Example Sulfate Reduction

As an example of a radio-tracer method, the measurement of sulfate reduction rates using according to Jorgensen (1978) Fossing and Jorgensen (1989) Kallmeyer et al. (2004) is described in brief (Fig. 5.14). The is 

Sulfate reduction rates in marine shelf sediments commonly lie in the range of 1-100 nmol cm May (Jorgensen 1982). Since the sulfate concentration in the pore water is around 28 mM or 20 pmol cm the turn-over time of the sulfate pool is in the order of 1-50 years. A purely chemical experiment would thus require a month to several years of incubation. This clearly illustrates why a radiotracer technique is required to measure the rate within several hours. In sediment cores from the open eastern equatorial Pacific obtained by the Ocean Drilling Program it has been possible to push the detectability of this radiotracer method to its physical limit by measuring sulfate reduction rates of 0.001 nmol cm d in 9 million year old sediments at 300 m below the seafloor (Parkes et al. 2005). 

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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... 

The conditions under which these function and their regulation depend on the organism. For example, in Escherichia coli, oxygen represses the synthesis of the other reductases, and under anaerobic conditions the reductases for fumarate, DMSO, and TMAO are repressed by nitrate. This does not apply to Wolinella succinogenes in which sulfur represses the synthesis of the more positive electron acceptors nitrate and fumarate (Lorenzen et al. 1993). The DMSO reductase from Escherichia coli (Weiner et al. 1988) has a broad substrate versatility, and is able to reduce a range of sulfoxides and A-oxides. Anaerobic sulfate reduction is not discussed here in detail. 

The Monod equation is the relation most commonly applied to describe the rate at which a microbe metabolizes its substrate (e.g., Panikov, 1995). Taking ace-totrophic sulfate reduction as an example, the redox reaction,... 

Sediment deposition on the seafloor traps interstitial water. After deposition, complex reactions take place in the sediment, most of them fueled by the decay of organic matter, such as sulfate reduction, denitrification,... Because of fast diffusion rates of most cations in seawater, the presence of interstitial water makes exchange between overlying sedimentary layers a much easier process than if sediment deposition was dry. The book by Berner (1980) is entirely dedicated to these processes and only a short example is given here. 

Startup effects. Startup effects must also be considered in the interpretation of laboratory experiments. For example, during sulfate reduction, the first small amormt of sulfur to pass through the chain of reaction steps would be subject to the kinetic isotope effects of all of the reaction steps. This is because it takes some time for the isotopic compositions of the pools of intermediates to become enriched in heavier isotopes as described above for the steady-state case. Accordingly, the first HjS produced would be more strongly enriched in the lighter isotopes than that produced after a steady state has been approached. This principle was modeled by Rashid and Krouse (1985) to interpret kinetic isotope effects occurring during abiotic reduction of Se(IV) to Se(0) (see below). Startup effects may be particularly relevant in laboratory experiments where Se or Cr concentrations are very small, as is the case in some of the studies reviewed below. 

A few examples of chemoautolithotrophic processes have been mentioned in this chapter, namely anaerobic methane oxidation coupled to sulfate reduction and the ones listed in Table 12.2 involving manganese, iron, and nitrogen. Another example are the microbial metabolisms that rely on sulfide oxidation. Since sulfide oxidation is a source of electrons, it is a likely source of energy that could be driving denitrification, and manganese and iron reduction where organic matter is scarce. 

In some cases the methods may be combined. Examples would include the biotechnological precipitation of chromium from Cr(VI)-containing wastes from electroplating factories by sulfate reduction to precipitate chromium sulfide. Sulfate reduction can use fatty acids as organic substrates with no accumulation of sulfide. In the absence of fatty acids but with straw as organic substrate, the direct reduction of chromium has been observed without sulfate reduction [43]. 

Another factor that is of great importance for the observed sulfur isotope variations of natural sulfides is whether sulfate reduction takes place in an open or closed system. An open system has an infinite reservoir of sulfate in which continuous removal from the source produces no detectable loss of material. Typical examples are the Black Sea and local oceanic deeps. In such cases, H2S is extremely depleted in " S while consumption and change in " S remain negligible for the sulfate. In a closed system, the preferential loss of the lighter isotope from the reservoir has a feedback on the isotopic composition of the unreacted source material. The changes in the " S-content of residual sulfate and of the H2S are modeled in Fig. 2.21, which shows that 5 S-values of the residual sulfate steadily increase with sulfate consumption (a linear relationship on the log-normal plot). The curve for the derivative H2S is parallel to the sulfate curve at a distance which depends on the magnitude of... 

