Sulfides in Sandy Sediments: New Insights on the Reactions Responsible for Sedimentary Pyrite Formation

Aquatic Geochemistry - Tập 5 - Trang 75-85 - 1999
John W. Morse1
1Department of Oceanography, Texas A&M University College Station, U.S.A.

Tóm tắt

The formation of sedimentary iron sulfides was studied in sandy sediments of the Laguna Madre, TX, in order to better understand how this process operates in sediments where reactive iron is likely to be limiting for sulfide mineral formation. These sediments usually had reactive iron and total reduced sulfide concentrations one to two orders of magnitude less than in typical shallow water terrigenous muds, but organic-C concentrations typical of fine-grained sediments due to the extensive presence of seagrass beds. This resulted in moderate (0–150 μm) dissolved H2S concentrations with maximum concentrations in the upper (3–:5 cm) root zone. Based on citrate dithionite extractable-Fe the degree of sulfidization was usually 100% or greater. Acid volatile sulfides (AVS) typically comprised roughly 60% of total reduced sulfur and the proportion of AVS generally increased instead of decreasing with depth. The unusual proportion of TRS as AVS and persistence of AVS are attributed to exceptionally slow pyrite formation kinetics. The probable reasons for these slow reaction kinetics are the high (>7.8) pH of the sediments, which favors the slow polysulfide pathway for pyrite formation, high (typically about 2–4 mm) dissolved organic carbon concentrations that inhibit growth of pyrite and the low concentration of reactants which greatly increases the average transport distances necessary for diffusion controlled reactions.

Tài liệu tham khảo

Aller R. C., Mackin J. E., and Cox R. T. (1986) Diagenesis of Fe and S in Amazon inner shelf muds: Apparent dominance of Fe reduction and implications for the genesis of iron stones. Cont. Shelf Res. 6, 263-289. Berner R. A. (1970) Sedimentary pyrite formation. Am. J. Sci. 268, 1-23. Berner R. A., Baldwin T., and Holdren, Jr. G. R. (1979) Authigenic iron sulfides as paleosalinity indicators. J. Sediment. Petrol. 49, 1345-1350. Berner R. A. (1984) Sedimentary pyrite formation: An update. Geochim. Cosmochim. Acta 48(4), 605-615. Berner R. A. and Raiswell R. (1984) C/S method for distinguishing freshwater from marine sedimentary rocks. Geology 12, 365-368. Boesen C. and Postma D. (1988) Pyrite formation in the anoxic sediments of the Baltic. Am. J Sci. 288, 575-603. Calvert S. E. and Karlin R. E. (1991) Relationships between sulfur, organic carbon and iron in the modern sediments of the Black Sea. Geochim. Cosmochim. Acta 55, 2483-2490. Canfield D. E. (1988) Sulfate reduction and the diagenesis of iron in anoxic marine sediments. Ph.D. dissertation. Yale University, New Haven, CT. Canfield D. E. (1989) Reactive iron in marine sediments. Geochim. Cosmochim. Acta 53, 619-632. Canfield D. E., Raiswell R., Westrich J. T., Reaves C. M., and Berner R. A. (1986) The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales. Chem. Geol. 54, 149-155. Canfield D. E., Raiswell R., and Bottrell S. (1992) The reactivity of sedimentary iron minerals toward sulfide. Am. J. Sci. 292, 659-683. Cline J. D. (1969) Spectrophotometric determination of hydrogen sulfide in natural waters. Limnol. Ocean. 14, 454-458. Cornwell J.C. and Morse J.W. (1987) The characterization of iron sulfide minerals in marine sediments. Mar. Chem. 22, 193-206. Goldhaber M. B. and Kaplan I. R. (1974) The sulfur cycle. In The Sea, Vol. 5, pp. 569-655 (ed. E. Goldberg). John Wiley, New York. Gagnon C., Mucci A., and Pelletier E. (1995) Anomalous accumulation of acid-volatile sulphides (AVS) in a coastal marine sediment, Saguenay Fjord, Canada. Geochim. Cosmochim. Acta 59, 2663-2676. Hansson I. (1973) A new set of acidity constants for carbonic acid and boric acid in seawater. Deep-Sea Res. 20, 461-478. Leventhal J. S. (1983) An interpretation of carbon and sulfur relationships in Black Sea sediments as indicators of environments of deposition. Geochim. Cosmochim. Acta 47, 133-137. Leventhal J. S. (1995) Carbon-sulfur plots to show diagenetic and epigenetic sulfidation in sediments. Geochim. Cosmochim. Acta 59, 1207-1212. Lin S. and Morse J.W. (1991) Sulfate reduction and iron sulfide mineral formation in Gulf of Mexico anoxic sediments. Am. J. Sci. 291, 55-89. Luther III G. W. (1991) Pyrite synthesis via polysulfide compounds. Geochim. Cosmochim. Acta 55, 2839-2849. Morse J. W. and Berner R. A. (1995) What determines sedimentary C/S ratios? Geochim. Cosmochim. Acta 59(6), 1073-1077. Morse J.W. and Wang Q. (1997) Pyrite formation under conditions approximating those in anoxic sediments: II. Influence of precursor iron minerals and organic matter. Mar. Chem. 57, 187-193. Raiswell R., Buckley F., Berner R. A., and Anderson T. F. (1988) Degree of pyritization of iron as a paleoenvironmental indicator of bottom-water oxygenation. J. Sediment. Petrol. 58, 812-819. Raiswell R. and Al-Biatty H. J. (1989) Depositional and diagenetic C-S-Fe signatures in early Paleozoic normal marine shales. Geochim. Cosmochim. Acta 53, 1147-1152. Raiswell R., Canfield D. E., and Berner R. A. (1994) A comparison of iron extraction methods for the determination of degree of pyritization and the recognition of iron limited pyrite formation. Chem. Geol. 111, 101-110. Raiswell R. and Canfield D. E. (1996) Rates of reaction between silicate iron and dissolved sulfide in Peru Margin sediments. Geochim. Cosmochim. Acta 60, 2777-2787. Reeburgh W.S. (1967) An improved interstitial water sampler. Limnol Ocean 14, 454-458. Rickard D. T. (1975) Kinetics and mechanisms of pyrite formation at low temperatures. Am. J. Sci. 275, 636-652. Rickard D. (1997) Kinetics of pyrite formation by the H2S oxidation of iron(II) monosulfide in aqueous solutions between 25°C and 125°C: The rate equation.Geochim. Cosmochim. Acta 61, 115-134. Rickard D. and Luther III G. W. (1997) Kinetics of pyrite formation by the H2S oxidation of iron(II) monosulfide in aqueous solutions between 25°C and 125°C: The mechanism.Geochim. Cosmochim. Acta 61, 135-147. Schoonen M. A. A. and Barens H.L. (1991) Reactions forming pyrite and marcasite from solution: II. Via FeS precursors below 100 °C. Geochim. Cosmochim. Acta 55,1505-1514. Wang Q. and Morse J.W. (1996) Pyrite formation under conditions approximating those in anoxic sediments: I. Mechanism and morphology. Mar. Chem. 52, 99-121.