Mechanisms and health implications of toxicity increment from arsenate-containing iron minerals through in vitro gastrointestinal digestion.

Inadvertent oral ingestion is an important exposure pathway of arsenic (As) containing soil and dust. Previous researches evidenced health risk of bioaccessible As from soil and dust, but it is unclear about As mobilization mechanisms in health implications from As exposure. In this study, we investigated As release behaviors and the solid-liquid interface reactions toward As(V)-containing iron minerals in simulated gastrointestinal bio-fluids. The maximum As release amount was 0.57 mg/L from As-containing goethite and 0.82 mg/L from As-containing hematite at 9 h, and the As bioaccessibility was 10.8% and 21.6%, respectively. The higher exposure risk from hematite-sorbed As in gastrointestinal fluid was found even though goethite initially contained more arsenate than hematite. Mechanism analysis revealed that As release was mainly coupled with acid dissolution and reductive dissolution of iron minerals. Proteases enhanced As mobilization and thus increased As bioaccessibility. The As(V) released and simultaneously transformed to high toxic As(III) by gastric pepsin, while As(V) reduction in intestine was triggered by pancreatin and freshly formed Fe(II) in gastric digests. CaCl2 reduced As bioaccessibility, indicating that calcium-rich food or drugs may be effective dietary strategies to reduce As toxicity. The results deepened our understanding of the As release mechanisms associated with iron minerals in the simulated gastrointestinal tract and supplied a dietary strategy to alleviate the health risk of incidental As intake.

Patterns of contamination and burden of lead and arsenic in rooftop harvested rainwater collected in Arizona environmental justice communities.

As climate change exacerbates water scarcity, rainwater harvesting for household irrigation and gardening becomes an increasingly common practice. However, the use and quality of harvested rainwater are not well studied, and the potential pollutant exposures associated with its use are generally unknown. There are currently no federal standards in the United States to assess metal(loid)s in harvested rainwater. Project Harvest, a community science research project, was created to address this knowledge gap and study the quality of harvested rainwater, primarily used for irrigation, in four environmental justice communities in Arizona, USA. Community scientists collected 577 unique rooftop harvested rainwater samples from 2017 to 2020, which were analyzed for metal(loid)s, where arsenic (As) concentrations ranged from 0.108 to 120 µg L-1 and lead (Pb) concentrations ranged from 0.013 to 350 µg L-1 and compared to relevant federal/state standards/recommendations. Community As and Pb concentrations decreased as: Hayden/Winkelman > Tucson > Globe/Miami > Dewey-Humboldt. Linear mixed models were used to analyze rooftop harvested rainwater data and results indicated that concentrations of As and Pb in the summer monsoon were significantly greater than winter; and contamination was significantly greater closer to extractive industrial sites in three of the four study communities (ASARCO Hayden Plant Superfund Alternative site in Hayden/Winkelman, Davis-Monthan United States Air Force Base in Tucson - Pb only, and Freeport McMoRan Copper and Gold Mine in Globe/Miami). Based on models, infrastructure such as proximity to roadway, roof material, presence of a cistern screen, and first-flush systems were not significant with respect to As and Pb when controlling for relevant spatiotemporal variables; whereas, cistern age was associated with Pb concentrations. These results however, indicate that concentrations vary seasonally and by proximity to industrial activity, not by decisions made regarding collection system infrastructures at the individual home level. This study shows that generally, individuals are not responsible for environmental contamination of rooftop harvested rainwater, rather activities and decisions of government and corporate industries control contaminant release.

Mechanisms of Arsenic Sequestration by Prosopis juliflora during the Phytostabilization of Metalliferous Mine Tailings.