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). 

Redox Reactions. Aquatic organisms may alter the particular oxidation state of some elements in natural waters during activity. One of the most significant reactions of this type is sulfate reduction to sulfide in anoxic waters. The sulfide formed from this reaction can initiate several chemical reactions that can radically change the types and amounts of elements in solution. The classical example of this reaction is the reduction of ferric iron by sulfide. The resultant ferrous iron and other transition metals may precipitate with additional sulfide formed from further biochemically reduced sulfate. Iron reduction is often accompanied by a release of precipitated or sorbed phosphate. Gardner and Lee (21) and Lee (36) have shown that Lake Mendota surface sediments contain up to 20,000 p.p.m. of ferrous iron and a few thousand p.p.m. of sulfide. The biochemical formation of sulfide is undoubtedly important in determining the oxidation state and amounts of several elements in natural waters. 

Not all measures of salinity convey the same degree of salinity. For example, compare Orca Basin, the Great Salt Lake, the Dead Sea, and Basque Lake (Table 5.1). All four of these waters contain about the same salinity % [25.1-26.4% salt (wt/wt)]. Note, however, that Basque Lake has a much more favorable (for life) aw (0.919) compared with Orca Basin (0.774), Great Salt Lake (0.776), and, especially, the Dead Sea (0.690). The impact of salts on life depends on the anions and cations and their charges and molecular weight. Bacterial sulfate reduction occurs with salt concentrations up to 24% (Oren 1988), but chloride salt solutions at such concentrations deals much more harshly with life. Only the most halophilic organisms can live in the Dead Sea (Table 4.2). The Dead Sea was called dead because it was only in 1936 that life forms (e.g., bacteria, algae, yeast) were first isolated from this hypersaline water (Ventosa et al. 1999). 

Microbial metabolic activity in general is known both to accelerate transitions to stable equilibria and to produce metastable intermediate dissolved species and mineral precipitates that otherwise would not exist or would not be abundant. In general, most metabolic schemes that intervene in the existence and abundance of one anionic species or complex will do so with others, too, and this also has a big effect on the evaporitic and freezing chemistry dealt with by FREZCHEM. For example, dolomite formation is linked to sulfate reduction in one biogeochemical scheme. Lacking microbial activity,... 

The biotransformations of sulfur compounds by microorganisms can have large-scale impacts on global chemistry. As an example, sulfate-reducing bacteria have, throughout histoiy, formed major deposits of elemental sulfur and iron sulfides on Earth, and these processes are continuing today (1). Contemporary sulfate-reduction coupled with the oxidation of reduced inorganic sulfur... 

It was shown earlier that aggregate types do not materially affect the performance of water-reducing admixtures. This is not true for cement and mixes containing special cements require particular care. Examples here are increased retardation with low C3A cement (for example, sulfate-resistant cement) and even an almost complete reduction in expansive properties with expansive cements in the presence of water-reducing admixtures. However, pozzolans such as fly ash appear to behave normally with water-reducing admixtures. 

These examples convincingly demonstrate that specific OSC are formed during the early stages of diagenesis by reactions of reduced sulfur species with specific biogenic substrates. The reactive substrates are proposed to contain either carbon-carbon double bonds or other reactive functional groups that react with either hydrogen sulfide or polysulfides to form the OSC (88). These views are consistent with evidence from sulfur isotopes that H2S produced by microbial sulfate reduction is the major source of reduced sulfur in sediments... 

For example, and 5 0 of SO was used to assess mixing between a vertically stacked aquifer system in contact with a salt dome located in northern Germany (Berner era/., 2002). Two major sulfate pools were identified based upon their isotopic compositions (i) SO from the dissolution of evaporite minerals, and (ii) SO derived from atmospheric deposition and from the oxidation of pyrite. Using both the and of the sol , zones of variable groundwater mixing and significant amounts of bacterial sulfate reduction were identified. The SOl derived from the dissolution of the rock salt in the highly saline deep brine showed nearly constant values between +9.6%c and 11.9%o and between +9.5%c and 12.1%o, consistent with the Permian evaporite deposits. Sulfate in near-surface... 

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