Abstract:
We combined synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy and binding affinity studies to determine the coordination, geometry, and strength of methyl mercury, CH3Hg (II), bonding in soil and stream organic matter. Samples of organic soil (OS), potentially soluble organic substances (PSOS) from the soil, and organic substances from a stream (SOS) draining the soil were taken along a short ''hydrological transect.'' We determined the sum of concentrations of highly reduced organic S groups (designated Org-SRED), such as thiol (RSH), disulfane (RSSH), sulfide (RSR), and disulfide (RSSR), using sulfur K-edge XANES. Org-SRED varied between 27% and 64% of total S in our samples. Hg LIII-edge EXAFS analysis were determined on samples added CH3Hg (II) to yield CH3Hg (II)/Org-SRED ratios in the range 0.01-1.62. At low ratios, Hg was associated to one C atom (the methyl group) at an average distance of 2.03 +/- 0.02 Α and to one S atom at an average distance of 2.34 +/- 0.03 Α, in the first coordination shell. At calculated CH3Hg(II)/Org-SRED ratios above 0.37 in OS, 0.32 in PSOS, and 0.24 in SOS, the organic S sites were saturated by CH3Hg+, and O (and/or N) atoms were found in the first coordination shell of Hg at an average distance of 2.09 +/- 0.01 Α. Based on the assumption that RSH (and possibly RSSH) groups take part in the complexation of CH3Hg+, whereas RSSR and RSR groups do not, approximately 17% of total organic S consisted of RSH (+ RSSH) functionalities in the organic soil. Corresponding figures for samples PSOS and SOS were 14% and 9%, respectively. Competitive complexation of CH3Hg+ by halide ions was used to determine the average binding strength of native concentrations of CH3Hg (II) in the OS sample. Using data for Org-SRED, calculated surface complexation constants were in the range from 1016.3 to 1016.7 for a model RSH site having an acidity constant of mercaptoacetic acid. These values compare favorably with identically defined stability constants (log K1) for the binding of methyl mercury to thiol groups in well-defined organic compounds.