Phytostabilization is a cost-effective long-term bioremediation technique for the immobilization of metalliferous mine tailings. However, the biogeochemical processes affecting metal(loid) molecular stabilization and mobility in the root zone remain poorly resolved. The roots of Prosopis juliflora grown for up to 36 months in compost-amended pyritic mine tailings from a federal Superfund site were investigated by microscale and bulk synchrotron X-ray absorption spectroscopy (XAS) and multiple energy micro-X-ray fluorescence imaging to determine iron, arsenic, and sulfur speciation, abundance, and spatial distribution. Whereas ferrihydrite-bound As(V) species predominated in the initial bulk mine tailings, the rhizosphere speciation of arsenic was distinctly different. Root-associated As(V) was immobilized on the root epidermis bound to ferric sulfate precipitates and within root vacuoles as trivalent As(III)-(SR)3 tris-thiolate complexes. Molar Fe-to-As ratios of root epidermis tissue were two times higher than the 15% compost-amended bulk tailings growth medium. Rhizoplane-associated ferric sulfate phases that showed a high capacity to scavenge As(V) were dissimilar from the bulk-tailings mineralogy as shown by XAS and X-ray diffraction, indicating a root-surface mechanism for their formation or accumulation.

Bacterial Rhizoplane Colonization Patterns of Buchloe dactyloides Growing in Metalliferous Mine Tailings Reflect Plant Status and Biogeochemical Conditions.

Plant establishment during phytostabilization of legacy mine tailings in semiarid regions is challenging due to low pH, low organic carbon, low nutrients, and high toxic metal(loid) concentrations. Plant-associated bacterial communities are particularly important under these harsh conditions because of their beneficial services to plants. We hypothesize that bacterial colonization profiles on rhizoplane surfaces reflect deterministic processes that are governed by plant health and the root environment. The aim of this study was to identify associations between bacterial colonization patterns on buffalo grass (Buchloe dactyloides) rhizoplanes and both plant status (leaf chlorophyll and plant cover) and substrate biogeochemistry (pH, electrical conductivity, total organic carbon, total nitrogen, and rhizosphere microbial community). Buffalo grass plants from mesocosm- and field-scale phytostabilization trials conducted with tailings from the Iron King Mine and Humboldt Smelter Superfund Site in Dewey-Humboldt, Arizona, were analyzed. These tailings are extremely acidic and have arsenic and lead concentrations of 2-4 g kg-1 substrate. Bacterial communities on rhizoplanes and in rhizosphere-associated substrate were characterized using fluorescence in situ hybridization and 16S rRNA gene amplicon sequencing, respectively. The results indicated that the metabolic status of rhizoplane bacterial colonizers is significantly related to plant health. Principal component analysis revealed that root-surface Alphaproteobacteria relative abundance was associated most strongly with substrate pH and Gammaproteobacteria relative abundance associated strongly with substrate pH and plant cover. These factors also affected the phylogenetic profiles of the associated rhizosphere communities. In summary, rhizoplane bacterial colonization patterns are plant specific and influenced by plant status and rhizosphere biogeochemical conditions.

Arsenic remediation by formation of arsenic sulfide minerals in a continuous anaerobic bioreactor.

Arsenic (As) is a highly toxic metalloid that has been identified at high concentrations in groundwater in certain locations around the world. Concurrent microbial reduction of arsenate (As(V) ) and sulfate (SO4 (2-) ) can result in the formation of poorly soluble arsenic sulfide minerals (ASM). The objective of this research was to study As biomineralization in a minimal iron environment for the bioremediation of As-contaminated groundwater using simultaneous As(V) and SO4 (2-) reduction. A continuous-flow anaerobic bioreactor was maintained at slightly acidic pH (6.25-6.50) and fed with As(V) and SO4 (2-) , utilizing ethanol as an electron donor for over 250 d. A second bioreactor running under the same conditions but lacking SO4 (2-) was operated as a control to study the fate of As (without S). The reactor fed with SO4 (2-) removed an average 91.2% of the total soluble As at volumetric rates up to 2.9 mg As/(L · h), while less than 5% removal was observed in the control bioreactor. Soluble S removal occurred with an S to As molar ratio of 1.2, suggesting the formation of a mixture of orpiment- (As2 S3 ) and realgar-like (AsS) solid phases. Solid phase characterization using K-edge X-ray absorption spectroscopy confirmed the formation of a mixture of As2 S3 and AsS. These results indicate that a bioremediation process relying on the addition of a simple, low-cost electron donor offers potential to promote the removal of As from groundwater with naturally occurring or added SO4 (2-) by precipitation of ASM.

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate.

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3 to 2.3). Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mM kg-1 (3080, 2200, and 2570 mg kg-1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2 fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25-54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0-35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface.

Evidence of both molecular cloud and fluid chemistry in Ryugu regolith.

