Concentrations of methyl mercury, CH3Hg (II), total mercury, Hg-tot = CH3Hg (II) + Hg (II), and organic sulphur species were determined in soils, soil solutions and streams of a small (50 ha) boreal forest catchment in northern Sweden. The CH3Hg (II)/Hg-tot ratio decreased from 1.2-17.2% in the peaty stream bank soils to 0.4-0.8% in mineral and peat soils 20 m away from the streams, indicating that conditions for net methylation of Hg (II) are most favourable in the riparian zone close to streams. Concentrations of CH3Hg (II) bound in soil and in soil solution were significantly, positively correlated to the concentration of Hg tot in soil solution. This, and the fact that the CH3Hg (II)/Hg-tot ratio was higher in soil solution than in soil may indicate that Hg (II) in soil solution is more available for methylation processes than soil bound Hg (II). Reduced organic S functional groups (Org-S (RED)) in soil, soil extract and in samples of organic substances from streams were quantified using S K-edge X-ray absorption near-edge structure (XANES) spectroscopy. Org-S (RED), likely representing RSH, RSSH, RSR and RSSR functionalities, made up 50 to 78% of total S in all samples examined. Inorganic sulphide [e.g. FeS2 (s)] was only detected in one soil sample out of 10, and in none of the stream samples. Model calculations showed that under oxic conditions nearly 100% of Hg (II) and CH3Hg (II) were complexed by thiol groups (RSH) in the soil, soil solution and in the stream water. Concentrations of free CH3Hg+ and Hg2+ ions in soil solution and stream were on the order of 10(-18) and 10(-32) M, respectively, at pH 5. For CH3Hg (II), inorganic bi-sulphide complexes may contribute to an overall solubility at concentrations of inorganic sulphides higher than 10(-9) M, whereas considerably higher concentrations of inorganic sulphides (lower redox-potential) are required to increase the solubility of Hg (II).
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