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Sulfur Biogeochemistry—Past and Present

Sulfur Biogeochemistry—Past and Present

Sulfur Biogeochemistry—Past and Present

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Microbially mediated sulfur-redox 29reactions 7.1–7.8 listed in Table 7B are also plotted as a functionof reaction number in Figure 5. Note in this figure that, withthe exception of reactions 7.2 <strong>and</strong> 7.6, in which CO 2serves asthe oxidant, all reactions are exergonic. However, the amount ofenergy released varies tremendously from only ~21 kJ/mol S 0 forreaction 7.4 at Acque Calde 2 to almost 750 kJ/mol S 0 for reaction7.5 at Grip, Acque Calde 2, <strong>and</strong> Pozzo Istmo. Not surprisingly,reactions in which O 2serves as the TEA are the most exergonic,yielding 171 ± 8 kJ/mol S 0 for reaction 7.1 <strong>and</strong> 710 ± 34 kJ/molS 0 for reaction 7.5. Again, per mole of electrons transferred, thesetwo reactions yield comparable amounts of energy (82–89 kJ forreaction 7.1 <strong>and</strong> 85–93 kJ for reaction 7.5).A COMPARISON OF DEEP AND SHALLOW MARINEVENTSMcCollom <strong>and</strong> Shock (1997) showed that at temperatures>40 °C in the deep-sea hydrothermal system at 21°N on the EastPacific Rise, sulfate-reduction (reaction 4.1) <strong>and</strong> S 0 -reduction(reaction 5.1) with H 2as the electron donor are exergonic, butS 0 -oxidation (reaction 6.1) <strong>and</strong> sulfide-oxidation (reaction 7.5)with O 2as the TEA are endergonic. By comparison, these fourreactions are all exergonic at the seven Vulcano sites investigatedhere. At temperatures between 50 <strong>and</strong> 100 °C, values of ∆G rforsulfate- <strong>and</strong> S 0 -reduction at the deep-sea site yield ~130 <strong>and</strong> ~30kJ/mol, respectively. The energetics of these reactions at Vulcanoare similar, yielding between 90 <strong>and</strong> 140 kJ/mol sulfate (except atPozzo Istmo) <strong>and</strong> between 16 <strong>and</strong> 38 kJ/mol S 0 . At temperaturesbetween 50 <strong>and</strong> 100 °C, the oxidation of S 0 <strong>and</strong> sulfide consumesFigure 5. ∆G r(kJ/mol) of the sulfide-oxidation reactions listed inTable 7A (data given in Table 7B) plotted against reaction number.Symbols are as in Figure 2. Equilibrium (∆G r= 0) is indicated by asolid horizontal line.

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