Abstract
One issue for the origin of life under a non-reducing atmosphere is the availability of the reduced nitrogen necessary for amino acids, nucleic acids, etc. One possible source of this nitrogen is the formation of ammonia from the reduction of nitrates and nitrites produced by the shock heating of the atmosphere and subsequent chemistry. Ferrous ions will reduce these species to ammonium, but not under acidic conditions. We wish to report results on the reduction of nitrite and nitrate by another source of iron (II), ferrous sulfide, FeS. FeS reduces nitrite to ammonia at lower pHs than the corresponding reduction by aqueous Fe+ 2. The reduction follows a first order decay, in nitrite concentration, with a half-life of about 150 min (room temperature, CO2, pH 6.25). The highest product yield of ammonia measured was 53%. Under CO2, the product yield decreases from pH 5.0 to pH 6.9. The increasing concentration of bicarbonate, at higher pH, interferes with the reaction. Comparing experiments under N2 CO2 shows the interference of bicarbonate. The reaction proceeds well in the presence of such species as chloride, sulfate, and phosphate, though the yield drops significantly with phosphate. FeS also reduces nitrate and, unlike with Fe+ 2, the reduction shows more reproducibility. Again, the product yield decreases with increasing pH, from 7% at pH 4.7 to 0% at pH 6.9. It appears that nitrate is much more sensitive to the presence of added species, perhaps not competing as well for binding sites on the FeS surface. This may be the cause of the lack of reproducibility of nitrate reduction by Fe+ 2 (which also can be sensitive to binding by certain species)
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Barley, M. E., Dunlop, J. S. R., Glover, J. E. and Groves, D. I.: 1979, Sedimentary Evidence for an Archaean Shallow-Water Volcanic-Sedimentary Facies, Eastern Pilbara Block, Western Australia, Earth Plant. Sci. Lett. 43, 74–84.
Chameides, W. L. and Walker, J. C. G.: 1981, Rates of Fixation by Lightning of Carbon and Nitrogen in Possible Primitive Atmospheres, Origins Life 11, 291–302.
Chang, S., DesMarais, D., Mack, R., Miller, S. L. and Strathearn, G. E.: 1983, ‘Prebiotic Organic Synthesis and the Orgin of Life’, in: J. W. Shopf (ed), Earth's Earliest Biosphere: Its Origin and Evolution, Princeton University Press, Princeton, NJ, 53–92.
Delano, J. W.: 2001, Redox History of the Earth's Interior Since ∼ 3900 Ma: Implications for Prebiotic Molecules, Orig. Life Evol. Biosph. 31, 311–341.
Derry, L. A. and Jacobsen, S. B.: 1990, The Chemical Evolution of Precambrian Seawater: Evidence from REEs in Banded Iron Formations, Geochem. Cosmochen. Acta 54, 2965–2975.
Drever, J. I.: 1974, Geochemical Model of the Origin of Precambrian Banded Iron Formations, Geological Soc. Am. Bull. 85, 1099–1106.
Fegley, B, Jr., Prinn, R. G., Hartman, H. and Watkins, G. H.: 1986, Chemical Effects of Large Impacts on the Earth's Primitive Atmosphere, Nature 319, 305–308.
Gregor, C. B., Garrels, R. M., Mackenzie, F. T. and Maynard, J. B.: 1988, Chemical Cycles in the Evolution of the Earth, John Wiley {&} Sons, NY.
Groves, D. I., Dunlop, J. S. R. and Buick, R.: 1981, An early Habitat for Life, Sci. Am. 245, 64–73.
Hannington, M. D., Jonasson, I. R., Herzig, P. M. and Petersen, S.: 1995, ‘Physical and Chemical Processes of Seafloor Mineralization at Mid-Ocean Ridges’, in: S. E. Humphris, R. A. Zierenberg, L. S. Mullineaux and R. E. Thomson (eds.), Seafloor Hydrothermal Systems: Physical, Chemical, Biological, and Geological Interactions, American Geophyscial Union, Washington, DC, 115–157.
Holland, H. D.: 1973, The Oceans: A Possible Source of Iron in Iron-Formations, Econ. Geol. 68, 1169–1172.
