Sulfide freshwater sediments

Lomans BP, R Maas, R Luderer, HJP op den Camp, A Pol, C van der Drift, GD Vogels (1999) Isolation and characterization of Methanomethylovorans hollandica gen. nov., sp. nov., isolated from freshwater sediment, a methylotrophic methanogen able to grow with dimethyl sulfide and methanethiol. Appl Environ Microbiol 65 3641-3650. 

Ankley, G.T., V.R. Mattson, E.N. Leonard, C.W. West, and J.L. Bennett. 1993. Predicting the acute toxicity of copper in freshwater sediments evaluation of the role of acid-volatile sulfide. Environ. Toxicol. Chem. 12 315-320. 

Hirsch, M.P. 1998a. Toxicity of silver sulfide-spiked sediments to the freshwater amphipod (Hyalella azteca). Environ. Toxicol. Chem. 17 601-604. 

Brouwer, H. and Murphy, T. 1995, Volatile sulfides andtheirtoxicity in freshwater sediments. Environ. Toxieol. Chem., 14 203-208. 

Pyrite is formed by two mechanisms in freshwater sediments. Fram-boidal pyrite results from reaction of iron monosulfides with S° (15), a slow reaction leading to gradual conversion of iron monosulfides to pyrite. In contrast, single crystals of pyrite are formed rapidly through reaction of Fe2+ and poly sulfides (161). Framboidal pyrite has been reported in lake sediments (37, 189), where it appears to form in microenvironments of plant or animal skeletons (cf. 35, 36). Rapid formation of pyrite has been observed in short-term measurements of sulfate reduction with SO/-. Up to 90% of reduced has been observed in pyrite after incubations of 1-24 h (72, 79, 98). A large fraction of inorganic S in the form of pyrite in surface sediments also has been interpreted to indicate rapid formation (112, 190). As discussed later, there is little evidence for extensive conversion of monosulfides to pyrite. 

Reactions 12a and 12b consume dissolved sulfide. This fact fits nicely with the data of White et al. (35), who could not detect free sulfide in their study. Dissolved sulfide is frequently absent in freshwater sediments (e.g., 39 see Urban, Chapter 10, for a discussion). This lack of sulfide is explained by an excess of reactive iron over the total sulfide concentration (19, 40). 

The observed sulfate reduction rates in freshwater sediments cannot be explained by diffusion of sulfate from the lake water into the sediment, because much steeper sulfate concentration gradients should then be observed. Assuming diffusive supply alone, Urban (28) calculated that the change of sulfate concentration with depth should take place within 1 mm instead of several centimeters, which are usually measured. This assumption, however, also means that the sulfate recycling process and the sulfate reduction rate should not be limited by the vertical transport of sulfide to (frequently solid) oxidants or to the oxic boundary layer. 

On the other hand, a permanent supply of ferric oxides to the sediments is provided by sedimentation of allochthonous material. It is unknown to what extent these oxides are reactive with respect to sulfide or whether a predigestion of ferric oxides by bacteria is needed. Various studies indicate that 50% of freshwater sediment iron exists as iron oxide and 20% of the iron is reactive (72). Future studies should be directed to a better understanding of the existence of reactive iron. 

Ankley, G.T., Liber, K., Call, D.J., Markee, T.P., Canfield, T.J. and Ingersoll, C.G. (1996) A field investigation of the relationship between zinc and acid volatile sulfide concentrations in freshwater sediments, Journal of Aquatic Ecosystem Health 5 (4), 255-264. 

Besser, J.M., Ingersoll, C.G. and Giesy, J.P. (1996) Effects of spatial and temporal variation of acid-volatile sulfide on the bioavailability of copper and zinc in freshwater sediments, Environmental Toxicology and Chemistry 15 (3), 286-293. 

DUNNETTE Origin of Hydrogen Sulfide in Freshwater Sediments... 

