Unraveling seasonal shifts in microbial and geochemical mediated arsenic mobilization at the estuarine sediment-water interface under redox changes

The mobilization of arsenic (As) at the sediment-water interface (SWI) is crucial for determining the accumulation of dissolved As to potentially toxic levels. However, the specific impacts of redox processes involving iron (Fe) and sulfur (S), as well as microbial activities occurring in sediments, on As mobilization at the marine SWI remain poorly understood. In this study, we investigated As mobilization at the SWI in the Changjiang Estuary during three different seasons with different benthic redox conditions. The preferential reduction of arsenate (As(V)) to arsenite (As(III)) and subsequent re-adsorption onto newly formed crystalline Fe oxides restricted As release in the As(V) reduction layer. Enhanced Fe(III) reduction in the Fe(III) reduction layer contributed to As release, while the presence of low As-high Fe-high SO42- levels resulted in As removal through adsorption onto pyrite in the sulfate reduction layer. Analysis of functional genes indicated that As(V) in sediments was released into porewater through the reductive dissolution of As(V)-bearing Fe(III) oxides by Geobacter species, followed by microbial reduction of the liberated As(V) to As(III) by microbes carrying the arrA gene. The dominant pathway governing As mobilization at the SWI in the Changjiang Estuary shifted from microbial reduction control during the hypoxic summer to Fe redox control during the aerobic autumn and winter. These findings provide valuable insights into the complex mechanisms driving As mobilization and highlight the importance of considering seasonal variations in understanding As dynamics at the marine SWI.