A self-sustaining effect induced by iron sulfide generation and reuse in pyrite-woodchip mixotrophic bioretention systems: an experimental and modeling study

Dual electron donor bioretention systems have emerged as a popular strategy to enhance dissolved nitrogen removal from stormwater runoff. Pyrite-woodchip mixotrophic bioretention systems showed a promoted and stabilized removal of dissolved nutrients under complex rainfall conditions, but the sulfate reduction process that can induce iron sulfide generation and reuse was overlooked. In this study, experiments and models were applied to investigate the effects of filler configuration and dissolved organic carbon (DOC) dissolution rate on treatment performance and iron sulfide generation in pyrite-woodchip bioretention systems. Key parameters govern that DOC dissolution and microbe-mediated processes were obtained by experiments. The water quality models that integrate one-dimensional constant flow, sorption and microbial transformation kinetics were used to predict the performance of bioretention systems. Results showed that the mixotrophic bioretention system with woodchip mixed in the vadose zone and pyrite in the saturated zone achieves a better performance in both nitrogen removal efficiency and by-product control. Comparably, woodchip and pyrite mixed in the saturated zone could encounter a high secondary pollution risk. The sensitivity coefficients of oxic/anoxic DOC dissolution rates to total nitrogen removal are 0.36 and -2.43 respectively. Iron sulfide generation was affected by DOC distribution and the competition between heterotrophic denitrifiers, autotrophic denitrifiers, and sulfate-reducing bacteria (SRB). DOC accumulation has an antagonistic effect on iron production and sulfate reduction. Extra DOC accumulation favors sulfate reduction while high DOC concentration inhibits pyrite-based denitrification and reduces Fe(III) production. The recycling of iron sulfide can improve the robustness and sustainability of bioretention systems.