The free proton concentration scale for seawater pH

Marine Chemistry

Volumn 149, Issue , 2013, Pages 8-22

  Waters, Jason F ^a   Millero, Frank J ^a  

^a UNIVERSITY OF MIAMI   (United States)

Author keywords

Activity coefficient; PH; Seawater; Standards

Indexed keywords

ELECTRON; MARINE ENVIRONMENT; PH; SEAWATER; STANDARD (REFERENCE); STOICHIOMETRY;

EID: 84872484103     PISSN: 03044203     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.marchem.2012.11.003     Document Type: Article

References (83)

1. Archer D.G. Thermodynamic properties of NaBr+H2O system. J. Phys. Chem. Ref. Data 1991, 20(3):509-555.
2. Archer D.G. Thermodynamic properties of NaCl+H2O system I. Thermodynamic properties of NaCl(cr). J. Phys. Chem. Ref. Data 1992, 21:1-21.
3. Archer D.G. Thermodynamic Properties of the NaCl+H2O System II. Thermodynamic Properties of NaCl(aq), NaCl+2H2O(cr), and Phase Equilibria. J. Phys. Chem. Ref. Data 1992, 21(4):793-829.
4. Bates R.G. Definitions of pH scales. Chem. Rev. 1948, 42:1-61.
5. Bates R.G. Determination of pH: Theory and Practice 1973, John Wiley & Sons, New York. 2nd edition.
6. Bates R.G. pH measurements in the marine environment. Pure Appl. Chem. 1982, 54:229-232.
7. Bates R.G., Bower V.E. Standard potential of the silver-silver-chloride electrode from 0 to 95°C and the thermodynamic properties of dilute hydrochloric acid solutions. J. Res. Natl. Bur. Stand. 1954, 53(5):283-290.
8. Bates R.G., Calais J.G. Thermodynamics of the dissociation of BisH+in seawater from 5 to 40°C. J. Solution Chem. 1981, 10(4):269-279.
9. Bates R.G., Erickson W.P. Thermodynamics of the dissociation of 2-aminopyridinium ion in synthetic seawater and a standard for pH in marine systems. J. Solution Chem. 1986, 15(11):891-901.
10. Bates R.G., Guggenheim E.a. Report on the standardization of pHand related terminology. Pure Appl. Chem. 1960, 1:163-168.
11. Bates R.G., Hetzer H.B. Dissociation constant of the protonated acid form of 2-Amino-2-(Hydroxymethyl)-1,3-propanediol [Tris- Hydroxymethyl-Aminomethane] and related thermodynamic quantities from 0 to 50°C. J. Phys. Chem. 1961, 65(4):667-671.
12. Baucke F.G.K., Brett C.M.A., Milton M.J.T., Mussini T., Naumann R., Pratt K.W., Spitzer P., Wilson G.S. Measurement of pH. Definition, standards, and procedures (IUPAC Recommendations 2002). Pure Appl. Chem. 2002, 74(11):2169-2200.
13. Buck R.P., Rondinini S., Covington A.K., Baucke F.G.K., Brett C.M.A., Milton M.J.T., Mussini T., Naumann R., Pratt K.W., Spitzer P., Wilson G.S. Measurement of pH. Definition, standards and procedures. Pure Appl. Chem. 2002, 74(11):2169-2200.
14. Caldeira K., Wickett M.E. Anthropogenic carbon and ocean pH. Nature 2003, 425:365.
15. Campbell D.M., Millero F.J., Roy R., Roy L., Lawson M., Vogel K.M., Porter Moore C. The standard potential for the hydrogen-silver, silver chloride electrode in synthetic seawater. Mar. Chem. 1993, 44:221-233.
16. Clayton T.D., Byrne R.H., Breland J.A., Feely R.A. The role of pH measurements in modern oceanic CO2-system characterizations: precision and thermodynamic consistency. Deep-Sea Res. 1995, 42(2-3):411-429.
17. Clegg S.L., Whitfield M. A chemical model of seawater including dissolved ammonia and the stoichiometric dissociation constant of ammonia in estuarine water and seawater from 2 to 40°C. Geochim. Cosmochim. Acta 1995, 59(12):2403-2421.
18. Clegg S.L., Pitzer K.S., Rard J.A. Thermodynamic properties of 0-6molkg-1 aqueous sulfuric acid from 273.15 to 328.15K. J. Chem. Soc. Faraday Trans. 1994, 90(13):1875-1894.
