Dissolution Potential of Elemental Mercury in the Presence of Bisulfide and Implications for Mobilization.

Liquid elemental mercury (Hg0L) pollution can remain in soils for decades and, over time, will undergo corrosion, a process in which the droplet surface oxidizes soil constituents to form more reactive phases, such as mercury oxide (HgO). While these reactive coatings may enhance Hg migration in the subsurface, little is known about the transformation potential of corroded Hg0L in the presence of reduced inorganic sulfur species to form sparingly soluble HgS particles, a process that enables the long-term sequestration of mercury in soils and generally reduces its mobility and bioavailability. In this study, we investigated the dissolution of corroded Hg0L in the presence of sulfide by quantifying rates of aqueous Hg release from corroded Hg0L droplets under different sulfide concentrations (expressed as the S:Hg molar ratio). For droplets corroded in ambient air, no differences in soluble Hg release were observed among all sulfide exposure levels (S:Hg mole ratios ranging from 10-4 to 10). However, for droplets oxidized in the presence of a more reactive oxidant (hydrogen peroxide, H2O2), we observed a 10- to 25-fold increase in dissolved Hg when the oxidized droplets were exposed to low sulfide concentrations (S:Hg ratios from 10-4 to 10-1) relative to droplets exposed to high sulfide concentrations. These results suggest two critical factors that dictate the release of soluble Hg from Hg0L in the presence of sulfide: the extent of surface corrosion of the Hg0L droplet and sufficient sulfide concentration for the formation of HgS solids. The mobilization of Hg0L in porous media, therefore, largely depends on aging conditions in the subsurface and chemical reactivity at the Hg0L droplet interface.

Crystal lattice defects in nanocrystalline metacinnabar in contaminated streambank soils suggest a role for biogenic sulfides in the formation of mercury sulfide phases.

At mercury (Hg)-contaminated sites, streambank erosion can act as a main mobilizer of Hg into nearby waterbodies. Once deposited into the waters, mercury from these soils can be transformed to MeHg by microorganisms. It is therefore important to understand the solid-phase speciation of Hg in streambanks as differences in Hg speciation will have implications for Hg transport and bioavailability. In this study, we characterized Hg solid phases in Hg-contaminated soils (100-1100 mg per kg Hg) collected from the incised bank of the East Fork Poplar Creek (EFPC) in Oak Ridge, TN (USA). The analysis of the soil samples by scanning electron microscopy-energy dispersive spectroscopy indicated numerous microenvironments where Hg and sulfur (S) are co-located. According to bulk soil analyses by extended X-ray absorption fine structure spectroscopy (EXAFS), the near-neighbor Hg molecular coordination in the soils closely resembled freshly precipitated Hg sulfide (metacinnabar, HgS); however, EXAFS fits indicated the Hg in the HgS structure was undercoordinated with respect to crystalline metacinnabar. This undercoordination of Hg-S observed by spectroscopy is consistent with transmission electron microspy images showing the presence of nanocrystallites with structural defects (twinning, stacking faults, dislocations) in individual HgS-bearing particles. Although the soils were collected from exposed parts of the stream bank (i.e., open to the atmosphere), the presence of reduced forms of S and sulfate-reducing microbes suggests that biogenic sulfides promote the formation of HgS nanoparticles in these soils. Altogether, these data demonstrate the predominance of nanoparticulate HgS with crystal lattice defects in the bank soils of an industrially impacted stream. Efforts to predict the mobilization and bioavailability of Hg associated with nano-HgS forms should consider the impact of nanocrystalline lattice defects on particle surface reactivity, including Hg dissolution rates and bioavailability on Hg fate and transformations.

Efficacy of Hair Total Mercury Content as a Biomarker of Methylmercury Exposure to Communities in the Area of Artisanal and Small-Scale Gold Mining in Madre de Dios, Peru.

Total mercury content (THg) in hair is an accepted biomarker for chronic dietary methylmercury (MeHg) exposure. In artisanal and small-scale gold mining (ASGM) communities, the validity of this biomarker is questioned because of the potential for contamination from inorganic mercury. As mining communities may have both inorganic and organic mercury exposures, the efficacy of the hair-THg biomarker needs to be evaluated, particularly as nations begin population exposure assessments under their commitments to the Minamata Convention. We sought to validate the efficacy of hair THg for public health monitoring of MeHg exposures for populations living in ASGM communities. We quantified both THg and MeHg contents in hair from a representative subset of participants (N = 287) in a large, population-level mercury exposure assessment in the ASGM region in Madre de Dios (MDD), Peru. We compared population MeHg-THg correlations and %MeHg values with demographic variables including community location, sex, occupation, and nativity. We observed that hair MeHg-THg correlations were high (r > 0.7) for all communities, regardless of location or nativity. Specifically, for individuals within ASGM communities, 81% (121 of 150 total) had hair THg predominantly in the form of MeHg (i.e., >66% of THg) and reflective of dietary exposure to mercury. Furthermore, for individuals with hair THg exceeding the U.S. EPA threshold (1.0 µg/g), 88 out of 106 (83%) had MeHg as the predominant form. As a result, had urine THg solely been used for mercury exposure monitoring, approximately 59% of the ASGM population would have been misclassified as having low mercury exposure. Our results support the use of hair THg for monitoring of MeHg exposure of populations in ASGM settings where alternative biomarkers of MeHg exposure are not feasible.

Sorption and coprecipitation of copper to ferrihydrite and humic acid organomineral complexes and controls on copper availability.

Coprecipitation of Fe oxide and organic matter in redox dynamic sediments controls the net retention and form of Cu in the solid precipitates. In this study, coprecipitation and sorption of Cu with organomineral precipitation solids formed at different Fe:organic carbon (OC) ratios were compared for net Cu removal and extractability. As more humic acid was present during precipitation of Fe, TEM images indicated smaller Fe oxide particles formed within an organic matrix as expected. In coprecipitation reactions, as the ratio of Fe:OC decreased, more Cu was removed from solution at pH 5.5 and below. However, in sorption reactions, there was an inhibition of Cu removal at low OC concentrations. As the pH increased from 5.5 to 7 and as solution phase OC concentration increased, more Cu remained dissolved in both coprecipitation and sorption reactions. The addition of Ca(2+), glycine, histidine and citric acid or lowering the pH resulted in more extractable Cu from the coprecipitation compared with the sorption reactions. The variations in Cu extraction were likely due to a combination of a more amorphous structure in CPT products, and the relative abundance of available Fe oxide or OC binding sites. This has implications for the assumption of additivity in binding phases and for researchers conducting binding or exposure experiments.