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Rates of elemental sulphur oxidation and associated oxygen and sulphur isotope fractionationSmith, Laura Ann 21 September 2009
Elemental sulphur (S<sup>0</sup>) is removed from sour gas deposits (high H<sub>2</sub>S) during refinement. The resulting S<sup>0</sup> is often stored onsite when the costs of shipping S<sup>0</sup> to market exceeds the costs of storing it in large above ground blocks. With the aid of acidiphilic bacteria, atmospheric air and water oxidize S<sup>0</sup> to sulphate (SO<sub>4</sub><sup>2-</sup>). Long term storage is under consideration; however, oxidation rates and the role of each oxygen source (O<sub>2(g)</sub> and H<sub>2</sub>O) is not clear.
S<sup>0</sup> oxidation experiments were conducted over a range of temperatures (6-32¡ãC) to investigate reaction rates and isotopic fractionation of O and S isotopes during oxidation. The experiments also investigated the effect of integrating S<sup>0</sup> oxidizing microorganisms and available nutrients on both the reaction rates and isotope fractionation. Results indicated > 95% of total SO<sub>4</sub><sup>2-</sup> generated can be attributed to autotrophic microbial activity. Experiments conducted in a nutrient rich mineral solution showed rates increase with temperature from 0.16 (6¡ãC) to 0.98 (32¡ãC) ¦Ìg S<sup>0</sup> cm<sup>-2</sup> d<sup>-1</sup> (Q<sub>10</sub> ¡Ö 1.7 - 1.9). Experiments conducted in a nutrient poor solution (deionized water) showed oxidation rates did not increase with temperature (0.06 to 0.08 ¦Ìg S<sup>0</sup> cm<sup>-2</sup> d<sup>-1</sup>) between 12 and 32¡ãC. Oxygen isotope analysis of the generated SO<sub>4</sub><sup>2-</sup> indicated essentially all oxygen incorporated into the SO<sub>4</sub><sup>2-</sup> originated from H<sub>2</sub>O. In addition, effluent samples obtained from S<sup>0</sup> block effluent at SCL indicated ¦Ä<sup>18</sup>O<sub>(SO4)</sub> generally reflected the ¦Ä<sup>18</sup>O<sub>(H2O)</sub> in the system at the time of oxidation. While covering the S<sup>0</sup> blocks with an impermeable cover would undoubtedly minimize total SO<sub>4</sub><sup>2-</sup> accumulation in block effluent, the results of this study suggest ¦Ä<sup>18</sup>O<sub>(SO4)</sub> can also be used to track water movement through the block.
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Rates of elemental sulphur oxidation and associated oxygen and sulphur isotope fractionationSmith, Laura Ann 21 September 2009 (has links)
Elemental sulphur (S<sup>0</sup>) is removed from sour gas deposits (high H<sub>2</sub>S) during refinement. The resulting S<sup>0</sup> is often stored onsite when the costs of shipping S<sup>0</sup> to market exceeds the costs of storing it in large above ground blocks. With the aid of acidiphilic bacteria, atmospheric air and water oxidize S<sup>0</sup> to sulphate (SO<sub>4</sub><sup>2-</sup>). Long term storage is under consideration; however, oxidation rates and the role of each oxygen source (O<sub>2(g)</sub> and H<sub>2</sub>O) is not clear.
S<sup>0</sup> oxidation experiments were conducted over a range of temperatures (6-32¡ãC) to investigate reaction rates and isotopic fractionation of O and S isotopes during oxidation. The experiments also investigated the effect of integrating S<sup>0</sup> oxidizing microorganisms and available nutrients on both the reaction rates and isotope fractionation. Results indicated > 95% of total SO<sub>4</sub><sup>2-</sup> generated can be attributed to autotrophic microbial activity. Experiments conducted in a nutrient rich mineral solution showed rates increase with temperature from 0.16 (6¡ãC) to 0.98 (32¡ãC) ¦Ìg S<sup>0</sup> cm<sup>-2</sup> d<sup>-1</sup> (Q<sub>10</sub> ¡Ö 1.7 - 1.9). Experiments conducted in a nutrient poor solution (deionized water) showed oxidation rates did not increase with temperature (0.06 to 0.08 ¦Ìg S<sup>0</sup> cm<sup>-2</sup> d<sup>-1</sup>) between 12 and 32¡ãC. Oxygen isotope analysis of the generated SO<sub>4</sub><sup>2-</sup> indicated essentially all oxygen incorporated into the SO<sub>4</sub><sup>2-</sup> originated from H<sub>2</sub>O. In addition, effluent samples obtained from S<sup>0</sup> block effluent at SCL indicated ¦Ä<sup>18</sup>O<sub>(SO4)</sub> generally reflected the ¦Ä<sup>18</sup>O<sub>(H2O)</sub> in the system at the time of oxidation. While covering the S<sup>0</sup> blocks with an impermeable cover would undoubtedly minimize total SO<sub>4</sub><sup>2-</sup> accumulation in block effluent, the results of this study suggest ¦Ä<sup>18</sup>O<sub>(SO4)</sub> can also be used to track water movement through the block.
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