Environmental fate of monosodium methanearsonate (MSMA)-Part 2: Modeling sequestration and transformation.

Monosodium methanearsonate (MSMA), a sodium salt of monomethylarsonic acid (MMA), is a selective contact herbicide used for the control of a broad spectrum of weeds. In water, MSMA dissociates to ions of sodium (Na+) and monomethylarsonate (MMA-) that is stable and does not transform abiotically. In soils characteristic of MSMA use, several simultaneous processes can occur: (1) microbial methylation of MMA to dimethylarsinic acid (DMA), (2) microbial demethylation of MMA to inorganic arsenic (iAs), (3) methylation of iAs to MMA, and (4) sorption and sequestration of MMA and its metabolites to soil minerals. Sequestered residues are residues that cannot be desorbed from soil in environmental conditions. Sequestration is rapid in the initial several days after MSMA application and continues at a progressively slower rate over time. Once sequestered, MMA and its metabolites are inaccessible to soil microorganisms and cannot be transformed. The rate and extent of the sorption and sequestration as well as the mobility of MMA and its metabolites depend on the local edaphic conditions. In typical MSMA use areas, the variability of the edaphic conditions is constrained. The goal of this research was to estimate the amount of iAs potentially added to drinking water as a result of the use of MSMA, with models and scenarios developed by the US Environmental Protection Agency for pesticide risk assessment. In this project, the estimated drinking water concentrations (EDWCs) for iAs were assessed as the average concentration in the reservoir over a 30-year simulation with annual applications of MSMA at maximum label rates. When the total area of suitable land was assumed to be treated, EDWCs ranged from <0.001 to 0.12 µg/L. When high estimates of actually treated acreage are considered, the EDWCs are below 0.06 µg/L across all scenarios. Integr Environ Assess Manag 2024;00:1-12. © 2024 The Author(s). Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Environmental fate of monosodium methanearsonate (MSMA)-Part 1: Conceptual model.

Monosodium methanearsonate (MSMA), the sodium salt of monomethylarsonic acid (MMA), is used as a selective, broad-spectrum contact herbicide to control weeds in cotton and a variety of turf. In water, MSMA dissociates into ions of sodium (Na+) and of MMA-, which is the herbicide's active component. Certain soil microorganisms can methylate MMA to dimethylarsinic acid (DMA) other microorganisms can demethylate MMA to inorganic arsenic (iAs). To predict the groundwater concentration of iAs that may result from MSMA application, the processes affecting the environmental behavior of MSMA must be quantified and modeled. There is an extensive body of literature regarding the environmental behavior of MSMA. There is a consensus among scientists that the fate of MMA in soil is controlled by microbial activity and sorption to solid surfaces and that iAs sorption is even more extensive than that of MMA. The sorption and transformation of MMA and its metabolites are affected by several factors including aeration condition, temperature, pH, and the availability of nutrients. The precise nature and extent of each of these processes vary depending on site-specific conditions; however, such variability is constrained in typical MSMA use areas that are highly managed. Monomethylarsonic acid is strongly sorbed on mineral surfaces and becomes sequestered into the soil matrix. Over time, a greater portion of MMA and iAs becomes immobile and unavailable to soil microorganisms and to leaching. This review synthesizes the results of studies that are relevant for the behavior of MSMA used as a herbicide to reliably predict the fate of MSMA in its use conditions. Integr Environ Assess Manag 2024;00:1-17. © 2024 The Author(s). Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Biogeochemical controls on methylmercury in soils and sediments: Implications for site management.

Management of Hg-contaminated sites poses particular challenges because methylmercury (MeHg), a potent bio-accumulative neurotoxin, is formed in the environment, and concentrations are not generally predictable based solely on total Hg (THg) concentrations. In this review, we examine the state of knowledge regarding the chemical, biological, and physical controls on MeHg production and identify those most critical for contaminated site assessment and management. We provide a list of parameters to assess Hg-contaminated soils and sediments with regard to their potential to be a source of MeHg to biota and therefore a risk to humans and ecological receptors. Because some measurable geochemical parameters (e.g., DOC) can have opposing effects on Hg methylation, we recommend focusing first on factors that describe the potential for Hg bio-accumulation: site characteristics, Hg and MeHg concentrations, Hg availability, and microbial activity, where practical. At some sites, more detailed assessment of biogeochemistry may be required to develop a conceptual site model for remedial decision making. Integr Environ Assess Manag 2017;13:249-263. © 2016 SETAC.

