Application of Thermodynamic Calculations to Geochemical Processes Involving Organic Acids

  • Everett L. Shock


This chapter summarizes some of the insights gained about the behavior of organic acids in geochemical processes through thermodynamic calculations. Such calculations are possible because of the combination of numerous experimental studies on aqueous organic acids and theoretical equations of state, which allow accurate extrapolations of the measurements as well as predictions of thermodynamic properties of aqueous organic acids for which data have not been measured. Estimates of thermodynamic data for aqueous organic acids allow quantitative tests of several hypotheses concerning the role of organic acids in geochemical processes. For example, thermodynamic calculations described in this chapter indicate that decarboxylation of organic acids is unlikely to proceed to any significant extent under sedimentary basin conditions. At the partial pressures of CO2 and CH4 associated with oil-field brines, equilibrium constants for the decarboxylation of acetic acid require the acid concentrations to be many orders of magnitude lower than reported values.

Although the concentrations of acetic acid in oil-field brines cannot be in equilibrium with both CO2 and CH4, they may be in redox equilibrium with CO2 as demonstrated by additional calculations described in this chapter. This means that there is an enormous kinetic barrier blocking reactions between acetic acid and CH4 under sedimentary basin conditions. Therefore, acetic acid is preserved in a metastable state in oil-field brines, and appears to be in metastable equilibrium with CO2.

In addition, thermodynamic evaluation of acetic acid and propanoic concentrations in many brines indicates that these acids are in homogeneous metastable equilibrium. As a consequence, the ratio of the concentrations of acetic and propanoic acids in basinal brines can be used as a tracer of the oxidation state of sedimentary basins. Additional thermodynamic calculations described in this chapter allow tests of the plausibility of the hypothesis that the complex mixture of liquid hydrocarbons found in petroleum may buffer the oxidation state recorded by the acid ratios. It is found that this is a plausible argument not only for sedimentary basins but for hydrous pyrolysis experiments as well.

Thermodynamic calculations can only demonstrate whether compounds are in equilibrium with one another (stable or metastable) and reveal nothing about the reaction mechanisms through which such equilibrium states are reached and maintained. In the case of metastable equilibrium among petroleum hydrocarbons, organic acids, and CO2 in sedimentary basins, thermophilic microorganisms may catalyze otherwise sluggish reactions so that the geologically observable metastable state is reached. If so, then many of the reactions shown to be in metastable equilibrium may represent overall metabolic processes, and the application of thermodynamic calculations enters the area of geochemical bioenergetics. Some preliminary examples for dehydrogenation, hydrogenation, sulfate reduction, and methanogenesis reactions involving organic acids are discussed in this context at the end of this chapter. It appears that chemical reactions, which supply energy to microorganisms at low temperatures, provide considerably more energy at the elevated temperatures encountered in sedimentary basins.


Organic Acid Thermodynamic Calculation Geochemical Process Metastable Equilibrium Standard Partial Molal Volume 
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  1. Abercrombie HJ(1991) Reservoir processes in steam-assisted recovery of bitumen, Leming pilot, Cold Lake, Alberta, Canada; compositions, mixing and sources of co-produced water. Appl Geochem 6: 495–508.Google Scholar
  2. Ackermann T, Schreiner F (1958) Molwärmen und Entropien einiger Fettsäuren und ihrer Anionen in wässriger Lösung. Z Elektrochem 62: 1143–1151.Google Scholar
  3. Alberty RA (1992) Equilibrium calculations on systems of biochemical reactions at specified pH and pMg. Biophys Chem 42: 117–131.Google Scholar
  4. Allred GC, Woolley EM (1981) Heat capacities of aqueous acetic acid, sodium acetate, ammonia, and ammonium chloride at 283.15, 298.15 and 313.15 K: for ionization of acetic acid and for dissociation of ammonium ion. J Chem Thermodynamics 13: 155–164.Google Scholar
