Organic matter degradation and arsenic enrichment in different floodplain aquifer systems along the middle reaches of Yangtze River: A thermodynamic analysis

Geogenic arsenic (As) contaminated groundwater has been widely accepted associating with dissolved organic matter (DOM) in aquifers, but the underlying enrichment mechanism at molecular-level from a thermodynamic perspective is poorly evidenced. To fill this gap, we contrasted the optical properties and molecular compositions of DOM coupled with hydrochemical and isotopic data in two floodplain aquifer systems with significant As variations along the middle reaches of Yangtze River. Optical properties of DOM indicate that groundwater As concentration is mainly associated with terrestrial humic-like components rather than protein-like components. Molecular signatures show that high As groundwater has lower H/C ratios, but greater DBE, AImod, and NOSC values. With the increase of groundwater As concentration, the relative abundance of CHON3 formulas gradually decreased while that of CHON2 and CHON1 increased, indicating the importance of N-containing organics in As mobility, which is also evidenced by nitrogen isotope and groundwater chemistry. Thermodynamic calculation demonstrated that organic matter with higher NOSC values preferentially favored the reductive dissolution of As-bearing Fe(III) (hydro)oxides minerals and thus promoted As mobility. These findings could provide new insights to decipher organic matter bioavailability in As mobilization from a thermodynamical perspective and are applicable to similar geogenic As-affected floodplain aquifer systems.