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