Methylmercury sorption onto engineered materials.

Four commercially available sorbents (BioChar (BC), ThiolSAMMS® (TS), SediMite (SM), and Organoclay™ PM-199 (OC-199)) were tested for their ability to sorb methylmercury (MeHg) and MeHg complexed with dissolved organic matter (DOM). Testing sorption behavior with DOM is more representative of the environmental conditions and mercury speciation expected during in-situ remediation efforts. Isotherms were fit using a robust, iterative re-weighting scheme. This fitting approach improves upon the traditionally used indirect sorption method by removing the dependence between aqueous and solid phase concentrations in isotherm fitting. Developed isotherms show that without DOM, BC, TS, and SM adsorbed similar amounts of MeHg while OC-199 sorbed substantially less MeHg. Below an equilibrium concentration of 5.6 ng L-1 BC was the best performing sorbent, between 5.6 and 20.9 ng L-1 SM sorbed the most MeHg, and above an equilibrium concentration of 20.9 ng L-1 TS outperformed the other sorbents. BC and OC-199 showed indication of MeHg sorption saturation over the tested concentration range of 3.5-680 ng L-1. With DOM, SM outperformed the other sorbents at equilibrium concentrations less than 0.98 ng L-1 and TS was the superior MeHg:DOM sorbent at higher concentrations. MeHg:DOM sorption was controlled by DOM-sorbent interactions. DOM decreased MeHg sorption onto BC and SM whereas TS exhibited similar sorption with and without DOM. OC-199 had slightly higher MeHg uptake with DOM. East Fork Poplar Creek (EFPC), an industrially Hg contaminated site, was used as a case study example to build a relationship between aqueous and fish MeHg concentrations and subsequently compare the cost of sorbent materials required to meet regulatory objectives. For this case study, SM provided the most cost-effective sorbent option for in-situ remediation efforts to reduce aqueous MeHg concentrations.

Transport and Retention of Concentrated Oil-in-Water Emulsions in Porous Media.

Oil-in-water emulsions are routinely used in subsurface remediation. In these applications, high oil loadings present a challenge to remedial design as mechanistic insights into transport and retention of concentrated emulsions is limited. Column experiments were designed to examine emulsion transport and retention over a range of input concentrations (1.3-23% wt). Droplet breakthrough and retention data from low concentration experiments were successfully described by existing particle transport models. These models, however, failed to capture droplet transport in more concentrated systems. At high oil fraction, breakthrough curves exhibited an early fall at the end of the emulsion pulse and extending tailing. Irrespective of input concentration, all retention profiles displayed hyper-exponential behavior. Here, we extended existing model formulations to include the additional mixing processes occurring when at high oil concentrations-with focus on the influence of deposited mass and viscous instabilities. The resulting model was parametrized with low concentration data and can successfully predict concentrated emulsion transport and retention. The role of retained mass and viscous instabilities on mixing conditions can also be applied more broadly to systems with temporal or spatially variant water saturation or when viscosity contrasts exist between fluids.

Kinetics of Methylmercury Production Revisited.

Laboratory measurements of the biologically mediated methylation of mercury (Hg) to the neurotoxin monomethylmercury (MMHg) often exhibit kinetics that are inconsistent with first-order kinetic models. Using time-resolved measurements of filter passing Hg and MMHg during methylation/demethylation assays, a multisite kinetic sorption model, and reanalyses of previous assays, we show that competing kinetic sorption reactions can lead to time-varying availability and apparent non-first-order kinetics in Hg methylation and MMHg demethylation. The new model employing a multisite kinetic sorption model for Hg and MMHg can describe the range of behaviors for time-resolved methylation/demethylation data reported in the literature including those that exhibit non-first-order kinetics. Additionally, we show that neglecting competing sorption processes can confound analyses of methylation/demethylation assays, resulting in rate constant estimates that are systematically biased low. Simulations of MMHg production and transport in a hypothetical periphyton biofilm bed illustrate the implications of our new model and demonstrate that methylmercury production may be significantly different than projected by single-rate first-order models.

Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils.

Mercury pollution threatens the environment and human health across the globe. This neurotoxic substance is encountered in artisanal gold mining, coal combustion, oil and gas refining, waste incineration, chloralkali plant operation, metallurgy, and areas of agriculture in which mercury-rich fungicides are used. Thousands of tonnes of mercury are emitted annually through these activities. With the Minamata Convention on Mercury entering force this year, increasing regulation of mercury pollution is imminent. It is therefore critical to provide inexpensive and scalable mercury sorbents. The research herein addresses this need by introducing low-cost mercury sorbents made solely from sulfur and unsaturated cooking oils. A porous version of the polymer was prepared by simply synthesising the polymer in the presence of a sodium chloride porogen. The resulting material is a rubber that captures liquid mercury metal, mercury vapour, inorganic mercury bound to organic matter, and highly toxic alkylmercury compounds. Mercury removal from air, water and soil was demonstrated. Because sulfur is a by-product of petroleum refining and spent cooking oils from the food industry are suitable starting materials, these mercury-capturing polymers can be synthesised entirely from waste and supplied on multi-kilogram scales. This study is therefore an advance in waste valorisation and environmental chemistry.

Emulsion-based recovery of a multicomponent petroleum hydrocarbon NAPL using nonionic surfactant formulations.

