Abstract
The thermodynamics of the FeS-H2S/FeS2 redox couple and a select number of reactions critical to the synthesis of simple carboxylic acids and amino acids have been evaluated as a function of temperature. This thermodynamic evaluation shows that the reducing power of the FeS-H2S/FeS2 redox couple decreases drastically with temperature. By contrast the equilibria describing the reduction of CO2 and the formation of simple carboxylic acids and amino acids require an increasingly higher reducing power with temperature. Given these two opposite trends, the thermodynamic driving force for CO2 reduction and amino acid formation with the FeS-H2S/FeS2 redox couple as reductant diminishes with increasing temperature. An evaluation of the mechanism of CO2 reduction by the FeS-H2S/FeS2 couple suggests that the electron transfer from pyrrhotite to CO2 is hindered by a high activation energy, even though the overall reaction is thermodynamically favorable. By comparison the electron transfer from pyrrhotite to either CS2, CO, or HCOOH are far more facile. This theoretical analysis explains the results of experimental work by Keefe et al. (1995), Heinen and Lauwers (1996) and Huber and Wächtershäuser (1997). The implication is that a reaction sequence involving the reduction of CO2 with the FeS-H2S/FeS2 couple as reductant is unlikely to initiate a proposed prebiotic carbon fixation cycle (Wächtershäuser, 1988b; 1990b, 1990a, 1992, 1993).
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Anderson, G. M.: 1996, Thermodynamics of Natural Systems, Wiley, New York, p. 382.
Anderson, G. M. and Crerar, D. A.: 1993, Thermodynamics in Geochemistry, Oxford, New York, p. 588.
Arico, A. S., Antonucci, V., Antonucci, P. L., Cocke, D. L., Russo, U. and Giordano, N.: 1990, Solar Energy Materials 20, 323–340.
Bada, J. L., Miller, S. L. and Zhao, M.: 1995, Origins Life Evol. Biosphere 25, 111–118.
Bard, A. J., Parsons, R. and Jordan, J.: 1985, Standard Potentials in Aqueous Solution, Marcel Dekker, New York, NY, p. 834.
Barker, W. W. and Parks, T. C.: 1986, Geochimica Cosmochimica Acta 50, 2185–94.
Bloechl, E., Keller, M., Wächtershäuser, G. and Stetter, K. O.: 1992, Proceedings of the National Academy of Science 89, 8117–8120.
Bockris, J. O. M. and Khan, S. U. M.: 1993, Surface Electrochemistry, Plenum, New York, NY, p. 1014.
Borg, R. J. and Dienes, G. J.: 1992, The Physical Chemistry of Solids, Academic Press, Boston, p. 584.
Cairns-Smith, A. G., Hall, A. J. and Russell, M. J.: 1992, Origins Life Evol. Biosphere 22, 161–180.
Campbell, A. C., Bowers, T. S., Measures, C. I., Falkner, K. K., Khadem, M. and Edmond, J. M.: 1988, J.Geophys. Res. 93, 4537–4549.
Chase, M. W., Davies, C. A., Downey, J. R., Frurip, D. J., McDonald, R. A. and Syverud, A. N.: 1985, J. Phys. Chem. Ref. Data, Suppl. 1 14, 1–1856.
Corliss, J. B.: 1990, Nature 347, 624.
Davis, E. E., Goodfellow, W. D., Bornhold, B. D., Adshead, J., Blaise, B., Villinger, H. and le Cheminant, G. M.: 1987, Earth Plan. Sci. Lett. 82, 49–61.
Drobner, E., Huber, H., Wächtershäuser, G., Rose, D. and K.O., S.: 1990, Nature 346, 742–44.
Gamsjäger, H., Reiterer, F. and Heindl, R.: 1982, Ber. Bunsenges. Phys. Chem. 86, 1046–1049.
Graetzel, M.: 1989, Heterogeneous Photochemical Electron Transfer, CRC, Boca Raton, p.
Graham, U. M., Bluth, G. J. and Ohmoto, H.: 1988, Can. Min. 26, 487–504.
Guevremont, J., Strongin, D. R. and Schoonen, M. A. A.: 1997a, Surface Chemistry 391, 109–124.
Guevremont, J. M., Strongin, D. R. and Schoonen, M. A. A.: 1997b, American Mineralogist, (submitted).
Hafenbradl, D., Keller, M., Wächtershäuser, G. and Stetter, K. O.: 1995, Tetrahedron Letters 36, 5179–5182.