Constraints on Precipitation of the Ferrous Arsenite Solid HFe(AsO).

Formation of Fe(II)-As(III) solids is suspected to limit dissolved As concentrations in anaerobic environments. Iron(II) precipitates enriched in As(III) have been observed after microbial reduction of As(V)-loaded lepidocrocite (γ-FeOOH) and symplesite (Fe(II)(As(V)O)]·8HO) and upon abiotic reaction of Fe(II) with As(III). However, the conditions favorable for Fe(II)-As(III) precipitation and the long-term stability (relative to dissolution) of this phase are unknown. Here we examine the composition, local structure, and solubility of an Fe(II)-As(III) precipitate to determine environments where such a solid may form and persist. We reveal that the Fe(II)-As(III) precipitate has a composition of HFe(AsO) and a log of 34 for the dissolution reaction defined as: HFe(AsO) + 8H = 4Fe + 5HAsO. Extended X-ray absorption fine structure spectroscopic analysis of HFe(AsO) shows that the molecular environment of Fe is dominated by edge-sharing octahedra within an Fe(OH) sheet and that As is dominated by corner-sharing AsO pyramids, which are consistent with previously published structures of As(III)-rich Fe(II) solids. The HFe(AsO) solid has a pH-dependent solubility and requires millimolar concentrations of dissolved Fe(II) and As(III) to precipitate at pH <7.5. By contrast, alkaline conditions are more conducive to formation of HFe(AsO); however, a high concentration of Fe(II) is required, which is unusual under alkaline conditions.

Dependence of arsenic fate and transport on biogeochemical heterogeneity arising from the physical structure of soils and sediments.

Reduction of As(V) and Fe(III) is commonly the dominant process controlling the fate and transport of As in soils and sediments. However, the physical structure of such environments produces complex heterogeneity in biogeochemical processes controlling the fate and transport of As. To resolve the role of soil and sediment physical structure on the distribution of biogeochemical processes controlling the fate and transport of As, we examined the biogeochemical transformations of As and Fe within constructed aggregates-a fundamental unit of soil structure. Spherical aggregates were made with As(V)- or As(III)-bearing, ferrihydrite-coated quartz that was fused with agarose and placed in a cylindrical reactor; advective flow of anoxic solutes was then initiated around the aggregates to examine As release from a dual-pore domain system. To examine the impact of biotic As(V) and Fe(III) reduction, constructed aggregates having As(V)-bearing, ferrihydrite-coated quartz inoculated with sp. ANA-3 were placed in flow-through reactors under anoxic and aerated advective flow. Consistent with desorption from advective columns, As(III) is released to advecting water more prevalently than As(V) within abiotic aggregate systems, indicating a greater lability and concomitant enhanced propensity for transport of As(III) relative to As(V). During reaction with , As release to advecting water was similar between anoxic and aerated systems for the first 20 d; thereafter, the anoxic advecting solutes increased As release relative to the aerated counterpart. With aerated advecting solutes, Fe remained oxidized (or was oxidized) in the aggregate exterior, forming a protective barrier that limited As release to the advective channel. However, anaerobiosis within the aggregate interior, even with aerated advective flow, promotes internal repartitioning of As to the exterior region.

Intra-particle migration of mercury in granular polysulfide-rubber-coated activated carbon (PSR-AC).

