Modeling PFAS Fate and Transport in Groundwater, with and Without Precursor Transformation.

Groundwater professionals require tools to evaluate a variety of technical issues related to per- and polyfluoroalkyl substances (PFAS). These include the potential impact of PFAS precursors on groundwater plumes of perfluoroalkyl acids (PFAAs). Numerical modeling results show that, by adjusting the mass loading rate, source zones with or without a precursor can produce similar PFAA plumes.

Characterization of manganese oxide amendments for in situ remediation of mercury-contaminated sediments.

Addition of Mn(iv)-oxide phases pyrolusite or birnessite was investigated as a remedial amendment for Hg-contaminated sediments. Because inorganic Hg methylation is a byproduct of bacterial sulfate reduction, reaction of Mn(iv) oxide with pore water should poise sediment oxidation potential at a level higher than favorable for Hg methylation. Changes in Mn(iv)-oxide mineralogy and oxidation state over time were investigated in sediment tank mesocosm experiments in which Mn(iv)-oxide amendment was either mixed into Hg-contaminated sediment or applied as a thin-layer sand cap on top of sediment.

Manganese(iv) oxide amendments reduce methylmercury concentrations in sediment porewater.

Manganese(iv) oxide (pyrolusite, birnessite) mineral amendments can reduce dissolved MeHg concentrations in sediment theoretically by inhibiting microbial sulfate reduction, which is a major methylation pathway in sediments. Anaerobic sediment slurry microcosms in which Hg methylation was stimulated by addition of labile organic carbon (acetate) and HgCl2 showed that manganese(iv) oxide reduced the percent MeHg in slurry porewater (filtered), by 1-2 orders of magnitude relative to controls. Sediment-water mesocosms with pyrolusite or birnessite either directly mixed into the top 5 cm or applied in a thin (5 cm) sand layer over sediment showed reductions in percent MeHg in porewater of 66-69% for pyrolusite and 81-89% for birnessite amendment.

Mechanism of Hg(II) Immobilization in Sediments by Sulfate-Cement Amendment.

Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg L- and S K-edge.

Immobilization of Hg(II) by coprecipitation in sulfate-cement systems.

Uptake and molecular speciation of dissolved Hg during formation of Al- or Fe-ettringite-type and high-pH phases were investigated in coprecipitation and sorption experiments of sulfate-cement treatments used for soil and sediment remediation. Ettringite and minor gypsum were identified by XRD as primary phases in Al systems, whereas gypsum and ferrihydrite were the main products in Hg-Fe precipitates. Characterization of Hg-Al solids by bulk Hg EXAFS, electron microprobe, and microfocused-XRF mapping indicated coordination of Hg by Cl ligands, multiple Hg and Cl backscattering atoms, and concentration of Hg as small particles.

Reactive Transport Modeling of Subaqueous Sediment Caps and Implications for the Long-Term Fate of Arsenic, Mercury, and Methylmercury.

A 1-D biogeochemical reactive transport model with a full set of equilibrium and kinetic biogeochemical reactions was developed to simulate the fate and transport of arsenic and mercury in subaqueous sediment caps. Model simulations (50 years) were performed for freshwater and estuarine scenarios with an anaerobic porewater and either a diffusion-only or a diffusion plus 0.1-m/year upward advective flux through the cap.

Mineral-Based Amendments for Remediation.

Amending soils with mineral-based materials to immobilize contaminants is both old and new. Although mineral amendments have been used for decades in agriculture, new applications with a variety of natural and reprocessed materials are emerging. By sequestering contaminants in or on solid phases and reducing their ability to partition into water or air, amendments can reduce the risk of exposure to humans or biota.

The influence of sulfur and iron on dissolved arsenic concentrations in the shallow subsurface under changing redox conditions.

The chemical speciation of arsenic in sediments and porewaters of aquifers is the critical factor that determines whether dissolved arsenic accumulates to potentially toxic levels. Sequestration of arsenic in solid phases, which may occur by adsorption or precipitation processes, controls dissolved concentrations. We present synchrotron x-ray absorption spectra of arsenic in shallow aquifer sediments that indicate the local structure of realgar (AsS) as the primary arsenic-bearing phase in sulfate-reducing conditions at concentrations of 1-3 mmol.