  5. Amend J, Helgeson HC (1991) Calculation of the relative stabilities at elevated temperatures and pressures of aqueous nucleosides, nucleotides, and other biochemical molecules required for bacterial metabolism in diagenetic processes. Geol Soc Am Abstr Programs 23: A212.Google Scholar
  6. Antweiler RC, Drever JI (1983) The weathering of a late Tertiary volcanic ash: importance of organic solutes. Geochim Cosmochim Acta 47: 623–629.Google Scholar
  7. Barth T (1987a) Quantitiative determination of volatile carboxylic acid in formation waters by isotachophoresis. Anal Chem 59: 2232–2237.Google Scholar
  8. Barth T (1987b) Multivariate analysis of aqueous organic acid concentrations and geological properties of North Sea reservoirs. Chemometrics Intelligent Lab Syst 2: 155–160.Google Scholar
  9. Barth T (1991) Organic acids and inorganic ions in waters from petroleum reservoirs, Norwegian continental shelf: a multivariate statistical analysis and comparison with American reservoir formation water. Appl Geochem 6: 1–15.Google Scholar
  10. Barth T, Borgund AE, Hopland AL, Graue A (1987) Volatile organic acids produced during kerogen maturation — amounts, composition and role in migration of oil. Adv Org Geochem 13: 461–465.Google Scholar
  11. Barth T, Borgund AE, Hopland AL (1989) Generation of organic compounds by hydrous pyrolysis of Kimmeridge oil shale-bulk results and activation energy calculations. Org Geochem 14: 69–76.Google Scholar
  12. Bennett PC, Melcer ME, Siegel DI, Hassett JP (1988) The dissolution of quartz in dilute aqueous solutions of organic acids at 25 °C. Geochim Cosmochim Acta 52: 1521–1530.Google Scholar
  13. Bevan J, Savage D (1989) The effect of organic acids on the dissolution of K-feldspar under conditions relevant to burial diagenesis. Mineral Mag 53: 415–425.Google Scholar
  14. Blair NE, Carter WD Jr (1992) The carbon isotope biogeochemistry of acetate from a methanogenic marine sediment. Geochim Cosmochim Acta 56: 1247–1258.Google Scholar
  15. Britton HTS (1925) Hydrogen and oxygen electrode titrations of some dibasic acids and of dextrose. J Chem Soc 127: 1896–1917.Google Scholar
  16. Brock TD, Brock KM, Belly RT, Weiss RL (1972) Sulfolobus: a new genus of sulfur-oxidizing bacteria living at low pH and high temperature. Arch Mikrobiol 84: 54–68.Google Scholar
  17. Carothers WW, Kharaka YK (1978) Aliphatic acid anions in oil-field waters-implications for origin of natural gas. Am Assoc Pet Geol Bull 62: 2441–2453.Google Scholar
  18. Choudhury NR, Ahluwalia JC (1982) Temperature dependence of heat capacities of sodium decanoate, sodium dodecanoate, and sodium dodecyl sulphate, in water. J Chem Thermodynamics 14: 281–289.Google Scholar
  19. Connolly CA, Walter LM, Baadsgaard H, Longstaffe FJ (1990) Origin and evolution of formation waters, Alberta Basin, Western Canada Sedimentary Basin. Appl Geochem 5: 375–395.Google Scholar
  20. Crossey LJ (1991) Thermal degradation of aqueous Oxalate species. Geochim Cosmochim Acta 55: 1515–1527.Google Scholar
  21. Crossey LJ, Frost BR, Surdam RC (1984) Secondary porosity in laumontite-bearing sandstones. In: McDonald DA, Surdam RC (eds) Clastic diagenesis. Am Assoc Pet Geol Mem 37, pp 225–237.Google Scholar
  22. Crossey LJ, Surdam RC, Lahann RW (1986) Application of organic/inorganic diagenesis to porosity prediction. In: Gautier D (ed) Roles of organic matter in sediment diagenesis. Soc Econ Paleontol Mineral Spec Publ 38, pp 147–156.Google Scholar
  23. Darken LS (1941) The ionization constants of oxalic acid at 25° from conductance measurements. J Am Chem Soc 63: 1007–1011.Google Scholar
  24. Decker K, Jungermann K, Thauer RK (1970) Energy production in anaerobic organisms. Angew Chem Int Ed 9: 138–158.Google Scholar
  25. De Lisi R, Perron G, Desnoyers JE (1980) Volumetric and thermochemical properties of ionic surfactants: sodium decanoate and octylamine hydrobromide in water. Can J Chem 58: 959–969.Google Scholar
  26. Dickey PA, Collins AG, Fajardo I (1972) Chemical composition of deep formation waters in southwestern Louisiana. Am Assoc Pet Geol Bull 56: 1530–1533.Google Scholar
  27. Dippy JFJ, Lewis RH (1937) Studies of the ortho-effect. Part II. The dissociation constants of some o-substituted acids. J Chem Soc 1937: 1426–1429.Google Scholar
  28. Domalski ES (1972) Selected values of heats of combustion and heats of formation of organic compounds containing the elements C H N O P, and S. J Phys Chem Ref Data 1: 221–277.Google Scholar
