The complexation of arsenic (As) with dissolved organic matter (DOM), although playing an important role in regulating As mobility and transformation, is poorly characterized, as evidenced by scarce reporting of fundamental parameters of As-DOM complexes. The complexation of arsenite (AsIII) with Aldrich humic acid (HA) at different pHs was characterized using a recently developed analytical technique to measure both free and DOM-bound As. Conditional distribution coefficient (KD), describing capacity of DOM in binding AsIII from the mass perspective, and apparent stability constant (Ks), describing stability of resulting AsIII-DOM complexes, were calculated to characterize AsIII-DOM complexation. LogKD of AsIII ranged from 3.7 to 2.2 (decreasing with increase of As/DOM ratio) at pH 5.2, from 3.6 to 2.6 at pH 7, and from 4.3 to 3.2 at pH=9.3, respectively. Two-site ligand binding models can capture the heterogeneity of binding sites and be used to calculate Ks by classifying the binding sites into strong (S1) and weak (S2) groups. LogKs for S1 sites are 7.0, 6.5, and 5.9 for pH 5.2, 7, and 9.3, respectively, which are approximately 1-2 orders of magnitude higher than for weak S2 sites. The results suggest that AsIII complexation with DOM increases with pH, as evidenced by significant spikes in concentrations of DOM-bound AsIII and in KD values at pH 9.3. In contrary to KD, logKs decreased with pH, in particular for S1 sites, probably due to the presence of negatively charged H2AsO3- and the involvement of metal-bridged AsIII-DOM complexation at pH 9.3.
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