The sulfur chemistry of (162173) Ryugu particles can be a powerful tracer of molecular cloud chemistry and small body processes, but it has not been well explored. We report identification of organosulfurs and a sulfate grain in two Ryugu particles, A0070 and A0093. The sulfate grain shows oxygen isotope ratios (δ17O = -11.0 ± 4.3 per mil, δ18O = -7.8 ± 2.3 per mil) that are akin to silicates in Ryugu but exhibit mass-independent sulfur isotopic fractionation (Δ33S = +5 ± 2 per mil). A methionine-like coating on the sulfate grain is isotopically anomalous (δ15N = +62 ± 2 per mil). Both the sulfate and organosulfurs can simultaneously form and survive during aqueous alteration within Ryugu's parent body, under reduced conditions, low temperature, and a pH >7 in the presence of N-rich organic molecules. This work extends the heliocentric zone where anomalous sulfur, formed by selective photodissociation of H2S gas in the molecular cloud, is found.

Release mechanism and interactions of cadmium and arsenic co-contaminated ferrihydrite by simulated in-vitro digestion assays.

Cadmium (Cd) and arsenic (As) co-contamination is widespread and threatens human health, therefore it is important to investigate the bioavailability of Cd and As co-exposure. Currently, the interactions of Cd and As by in vitro assays are unknown. In this work, we studied the concurrent Cd-As release behaviors and interactions with in vitro simulated gastric bio-fluid assays. The studies demonstrated that As bioaccessibility (2.04 to 0.18 ± 0.03%) decreased with Cd addition compared to the As(V) single system, while Cd bioaccessibility (11.02 to 39.08 ± 1.91%) increased with As addition compared to the Cd single system. Release of Cd and As is coupled to proton-promoted and reductive dissolution of ferrihydrite. The As(V) is released and reduced to As(Ⅲ) by pepsin. Pepsin formed soluble complexes with Cd and As. X-ray photoelectron spectroscopy showed that Cd and As formed Fe-As-Cd ternary complexes on ferrihydrite surfaces. The coordination intensity of As-O-Cd is lower than that of As-O-Fe, resulting in more Cd release from Fe-As-Cd ternary complexes. Our study deepens the understanding of health risks from Cd and As interactions during environmental co-exposure of multiple metal(loid)s.

Microscale speciation of arsenic and iron in ferric-based sorbents subjected to simulated landfill conditions.

During treatment for potable use, water utilities generate arsenic-bearing ferric wastes that are subsequently dispatched to landfills. The biogeochemical weathering of these residuals in mature landfills affects the potential mobilization of sorbed arsenic species via desorption from solids subjected to phase transformations driven by abundant organic matter and bacterial activity. Such processes are not simulated with the toxicity characteristic leaching procedure (TCLP) currently used to characterize hazard. To examine the effect of sulfate on As retention in landfill leachate, columns of As(V) loaded amorphous ferric hydroxide were reacted biotically at two leachate sulfate concentrations (0.064 mM and 2.1 mM). After 300 days, ferric sorbents were reductively dissolved. Arsenic released to porewaters was partially coprecipitated in mixed-valent secondary iron phases whose speciation was dependent on sulfate concentration. As and Fe XAS showed that, in the low sulfate column, 75-81% of As(V) was reduced to As(III), and 53-68% of the Fe(III) sorbent was transformed, dominantly to siderite and green rust. In the high sulfate column, Fe(III) solids were reduced principally to FeS(am), whereas As(V) was reduced to a polymeric sulfide with local atomic structure of realgar. Multienergy micro-X-ray fluorescence (ME-µXRF) imaging at Fe and As K-edges showed that As formed surface complexes with ferrihydrite > siderite > green rust in the low sulfate column; while discrete realgar-like phases formed in the high sulfate systems. Results indicate that landfill sulfur chemistry exerts strong control over the potential mobilization of As from ferric sorbent residuals by controlling secondary As and Fe sulfide coprecipitate formation.

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach.

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7-9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8 - 9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)-Fe bond distances of ~2.92-2.94 and 3.41-3.44 Å, respectively. The As-Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As-Fe bonding mechanisms.

Molecular speciation controls arsenic and lead bioaccessibility in fugitive dusts from sulfidic mine tailings.