  29. Domalski ES, Evans WH, Hearing ED (1984) Heat capacities and entropies of organic compounds in the condensed phase. J Phys Chem Ref Data 13(Suppl 1): 286 pp.Google Scholar
  30. Domalski ES, Hearing ED (1990) Heat capacities and entropies of organic compounds in the condensed phase, vol II. J Phys Chem Ref Data 19: 881–1047.Google Scholar
  31. Drucker C (1920) Weitere Untersuchungen über die Dissoziation ternärer Elektrolyte. Z Phys Chem 96: 381–427.Google Scholar
  32. Drummond SE, Palmer DA (1986) Thermal decarboxylation of acetate. Part II. Boundary conditions for the role of acetate in the primary migration of natural gas and the transportation of metals in hydrothermal systems. Geochim Cosmochim Acta 50: 825–833.Google Scholar
  33. Edman JD, Surdam RC (1986) Organic-inorganic interactions as a mechanism for porosity enhancement in the Upper Cretaceous Ericson sandstone, Green River Basin, Wyoming. In: Gautier D (ed) Roles of organic matter in sediment diagenesis. Soc Econ Paleontol Mineral Spec Publ 38: 85–109.Google Scholar
  34. Eglinton TI, Curtis CD, Rowland SJ (1987) Generation of water-soluble organic acids from kerogen during hydrous pyrolysis: implications for porosity development. Mineral Mag 51: 495–503.Google Scholar
  35. Ellis AJ (1963) The ionizaton of acetic, propionic, n-butyric and benzoic acid in water, from conductance measurements up to 225°. J Chem Soc 1963: 2299–2310.Google Scholar
  36. Everett DH, Wynne-Jones WFK (1939) The thermodynamics of acid-base equilibria. Trans Faraday Soc 35: 1380–1401.Google Scholar
  37. Fein JB (1991) Experimental study of aluminum-, calcium-, and magnesium-acetate complexing at 80 °C. Geochim Cosmochim Acta 55: 955–964.Google Scholar
  38. Fiala G, Stetter KO (1986) Pyrococcus furiosus sp. nov. represents a novel genus of a heterotrophic archaebacteia growing optimally at 100 °C. Arch Microbiol 145: 56–61.Google Scholar
  39. Fiala G, Stetter KO, Jannasch HW, Langworthy TA, Madon J (1986) Staphylothermus marinus sp. nov. represents a novel genus of extremely thermophilic submarine heterotrophic archaebacteria growing up to 98 °C. Syst Appl Microbiol 8: 106–113.Google Scholar
  40. Fischer A, Mann BR, Vaughan J (1961) Influence of pressure on the Hammett reaction constant: dissociation of benzoic acids and phenylacetic acids. J Chem Soc 1961: 1093–1097.Google Scholar
  41. Fisher JB (1987) Distribution and occurrence of aliphatic acid anions in deep subsurface waters. Geochim Cosmochim Acta 51: 2459–2468.Google Scholar
  42. Fisher JR, Barnes HL (1972) The ion-product constant of water to 350°. J Phys Chem 76: 90–99.Google Scholar
  43. Fisher JB, Boles JR (1990) Water-rock interaction in Tertiary sandstones, San Joaquin Basin, California, USA: diagenetic controls on water composition. Chem Geol 82: 83–101.Google Scholar
  44. Gelwicks JT, Risatti JB, Hayes JM (1989) Carbon isotope effects associated with auto-trophi cacetogenesis. Org Geochem 14: 441–446.Google Scholar
  45. Giles MR, deBoer RB (1989) Secondary porosity: creation of enhanced porosities in the subsurface from the dissolution of carbonate cements as a result of cooling formation waters. Mar Pet Geol 6: 261–269.Google Scholar
  46. Giles MR, deBoer RB (1990) Origin and significance of redistributional secondary porosity. Mar Pet Geol 7: 378–397.Google Scholar
  47. Giles MR, Marshall JD (1986) Constraints on the development of secondary porosity in the subsurface: re-evaluation of processes. Mar Pet Geol 3: 243–255.Google Scholar
  48. Giordano TH (1985) A preliminary evaluation of organic ligands and metal-organic complexing in Mississippi Valley-type ore solutions. Econ Geol 80: 96–106.Google Scholar
  49. Giordano TH, Barnes HL (1981) Lead transport in Mississippi Valley-type ore solutions. Econ Geol 76: 2200–2211.Google Scholar
  50. Goldberg RN, Bella D, Tewari YB, McLaughlin MA (1991) Thermodynamics of hydrolysis of Oligosaccharides. Biophys Chem 40: 69–76.Google Scholar
  51. Hamann SD, Strauss W (1955) The chemical effects of pressure. Part 3. Ionization constants at pressures up to 1200 atm. Trans Faraday Soc 51: 1684–1690.Google Scholar
  52. Hanor JS, Workman AL (1986) Distribution of dissolved volatile fatty acids in some Louisiana oil field brines. Appl Geochem 1: 37–46.Google Scholar
  53. Harned HS, Ehlers RW (1933) The dissociation constant of acetic acid from 0 to 60° centigrade. J Am Chem Soc 55: 652–656.Google Scholar
