Novel insight into arsenic enrichment in aquifer sediments under different paleotemperatures from a molecular-level characterization of sedimentary organic matter

Abstract

The heterogeneous distribution of As in sediments is governed by the abundance and type of SOM, which is closely associated with the depositional environment. However, few studies have revealed the effect of depositional environment (e.g., paleotemperature) on As sequestration and transport in sediments from the perspective of the molecular characteristics of sedimentary organic matter (SOM). In this study, we characterized the optical and molecular characteristics of SOM coupled with organic geochemical signatures to illustrate in detail the mechanisms of sedimentary As burial under different paleotemperatures. We identified that alternating paleotemperature changes result in the fluctuation of H-rich and H-poor organic matter in sediments. Further, we found aliphatic and saturated compounds with higher nominal oxidation state of carbon (NOSC) values predominate under high-paleotemperature (HT) conditions, while polycyclic aromatics and polyphenols with lower NOSC values accumulate under low-paleotemperature (LT) conditions. Under LT conditions, thermodynamically favorable organic compounds (higher NOSC values) are preferentially degraded by microorganisms to provide sufficient energy to sustain sulfate reduction, favoring sedimentary As sequestration. Under HT conditions, the energy gained from the decomposition of low NOSC value organic compounds approaches the energy required to sustain dissimilatory Fe reduction, leading to sedimentary As release into groundwater. This study provides molecular-scale evidence of SOM that indicates LT depositional environments favor sedimentary As burial and accumulation.