Identification of processes mobilizing organic molecules and arsenic in geothermal confined groundwater from Pliocene aquifers.

Organic matter (OM) has been accepted as an important trigger fueling Fe(III) oxide reduction and arsenic release in the late Pleistocene-Holocene anoxic aquifers, whereas its fates and roles on arsenic mobility in the Pliocene aquifer are unclear. To fill this gap, groundwaters from a confined Pliocene aquifer (CG) and an unconfined Holocene aquifer (UG) were sampled in the Guide Basin, China, to monitor evolutions of groundwater geochemistry and OM molecular signatures along the groundwater flow path. The outcomes showed that groundwater pH, temperature, and arsenic concentrations in the CG samples generally increased along the groundwater flow path, which were much higher than those in the UG samples. The numbers and intensities of recalcitrant molecules (polycyclic aromatics and polyphenols) in the CG samples remarkably increased along the path, but relatively labile molecules (highly unsaturated and phenolic compounds and aliphatic compounds) showed the opposite trends. The arsenic-poor (<10 μg/L) UG samples contained more labile molecules than the arsenic-rich CG samples. High groundwater pH, temperature, and sediment age in the confined aquifers may be responsible for the selective mobilization of the unique polycyclic aromatics and polyphenols. The mobilized recalcitrant organic molecules may enhance arsenic release via electron shuttling, complexation, and competition. Furthermore, high temperature and pH may also facilitate arsenic desorption. The study provides molecular-scale evidences that the mobilization of recalcitrant organic molecules and arsenic were concurrent in the geothermal confined groundwater.