  54. Harned HS, Fallon LD (1939) The second ionization constant of oxalic acid from 0 to 50 degrees. J Am Chem Soc 61: 3111–3113.Google Scholar
  55. Harned HS, Sutherland RO (1934) The ionization constant of n-butyric acid from 0 to 60°. J Am Chem Soc 56: 2039–2041.Google Scholar
  56. Harrison WJ, Thyne GD (1992) Predictions of diagenetic reactions in the presence of organic acids. Geochim Cosmochim Acta 56: 565–586.Google Scholar
  57. Helgeson HC (1969) Thermodynamics of hydrothermal systems at elevated temperatures and pressures. Am J Sci 267: 729–804.Google Scholar
  58. Helgeson HC (1985) Some thermodynamic aspects of geochemistry. Pure Appl Chem 57: 31–44.Google Scholar
  59. Helgeson HC (1992) Calculation of the thermodynamic properties and relative stabilities of aqueous acetic and chloroacetic acids, acetate and chloracetates, and acetyl and chloroacetyl chlorides at high and low temperatures and pressures. Appl Geochem 7: 291–308.Google Scholar
  60. Helgeson HC, Kirkham DH, Flowers GC (1981) Theoretical prediction of the ther-modynamic behavior of aqueous electrolytes at high pressures and temperatures. IV. Calculation of activity coefficients, osmotic coefficients, and apparent molai and standard and relative partial molai properties to 600 °C and 5 KB. Am J Sci 281: 1249–1516.Google Scholar
  61. Helgeson HC, Knox A, Shock EL (1991) Petroleum, oil field brines and authigenic mineral assemblages: are they in metastable equilibrium in hydrocarbon reservoirs? 15th Int European Assoc Meet of Organic Geochemists, Manchester, Program and Abstracts, p 39.Google Scholar
  62. Hennet R, Crerar DA, Schwartz J (1988) Organic complexes in hydrothermal systems. Econ Geol 83: 742–764.Google Scholar
  63. Huang WH, Keller WD (1971) Dissolution of clay minerals in dilute organic acids at room temperature. Am Mineral 56: 1082–1095.Google Scholar
  64. Huang WH, Keller WD (1972a) Kinetics and mechanisms of dissolution of Fithian illite in two complexing organic acids. In: Serratosa JM (ed) Proc Int Clay Conf in Madrid, Spain. Tipografia Artistica, Madrid, pp 321–331.Google Scholar
  65. Huang WH, Keller WD (1972b) Organic acids as agents of chemical weathering of silicate minerals. Nature 239: 149–151.Google Scholar
  66. Huang WH, Keller WD (1972c) Geochemical mechanics for the dissolution, transport, and deposition of aluminum in the zone of weathering. Clays Clay Minerals 20: 69–74.Google Scholar
  67. Huang WH, Kiang WC (1972) Laboratory dissolution of plagioclase feldspars in water and organic acids at room temperature. Am Mineral 57: 1849–1859.Google Scholar
  68. Huber R, Kurr M, Jannasch HW, Stetter KO (1989) A novel group of abyssal methano-genic archaebacteria (Methanopyrus) growing at 110°C. Nature 342: 833–834.Google Scholar
  69. Jaffe R, Albrecht P, Oudin J-L (1988a) Carboxylic acids as indicators of oil migration. I. Occurrence and geochemical significance of C-22 diastereoisomers of the (17βH, 21βH) C30 hopanoic acid in geological samples. Adv Org Geochem 13: 483–488.Google Scholar
  70. Jaffe R, Albrecht P, Oudin JL (1988b) Carboxylic acids as indicators of oil migration. II. Case of the Mahakam Delta, Indonesia. Geochim Cosmochim Acta 52: 2599–2607.Google Scholar
  71. Johnson JW, Oelkers EH, Helgeson HC (1992) SUPCRT92: a software package for calculating the standard molai thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bars and 0° to 1000°C. Comput Geosci 18: 899–947.Google Scholar
  72. Jones WJ, Leigh JA, Mayer F, Woese CR, Wolfe RS (1983) Methanococcus jannaschii sp. nov., an extremely thermophilic methanogen from a submarine hydothermal vent. Arch Microbiol 136: 254–261.Google Scholar
  73. Jørgensen BB, Isaksen MF, Holger WJ (1992) Bacterial sulfate reduction above 100°C in deep-sea hydrothermal vent sediments. Science 258: 2756–2758.Google Scholar
  74. Kawamura K, Tannenbaum E, Huizinga, BJ, Kaplan IR (1986) Volatile organic acids generated from kerogen during laboratory heating. Geochem J 20: 51–59.Google Scholar
  75. Kettler RM, Palmer DA, Wesolowski DJ (1991) Dissociation quotients of oxalic acid in aqueous sodium chloride media to 175 °C. J Solution Chem 20: 905–927.Google Scholar
  76. Kharaka YK, Lieo MS, Wright VA, Carothers WW (1979) Geochemistry of formation waters from Pleasant Bayou No. 2 well and adjancent areas in coastal Texas. In: Dorfman MH, Fisher WL (eds) 4th Proc United States Gulf Coast Geopressured-Geothermal Energy Conf, Austin, Texas, pp 168-193.Google Scholar
