Sulfate reduction zone

The profile of Mg2+ in Figure 8.25 indicates downward diffusion of this constituent into the sediments. Mass balance calculations show that sufficient Mg2+ can diffuse into the sediments to account for the mass of organogenic dolomite formed in DSDP sediments (Baker and Bums, 1985 Compton and Siever, 1986). In areas of slow sedimentation rates, the diffusive flux of Mg2+ is high, and the pore waters have long residence times. Dolomites form under these conditions in the zone of sulfate reduction, are depleted in 13c, and have low trace element contents. With more rapid sedimentation rates, shallowly-buried sediments have shorter residence times, and dolomites with depleted 13C formed in the sulfate-reduction zone pass quickly into the underlying zone of methanogenesis. In this zone the DIC is enriched in 13C because of the overall reaction... 

Rates of methane production via both acetate fermentation and C02 reduction were directly measured with radiotracer techniques in the sulfate-depleted sediments of Saanich and Princess Louisa Inlets (Kuivila etal., 1990). Comparison of measured and modeled rates suggests that these two pathways account for the majority of methane produced below the sulfate reduction zone in the sediments of both the basins. Prior aerobic degradation of the organic matter has little influence on the pathways of methane production. 

In Figure 3.14 a sulfate reduction zone is documented by measured profiles of sulfate and methane in pore water. Estimate the diffusive methane flux [mol m a ] and use for the calculation the more reliable profile of sulfate concentrations. Use a temperature of 5°C and a sediment porosity of ([) = 0.7. 

In fully marine systems siderite formation is probable to occur below the sulfate reduction zone where dissolved sulfide is absent, if reactive iron is still present and the Fe/Ca-ratio of pore water is high enough to stabilize siderite over calcite (Berner 1971). The coexistence of siderite and pyrite in anoxic marine sediments was shown by Ellwood et al. (1988) and Haese et al. (1997). Both studies attribute this observation to the presence of microenvironments resulting in different characteristic early diagenetic reactions next to each other within the same sediment depth. It appears that in one microenvironment sulfate reduction and the formation of pyrite is predominant, whereas at another site dissimilatory iron reduction and local supersaturation with respect to siderite occurs. Similarly, the importance of microenvironments has been pointed out for various other processes (Jorgensen 1977 Bell et al. 1987 Canfield 1989 Gingele 1992). 

By a relatively thin oxic and suboxic zone, e g. in organic-rich sediments or in oxygen-deficient enviromnents, relatively more organic material is buried down into the sulfate zone. Bioturbation enhances the burial of relatively fresh organic material into the sulfate reduction zone. At the same time, however, bioturbation and bioirrigation deepen the oxic-suboxic zones and thereby push down the zone of sulfate reduction. 

In water containing sulfate, the use of the electrolysis protection process with low water consumption can sometimes result in the formation of small amounts of HjS, which is detectable by the smell. Sulfate reduction occurs through the action of bacteria in anaerobic areas (e.g., in the slurry zone of the tank). 

Chapelle, F. H. and D. R. Lovley, 1992, Competitive exclusion of sulfate reduction by Fe(III)-reducing bacteria a mechanism for producing discrete zones of high-iron ground water. Ground Water 30, 29-36. 

The other metals exhibit different vertical profiles. The dissolved concentrations of Pb and Cu do not exhibit subsurface concentration maxima and, hence, do not appear to undergo any redox reactions. Their dissolved concentrations decline with increasing depth and are likely controlled by precipitation into sulfide minerals as the particulate concentrations increase rapidly with depth in the anoxic zone. In the anoxic waters, sulfide is supplied by in situ sulfate reduction. 

In sediments that lie in coastal waters, organic carbon levels are high enough to support denitrification, iron respiration, sulfate reduction and methanogenesis. As shown in the idealized profile presented in Figure 12.3b, the depth of O2 penetration in organic-rich sediments is typically so shallow as to make the zones of aerobic respiration. 

Much confusion exists over the effects of sulfate concentration and carbon availability on rates of sulfate reduction (cf. 1, 4, 5, 72, 85, 106). Sulfate reducers in lake sediments exhibit low half-saturation constants for sulfate (10-70 xmol/L 4, 72, 78, 85) as well as for acetate and hydrogen (4, 13, 87). The low half-saturation constants allow them to outcompete methano-gens for these substrates until sulfate is largely consumed within pore waters (4, 90). Low concentrations of sulfate in lakes confine the zone of sulfate reduction to within a few centimeters of the sediment surface (e.g., 4, 90, 98). The comparability of rates of sulfate reduction in freshwater and marine... 

Abiotic oxidation of sulfide by oxygen cannot supply sulfate at rates comparable to rates of sulfate reduction. Unless high concentrations of sulfide develop and the zone of oxidation is much greater than 1 cm, rates of chemical oxidation of sulfide by oxygen will be much less than 1 mmol/m2 per day (calculated from rates laws found in refs. 115-118). Such conditions can exist in stratified water columns in the Black Sea water column chemical oxidation rates may be as high as 10 mmol/m2 per day (84). However, in lakes in which sulfide is undetectable in the water column and oxygen disappears within millimeters of the sediment-water interface (e.g., 113), chemical oxidation of sulfide by oxygen is unlikely to be important. 

