Persistent Trace Organic Contaminants Are Transformed Rapidly under Sulfate- and Fe(III)-Reducing Conditions in a Nature-Based Subsurface Water Treatment System

[Image: see text] Subsurface treatment systems, such as constructed wetlands, riverbank filtration systems, and managed aquifer recharge systems, offer a low-cost means of removing trace organic contaminants from treated municipal wastewater. To assess the processes through which trace organic contaminants are removed in subsurface treatment systems, pharmaceuticals and several major metabolites were measured in porewater, sediment, and plants within a horizontal levee (i.e., a subsurface flow wetland that receives treated municipal wastewater). Concentrations of trace organic contaminants in each wetland compartment rapidly declined along the flow path. Mass balance calculations, analysis of transformation products, microcosm experiments, and one-dimensional transport modeling demonstrated that more than 60% of the contaminant removal could be attributed to transformation. Monitoring of the system with and without nitrate in the wetland inflow indicated that relatively biodegradable trace organic contaminants, such as acyclovir and metoprolol, were rapidly transformed under both operating conditions. Trace organic contaminants that are normally persistent in biological treatment systems (e.g., sulfamethoxazole and carbamazepine) were removed only when Fe(III)- and sulfate-reducing conditions were observed. Minor structural modifications to trace organic contaminants (e.g., hydroxylation) altered the pathways and extents of trace organic contaminant transformation under different redox conditions. These findings indicate that subsurface treatment systems can be designed to remove both labile and persistent trace organic contaminants via transformation if they are designed and operated in a manner that results in sulfate-and Fe(III)-reducing conditions.