  77. Kharaka YK, Carothers WW, Rosenbauer RJ (1983) Thermal decarboxylation of acetic acid: implications for origin of natural gas. Geochim Cosmochim Acta 47: 397–402.Google Scholar
  78. Kharaka YK, Law LM, Carothers WW, Goerlitz DF (1986) Role of organic species dissolved in formation waters from sedimentary basins in mineral diagenesis. In: Gautier D (ed) Roles of organic matter in sediment diagenesis. Soc Econ Paleontol Mineral Spec Publ 38, pp 111-122.Google Scholar
  79. Kharaka YK, Maest AS, Carothers WW, Law LM, Lamothe PJ, Fries TL (1987) Geochemistry of metal-rich brines from central Mississippi Salt Dome Basin, USA. Appl Geochem 2: 543–561.Google Scholar
  80. Konicek J, Wadsö I (1971) Thermochemical properties of some carboxlic acids, amines and n-substituted amides in aqueous solution. Acta Chem Scand 25: 1541–1551.Google Scholar
  81. Kurz JL, Farrar JM (1969) The entropies of dissociation of some moderately strong acids. J Am Chem Soc 91: 6057–6062.Google Scholar
  82. Land LS, MacPherson GL (1992) Origin of saline formation waters, Cenozoic section, Gulf of Mexico sedimentary basin. Am Assoc Pet Geol Bull 76: 1344–1362.Google Scholar
  83. Land LS, MacPherson GL, Mack LE (1988) The geochemistry of saline formation waters, Miocene, offshore Louisiana. Trans Gulf Coast Assoc Geol Soc 38: 503–511.Google Scholar
  84. Larsson E, Adell B (1931) Die elektrolytische Dissoziation von Säuren in Salzlösungen II. Die Dissoziationskonstanten einiger Fettsäuren und die Aktivitätsverhältnisse ihrer Ionen in Natriumchlorid-und Kaliumchloridlösungen. Z Phys Chem A 157: 381–396.Google Scholar
  85. Lauerer G, Kristjansson JK, Langworthy TA, König H, Stetter KO (1986) Methano-thermus sociabilis sp. nov., a second species within the Methanothermaceae growing at 97 °C. Syst Appl Microbiol 8: 100–105.Google Scholar
  86. Lown DA, Thirsk HR, Lord Wynne-Jones (1970) Temperature and pressure dependence of the volume of ionization of acetic acid in water from 25 to 225 °C and 1 to 3000 bars. Trans Faraday Soc 66: 51–73.Google Scholar
  87. Lundegard PD (1985) Carbon dioxide and organic acids: origin and role in burial diagenesis (Texas Gulf Coast Tertiary). PhD Thesis, University of Texas, Austin, 144 PP.Google Scholar
  88. Lundegard PD, Kharaka YK (1990) Geochemistry of organic acids in subsurface waters: field data, experimental data and models. In: Melchior DC, B asseti RL (eds) Chemical modeling of aqueous systems II. Am Chem Soc Symp Ser 416, Washington DC, pp 169-189.Google Scholar
  89. Lundegard PD, Land LS (1986) Carbon dioxide and organic acids: their role in porosity enhancement and cementation, Paleogene of the Texas Gulf Coast. In: Gautier D (ed) Role of organic matter in mineral diagenisis. Soc Econ Paleontol Mineral Spec Publ 38, pp 129-146.Google Scholar
  90. Lundegard PD, Land LS (1989) Carbonate equilibria and pH-buffering by organic acids-response to changes in pCO2. Chem Geol 74: 277–287.Google Scholar
  91. Lundegard PD, Senftle JT (1987) Hydrous pyrolysis: a tool for the study of organic acid synthesis. Appl Geochem 2: 605–612.Google Scholar
  92. MacGowan DB, Surdam RC (1988) Difunctional carboxylic acid anions in oilfield waters. Org Geochem 12: 245–259.Google Scholar
  93. MacGowan DB, Surdam RC (1990) Importance of organic-inorganic reactions to modeling water-rock interactions during progressive clastic diagenesis. In: Melchior DC, Bassett RL (eds) Chemical modeling of aqueous systems II. Am Chem Soc Symp Ser 416, Washington DC, pp 494-507.Google Scholar
  94. Maclnnes DA, Shedlovsky T (1932) The determination of the ionization constant of acetic acid, at 25 degrees, from conductance measurements. J Am Chem Soc 54: 1429–1438.Google Scholar
  95. Makhatadze GI, Privalov PL (1990) Heat capacity of proteins. I. Partial molar heat capacity of individual amino acid residues in aqueous solution: hydration effect. J Mol Biol 213: 375–384.Google Scholar
  96. Makhatadze GI, Medvedkin VN, Privalov PL (1990) Partial molar volumes of poly-peptides and their constituent groups in aqueous solution over a broad temperature range. Biopolymer Chem 30: 1001–1010.Google Scholar
  97. Manley EP, Evans LJ (1986) Dissolution of feldspars by low-molecular-weight aliphatic and aromatic acids. Soil Sci 141: 106–112.Google Scholar
  98. Martens CS (1990) Generation of short chain organic acid anions in hydrothermally altered sediments of the Guaymas Basin, Gulf of California. Appl Geochem 5: 71–76.Google Scholar
