-6 mol/kg aqueous sulfuric-acid from 273.15 to 328.15K, J. Chem. Soc.-Faraday Trans., 90 (13), 1875-1894.
6. Coggon, R. M., D. A. H. Teagle, C. E. Smith-Duque, J. C. Alt, and, M. J. Cooper, (2010), Reconstructing past seawater Mg/Ca and Sr/Ca from mid-ocean ridge flank calcium carbonate veins, Science, 327 (5969), 1114-1117.
7. Criss, C. M., and, F. J. Millero, (1996), Modeling the heat capacities of aqueous 1-1 electrolyte solutions with Pitzer's equations, J. Phys. Chem., 100 (4), 1288-1294.
8. Criss, C. M., and, F. J. Millero, (1999), Modeling heat capacities of high valence-type electrolyte solutions with Pitzer's equations, J. Solution Chem., 28 (7).
9. de Nooijer, L. J., T. Toyofuku, and, H. Kitazato, (2009), Foraminifera promote calcification by elevating their intracellular pH, Proc. Natl. Acad. Sci. U.S.A., 106, 15,374-15,378.
10. 2 since 60 Ma from records of seawater pH, calcium, and primary carbonate mineralogy, Geology, 31 (9), 793-796.
11. Demicco, R. V., T. K. Lowenstein, L. A. Hardie, and, R. J. Spencer, (2005), Model of seawater composition for the Phanerozoic, Geology, 33, 877-880.
12. Dickens, G. R., J. R. Oneil, D. K. Rea, and, R. M. Owen, (1995), Dissociation of oceanic methane hydrate as a cause of the carbon-isotope excursion at the end of the Paleocene, Paleoceanography, 10 (6), 965-971, doi: 10.1029/95PA02087.
13. 4 in synthetic sea-water from 273.15 to 318.15K, J. Chem. Thermodyn., 22 (2), 113-127.
14. Dickson, A. G., (1990b), Thermodynamics of the dissociation of boric-acid in synthetic seawater from 273.15 to 318.15K, Deep Sea Res., Part A, 37 (5), 755-766.
15. Dickson, A. G., (2010), The carbon dioxide system in seawater: Equilibrium chemistry and measurements, in Guide to Best Practices for Ocean Acidification Research and Data Reporting, edited by, V. J. F. U. Riebesell, L. Hansson, and, J. P. Gattuso, pp. 17-40, European Commission, Brussels, Belgium.
16. 2 Measurements, 176 pp., North Pacific Marine Science Organization, Sidney, British Columbia.
17. Dickson, J. A. D., (2002), Fossil echinoderms as monitor of the Mg/Ca ratio of Phanerozoic oceans, Science, 298 (5596), 1222-1224.
18. Dickson, J. A. D., (2004), Echinoderm skeletal preservation: Calcite-aragonite seas and the Mg/Ca ratio of Phanerozoic oceans, J. Sediment. Res., 74 (3), 355-365.
19. Egleston, E. S., C. L. Sabine, and, F. M. M. Morel, (2010), Revelle revisited: Buffer factors that quantify the response of ocean chemistry to changes in DIC and alkalinity, Global Biogeochem. Cycles, 24, doi: 10.1029/2008GB003407.
20. Felmy, A. R., and, J. H. Weare, (1986), The prediction of borate mineral equilibria in natural-waters-Application to Searles Lake, California, Geochim. Cosmochim. Acta, 50 (12), 2771-2783.
21. 2, ice volume and climate during the middle Miocene, Earth Planet. Sci. Lett., 341, 243-254.
22. 2 system in seawater, J. Mar. Syst., 5 (2), 111-118.
23. Gagnon, A. C., J. F. Adkins, and, J. Erez, (2012), Seawater transport during coral biomineralization, Earth Planet. Sci. Lett., 329, 150-161.
24. Garrels, R. M., and, M. E. Thompson, (1962), A chemical model for sea water at 25°C and one atmosphere total pressure, Am. J. Sci., 260, 57-66.
25. Gattuso, J. P., M. Frankignoulle, I. Bourge, S. Romaine, and, R. W. Buddemeier, (1998), Effect of calcium carbonate saturation of seawater on coral calcification, Global Planet. Change, 18 (1-2), 37-46.
26. 2O system to high-concentration from 0°C to 250°C, Geochim. Cosmochim. Acta, 53 (10), 2503-2518.
27. Gothmann, A. M., J. Stolarski, J. F. Adkins, B. Schoene, K. J. Dennis, D. P. Schrag, M. Mazur, and, M. L. Bender, (2015), Fossil corals as an archive of secular variations in seawater chemistry since the mesozoic, Geochim. Cosmochim. Acta, doi: 10.1016/j.gca.2015.03.018.