Surfactants can aid subsurface remediation through three primary mechanisms - solubilization, mobilization and/or emulsification. Among these mechanisms, emulsification in porous media is generally not well studied or well understood; particularly in the context of treating sources containing multicomponent NAPL. The objective of this research was to elucidate the processes responsible for recovery of a multicomponent hydrocarbon NAPL when surfactant solutions are introduced within a porous medium to promote the formation of kinetically-stable oil-in-water emulsions. Emulsifier formulations considered here were selected to offer similar performance characteristics while relying on different families of non-ionic surfactants - nonylphenol ethoxylates or alcohol ethoxylates - for emulsification. The families of surfactants have particular environment relevance, as alcohol ethoxylates are often used where replacement of nonylphenol content is necessary. Results from batch and column studies suggest performance of the two formulations was similar. With both, a synergistic combination of emulsification and mobilization led to recovery of a synthetic gasoline NAPL. The relative contribution of solubilization to the recovery was found to be minor. Moreover, the physical processes associated with emulsification and mobilization acted to limit the amount of preferential recovery (or fractionation) of the multicomponent NAPL.

Incorporating concentration-dependent sediment microbial activity into methylmercury production kinetics modeling.

In anoxic environments, anaerobic microorganisms carrying the hgcAB gene cluster can mediate the transformation of inorganic mercury (Hg(II)) to monomethylmercury (MMHg). The kinetics of Hg(II) transformation to MMHg in periphyton from East Fork Poplar Creek (EFPC) in Oak Ridge, TN have previously been modeled using a transient availability model (TAM). The TAM for Hg(II) methylation combines methylation/demethylation kinetics with kinetic expressions for processes that decrease Hg(II) and MMHg availability for methylation and demethylation (multisite sorption of Hg(II) and MMHg, Hg(II) reduction/Hg(0) oxidation). In this study, the TAM is used for the first time to describe MMHg production in sediment. We assessed MMHg production in sediment microcosms using two different sediment types from EFPC: a relatively anoxic, carbon-rich sediment with higher microbial activity (higher CO2 production from sediment) and a relatively oxic, sandy, carbon-poor sediment with lower microbial activity (lower CO2 production from sediment). Based on 16s rRNA sequencing, the overall microbial community structure in the two sediments was retained during the incubations. However, the hgcA containing methanogenic Euryarchaeota communities differed between sediment types and their growth followed different trajectories over the course of incubations, potentially contributing to the distinct patterns of MMHg production observed. The general TAM paradigm performed well in describing MMHg production in the sediments. However, the MMHg production and ancillary data suggested the need to revise the model structure to incorporate terms for concentration-dependent microbial activity over the course of the incubations. We modified the TAM to include Monod-type kinetics for methylation and demethylation and observed an improved fit for the carbon-rich, microbially active sediment. Overall our work shows that the TAM can be applied to describe Hg(II) methylation in sediments and that including expressions accounting for concentration-dependent microbial activity can improve the accuracy of the model description of the data in some cases.

Nutrient Exposure Alters Microbial Composition, Structure, and Mercury Methylating Activity in Periphyton in a Contaminated Watershed.

The conversion of mercury (Hg) to monomethylmercury (MMHg) is a critical area of concern in global Hg cycling. Periphyton biofilms may harbor significant amounts of MMHg but little is known about the Hg-methylating potential of the periphyton microbiome. Therefore, we used high-throughput amplicon sequencing of the 16S rRNA gene, ITS2 region, and Hg methylation gene pair (hgcAB) to characterize the archaea/bacteria, fungi, and Hg-methylating microorganisms in periphyton communities grown in a contaminated watershed in East Tennessee (United States). Furthermore, we examined how nutrient amendments (nitrate and/or phosphate) altered periphyton community structure and function. We found that bacterial/archaeal richness in experimental conditions decreased in summer and increased in autumn relative to control treatments, while fungal diversity generally increased in summer and decreased in autumn relative to control treatments. Interestingly, the Hg-methylating communities were dominated by Proteobacteria followed by Candidatus Atribacteria across both seasons. Surprisingly, Hg methylation potential correlated with numerous bacterial families that do not contain hgcAB, suggesting that the overall microbiome structure of periphyton communities influences rates of Hg transformation within these microbial mats. To further explore these complex community interactions, we performed a microbial network analysis and found that the nitrate-amended treatment resulted in the highest number of hub taxa that also corresponded with enhanced Hg methylation potential. This work provides insight into community interactions within the periphyton microbiome that may contribute to Hg cycling and will inform future research that will focus on establishing mixed microbial consortia to uncover mechanisms driving shifts in Hg cycling within periphyton habitats.

Ecosystem Controls on Methylmercury Production by Periphyton Biofilms in a Contaminated Stream: Implications for Predictive Modeling.

Periphyton biofilms produce a substantial fraction of the overall monomethylmercury (MMHg) flux in East Fork Poplar Creek, an industrially contaminated, freshwater creek in Oak Ridge, Tennessee. We examined periphyton MMHg production across seasons, locations, and light conditions using mercury stable isotopes. Methylation and demethylation rate potentials (km, trans av and kd, trans av , respectively) were calculated using a transient availability kinetic model. Light exposure and season were significant predictors of km, trans av , with greater values in full light exposure and in the summer. Season, light exposure, and location were significant predictors of kd, trans av , which was highest in dark conditions, in the spring, and at the upstream location. Light exposure was the controlling factor for net MMHg production, with positive production for periphyton grown under full light exposure and net demethylation for periphyton grown in the dark. Ambient MMHg and km, trans av were significantly correlated. Transient availability rate potentials were 15 times higher for km and 9 times higher for kd compared to full availability rate potentials (km, full av and kd, full av ) calculated at 1 d. No significant model for the prediction of km, full av or kd, full av could be constructed using light, season, and location. In addition, there were no significant differences among treatments for the full availability km, full av , kd, full av , or net MMHg calculated using the full availability rate potentials. km, full av was not correlated with ambient MMHg concentrations. The present results underscore the importance of applying transient availability kinetics to MMHg production data when estimating MMHg production potential and flux. Environ Toxicol Chem 2019;38:2426-2435. © 2019 SETAC.