19. Cooley S.R., Doney S.C. Anticipating ocean acidification's economic consequences for commercial fisheries. Environ. Res. Lett. 2009, 4(2):024007.
20. Covington A.K., Bates R.G., Durst R.A. Definition of pH scales, standard reference values, measurement of pH and related terminology. Pure Appl. Chem. 1985, 57(2):533-542.
21. Culberson C., Pytkowicz R.M., Hawley J.E. Sea water alkalinity determination by the pH method. J. Mar. Res. 1970, 28:15-21.
22. Czerminski J.B., Dickson A.G., Bates R.G. Thermodynamics of the dissociation of morpholinium ion in seawater from 5 to 40°C. J. Solution Chem. 1982, 11(2):79-89.
23. de Lima M.C.a.P., Pitzer K.S. Thermodynamics of saturated electrolyte mixtures of NaCl with Na2SO4 and with MgCl2. J. Solution Chem. 1983, 12(3):187-199.
24. DelValls T.A., Dickson A.G. The pH of buffers based on 2-amino-2-hydroxymethyl-1,3-propanediol ('tris') in synthetic sea water. Deep-Sea Res. I 1998, 45(9):1541-1554.
25. Dickson A.G. An exact definition of total alkalinity and a procedure for the estimation of alkalinity and total inorganic carbon from titration data. Deep-Sea Res. A Oceanogr. Res. Pap. 1981, 28(6):609-623.
26. Dickson A.G. pH scales and proton-transfer reactions in saline media such as sea water. Geochim. Cosmochim. Acta 1984, 48(11):2299-2308.
27. Dickson A.G. Standard potential of the reaction: AgCl(s)+1/2H2(g)=Ag(s)+HCl(aq), and the standard acidity constant of the ion in synthetic sea water from 273.15 to 318.15K. J. Chem. Thermodyn. 1990, 22:113-127.
28. Dickson A.G. The measurement of sea water pH. Mar. Chem. 1993, 44(2-4):131-142.
29. Dickson A.G., Millero F.J. A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media. Deep-Sea Res. 1987, 34:1733-1743.
30. Dickson A.G., Wesolowski D.J., Palmer D.A., Mesmer R.E. Dissociation constant of bisulfate ion in aqueous sodium chloride solutions to 250°C. J. Phys. Chem. 1990, 94:7978-7985.
31. Dickson A.G., Sabine C.L., Christian J.R. Guide to Best Practices for Ocean CO2 Measurements 2007, 3. PICES Special Publication, (191 pp.).
32. Doney S.C., Fabry V.J., Feely R.A., Kleypas J.A. Ocean acidification: the other CO2 problem. Annu. Rev. Mar. Sci. 2009, 1:169-192.
33. Dyrssen D., Hansson I. Ionic medium effects in sea water - a comparison of acidity constants of carbonic acid and boric acid in sodium chloride and synthetic sea water. Mar. Chem. 1973, 1:137-149.
34. Feely R.A., Sabine C.L., Lee K., Berelson W., Kleypas J., Fabry V.J., Millero F.J. Impact of anthropogenic CO2 on the CaCO3 system in the oceans. Science 2004, 305(5682):362-366.
35. Greenberg J.P., Møller N. The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the system to high concentration from 0 to 250°C. Geochim. Cosmochim. Acta 1989, 53:2503-2518.
36. Guinotte J.M., Fabry V.J. The threat of acidification to ocean ecosystems. J. Mar. Ed. 2009, 25:2-7.
37. Harned H.S., Bonner F.T. The first ionization constant of carbonic acid in aqueous solutions of sodium chloride. J. Am. Chem. Soc. 1945, 67:1026-1031.
38. Harned H.S., Scholes S.R. The ionization constant of HCO3? from 0 to 50°C. J. Am. Chem. Soc. 1941, 63:1706-1709.
39. Harvie C.E., Møller N., Weare J.H. The prediction of mineral solubilities in natural waters: The Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25°C. Geochim. Cosmochim. Acta 1984, 48(4):723-751.
40. Hetzer H.B., Bates R.G., Robinson R.A. Dissociation constant of morpholinium ion and related thermodynamic quantities from 0 to 50. J. Phys. Chem. 1966, 70(9):2869-2872.