Communities nearby mine wastes in arid and semi-arid regions are potentially exposed to high concentrations of toxic metal(loid)s from fugitive dusts deriving from impoundments. To assess the relation between potentially lofted particles and human health risk, we studied the relationship between pharmacokinetic bioaccessibility and metal(loid) molecular speciation for mine tailings dust particulate matter (PM), with elevated levels of arsenic and lead (up to 59 and 34 mmol kg-1, respectively), by coupling in vitro bioassay (IVBA) with X-ray absorption spectroscopy (XAS). Mine tailing efflorescent salts (PMES) and PM from the surface crust (0-1 cm, PMSC) and near surface (0-25 cm) were isolated to <10 µm and <150 µm effective spherical diameter (PM10 and PM150) and reacted with synthetic gastric and lung fluid for 30 s to 100 h to investigate toxic metal(loid) release kinetics. Bioaccessible (BAc) fractions of arsenic and lead were about 10 and 100 times greater in gastric than in lung fluid simulant, respectively, and 10-100% of the maximum gastric BAc from PM10 and PM150 occurred within 30 s, with parabolic dissolution of fine, highly-reactive particles followed by slower release from less soluble sources. Evaporite salts were almost completely solubilized in gastric-fluid simulants. Arsenate within jarosite and sorbed to ferrihydrite, and lead from anglesite, were identified by XAS as the principal contaminant sources in the near surface tailings. In the synthetic lung fluid, arsenic was released continuously to 100 h, suggesting that residence time in vivo must be considered for risk determination. Analysis of pre- and post-IVBA PM indicated the release of arsenic in lung fluid was principally from arsenic-substituted jarosite, whereas in synthetic gastric fluid arsenic complexed on ferrihydrite surfaces was preferentially released and subsequently repartitioned to jarosite-like coordination at extended exposures. Lead dissolved at 30 s was subsequently repartitioned back to the solid phase as pyromorphite in phosphate rich lung fluid. The bioaccessibility of lead in surface tailings PM was limited due to robust sequestration in plumbojarosite. Kinetic release of toxic elements in both synthetic biofluids indicated that a single IVBA interval may not adequately describe release dynamics.

The effect of biogeochemical redox oscillations on arsenic release from legacy mine tailings.

Exposed and un-remediated metal(loid)-bearing mine tailings are susceptible to wind and water erosion that disperses toxic elements into the surrounding environment. Compost-assisted phytostabilization has been successfully applied to legacy tailings as an inexpensive, eco-friendly, and sustainable landscape rehabilitation that provides vegetative cover and subsurface scaffolding to inhibit offsite transport of contaminant laden particles. The possibility of augmented metal(loid) mobility from subsurface redox reactions driven by irrigation and organic amendments is known and arsenic (As) is of particular concern because of its high affinity for adsorption to reducible ferric (oxyhydr)oxide surface sites. However, the biogeochemical transformation of As in mine tailings during multiple redox oscillations has not yet been addressed. In the present study, a redox-stat reactor was used to control oscillations between 7 d oxic and 7 d anoxic half-cycles over a three-month period in mine tailings with and without amendment of compost-derived organic matter (OM) solution. Aqueous and solid phase analyses during and after redox oscillations by mass spectrometry and synchrotron X-ray absorption spectroscopy revealed that soluble OM addition stimulated pyrite oxidation, which resulted in accelerated acidification and increased aqueous sulfate activity. Soluble OM in the reactor solution significantly increased mobilization of As under anoxic half-cycles primarily through reductive dissolution of ferrihydrite. Microbially-mediated As reduction was also observed in compost treatments, which increased partitioning to the aqueous phase due to the lower affinity of As(III) for complexation on ferric surface sites, e.g. ferrihydrite. Oxic half-cycles showed As repartitioned to the solid phase concurrent with precipitation of ferrihydrite and jarosite. Multiple redox oscillations increased the crystallinity of Fe minerals in the Treatment reactors with compost solution due to the reductive dissolution of ferrihydrite and precipitation of jarosite. The release of As from tailings gradually decreased after repeated redox oscillations. The high sulfate, ferrous iron, and hydronium activity promoted the precipitation of jarosite, which sequestered arsenic. Our results indicated that redox oscillations under compost-assisted phytostabilization can promote As release that diminishes over time, which should inform remediation assessment and environmental risk assessment of mine site compost-assisted phytostabilization.