Sulfidization occurred to a much lesser degree in this freshwater sediment than in that near the saline-freshwater sediment interface. 

Lomans B. P., denCamp H. J. M. O., Pol A., and Vogels G. D. (1999a) Anaerobic versus aerobic degradation of dimethyl sulfide and methanethiol in anoxic freshwater sediments. Appl. Environ. Microbiol. 65, 438—443. 

Carlson, A.R., Phipps, G.L., Mattson, V.R., Kosnian, P.A. and Cotter, A.M. (1991) The role of acid-volatile sulfide in determining cadmium bioavailability and toxicity in freshwater sediments. Environ. Toxicol. Chem., 10, 1309-1319. 

Adams, D.D., 1994. Sediment pore water sampling. In Mudroch, A., MacKnight. S.D. (Eds.), Handbook of Techniques for Aquatic Sediments Sampling, 2nd ed. Lewis, Boca Raton, FL. pp. 171-202 Allen, H.E., Fu, G., Deng, B., 1993. Analysis of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) for the estimation of potential toxicity in aquatic sediments. Environ. Toxicol. Chem. 12, 1441-1453. Ankley, G.T., Mattson, V.R., Leonard, E.N., West, C.W., Bennett, J.L., 1993. Predicting the acute toxicity of copper in freshwater sediments evaluation of the role of acid-volatile sulfide. Environ. Toxicol. Chem. 12, 315-320,... 

Huerta-Diaz, M.A., Carignan, R., Tessier, A., 1993. Measurement of trace metals associated with acid volatile sulfides and pyrite in organic freshwater sediments. Environ. Sci. Technol. 27, 2367-2372. 

The redox potential-pH stability diagram (Figure 12.11) indicates that between pH 7 and 8, zinc carbonate (ZnCOj) is formed when the concentration of dissolved carbon dioxide (CO2) is 10 mol L . At low redox values, zinc sulfide is the most stable combination. Zinc precipitation by the hydrous metal oxides of manganese and iron is the principal control mechanism for zinc in wetland soils and freshwater sediments. The occurrence of these oxides as coatings on clay and silt enhances their chemical activity in excess of their total concentration. The uptake and release of the metals is governed by the concentration of other heavy metals, pH, organic and inorganic compounds, clays, and carbonates. 

Copper concentrations in sediment interstitial pore waters correlate positively with concentrations of dissolved copper in the over-lying water column and are now used to predict the toxicity of test sediments to freshwater amphipods. Sediment-bound copper is available to deposit-feeding clams, especially from relatively uncontaminated anoxic sediments of low pH. The bioavailability of copper from marine sediments, as judged by increased copper in sediment interstitial waters, is altered by increased acid volatile sulfide (AVS) content. But AVS is not an appropriate partitioning phase for predicting copper bioavailability of freshwater sediments. 

Free ionic silver readily forms soluble complexes or insoluble materials with dissolved and suspended material present in natural waters, such as sediments and sulfide ions (44). The hardness of water is sometimes used as an indicator of its complex-forming capacity. Because of the direct relationship between the availabiUty of free silver ions and adverse environmental effects, the 1980 ambient freshwater criterion for the protection of aquatic life is expressed as a function of the hardness of the water in question. The maximum recommended concentration of total recoverable silver, in fresh water is thus given by the following expression (45) in Fg/L. 

The case of bacterial reduction of sulfate to sulfide described by Berner (1984) provides a useful example. The dependence of sulfate reduction on sulfate concentration is shown in Fig. 5-4. Here we see that for [SO ] < 5 mM the rate is a linear function of sulfate concentration but for [SO4 ] > 10 itiM the rate is reasonably independent of sulfate concentration. The sulfate concentration in the ocean is about 28 mM and thus in shallow marine sediments the reduction rate does not depend on sulfate concentration. (The rate does depend on the concentration of organisms and the concentration of other necessary reactants - organic carbon in this case.) In freshwaters the sulfate concentration is... 

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