41. Holmes H.F., Mesmer R.E. Thermodynamic properties of aqueous solutions of the alkali metal chlorides to 250°C. J. Phys. Chem. 1986, 87:1242-1255.
42. Climate Change 2001: The Scientific Basis: Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change 2001, Cambridge University Press, Cambridge, UK and New York, NY, USA. J. Houghton, Y. Ding, J., G. D., M., N., P.J. van der Linden, X., D., K., M., A., J. C. (Eds.).
43. Hovey J.K., Hepler L.G. Thermodynamics of sulphuric acid: apparent and partial molar heat capacities and volumes of aqueous HSO4 from 10-55°C and calculation of the second dissociation constant to 350°C. J. Chem. Soc. Faraday Trans. 1990, 16:2831-2839.
44. Khoo K.H., Ramette R.W., Culberson C.H., Bates R.G. Determination of hydrogen ion concentrations in seawater from 5 to 40°C: standard potentials at salinities from 20 to 45%. Anal. Chem. 1977, 49:29-34.
45. Marion G.M. A molal-based model for strong acid chemistry at low temperatures (<200 to 298K). Geochim. Cosmochim. Acta 2002, 66(14):2499-2516.
46. Marion G.M., Kargel J.S., Catling D.C. A molal-based model for strong acid chemistry at low temperatures (<200 to 298K). Geochim. Cosmochim. Acta 2008, 72:242-266.
47. Marion G.M., Millero F.J., Camoes M., Spitzer P., Feistel R., Chen C.-T. pH of seawater. Mar. Chem. 2011, 1-8.
48. Matsushima Y., Okuwaki A. The second dissociation constant of sulfuric acid at elevated temperatures from potentiometric measurements. Bull. Chem. Soc. Jpn. 1988, 61(9):3344-3346.
49. Mehrbach C., Culberson C.H., Hawley J.E., Pytkowicz R.M. Measurement of the apparent dissociation constants of carbonic acid in seawater at atmospheric pressure. Limnol. Oceanogr. 1973, 18(6):897-907.
50. Millero F.J. The estimation of the pK*HA of acids in seawater using the Pitzer equations. Geochim. Cosmochim. Acta 1983, 47(1979):2121-2129.
51. Millero F.J. The pH of estuarine waters. Limnol. Oceanogr. 1986, 31(4):839-847.
52. Millero F.J. Physical Chemistry of Natural Waters 2001, Wiley-Interscience, N.Y., 496 pp.
53. Millero F.J. The marine inorganic carbon cycle. Chem. Rev. 2007, 107(2):308-341.
54. Millero F.J. Carbonate constants for estuarine waters. Mar. Freshwater Res. 2010, 61:139-142.
55. Millero F.J., DiTrolio B. Use of thermodynamics in examining theeffects of ocean acidification. Elements 2010, 6(5):299-303.
56. Millero F.J., Pierrot D. A chemical equilibrium model for natural waters. Aquat. Geochem. 1998, 4:153-199.
57. Millero F.J., Roy R.N. A chemical equilibrium model for the carbonate system in natural waters. Croat. Chem. Acta 1997, 70:1-38.
58. Millero F.J., Schreiber D.R. Use of the ion pairing model to estimate activity coefficients of the ionic components of natural waters. Am. J. Sci. 1982, 282:1508-1540.
59. Millero F.J., Zhang J.-Z., Fiol S., Sotolongo S., Roy R.N., Lee K., Mane S. The use of buffers to measure the pH of seawater. Mar. Chem. 1993, 44:143-152.
60. Millero F.J., Graham T.B., Huang F., Bustos-Serrano H., Pierrot D. Dissociation constants of carbonic acid in seawater as a function of salinity and temperature. Mar. Chem. 2006, 100(1-2):80-94.
61. Millero F.J., Woosley R., DiTrolio B., Waters J. Effect of ocean acidification on the speciation of metals. Oceanography 2009, 22(4):72-85.
62. Mojica Prieto F., Millero F.J. The values of pK1+pK2 for the dissociation of carbonic acid in seawater. Geochim. Cosmochim. Acta 2002, 66(14):2529-2540.
63. Møller N. The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-Ca-Cl-SO4-H2O system, to high temperature and concentration. Geochim. Cosmochim. Acta 1988, 52(4):821-837.