The depth profile of mercuric ion after the reaction with polysulfide-rubber-coated activated carbon (PSR-AC) was investigated using micro-X-ray fluorescence (µ-XRF) imaging techniques and mathematical modeling. The µ-XRF results revealed that mercury was concentrated at 0-100 µm from the exterior of the particle after 3 months of treatment with PSR-AC in 10 ppm HgCl(2) aqueous solution. The µ-X-ray absorption near edge spectroscopic (µ-XANES) analyses indicated HgS as a major mercury species, and suggested that the intra-particle mercury transport involved a chemical reaction with PSR polymer. An intra-particle mass transfer model was developed based on either a Langmuir sorption isotherm with liquid phase diffusion (Langmuir model) or a kinetic sorption with surface diffusion (kinetic sorption model). The Langmuir model predicted the general trend of mercury diffusion, although at a slower rate than observed from the µ-XRF map. A kinetic sorption model suggested faster mercury transport, which overestimated the movement of mercuric ions through an exchange reaction between the fast and slow reaction sites. Both µ-XRF and mathematical modeling results suggest mercury removal occurs not only at the outer surface of the PSR-AC particle but also at some interior regions due to a large PSR surface area within an AC particle.

Dehalogenation of polybrominated diphenyl ethers and polychlorinated biphenyl by bimetallic, impregnated, and nanoscale zerovalent iron.

Nanoscale zerovalent iron particles (nZVI), bimetallic nanoparticles (nZVI/Pd), and nZVI/Pd impregnated activated carbon (nZVI/Pd-AC) composite particles were synthesized and investigated for their effectiveness to remove polybrominated diphenyl ethers (PBDEs) and/or polychlorinated biphenyls (PCBs). Palladization of nZVI promoted the dehalogenation kinetics for mono- to tri-BDEs and 2,3,4-trichlorobiphenyl (PCB 21). Compared to nZVI, the iron-normalized rate constants for nZVI/Pd were about 2-, 3-, and 4-orders of magnitude greater for tri-, di-, and mono-BDEs, respectively, with diphenyl ether as a main reaction product. The reaction kinetics and pathways suggest an H-atom transfer mechanism. The reaction pathways with nZVI/Pd favor preferential removal of para-halogens on PBDEs and PCBs. X-ray fluorescence mapping of nZVI/Pd-AC showed that Pd mainly deposits on the outer part of particles, while Fe was present throughout the activated carbon particles. While BDE 21 was sorbed onto activated carbon composites quickly, debromination was slower compared to reaction with freely dispersed nZVI/Pd. Our XPS and chemical data suggest about 7% of the total iron within the activated carbon was zerovalent, which shows the difficulty with in-situ synthesis of a significant fraction of zerovalent iron in the microporous material. Related factors that likely hinder the reaction with nZVI/Pd-AC are the heterogeneous distribution of nZVI and Pd on activated carbon and/or immobilization of hydrophobic organic contaminants at the adsorption sites thereby inhibiting contact with nZVI.

Transport implications resulting from internal redistribution of arsenic and iron within constructed soil aggregates.

Soils are an aggregate-based structured media that have a multitude of pore domains resulting in varying degrees of advective and diffusive solute and gas transport. Consequently, a spectrum of biogeochemical processes may function at the aggregate scale that collectively, and coupled with solute transport, determine element cycling in soils and sediments. To explore how the physical structure impacts biogeochemical processes influencing the fate and transport of As, we examined temporal changes in speciation and distribution of As and Fe within constructed aggregates through experimental measurement and reactive transport simulations. Spherical aggregates were made with As(V)-bearing ferrihydrite-coated sand inoculated with Shewanella sp. ANA-3; aerated solute flow around the aggregate was then induced. Despite the aerated aggregate exterior, where As(V) and ferrihydrite persist as the dominant species, anoxia develops within the aggregate interior. As a result, As and Fe redox gradients emerge, and the proportion of As(III) and magnetite increases toward the aggregate interior. Arsenic(III) and Fe(II) produced in the interior migrate toward the aggregated exterior and result in coaccumulation of As and Fe(III) proximal to preferential flow paths as a consequence of oxygenic precipitation. The oxidized rind of aggregates thus serves as a barrier to As release into advecting pore-water, but also leads to be a buildup of this hazardous element at preferential flow boundaries that could be released upon shifting geochemical conditions.