Holland, H. D.: 1984, The Chemical Evolution of the Atmosphere and Oceans, Princeton University Press, Princeton, NJ.
Holland, H. D., Lazar, B. and McCaffrey, M.: 1986, Evolution of the Atmosphere and Oceans, Nature 320, 27–33.
Kasting, J. F.: 1987, Theoretical Constraints on Oxygen and Carbon Dioxide Concentrations in the Precambrian Atmosphere, Precambrian Res. 34, 205–229.
Kasting, J. F.: 1990, Bolide Impacts and the Oxidation State of Carbon in the Earth's Early Atmosphere, Origins Life Evol. Biosph. 20, 199–231.
Kasting, J. F.: 1993, ‘Evolution of the Earth's Atmosphere and Hydrosphere: Hadean to Recent’, in: M. H. Engel and S. A. Macko (eds.), Organic Geochemistry: Principles and Applications, Plenum Press, New York, 611–623.
Kasting, J. F. and Ackerman, T. P.: 1986, Climatic Consequences of Very High Carbon Dioxide Level in the Earth's Early Atmosphere, Science 234, 1383–1385.
Löb, W.: 1906, Studien über die Chemische Wirkung der Stilen Elektrischen Entladung, Z. {Elektrochem.} 11, 282–316.
Löb, W.: 1914, Über das Verhalten des Formamids unter der Wirkung der Stillen Entladung. Ein Beitrag zur Frage der Stickstoff-Assimilation, Ber. Dtsch. Chem. Ges. 46, 684–697.
Mancinelli, R. L. and McKay, C. P.: 1988, The Evolution of Nitrogen Cycling, Orig. Life Evol. Biosph. 18, 311–325.
Mattioli, G. S. and Wood, B. J.: 1986, Upper Mantle Oxygen Fugacity Recorded by Spinel Lherzolites, Nature 322, 626–628.
Stribling, R. E. and Miller, S. L.: 1987, Energy Yields for Hydrogen Cyanide and Formaldehyde Syntheses: The HCN and Amino Acid Concentrations in the Primitive Ocean, Orig. Life Evol. Biosph. 17, 261–273.
Summers, D. P. and Chang, S.: 1993, Prebiotic Ammonia from Reduction of Nitrite by Iron(II) on the Early Earth, Nature 365, 630–633.
Turcotte, D. L.: 1980, On the Thermal Evolution of the Earth, Earth Planet. Sci. Lett. 48, 53–58.
Veizer, J.: 1978, Secular Variations in the Composition of Sedimentary Carbonate Rocks, II. Fe, Mn, CA, Mg, Si and Minor Constitutents, Precambrian Res. 6, 381–413.
Walker, J. C. G.: 1977, Evolution of the Atmosphere, Macmillan, New York, NY.
Walker, J. C. G.: 1986, Carbon Dioxide on the Early Earth, Origins Life 16, 117–127.
Walker, J. C. G. and Brimblecombe, P.: 1985, Iron and Sulfur in the Pre-Biological Ocean, Precambrian. Res. 28, 205–222.
Walker, J. C. G., Klein, C., Schidlowski, M., Schopf, J. W., Stevenson, D. J. and Walker, M. R.: 1983, ‘Environmental Evolution on the Archean-Early Proterozoic Earth’, in: J. W. Schopf (ed.), Earth's Earliest Biosphere: Its Origin and Evolution, Princeton University Press, Princeton, NJ, 261–290.
Windley, B. F. E.: 1976, The Early History of the Earth, John Wiley {&} Sons, NY.
Wood, B. J. and Vigo, D.: 1989, Upper Mantle Oxidation State: Ferric Iron Contents of lherzolite Spinels by 57Fe Mossbauer Spectroscopy and Resultant Oxygen Fugacities, Geochemica Cosmochemica Acta 53, 1277–1989.
Yung, Y. L. and McElroy, M. B.: 1979, Fixation of Nitrogen in the Prebiotic Atmosphere, Science 203, 1002–1004.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Summers, D.P. Ammonia Formation By The Reduction Of Nitrite/Nitrate By Fes: Ammonia Formation Under Acidic Conditions. Orig Life Evol Biosph 35, 299–312 (2005). https://doi.org/10.1007/s11084-005-2040-1
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s11084-005-2040-1