Treatment of the insensitive munitions compound, 3-nitro-1,2,4-triazol-5-one (NTO), in flow-through columns packed with zero-valent iron.

The need for effective technologies to remediate the insensitive munitions compound 3-nitro-1,2,4-triazol-5-one (NTO) is emerging due to the increasing use by the US Army and environmental concerns about the toxicity and aqueous mobility of NTO. Reductive treatment is essential for the complete degradation of NTO to environmentally safe products. The objective of this study is to investigate the feasibility of applying zero-valent iron (ZVI) in a continuous-flow packed bed reactor as an effective NTO remediation technology. The ZVI-packed columns treated an acidic influent (pH 3.0) or a circumneutral influent (pH 6.0) for 6 months (ca. 11,000 pore volumes, PVs). Both columns effectively reduced NTO to the amine product, 3-amino-1,2,4-triazol-5-one (ATO). The column treating the pH-3.0 influent exhibited prolonged longevity in reducing NTO, treating 11-fold more PVs than the column treating pH-6.0 influent until the breakthrough point (defined as when 85% of NTO was removed). The exhausted columns (defined as when only 10% of NTO was removed) regained the NTO reducing capacity by reactivation using 1 M HCl, fully removing NTO. After the experiment, solid-phase analysis of the packed-bed material showed that ZVI was oxidized to iron (oxyhydr)oxide minerals such as magnetite, lepidocrocite, and goethite during NTO treatment. This is the first report on the reduction of NTO and the concomitant oxidation of ZVI in continuous-flow column experiments. The evidence indicates that treatment in a ZVI-packed bed reactor is an effective approach for the removal of NTO.

Dissolved arsenic and lead concentrations in rooftop harvested rainwater: Community generated dataset.

Here, we detail arsenic (As) and lead (Pb) concentrations in community science generated rooftop harvested rainwater data from Project Harvest (PH), a co-created community science study, and National Atmospheric Deposition Program (NADP) National Trends Network wet-deposition AZ samples as analyzed by Palawat et al. [1]. 577 field samples were collected in PH and 78 field samples were collected by NADP. All samples were analyzed via inductively coupled plasma mass spectrometry (ICP-MS) for dissolved metal(loid)s including As and Pb by the Arizona Laboratory for Emerging Contaminants after 0.45 um filtration and acidification. Method limits of detection (MLOD) were assessed and sample concentrations above MLODs were considered detects. Summary statistics and box and whisker plots were generated to assess variables of interest such as community and sampling window. Finally, As and Pb data is provided for potential reuse; the data can be used to assess contamination of harvested rainwater in AZ and to inform community use of natural resources.

Arsenic in Drinking Water and Diabetes.

Arsenic is ubiquitous in soil and water environments and is consistently at the top of the Agency for Toxic Substances Disease Registry (ATSDR) substance priority list. It has been shown to induce toxicity even at low levels of exposure. One of the major routes of exposure to arsenic is through drinking water. This review presents current information related to the distribution of arsenic in the environment, the resultant impacts on human health, especially related to diabetes, which is one of the most prevalent chronic diseases, regulation of arsenic in drinking water, and approaches for treatment of arsenic in drinking water for both public utilities and private wells. Taken together, this information points out the existing challenges to understanding both the complex health impacts of arsenic and to implementing the treatment strategies needed to effectively reduce arsenic exposure at different scales.

Response of key soil parameters during compost-assisted phytostabilization in extremely acidic tailings: effect of plant species.

