Arsenic-dissolved organic matter complexation in water soluble extracts from lignite

Arsenic in groundwater is a global threat to public health. Recently, As mobility has been tied to the concentration and chemical characteristics of dissolved organic matter (DOM) through formation of As-DOM complexes. To date, there has been a wide range of DOM types studied to understand As-DOM interactions, but most of these have focused on surface water derived materials and not groundwater DOM. We address this gap in knowledge by simulating groundwater DOM using water extractable organic matter (WEOM) from two lignite deposits and treating the extracts with increasing concentrations of As. As-DOM complexes were measured using size-exclusion chromatography coupled to multiple detectors including an inductively coupled plasma mass spectrometer (ICPMS) for As detection as well as fluorescence and variable wave detectors for organic matter detection. First, we found two different size fractions of As-DOM, one of ∼1 kDa and another of ∼15 kDa, depending on the DOM types. The smaller As-DOM complex (∼1 kDa) was approximately 10 times more abundant than the larger complex (∼15 kDa). Second, we found that the lignite derived DOMs showed higher conditional distribution coefficients than did the surface water reference material (Suwanee River Natural Organic Matter, SRNOM). Finally, the data showed good fit (R² > 0.92) to one-site ligand binding models, and the lignite derived DOMs showed higher maximum sorbate concentrations (B_max) compared to SRNOM. Together, this study shows that As-DOM complexation is an important control on As speciation, even in groundwater systems.