Molecular characteristics of natural organic matter (NOM) and their potential connections to arsenic enrichment processes remain poorly understood. Here, we examine dissolved organic matter (DOM) in groundwater and water-soluble organic matter (WSOM) in aquifer sediments being depth-matched with groundwater samples from a typical arid–semiarid basin (Hetao Basin, China) hosting high arsenic groundwater. We used Fourier transform ion cyclotron resonance mass spectrometry to determine molecular characteristics of DOM and WSOM and evaluate potential roles of biodegradable compounds in microbially mediated arsenic mobility at the molecular level. High-arsenic groundwater DOM was generally enriched in recalcitrant molecules (including lignins and aromatic structures). Although potential contribution of recalcitrant compounds to arsenic enrichment cannot be ruled out, preferential degradation of the labile molecules coupled with reduction of Fe­(III) (oxyhydr)­oxides seemed to dominate arsenic mobilization. Both the number and the intensity of biodegradable compounds (including aliphatic/proteins and carbohydrates) were higher in WSOM than those in DOM in depth-matched high-arsenic groundwater (arsenic >0.67 μmol/L or 50 μg/L). Groundwater arsenic concentration generally increased with the increase in the number and the intensity of unique biodegradable compounds (especially N-containing compounds) in WSOM at matched depths. Anoxic incubations of sediments and deionized water show that more arsenic and Fe­(II) were released from aquifer sediments with greater numbers and intensities of consumed biodegradable compounds in WSOM (especially N-containing compounds), with a higher proportion of microbially derived compounds produced. These observations indicate that the biodegradation of aliphatic/proteins and carbohydrates (especially CHON formulas) in WSOM fueling the reductive dissolution of Fe­(III) (oxyhydr)­oxides predominantly promotes arsenic release from aquifer solids. Our unique data present a better understanding of arsenic mobilization shaped by microbial degradation of labile organic compounds in anoxic aquifers at the molecular level.

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High arsenic (As) groundwater (>10 μg/L) has been increasingly observed throughout the world (Bundschuh