Phytostabilization of mine tailings acts to mitigate both eolian dispersion and water erosion events which can disseminate barren tailings over large distances. This technology uses plants to establish a vegetative cover to permanently immobilize contaminants in the rooting zone, often requiring addition of an amendment to assist plant growth. Here we report the results of a greenhouse study that evaluated the ability of six native plant species to grow in extremely acidic (pH ∼ 2.5) metalliferous (As, Pb, Zn: 2000-3000 mg kg(-1)) mine tailings from Iron King Mine Humboldt Smelter Superfund site when amended with a range of compost concentrations. Results revealed that three of the six plant species tested (buffalo grass, mesquite, and catclaw acacia) are good candidates for phytostabilization at an optimum level of 15% compost (w/w) amendment showing good growth and minimal shoot accumulation of metal(loid)s. A fourth candidate, quailbush, also met all criteria except for exceeding the domestic animal toxicity limit for shoot accumulation of zinc. A key finding of this study was that the plant species that grew most successfully on these tailings significantly influenced key tailings parameters; direct correlations between plant biomass and both increased tailings pH and neutrophilic heterotrophic bacterial counts were observed. We also observed decreased iron oxidizer counts and decreased bioavailability of metal(loid)s mainly as a result of compost amendment. Taken together, these results suggest that the phytostabilization process reduced tailings toxicity as well as the potential for metal(loid) mobilization. This study provides practical information on plant and tailings characteristics that is critically needed for successful implementation of assisted phytostabilization on acidic, metalliferous mine tailings sites.

Metal Lability and Mass Transfer Response to Direct-Planting Phytostabilization of Pyritic Mine Tailings.

Understanding the temporal effects of organic matter input and water influx on metal lability and translocation is critical to evaluate the success of the phytostabilization of metalliferous mine tailings. Trends of metal lability, e.g., V, Cr, Mn, Co, Ni, Cu, Zn, and Pb, were investigated for three years following a direct-planting phytostabilization trial at a Superfund mine tailings site in semi-arid central Arizona, USA. Unamended tailings were characterized by high concentrations (mmol kg-1) of Fe (2100), S (3100), As (41), Zn (39), and Pb (11), where As and Pb greatly exceeded non-residential soil remediation levels established by Arizona. Phytostabilization treatments included a no-compost control, 100 g kg-1 compost with seed, and 200 g kg-1 compost with and without seed to the top 20 cm of the tailings profile. All plots received supplemental irrigation, effectively doubling the mean annual precipitation. Tailings cores up to 90 cm were Collected at the time of planting and every summer for 3 years. The cores were sub-sectioned at 20 cm increments and analyzed via total digestion and an operationally defined sequential extraction for elemental analysis and the calculation of a mass transfer coefficient normalized to Ti as an assigned immobile element. The results indicate that Pb was recalcitrant and relatively immobile in the tailings environment for both the uncomposted control and composted treatments with a maximum variation in the total concentration of 9-14 mmol kg-1 among all samples. Metal lability and translocation above the redox boundary (ca. 30 cm depth) was governed by acid generation, where surficial pH was measured as low as 2.7 ± 0.1 in year three and strongly correlated with the increased lability of Mn, Co, Ni, Cu, and Zn. There was no significant pH effect on the lability of V, Cr, or Pb. Translocation to depths was greatest for Mn and Co; however, Zn, Ni, Cr, and Cu were also mobilized. The addition of organic matter enhanced the mobilization of Cr from the near surface to 40-60 cm depth (pH > 6) over the three-year phytostabilization study compared to the control. The increased enrichment of some metals at 60-90 cm indicates that the long-term monitoring of elemental translocation is necessary to assess the efficacy of phytostabilization to contain subsurface metal contaminants and thereby protect the surrounding community from exposure.

Reductive transformation of the insensitive munitions compound nitroguanidine by different iron-based reactive minerals.

Nitroguanidine (NQ) is an emerging contaminant being used by the military as a constituent of new insensitive munitions. NQ is also used in rocket propellants, smokeless pyrotechnics, and vehicle restraint systems. Its uncontrolled transformation in the environment can generate toxic and potentially mutagenic products, posing hazards that need to be remediated. NQ transformation has only been investigated to a limited extent. Thus, it is crucial to expand the narrow spectrum of NQ remediation strategies and understand its transformation pathways and end products. Iron-based reactive minerals should be investigated for NQ treatment because they are successfully used in existing technologies, such as permeable reactive barriers, for treating a wide range of organic pollutants. This study tested the ability of micron-sized zero-valent iron (m-ZVI), mackinawite, and commercial FeS, to transform NQ under anoxic conditions. NQ transformation followed pseudo-first-order kinetics. The reaction rate constants decreased as follows: commercial FeS > mackinawite > m-ZVI. For the assessed minerals, the NQ transformation started with the reduction of the nitro group forming nitrosoguanidine (NsoQ). Then, aminoguanidine (AQ) was accumulated during the reaction of NQ with m-ZVI, accounting for 86% of the nitrogen mass recovery. When NQ was reacted with commercial FeS, 45% and 20% of nitrogen were recovered as AQ and guanidine, respectively, after 24 h. Nonetheless, NsoQ persisted, contributing to the N-balance. When mackinawite was present, NsoQ disappeared, but AQ was not detected, and guanidine accounted for 11% of the nitrogen recovery. AQ was ultimately transformed into cyanamide, whose dimerization triggered the formation of cyanoguanidine. Alternatively, NsoQ was transformed into guanidine, which reacted with cyanamide to form biguanide. This is the first report systematically investigating the NQ transformation by different iron-based reactive minerals. The evidence indicates that these minerals are attractive alternatives for developing NQ remediation strategies.

