Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pHT was between 2.20 and 9.30 at the discharge temperature and the SO4 and Cl concentrations were 0.020–52.7 and <0.01–10.0 mmol kg−1, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO42−), thiosulfate (S2O32−) and polythionates (SxO62−) and titration and/or colorimetry for total dissolved sulfide (S2−). Sulfite (SO32−) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S2− were detected in all samples with concentrations of 0.02–52.7 mmol kg−1 and <1–4100 μmol kg−1, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1–394 μmol kg−1 (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1–3 μmol kg−1. Thiosulfate and SO32− were not detected in <100 °C well waters and S2O32− was observed only at low concentrations (<1–8 μmol kg−1) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S2O32− was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (STOT). In steam-heated acid-sulfate waters, S2O32− was not a significant sulfur species. The results demonstrate that S2O32− and SO32− do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200–300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O2, S2− is degassed and oxidized to SO32− and S2O32− and eventually to SO42− at pH >8. In near-neutral hydrothermal waters the oxidation of S2− and the interaction of S2− and S0 resulting in the formation of Sx2− are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO42− and the sulfur chemistry of acid-sulfate pools was dominated by SO42−, which corresponded to >99% of STOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.