Measured rates of sulfate reduction can be sustained only if rapid reoxidation of reduced S to sulfate occurs. A variety of mechanisms for oxidation of reduced S under aerobic and anaerobic conditions are known. Existing measurements of sulfide oxidation under aerobic conditions suggest that each known pathway is rapid enough to resupply the sulfate required for sulfate reduction if sulfate is the major end product of the oxidation (Table IV). Clearly, different pathways will be important in different lakes, depending on the depth of the anoxic zone and the availability of light. All measurements of sulfate reduction in intact cores point to the importance of anaerobic reoxidation of sulfide. Little is known about anaerobic oxidation of sulfide in fresh waters. There are no measurements of rates of different pathways, and it is not yet clear whether iron or manganese oxides are the primary electron acceptors. 

On the basis of this model, Lovley et al. (17) argued that reductive dissolution of ferric oxides must be a microbiological process because the zone of sulfide generation is distinct from the zone of maximum ferric oxide reduction. Highly eutrophic environments would be an exception. In these systems the zone of decomposition with oxygen as terminal electron acceptor directly overlies the zone of sulfate reduction. 

Pore-water profiles are frequently interpreted according to this concept. For example, White et ah (35) described a conceptual model of biogeo-chemical processes of sediments in an acidic lake (cf. Figure 4). They discussed the numbered points in Figure 4 as follows Diffusion of dissolved oxygen across the sediment-water interface leads to oxidation of ferrous iron and to an enrichment of ferric oxide (point 1). Bacterial reductive dissolution of the ferric oxides in the deeper zones releases ferrous iron (point 2). The decrease in sulfate concentration stems from sulfate reduction, which produces H2S to react with ferrous iron to form mostly pyrite in the zone below the ferric oxide accumulation (point 3). 

Figure 8.25. Some chemical and diagenetic properties of organic-rich marine sediments as a function of depth based on DSDP interstitial water profiles. A. Schematic gradients of SO42-, total alkalinity, Ca2+ and Mg2+ in pore waters, and zones of sulfate reduction, methanogenesis and fermentation. Magnesium diffuses into the sediment and organogenic dolomite forms at depth. B. Logarithm of calculated saturation states of interstitial waters with respect to dolomite. Dolomite saturation=0. All these pore waters are oversaturated with respect to dolomite. (After Compton, 1988.)...

Jacobsen, R., and Postma, D. (1999) Redox zoning, rates of sulfate reduction and interactions with Fe-reduction and methanogenesis in a shallow sandy aquifer, Romo, Denmark. Geochim. Cosmochim. Acta 63, 137-151. 

The most recent studies of the isotopic composition of the sulfate and dissolved sulfide in the BCL conducted in 2004, however, did not confirm the existence of the lower isotopic trend in the isotopic composition of sulfide. The average sulfur isotopic composition of sulfide below 1750 m was - 40.0%o and varied between - 39.1 and - 41.5% [52], which is very similar to the isotopic composition of most of the anoxic zone (Fig. 6). In contrast, the isotope composition of sulfate in the BCL varied between + 19.9 and + 21.6% (average + 20.8%o) suggesting a slight 34S enrichment of about 1.3%o compared to the entire anoxic zone. Volkov and Rimskaya-Korsakova [52] hypothesized that the observed enrichment in sulfate sulfur was a result of the relative depletion of sulfate during bacterial sulfate reduction in this zone. These data are supported by the 2% decrease in the sulfate/chlorinity ratio observed in the BCL. 

Tg year x. Lein and Ivanov [71] have estimated the total sulfide burial in the Black Sea of 2.4 Tgyear 1 including about 1 Tgyear-1 that is buried in the anoxic zone. Using these data and integrated over the upper 20 cm of sediment sulfate reduction rates, Neretin and co-authors [75] concluded that the annual sulfide flux into the water column from sediments of the anoxic zone is between 3 and 5 Tgyear x. The value is likely to be overestimated due to spatial differences in pyrite burial rates and possible sulfide diffusion downward into the deeper sediment layers. 

In recent years various workers f1-7J have successfully developed models based on the mathematics of diffusion (8) to describe vertical profiles of selected chemical parameters in marine sediments dominated by sulfate reduction. Several papers 9, 10) have also proposed models for nitrogen diagenesis in the upper aerobic zone of such sediments. Most of these models, however, deal with only one or two relatively well behaved parameters, such as SO5" or CO2, which do not interact strongly with other components of the sediment besides organic matter. A truly comprehensive model for such sediment should deal simultaneously with all of the major chemical parameters of the system and ideally should be formulated as an initial value prob-... 

This paper proposes a system of 10 non-linear, simultaneous differential equations (Table I) tdiich upon further development and validation, may serve as a comprehensive model for predicting steady state, vertical profiles of chemical parameters in the sulfide dominated zones of marine sediments. The major objective of the model is to predict the vertical concentration profiles of H2S, hydrotriolite (FeS) and p3nrite (FeS2). As with any model there are a number of assumptions involved in its construction that may limit its application. In addition to steady state, the major limiting assumptions of this model are the assumptions that the sediment is free of CaC03, that the diffusion coefficients of all dissolved sulfur species are equivalent and that dissolved oxygen does not penetrate into the zone of sulfate reduction. 

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