  99. Mast MA, Drever JI (1987) The effect of Oxalate on the dissolution rates of oligoclase and tremolite. Geochim Cosmochim Acta 51: 2559–2568.Google Scholar
  100. Matsui T, Ko HC, Hepler LG (1974) Thermodynamics of ionization of benzoic acid and substituted benzoic acids in relation to the Hammett equation. Can J Chem 52: 2906–2911.Google Scholar
  101. McAuley A, Nancollas GH (1961) Thermodynamics of ion association. Part VII. Some transition-metal Oxalates. J Chem Soc 1961: 2215–2221.Google Scholar
  102. Means JL, Hubbard N (1987) Short-chain aliphatic acid anions in deep subsurface brines: a review of their origin, occurrence, properties, and importance and new data on their distribution and geochemical implications in the Palo Duro Basin, Texas. Org Geochem 11: 177–191.Google Scholar
  103. Mesmer RE, Patterson CS, Busey RH, Holmes HF (1989) Ionization of acetic acid in NaCl(aq) media: a Potentiometric study to 573 K and 130 bar. J Phys Chem 93: 7483–7490.Google Scholar
  104. Moldovanyi EP (1990) Evolution of basinal brines: elemental and isotopic evolution of formation waters and diagenetic minerals during burial of carbonate sediments, Upper Jurassic Smackover Formation, southwest Arkansas, US Gulf Coast. PhD Thesis, Washington University, St. Louis, 247 pp.Google Scholar
  105. Nikolaeva NM, Antipina VA (1972) The dissociation constants of oxalic acid in water at temperatures from 25 to 90 °C. Izv Sib Otd Akad Nauk SSSR Ser Khimicheskikh Nauk 6: 13–17 (in Russian).Google Scholar
  106. Noyes AA, Kato Y, Sosman RB (1910) The hydrolysis of ammonium acetate and the ionization of water at high temperatures. J Am Chem Soc 32: 159–178.Google Scholar
  107. Oscarson JL, Gillespie SE, Christensen JJ, Izatt RM, Brown PR (1988) Thermodynamic quantities for the interaction of H+ and Na+ with C2H3O- 2 and Cl- in aqueous solution from 275 to 320 °C. J Solution Chem 17: 865–885.Google Scholar
  108. Ostiguy C, Ahluwalia JC, Perron G, Desnoyers JE (1977) Heat capacities, volumes, and expansibilities of sodium phenyl carboxylates in water. Can J Chem 55: 3368–3370.Google Scholar
  109. Palma M, Morel J-P (1976) Viscosite; des solutions aqueuses d’acides carboxyliques aliphatiques et des carboxylates de potassium a 25°C. J Chim Phys 73: 643–649.Google Scholar
  110. Palmer DA, Drummond SE (1986) Thermal decarboxylation of acetate. Part I. The kinetics and mechanism of reaction in aqueous solution. Geochim Cosmochim Acta 50: 813–823.Google Scholar
  111. Parton HN, Gibbons RC (1939) The thermodynamic dissociation constants of oxalic acid. Trans Faraday Soc 35: 542–545.Google Scholar
  112. Pinching GD, Bates RG (1948) Second dissociation constant of oxalic acid from 0 to 50 °C, and the pH of certain Oxalate buffer solutions. J Res Natl Bur Standards 40: 405–416.Google Scholar
  113. Pronk JT, Liem K, Bos P, Kuenen JG (1991) Energy transduction by anaerobic ferric iron respiration in Thibacillus ferrooxidans. Appl Environ Microbiol 57: 2063–2068.Google Scholar
  114. Read AJ (1981) Ionization constants of benzoic acid from 25 to 250 °C and to 2000 bar. J Solution Chem 10: 437–450.Google Scholar
  115. Rossini FD, Mair BJ (1959) The work of the API research project 6 on the composition of petroleum. 5th World Petroleum Congr, Proc New York, 1959, vol 5, pp 223-245.Google Scholar
  116. Rossini RD, Mair BJ, Streiff AJ (1953) Hydrocarbons from petroleum. Am Chem Monogr Ser 121. Reinhold, New York, 556 pp.Google Scholar
  117. Sassani DC, Shock EL (1990) Speciation and solubility of palladium in aqueous magmatic-hydrothermal solutions. Geology 18: 925–928.Google Scholar
  118. Sassani DC, Shock EL (1992) Estimation of standard partial molai entropies of aqueous ions at 25 °C and 1 bar. Geochim Cosmochim Acta 56: 3895–3908.Google Scholar
  119. Sassani DC, Shock EL (1993) Solubility and transport of platinum-group elements in supercritical aqueous fluids: thermodynamic properties of Ru, Rh, Pd, and Pt solids, aqueous ions, and aqueous complexes to 5 kbar and 1000°C. Geochim Cosmochim Acta (in press).Google Scholar
  120. Schalscha EB, Appelt H, Schatz A (1967) Chelation as a weathering mechanism. I. Effect of complexing agents on the solubilization of iron from minerals and granodiorite. Geochim Cosmochim Acta 31: 587–596.Google Scholar
  121. Schleusener JL, Drummond SE, Palmer DA, Barnes HL (1987) Effects of common minerals on acetate decarboxylation kinetics. Geol Soc Am Abstr Programs 19: 832–833.Google Scholar