64. Orr J.C., Calderia K., Fabry V., Gattuso J.-P., Haugan P., Lehodey P., Pantoja S., Portner H.-O., Riebesell U., Trull T., Hood M., Urban E., Broadgate W. Research Priorities for Ocean Acidification, report from the Second Symposium on the Ocean in a High-CO2 World, Monaco, October 6-9, 2009 2009, Convened by SCOR, UNESCO-IOC, IAEA and IGBP.
65. Pabalan R., Pitzer K. Thermodynamics of NaOH(aq) in hydrothermal solutions. Geochim. Cosmochim. Acta 1987, 51(4):829-837.
66. Parkhurst D.L., Appelo C.A.J. User's guide to PHREEQC (version2) - A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. Tech. Rep. 99-4259, U.S. Geological Survey Water-Resources Investigations Report 1999.
67. Pascal P.-Y., Fleeger J.W., Galvez F., Carman K.R. The toxicological interaction between ocean acidity and metals in coastal meiobenthic copepods. Mar. Pollut. Bull. 2010, 60(12):2201-2208.
68. Perez F.F., Fraga F. Association constant of fluoride and hydrogen ions in seawater. Mar. Chem. 1987, 21(2):161-168.
69. Phutela R.C., Pitzer K.S. Heat capacity and other thermodynamic properties of aqueous magnesium sulfate to 473K. J. Phys. Chem. 1986, 90(5):895-901.
70. Pitzer K.S. Activity Coefficients in Electrolyte Solutions 1991, CRC Press, Boca Raton, FL. 2nd edition.
71. Pitzer K.S., Roy R.N., Silvester L.F. Thermodynamics of electrolytes. 7. Sulfuric acid. J. Am. Chem. Soc. 1977, 99(15):4930-4936.
72. Pitzer K.S., Wang P., Rard J.A., Clegg S.L. Thermodynamics of Electrolytes. 13. Ionic Strength Dependence of Higher-Order Terms; Equations for CaCl2 and MgCl2. J. Solution Chem. 1999, 28(4):265-282.
73. Ramette R.W., Culberson C.H., Bates R.G. Acid-base properties of tris(hydroxymethyl)aminomethane (Tris) buffers in sea water from 5 to40°C. Anal. Chem. 1977, 49(6):867-870.
74. Rard J.A., Clegg S.L. Isopiestic determination of the osmotic and activity coefficients of zH2SO4+ (1 -z)MgSO4(aq) at T=298.15K. II. Results for z=(0.43040, 0.28758, and 0.14399) and analysis with Pitzer's model. J. Chem. Thermodyn. 1999, 31(3):399-429.
75. Raven J., Caldeira K., Elderfield H., Hoegh-Guldberg O., Liss P., Riebesell U., Shepherd J., Turley C., Watson A. Ocean Acidification due to Increasing Atmospheric Carbon Dioxide 2005, The Royal Society, London.
76. Guide to Best Practices for Ocean Acidification Research and Data Reporting 2010, Publications Office of the European Union, Luxembourg. U. Riebesell, V. Fabry, L. Hansson, J.-P. Gattuso (Eds.).
77. Roy R.N., Gibbons J.J., Bliss D.P.J., Casebolt R.G., Baker B.K. Activity coefficients for ternary systems: VI. The System HCl+MgCl2+H20 at different temperatures; application of Pitzer's equations. J. Solution Chem. 1980, 9(12):911-930.
78. Roy R.N., Gibbons J.J., Ovens L.K., Bliss G.a, Hartley J.J. Activity coefficients for the system HCl+CaCl2+H2O at various temperatures. Applications of Pitzer's Equations. J. Chem. Soc. Faraday Trans. 1982, 178(5):1405.
79. Shi D., Xu Y., Hopkinson B.M., Morel F.M.M. Effect of ocean acidification on iron availability to marine phytoplankton. Science 2010, 327:676-679.
80. Sippola H. Critical evaluation of the 2nd dissociation constants for aqueous sulfuric acid. Thermochim. Acta 2012, 532:65-77.
81. Spitzer P. Summary report: comparison of primary standard measurement devices for pH. Metrologia 2000, 37:85-86.
82. Spitzer P. Traceable measurements of pH. Accredit. Qual. Assur. 2001, 6:55-60.
83. Whitfield M. The extension of chemical models for seawater to include trace components at 25°C and 1atm pressure. Geochim. Cosmochim. Acta 1975, 39(11):1545-1557.