Sulfur Cycle
Sulfur (S) is an important redox element in estuaries because of its linkage with biogeochemical processes such as SO42− reduction (Howarth and Teal, 1979; Jørgensen, 1982; Luther et al., 1986; Roden and Tuttle, 1992, 1993a,b; Miley and Kiene, 2004), pyrite (FeS2) formation (Giblin, 1988; Hsieh and Yang, 1997; Morse and Wang, 1997), metal cycling (Krezel and Bal, 1999; Leal et al., 1999; Tang et al., 2000), ecosystem energetics (King et al., 1982; Howarth and Giblin, 1983; Howes et al., 1984), and atmospheric S emissions (Dacey et al., 1987; Turner et al., 1996; Simo et al., 1997). The range of oxidations for S intermediates formed in each of these processes is between +VI and −II. Many of the important naturally occurring molecular species of S are shown in table 12.1. On a global scale, most of the S is located in the lithosphere; however, there are important interactions between the hydrosphere, biosphere, and atmosphere where important transfers of S occur (Charlson, 2000). For example, coal and biomass burning, along with volcano emissions inject SO2 into the atmosphere, which can then be further oxidized in the atmosphere and removed as SO42− in rainwater (Galloway, 1985). An example of biogenic sulfur formation is the reduction of seawater SO42− to sulfide by phytoplankton and eventual incorporation of the S into dimethylsulfoniopropionate (DMSP). DMSP, in turn, is converted to volatile dimethyl sulfide (DMS; CH3SCH3)m which is emitted to the atmosphere. In the seawater, SO42− represents one of the major ions, with concentrations that range from 24 to 28 mM, which is considerably higher than the concentrations found in freshwaters (∼0.1 mM). This marked difference makes seawater the major input to estuaries and sets up an important gradient in estuarine biogeochemical cycling. In this chapter, the focus will be on the nonanthropogenic biogenic transformations of S that are relevant to biogeochemical cycling in estuarine and coastal waters. Approximately 50% of the global flux of S to the atmosphere is derived from marine emissions of DMS. Oxidation of DMS in the atmosphere leads to production of SO42− aerosols, which can influence global climate patterns (Charlson et al., 1987; Andreae and Crutzen, 1997).