  122. Schleusener JL, Barnes HL, Drummond SE, Palmer DA (1988) Activation parameters and low temperature half-lives for the decarboxylation of acetate in sedimentary basin fluids. Geol Soc Am Abstr Programs 20: 150.Google Scholar
  123. Schulte MD, Shock EL (1993) Aldehydes in hydrothermal solution: standard partial molai thermodynamic properties and relative stabilities at high temperatures and pressures. Geochim Cosmochim Acta (in press).Google Scholar
  124. Seewald JS, Seyfried WE Jr, Thornton EC (1990) Organic-rich sediment alteration: an experimental and theoretical study at elevated temperatures and pressures. Appl Geochem 5: 193–209.Google Scholar
  125. Sengupta M, Pal K, Chakravarti A, Mahapatra P (1978) Dissociation constants of toluic acids in aqueous solution at different temperatures and study of related thermodynamic parameters. J Chem Eng Data 2: 103–107.Google Scholar
  126. Shaw DG, Alperin MJ, Reeburgh WS, Mclntosh DJ (1984) Biogeochemistry of acetate an anoxic sediment of Skan Bay, Alaska. Geochim Cosmochim Acta 48: 1819–1825.Google Scholar
  127. Shock EL (1988) Organic acid metastability in sedimentary basins. Geology 16: 886–890.Google Scholar
  128. Shock EL (1989) Corrections to “Organic acid metastability in sedimentary basins” Geology 17: 572–573.Google Scholar
  129. Shock EL (1990a) Geochemical constraints on the origin of organic compounds in hydro-thermal systems. Origins Life Evol Biosphere 20: 331–367.Google Scholar
  130. Shock EL (1990b) Do amino acids equilibrate in hydrothermal fluids? Geochim Cosmochim Acta 4: 1185–1189.Google Scholar
  131. Shock EL (1992a) Stability of peptides in high temperature aqueous solutions. Geochim Cosmochim Acta 56: 3481–3491.Google Scholar
  132. Shock EL (1992b) Chemical environments of submarine hydrothermal systems. Origins Life Evol Biosphere 22: 66–107.Google Scholar
  133. Shock EL (1993a) Organic acids in hydrothermal solutions: standard molai thermodynamic properties of carboxylic acids, and estimates of dissociation constants at high temperatures and pressures. Am J Sci (in press).Google Scholar
  134. Shock EL (1993b) Hydrothermal dehydration of aqueous organic compounds. Geochim Cosmochim Acta (in press).Google Scholar
  135. Shock EL, Helgeson HC (1988) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000 °C. Geochim Cosmochim Acta 52: 2009–2036.Google Scholar
  136. Shock EL, Helgeson HC (1990) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: standard partial molai properties of organic species. Geochim Cosmochim Acta 54: 915–945.Google Scholar
  137. Shock EL, Koretsky CM (1993) Metal-organic complexes in geochemical processes: calculation of standard partial molai thermodynamic properties of aqueous acetate complexes at high pressures and temperatures. Geochim Cosmochim Acta (in press).Google Scholar
  138. Shock EL, McKinnon WB (1993) Hydrothermal processing of cometary volatiles — application to triton. Icarus (in press).Google Scholar
  139. Shock EL, Schulte MD (1990) Summary and implications of reported amino acid concentrations in the Murchison meteorite. Geochim Cosmochim Acta 54: 3159–3173.Google Scholar
  140. Shock EL, Sverjensky DA (1989) Hydrothermal organometallic complexes of base metals. Geol Soc Am Abstr Programs 21: A8.Google Scholar
  141. Shock EL, Helgeson HC, Sverjensky DA (1989) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: standard partial molai properties of inorganic neutral species. Geochim Cosmochim Acta 53: 2157–2183.Google Scholar
  142. Shock EL, Oelkers EH, Johnson JW, Sverjensky D A, Helgeson H C (1992) Calculation of the thermodynamic properties of aqueous species at high pressures and temperatures: effective electrostatic radii, dissociation constants, and standard partial molai properties to 1000°C and 5 kb. J Chem Soc Faraday Trans 88: 803–826.Google Scholar
  143. Smolyakov BS, Primanchuk MP (1966) Dissociation constants of benzoic acid at temperatures between 25° and 90°. Russian J Phys Chem 40: 331–333.Google Scholar
  144. Stetter KO, König H, Stackebrandt E (1983) Pyrodictium gen. nov., a new genus of submarine disc-shaped sulphur reducing archaebacteria growing optimally at 105 °C. Syst Appl Microbiol 4: 535–551.Google Scholar
  145. Strong LE, Kinney T, Fischer P (1979) Ionization of aqueous benzoic acid: conductance and thermodynamics. J Solution Chem 8: 329–345.Google Scholar