28. Harned, H. S., and, B. B. Owen, (1958), The Physical Chemistry of Electrolytic Solutions, Reinhold Publishing Corp, New York.
29. - from 0 to 50°C, J. Am. Chem. Soc., 63, 1706-1709.
30. 2O system to high ionic strengths at 25°C, Geochim. Cosmochim. Acta, 48 (4), 723-751.
31. 4 solutions from 0 to 90°C, Geochim. Cosmochim. Acta, 57 (15), 3533-3554.
32. Heinze, M., and, T. Ilyina, (2015), Ocean biogeochemistry in the warm climate of the late Paleocene, Clim Past, 11, 63-79, doi: 10.5194/cp-11-63-2015.
33. Hershey, J. P., M. Fernandez, P. J. Milne, and, F. J. Millero, (1986), The ionization of boric-acid in NaCl, Na-Ca-Cl and Na-Mg-Cl solutions at 25°C, Geochim. Cosmochim. Acta, 50 (1), 143-148.
34. Higgins, J. A., and, D. P. Schrag, (2006), Beyond methane: Towards a theory for the Paleocene-Eocene Thermal Maximum, Earth Planet. Sci. Lett., 245, 523-537.
35. Horita, J., H. Zimmermann, and, H. D. Holland, (2002), Chemical evolution of seawater during the Phanerozoic: Implications from the record of marine evaporites, Geochim. Cosmochim. Acta, 66 (21), 3733-3756.
36. 2 world, Science, 320, 336-340.
37. Intergovernmental Panel on Climate Change (2013), Detection and attribution of climate change: From global to regional, in Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change, edited by, T. F. Stocker, et al., pp. 867-952, Cambridge Univ. Press, Cambridge, U. K.
38. Lear, C. H., Y. Rosenthal, and, N. Slowey, (2002), Benthic foraminiferal Mg/Ca-paleothermometry: A revised core-top calibration, Geochim. Cosmochim. Acta, 66 (19), 3375-3387.
39. Lowenstam, H. A., and, S. Weiner, (1989), On Biomineralization, 324 pp., Oxford Univ. Press, Oxford, U. K.
40. Lowenstein, T. K., M. N. Timofeeff, S. T. Brennan, L. A. Hardie, and, R. V. Demicco, (2001), Oscillations in Phanerozoic seawater chemistry: Evidence from fluid inclusions, Science, 294 (5544), 1086-1088.
41. Lowenstein, T. K., L. A. Hardie, M. N. Timofeeff, and, R. V. Demicco, (2003), Secular variations in seawater chemistry and the origin of calcium chloride basinal brines, Geology, 31, 857-860, doi: 10.1130/G19728R.1.
42. 2 in gas and seawater at equilibrium, Mar. Chem., 70 (1-3), 105-119.
43. Mackinder, L., G. Wheeler, D. Schroeder, U. Riebesell, and, C. Brownlee, (2010), Molecular mechanisms underlying calcification in coccolithophores, Geomicrobiol. J., 27, 585-595.
44. Manov, G. G., N. J. DeLollis, and, S. F. Acree, (1944), Ionization constant of boric acid and the pH of certain borax-chloride buffer solutions from 0° to 60°C, J. Res. Nat. Bur. Stds., 33, 287-306.
45. Millero, F. J., (1979), Thermodynamics of carbonate system in seawater, Geochim. Cosmochim. Acta, 43 (10), 1651-1661.
46. Millero, F. J., (1995), Thermodynamics of the carbon-dioxide system in the oceans, Geochim. Cosmochim. Acta, 59 (4), 661-677.
47. Millero, F. J., and, D. Pierrot, (1998), A chemical equilibrium model for natural waters, Aquat. Geochem., 4 (1), 153-199.
48. Millero, F. J., and, D. R. Schreiber, (1982), Use of the ion-pairing model to estimate activity-coefficients of the ionic components of natural-waters, Am. J. Sci., 282 (9), 1508-1540.
49. Millero, F. J., and, R. N. Roy, (1997), A chemical equilibrium model for the carbonate system in natural waters, Croat. Chem. Acta, 70 (1), 1-38.
50. Millero, F. J., R. Feistel, D. G. Wright, and, T. J. McDougall, (2008), The composition of standard seawater and the definition of the reference-composition salinity scale, Deep Sea Res., Part A, 55, 50-72.
51. 2O system, to high-temperature and concentration, Geochim. Cosmochim. Acta, 52 (4), 821-837.
52. Mucci, A., (1983), The solubility of calcite and aragonite in seawater at various salinities, temperatures, and one atmosphere total pressure, Am. J. Sci., 283 (7), 780-799.
53. Mucci, A., and, J. W. Morse, (1984), The solubility of calcite in seawater solutions of various magnesium concentration, It=0.697M at 25°C and one atmosphere total pressure, Geochim. Cosmochim. Acta, 48 (4), 815-822.