Hamilton, I. C. and Woods, R.: 1981, Journal of Electroanalytical Chemistry 118, 327–343.
Hannington, M. D., Jonasson, I. R., Herzig, P. M. and Petersen, S.: 1995, in S. E. Humphris, R. A. Zierenberg, L. S. Mullineaux and R. E. Thomson (eds.), Seafloor Hydrothermal Systems, Vol. 91, AGU, Washington, pp. 115–158.
Heinen, W. and Lauwers, A. M.: 1996, Origins Life Evol. Biosphere 26, 131–150.
Helgeson, H. C., Delany, J. M., Nesbitt, H. W. and Bird, D. K.: 1978, American Journal of Science 278-A, 1–229.
Hoffmann, R.: 1988, Solids and Surfaces; A Chemist's View of Bonding in Extended Structures, Verlag Chemie, New York, p. 142.
Holm, N. G.: 1992, Origins Life Evol. Biosphere 22, 5–14.
Huber, C. and Wächtershäuser, G.: 1997, Science 276, 245–247.
Inoue, T., Fujishima, A., Konishi, S. and Honda, K.: 1979, Nature 277, 637–638.
Janecky, D. R. and Seyfried, W. E. J.: 1984, Geochimica Cosmochimica Acta 48, 2723–2738.
Janecky, D. R. and Shanks, W. C. I.: 1988, Canadian Mineralogist 26, 805–825.
Jannasch, H. W. and Mottl, M. J.: 1985, Science 229, 717–25.
Johnson, J.W., Oelkers, E. H. and Helgeson, H. C.: 1992, Computers and Geosciences 18, 899–947.
Joyce, G.: 1988, Nature 334, 564.
Kanemoto, M., Shiragami, T., Pac, C. and Yangida, S.: 1992, Journal of Physical Chemistry 96, 3521–3526.
Kaschke, M. and Russell, M. J.: 1994, Origins Life Evol. Biosphere 24, 43–56.
Kasting, J. F.: 1990, Origins Life Evol. Biosphere 20, 199–231.
Keefe, A. D., Miller, S. L., McDonald, G. and Bada, J.: 1995, Proceedings of the National Academy of Science 92, 11904–11906.
Keller, M., Bloechli, E., Wächtershäuser, G. and Stetter, K. O.: 1994, Nature 368, 836–838.
Lias, S. G.: 1977, NIST Standard Reference Database Number 69, Mallard, W. G. and Linstrom, P. J. (eds.), National Institute of Standards and Technology, Gaithersburg MD (http://webbook.nist.gov)
Lilley, M. D., Baross, J. A. and Gordon, L. I.: 1983, in ‘Hydrothermal Processes at Spreading Centers’, Rona, P. A., Bostrom, K., Laubier, L. and Smith, K. L. (eds.), pp. 1411–450.
Luther, G. W.: 1987, Geochimica Cosmochimica Acta 51, 3193–3201.
Luther, G. W.: 1990, in W. Stumm (ed.), Aquatic Chemical Kinetics, Wiley, New York, pp. 173–198.
Merlivat, L., Pineau, F. and Javoy, M.: 1987, Earth and Planetary Science Letters 84, 100–108.
Miller, S. L. and Bada, J. L.: 1988, Nature 334, 609–611.
Morrison, S. R.: 1990, The Chemical Physics of Surfaces, Plenum, New York, NY, p. 438.
Norton, P. R. and Richards, P. J.: 1975, Surface Science 49, 567–576.
Nozik, A. J.: 1978, Annual Review Physical Chemistry 29, 189–222.
Pearson, R. G.: 1988, Inorganic Chemistry 27, 734–740.
Pratt, A. R., Muir, I. J. and Nesbitt, H. W.: 1994, Geochimica et Cosmochimica Acta 58, 827–841.
Rickard, D.: 1997, Geochimica Cosmochimica Acta 61, 115–134.
Rickard, D. and Luther, G. W.: 1997, Geochimica Cosmochimica Acta 61, 135–148.
Rickard, D., Schoonen, M. A. A. and Luther, G. W.: 1995, in M. A. Vairavamurthy and M. A. A. Schoonen (eds.), Geochemical Transformations of Sedimentary Sulfur, Vol. 612, Am. Chem. Soc., Washington, D.C., pp. 168–193.
Robie, R. A., Hemingway, B. S. and Fisher, J. R.: 1978, Thermodynamic Properties of Minerals and Related Substances at 298 K and 1 Bar (10 5 Pascals) Pressure and at Higher Temperatures, U.S. Government Printing Office, Washington, p. 456.
