Molecule-based quantification of dissolved organic matter sources in high-arsenic groundwater

[Display omitted] •The recharged groundwater acted as the primary source of groundwater DOM.•Relative contribution of in-situ mobilized OM to DOM increased along the flow path.•The mobilized OM introduced considerable biodegradable compounds into groundwater.•The in-situ mobilized OM was the primary trigger of groundwater arsenic enrichment. Compositions of dissolved organic matter (DOM) in high-arsenic groundwater are usually sourced from the recharged groundwater DOM and the in-situ mobilized organic matter (OM) from aquifer sediments. However, relative importance of the two sources in DOM remains unclear. To quantify sources of DOM, Fourier transform ion cyclotron resonance mass spectrometry was used to analyze molecular characteristics of groundwater DOM and water-soluble organic matter (WSOM) in sediments along an inferred groundwater flow path in the Hetao Basin, China. Results showed that dissolved arsenic concentrations gradually increased from 1.92 to 402 μg/L along the flow path, being mainly due to the DOM degradation-triggered Fe(III) oxide reduction. The DOM molecules being unique to the background groundwater represented the in-situ mobilized OM, which showed the similar abundance to the DOM molecules being common to its depth-matched WSOM. An increasing trend of the relative abundance of the in-situ mobilized OM to the total DOM molecules along the flow path was recognized (from 0 % to 44.5 %). This suggests that the relative contribution of the in-situ mobilized OM to the groundwater DOM increased along with dissolved arsenic concentration. Furthermore, the biodegradable pool among the in-situ mobilized OM was significantly positively correlated with dissolved arsenic, indicating that this in-situ mobilized OM exhibited a dominant role in groundwater arsenic enrichment. The study provides novel insights into contribution of the in-situ mobilized OM to DOM and arsenic mobility in groundwater systems.