54. Owen, B. B., (1934), The dissociation constant of boric acid from 10 to 50°C, J. Am. Chem. Soc., 65, 1695-1697.
55. 2O, Geochim. Cosmochim. Acta, 51 (9), 2429-2443.
56. Pagani, M., D. Lemarchand, A. Spivack, and, J. Gaillardet, (2005), A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates, Geochim. Cosmochim. Acta, 69, 953-961.
57. Pagani, M., K. Caldeira, D. Archer, and, J. C. Zachos, (2006), An ancient carbon mystery, Science, 314, 1556-1557.
58. Pälike, H., et al., (2012), A Cenozoic record of the equatorial Pacific carbonate compensation depth, Nature, 488, 609-614.
59. Parkhurst, D. L., (1995), User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations, U.S. Geological Survey; U.S. Geological Survey, Earth Science Information Center, Water-Resources Investigations Report 95-4227.
60. Pearson, P. N., and, M. R. Palmer, (1999), Middle Eocene seawater pH and atmospheric carbon dioxide concentrations, Science, 284 (5421), 1824-1826.
61. Pearson, P. N., and, M. R. Palmer, (2000), Atmospheric carbon dioxide concentrations over the past 60 million years, Nature, 406 (6797), 695-699.
62. Peiper, J. C., and, K. S. Pitzer, (1982), Thermodynamics of aqueous carbonate solutions including mixtures of sodium-carbonate, bicarbonate, and chloride, J. Chem. Thermodyn., 14 (7), 613-638.
63. 4 solutions from 0 to 50 degrees C and ionic strengths up to 6 molal, J. Solution Chem., 26 (1), 31-45.
64. Pitzer, K. S., (1973), Thermodynamics of electrolytes: 1. Theoretical basis and general equations, J. Phys. Chem., 77 (2), 268-277.
65. Pitzer, K. S., (1991), Ion interaction approach: Theory and data correlation, in Activity Coefficients in Electrolyte Solutions, edited by, K. S. Pitzer, pp. 75-153, C.R.C. Press, Boca Raton, Fla.
66. Pitzer, K. S., and, G. Mayorga, (1973), Thermodynamics of electrolytes: 2. Activity and osmotic coefficients for strong electrolytes with one or both ions univalent, J. Phys. Chem., 77 (19), 2300-2308.
67. Pitzer, K. S., and, G. Mayorga, (1974), Thermodynamics of electrolytes. III Activity and osmotic coefficients for 2-2 electrolytes, J. Solution Chem., 3 (7), 539-546.
68. Pitzer, K. S., J. Olsen, J. M. Simonson, R. N. Roy, J. J. Gibbons, and, L. Rowe, (1985), Thermodynamics of aqueous magnesium and calcium bicarbonate and mixtures with chloride, J. Chem. Eng. Data, 30 (1), 14-17.
69. 2O, Geochim. Cosmochim. Acta, 46 (6), 1011-1040.
70. 3 solutions, J. Solution Chem., 31 (5), 343-367.
71. Rausch, S., F. Boehm, W. Bach, A. Kluegel, and, A. Eisenhauer, (2013), Calcium carbonate veins in ocean crust record a threefold increase of seawater Mg/Ca in the past 30 million years, Earth Planet. Sci. Lett., 362, 215-224.
72. Reinfelder, J. R., (2011), Carbon concentrating mechanisms in eukaryotic marine phytoplankton, Annu. Rev. Mar. Sci., 3, 291-315.
73. Ridgwell, A., (2005), A mid Mesozoic revolution in the regulation of ocean chemistry, Mar. Geol., 217, 339-357.
74. Ries, J. B., (2005), Aragonite production in calcite seas: Effect of seawater Mg/Ca ratio on the calcification and growth of the calcareous alga Penicillus capitatus, Paleobiology, 31, 445-458.
75. Ries, J. B., (2006a), Mg fractionation in crustose coralline algae: Geochemical, biological, and sedimentological implications of secular variation in the Mg/Ca ratio of seawater, Geochim. Cosmochim. Acta, 70, 891-900.
76. Ries, J. B., (2006b), Aragonitic algae in calcite seas: Effect of seawater Mg/Ca ratio on algal sediment production, J. Sediment. Res., 76, 515-523.
77. Ries, J. B., S. M. Stanley, and, L. A. Hardie, (2006), Scleractinian corals produce calcite, and grow more slowly, in artificial Cretaceous seawater, Geology, 34, 525-528.
78. 2-induced ocean acidification, Geology, 37, 1131-1134.
79. Risacher, F., and, A. Clemant, (2001), A computer program for the simulation of evaporation of natural waters to high concentration, Comput. Geosci., 27 (2), 191-201.