Biochar-templated surface precipitation and inner-sphere complexation effectively removes arsenic from acid mine drainage.

Treatment of aqueous leachate from acid mine tailings with pristine biochar (BC) resulted in the removal of more than 90% of the dissolved arsenic with an attendant rapid and sustained pH buffering from 3 to 4. Pine forest waste BC was transformed to a highly effective adsorbent for arsenic remediation of acid mine drainage (AMD) because the dissolved iron induced "activation" of BC through accumulation of highly reactive ferric hydroxide surface sites. Physicochemical properties of the BC surface, and molecular mechanisms of Fe, S, and As phase transfer, were investigated using a multi-method, micro-scale approach (SEM, XRD, FTIR, XANES, EXAFS, and STXM). Co-located carbon and iron analysis with STXM indicated preferential iron neo-precipitates at carboxylic BC surface sites. Iron and arsenic X-ray spectroscopy showed an initial precipitation of ferrihydrite on BC, with concurrent adsorption/coprecipitation of arsenate. The molecular mechanism of arsenic removal involved bidentate, binuclear inner-sphere complexation of arsenate at the surfaces of pioneering ferric precipitates. Nucleation and crystal growth of ferrihydrite and goethite were observed after 1 h of reaction. The high sulfate activity in AMD promoted schwertmannite precipitation beginning at 6 h of reaction. At reaction times beyond 6 h, goethite and schwertmannite accumulated at the expense of ferrihydrite. Results indicate that the highly functionalized surface of BC acts as a scaffolding for the precipitation and activation of positively charged ferric hydroxy(sulf)oxide surface sites from iron-rich AMD, which then complex oxyanion arsenate, effectively removing it from porewaters. Graphical abstract.

Iron(II) monosulfide (FeS) minerals reductively transform the insensitive munitions compounds 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO).

As military applications of the insensitive munitions compounds (IMCs) 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO) increase, there is a growing need to understand their environmental fate and to develop remediation strategies to mitigate their impacts. Iron (II) monosulfide (FeS) minerals are abundant in freshwater and marine sediments, marshes, and hydrothermal environments. This study shows that FeS solids can reduce DNAN and NTO to their corresponding amines under anoxic ambient conditions. The reactions between IMCs and the FeS minerals were surface-mediated since they did not occur when only dissolved Fe2+(aq) and S2-(aq) were present. Mackinawite, a tetragonal FeS with a layered structure, reduced DNAN mainly to 2-methoxy-5-nitroaniline (MENA), which in turn was partially reduced to 2-4-diaminoanisole (DAAN). The layered structure of mackinawite provided intercalation sites likely responsible for partial adsorption of MENA and DAAN. Mackinawite entirely reduced NTO to 3-amino-1,2,4-triazol-5-one (ATO). The reduction of IMCs showed concurrent oxidation of mackinawite to goethite and elemental sulfur. A commercial FeS product, composed mainly of pyrrhotite and troilite, reduced DNAN to DAAN and NTO to ATO. At pH 6.5, DNAN and NTO transformation rates were 667 and 912 µmol h-1 m-2, respectively, on the mackinawite surface and 417 and 1344 µmol h-1 m-2, respectively, on the commercial FeS surface. This is the first report of the reduction of a nitro-heterocyclic compound (NTO) by FeS minerals. The evidence indicates that DNAN and NTO can be rapidly transformed to their succeeding amines in anoxic subsurface environments and aquatic sediments rich in FeS minerals.