Uptake Mechanisms of a Novel, Activated Carbon-Based Equilibrium Passive Sampler for Estimating Porewater Methylmercury.

We describe the validation of a novel polymeric equilibrium passive sampler comprised of agarose gel with embedded activated carbon particles (ag+AC), to estimate aqueous monomethylmercury (MeHg) concentrations. Sampler behavior was tested using a combination of idealized media and realistic sediment microcosms. Isotherm bottle experiments with ag+AC polymers were conducted to constrain partitioning to these materials by various environmentally relevant species of MeHg bound to dissolved organic matter (MeHgDOM) across a range of sizes and character. Log of partitioning coefficients for passive samplers (Kps ) ranged from 1.98 ± 0.09 for MeHg bound to Suwannee River humic acid to 3.15 ± 0.05 for MeHg complexed with Upper Mississippi River natural organic matter. Reversible equilibrium exchange of environmentally relevant MeHg species was demonstrated through a series of dual isotope-labeled exchange experiments. Isotopically labeled MeHgDOM species approached equilibrium in the samplers over 14 days, while mass balance was maintained, providing strong evidence that the ag+AC polymer material is capable of equilibrium measurements of environmentally relevant MeHg species within a reasonable deployment time frame. Samplers deployed across the sediment-water interface of sediment microcosms estimated both overlying water and porewater MeHg concentrations within a factor of 2 to 4 of measured values, based on the average measured Kps values for species of MeHg bound to natural organic matter in the isotherm experiments. Taken together, our results indicate that ag+AC polymers, used as equilibrium samplers, can provide accurate MeHg estimations across many site chemistries, with a simple back-calculation based on a standardized Kps. Environ Toxicol Chem 2022;41:2052-2064.