80. Roberts, C. D., and, A. K. Tripati, (2009), Modeled reconstructions of the oceanic carbonate system for different histories of atmospheric carbon dioxide during the last 20 Ma, Global Biogeochem. Cycles, 23, doi: 10.1029/2008GB003310.
81. Roy, R. N., J. J. Gibbons, M. D. Wood, R. W. Williams, J. C. Peiper, and, K. S. Pitzer, (1983), The 1st ionization of carbonic-acid in aqueous-solutions of KCl including the activity-coefficients of potassium bicarbonate, J. Chem. Thermodyn., 15 (1), 37-47.
82. Silvester, L. F., and, K. S. Pitzer, (1978), Thermodynamics of electrolytes. 10 Enthalpy and effect of temperature on activity-coefficients, J. Solution Chem., 7 (5), 327-337.
83. Simonson, J. M., R. N. Roy, and, J. J. Gibbons, (1987a), Thermodynamics of aqueous mixed potassium carbonate, bicarbonate, and chloride solutions to 368 K, J. Chem. Eng. Data, 32 (1), 41-45.
84. Simonson, J. M., R. N. Roy, L. N. Roy, and, D. A. Johnson, (1987b), The thermodynamics of aqueous borate solutions. 1 Mixtures of boric-acid with sodium or potassium borate and chloride, J. Solution Chem., 16 (10), 791-803.
85. Simonson, J. M., R. N. Roy, D. Mrad, P. Lord, L. N. Roy, and, D. A. Johnson, (1988), There thermodynamics of aqueous borate solutions. 2 Mixtures of boric-acid with calcium or magnesium borate and chloride, J. Solution Chem., 17 (5), 435-446.
86. Stanley, S. M., (2006), Influence of seawater chemistry on biomineralization throughout Phanerozoic time: Paleontological and experimental evidence, Palaeogeogr. Palaeoclimatol. Palaeoecol., 232, 214-236.
87. Stanley, S. M., and, L. A. Hardie, (1998), Secular oscillations in the carbonate mineralogy of reef-building and sediment-producing organisms driven by tectonically forced shifts in seawater chemistry, Palaeogeogr. Palaeoclimatol. Palaeoecol., 144 (1-2), 3-19.
88. Stanley, S. M., and, L. A. Hardie, (1999), Hypercalcification: Paleontology links plate tectonics and geochemistry to sedimentology, Geol. Soc. Am. Bull., 9 (2), 1-7.
89. Stanley, S. M., J. B. Ries, and, L. A. Hardie, (2002), Low-magnesium calcite produced by coralline algae in seawater of Late Cretaceous composition, Proc. Natl. Acad. Sci. U.S.A., 99 (24), 15,323-15,326.
90. Stanley, S. M., J. B. Ries, and, L. A. Hardie, (2005), Seawater chemistry, coccolithophore population growth, and the origin of Cretaceous chalk, Geology, 33, 593-596.
91. Stanley, S. M., J. B. Ries, and, L. A. Hardie, (2010), Increased production of calcite and slower growth for the major sediment-producing alga Halimeda as the Mg/Ca ratio of seawater is lowered to a "calcite sea" level, J. Sediment. Res., 80, 6-16.
92. Steuber, T., and, A. Veizer, (2002), Phanerozoic record of plate tectonic control of seawater chemistry and carbonate sedimentation, Geology, 30 (12), 1123-1126.
93. 2, and seasonal biological and temperature effects, Deep Sea Res., Part II, 49 (9-10), 1601-1622.
94. Thurmond, V., and, F. J. Millero, (1982), Ionization of carbonic-acid in sodium-chloride solutions at 25°C, J. Solution Chem., 11 (7), 447-456.
95. Timofeeff, M. N., T. K. Lowenstein, M. A. da Silva, and, N. B. Harris, (2006), Secular variation in the major-ion chemistry of seawater: Evidence from fluid inclusions in Cretaceous halites, Geochim. Cosmochim. Acta, 70, 1977-1994.
96. Tyrrell, T., and, R. E. Zeebe, (2004), History of carbonate ion concentration over the last 100 million years, Geochim. Cosmochim. Acta, 68 (17), 3521-3530.
97. Weiss, R. F., (1974), Carbon dioxide in water and seawater: The solubility of a non-ideal gas, Mar. Chem., 2, 203-215.
98. Zeebe, R. E., (2013), What caused the long duration of the Paleocene-Eocene Thermal Maximum?, Paleoceanography, 28, 440-452, doi: 10.1002/palo.20039.
99. Zeebe, R. E., J. C. Zachos, and, G. R. Dickens, (2009), Carbon dioxide forcing alone insufficient to explain Palaeocene-Eocene Thermal Maximum warming, Nat. Geosci., 2, 576-580, doi: 10.1038/ngeo578.