Chromium(III) Complexation to Natural Organic Matter: Mechanisms and Modeling

Chromium is a common soil contaminant, and it often exists as chromium­(III). However, limited information exists on the coordination chemistry and stability of chromium­(III) complexes with natural organic matter (NOM). Here, the complexation of chromium­(III) to mor layer material and to Suwannee River Fulvic Acid (SRFA) was investigated using EXAFS spectroscopy and batch experiments. The EXAFS results showed a predominance of monomeric chromium­(III)-NOM complexes at low pH (<5), in which only Cr···C and Cr–O–C interactions were observed in the second coordination shell. At pH > 5 there were polynuclear chromium­(III)-NOM complexes with Cr···Cr interactions at 2.98 Å and for SRFA also at 3.57 Å, indicating the presence of dimers (soil) and tetramers (SRFA). The complexation of chromium­(III) to NOM was intermediate between that of iron­(III) and aluminum­(III). Chromium­(III) complexation was slow at pH < 4: three months or longer were required to reach equilibrium. The results were used to constrain chromium-NOM complexation in the Stockholm Humic Model (SHM): a monomeric complex dominated at pH < 5, whereas a dimeric complex dominated at higher pH. The optimized constant for the monomeric chromium­(III) complex was in between those of the iron­(III) and aluminum­(III) NOM complexes. Our study suggests that chromium­(III)-NOM complexes are important for chromium speciation in many environments

Monothioarsenate Transformation Kinetics Determining Arsenic Sequestration by Sulfhydryl Groups of Peat

In peatlands, arsenite was reported to be effectively sequestered by sulfhydryl groups of natural organic matter. To which extent porewater arsenite can react with reduced sulfur to form thioarsenates and how this affects arsenic sequestration in peatlands is unknown. Here, we show that, in the naturally arsenic-enriched peatland <i>Gola di Lago</i>, Switzerland, up to 93% of all arsenic species in surface and porewaters were thioarsenates. The dominant species, monothioarsenate, likely formed from arsenite and zerovalent sulfur-containing species. Laboratory incubations with sulfide-reacted, purified model peat showed increasing total arsenic sorption with decreasing pH from 8.5 to 4.5 for both, monothioarsenate and arsenite. However, X-ray absorption spectroscopy revealed no binding of monothioarsenate via sulfhydryl groups. The sorption observed at pH 4.5 was acid-catalyzed dissociation of monothioarsenate, forming arsenite. The lower the pH and the more sulfhydryl sites, the more arsenite sorbed which in turn shifted equilibrium toward further dissociation of monothioarsenate. At pH 8.5, monothioarsenate was stable over 41 days. In conclusion, arsenic can be effectively sequestered by sulfhydryl groups in anoxic, slightly acidic environments where arsenite is the only arsenic species. At neutral to slightly alkaline pH, monothioarsenate can form and its slow transformation into arsenite and low affinity to sulfhydryl groups suggest that this species is mobile in such environments