Phosphate enhanced abiotic and biotic arsenic mobilization in the wetland rhizosphere

Although abiotic process of competitive sorption between phosphate (P) and arsenate (As(V)), especially onto iron oxides, are well understood, P-mediated biotic processes of Fe and As redox transformation contributing to As mobilization and speciation in wetlands remain poorly defined. To gain new insights into the effects of P on As mobility, speciation, and bioavailability in wetlands, well-controlled greenhouse experiments were conducted. As expected, increased P levels contributed to more As desorption, but more interestingly the interactions between P and wetland plants played a synergistic role in the microbially-mediated As mobilization and enhanced As uptake by plants. High levels of P promoted plant growth and the exudation of labile organic carbon from roots, enhancing the growth of heterotrophic bacteria, including As and Fe reducers. This in turn resulted in both, more As desorption into solution due to reductive iron dissolution, and a higher fraction of the dissolved As in the form of As(III) due to the higher number of As(V) reducers. Consistent with the dissolved As results, arsenic-XANES spectra from solid medium samples demonstrated that more As was sequestered in the rhizosphere as As(III) in the presence of high P levels than for low P levels. Hence, increased P loading to wetlands stimulates both abiotic and biotic processes in the wetland rhizosphere, resulting in more As mobilization, more As reduction, as well as more As uptake by plants. These interactions are important to be taken into account in As fate and transport models in wetlands and management of wetlands containing As.