Russell, M. J., Hall, A. J., Cairns-Smith, A. G. and Braterman, P. S.: 1988, Nature 336, 117.
Russell, M. J., Hall, A. J. and Turner, D.: 1989, Terra Nova 1, 238–241.
Sakata, T.: 1989, in N. Serpone and E. Pelizetti (eds.), Photocatalysis: Fundamentals and Applications, Wiley Interscience, New York, pp. 311–338.
Sakkapoulos, S., 59: 1986, J. Appl. Phys. 59, 3540–3542.
Sakkopoulos, S., Vitoratos, E. and Argyreas, T.: 1984, Journal of Physical Chemistry of Solids 45, 923–928.
Schiavello, M. and Sclafani, A.: 1989, in N. Serpone and E. Pelizetti (eds.), Photocatalysis: Fundamentals and Applications, Wiley Interscience, New York, pp. 159–174.
Schoonen, M. A. A. and Barnes, H. L.: 1991a, Geochimica Cosmochimica Acta 55, 1495–1504.
Schoonen, M. A. A. and Barnes, H. L.: 1991b, Geochimica Cosmochimica Acta 55, 3491–3504.
Schoonen, M. A. A., Xu, Y. and Strongin, D. R.: 1998, Journal of Exploration Geochemistry, (accepted).
Schulte, M. and Shock, E.: 1993, Geochimica Cosmochimica Acta 57, 3835–3846.
Shock, E.: 1995, American Journal of Science 295, 496–580.
Shock, E. L.: 1990, Origins Life Evol. Biosphere 20, 331–367.
Shock, E. L., McCollom, T. and Schulte, M. D.: 1995, Origins Life Evol. Biosphere 25, 141–159.
Taniguchi, I.: 1989, in J. O. M. Bockris, R. E. White and B. E. Conway (eds.), Modern Aspects of Electrochemistry, Vol. 20, Plenum, New York, NY, pp. 327–400.
Tivey, M. K.: 1995, in S. E. Humphris, R. A. Zierenberg, L. S. Mullineaux and R. E. Thomson (eds.), Seafloor Hydrothermal Systems, Vol. 91, AGU, Washington, pp. 158–193.
Tributsch, H.: 1989, in N. Serpone and E. Pelizetti (eds.), Photocatalysis: Fundamentals and Applications, Wiley Interscience, New York, pp. 339–384.
van Trump, J. E. and Miller, S. L.: 1973, Earth Planetary Science Letters 20, 145–150.
von Damm, K. L.: 1995, in S. E. Humphris, R. A. Zierenberg, L. S. Mullineaux and R. E. Thomson (eds.), Seafloor Hydrothermal Systems, Vol. 91, AGU, Washington, pp. 222–247.
Wächtershäuser, G.: 1988a, Proceedings of the National Academy of Science 85, 1134–1135.
Wächtershäuser, G.: 1988b, Microbiological Review 52, 452–484.
Wächtershäuser, G.: 1990a, Origins Life Evol. Biosphere 20, 173–176.
Wächtershäuser, G.: 1990b, Proceedings of the National Academy of Science 87, 200–204.
Wächtershäuser, G.: 1991, Medical Hypotheses 36, 307–311.
Wächtershäuser, G.: 1992, Progress in Biophysics and Molecular Biology 58, 85–201.
Wächtershäuser, G.: 1993, Journal of Pure and Applied Chemistry 65, 1343–1348.
Wächtershäuser, G.: 1994, in B. S. (ed.), Early Life on Earth, Vol. Nobel Symposium No. 84, Columbia University Press, pp. 124–132.
Xu, Y. and Schoonen, M. A. A.: 1995, Geochimica Cosmochimica Acta 59, 4605–4622.
Xu, Y., Schoonen, M. A. A. and Strongin, D. R.: 1996, Geochimica Cosmochimica Acta 60, 4701–4710.
Xu, Y. and Schoonen, M. A. A.: 1997, Paper presented at the ACS Northeast Regional Meeting, Saratoga Springs, NY.
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Schoonen, M.A.A., Xu, Y. & Bebie, J. Energetics and Kinetics of the Prebiotic Synthesis of Simple Organic Acids and Amino Acids with the FES-H2S/FES2 Redox Couple as Reductant. Orig Life Evol Biosph 29, 5–32 (1999). https://doi.org/10.1023/A:1006558802113
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DOI: https://doi.org/10.1023/A:1006558802113