  146. Strong LE, Copeland TG, Darragh M, van Waes C (1980) Ionization of aqueous toluic acids: conductance and thermodynamics. J Solution Chem 9: 109–128.Google Scholar
  147. Stull DR, Westrum EF Jr, Sinke GC (1969) The chemical thermodynamics of organic compounds. Wiley, New York, 865 pp.Google Scholar
  148. Surdam RC, Crossey LJ (1985) Organic-inorganic reactions during progressive burial: key to porosity and permeability enhancement and preservation. Philos Trans R Soc Lond Ser A 315: 135–156.Google Scholar
  149. Surdam RC, MacGowan DB (1987) Oilfield waters and sandstone diagenesis. Appl Geochem 2: 613–619.Google Scholar
  150. Surdam RC, Boese SW, Crossey LJ (1984) The chemistry of secondary porosity. In: McDonald DA, Surdam RC (eds) Clastic diagenesis. Am Assoc Pet Geol Mem 37, pp 127–149.Google Scholar
  151. Surdam RC, Crossey LJ, Hagen ES, Heasler HP (1989) Organic-inorganic interactions and sandstone diagenesis. Am Assoc Pet Geol Bull 73: 1–23.Google Scholar
  152. Sverjensky DA (1984) Oil field brines as ore-forming solutions. Econ Geol 79: 23–37.Google Scholar
  153. Sverjensky DA, Hemley JJ, D’Angelo WM (1991) Thermodynamic assessment of hydro-thermal alkali feldspar-mica-aluminosilicate equilibria. Geochim Cosmochim Acta 55: 989–1004.Google Scholar
  154. Tanger JC, Helgeson HC (1988) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: revised equations of state for the standard partial molai properties of ions and electrolytes. Am J Sci 288: 19–98.Google Scholar
  155. Tewari YB, Goldberg RN (1991) Thermodynamics of hydrolysis of disacchrides: lactulose, α-D-melibiose, palatinose, D-trehalose, D-turanose and 3-o-β-D-galactopyranosyl-D-arabinose. Biophys Chem 40: 59–67.Google Scholar
  156. Thauer RK (1990) Energy metabolism of methanogenic bacteria. Biochim Biophys Acta 1018: 256–259.Google Scholar
  157. Thauer RK, Jungermann K, Decker K (1977) Energy conservation in chemotrophic anaerobic bacteria. Bacteriol Rev 1977: 100–180.Google Scholar
  158. Thornton EC, Seyfried WE Jr (1987) Reactivity of organic-rich sediment in seawater at 350 °C, 500 bars: experimental and theoretical constraints and implications for the Guaymas Basin hydrothermal system. Geochim Cosmochim Acta 51: 1997–2010.Google Scholar
  159. Travers JG, McCurdy KG, Dolman D, Hepler LG (1975) Glass-electrode measurements over a wide range of temperatures: the ionization constants (5-90°C) and thermodynamics of ionization of aqueous benzoic acid. J Solution Chem 4: 267–274.Google Scholar
  160. Warford AL, Kosiur DR, Doose PR (1979) Methane production in Santa Barbara Basin sediments. Geomicrobiol J 1: 117–137.Google Scholar
  161. Willey LM, Kharaka YK, Presser TS, Rapp JB, Barnes I (1975) Short chain aliphatic acid anions in oil field waters and their contribution to the measured alkalinity. Geochim Cosmochim Acta 39: 1707–1711.Google Scholar
  162. Wilson JM, Gore NE, Sawbridge JE, Cardenas-Cruz F (1967) Acid-base equilibria of substituted benzoic acids. Part I. J Chem Soc (B) 1967: 852–859.Google Scholar
  163. Wogelius RA, Walther JV (1991) Olivine dissolution at 25 °C: effects of pH, CO2, and organic acids. Geochim Cosmochim Acta 55: 943–954.Google Scholar
  164. Workman AL, Hanor JS (1985) Evidence for large-scale vertical migration of dissolved fatty acids in Louisiana oil field brines: Iberia field, south-central Louisiana. Trans Gulf Coast Assoc Geol Soc 35: 293–300.Google Scholar
  165. Zawidzki TW, Papèe HM, Laidler KJ (1959) Thermodynamics of ionization processes in aqueous solution. Trans Faraday Soc 55: 1743–1745.Google Scholar
  166. Zillig WI, Holz I, Janekovic D, Schäfer W, Reiter W-D (1983) The archaebacterium Thermococcus celer represents a novel genus within the thermophilic branch of the archaebacteria. Syst Appl Microbiol 4: 88–94.Google Scholar
  167. Zillig W, Holz I, Janekovic D, Klenk H-P, Imsel E, Trent J, Wunderl S, Forjaz VH, Coutinho R, Ferreira T (1990) Hyperthermus butylicus, a hyperthermophilic sulfur-reducing archaebacterium that ferments peptides. J Bacteriol 172: 3959–3965.Google Scholar
  168. Zinger AS, Kravchik TE (1970) The simpler organic acids in ground water of the lower Volga region (genesis and possible use in prospecting for oil). Dokl Akad Nauk SSSR 202: 218–221.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1994

Authors and Affiliations

  • Everett L. Shock
    • 1
  1. 1.Department of Earth and Planetary SciencesWashington UniversitySt. LouisUSA

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