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At least 1,135 records · Page 63

Use of carbon stable isotopes to monitor biostimulation and electron donor fate in chromium-contaminated groundwater

Hexavalent chromium Cr(VI) is a common inorganic contaminant in industrial areas and represents a serious threat to human health due its toxicity. Here we report experimental results from a field-scale investigation of Cr(VI) bio-immobilization at Hanford 100H reservation, a U.S Department of Energy facility (Washington State, USA). Microbial Cr(VI) reduction was stimulated via injection of a 13 C-labeled sodium lactate solution into the high-permeability aquifer consisting of gravel and coarse sand sediments. Concentrations and carbon isotope ratios of metabolites, including dissolved inorganic carbon and total organic carbon, and compound-specific analysis of acetate and propionate, together with phospholipid fatty acids (biomass) have been analyzed to help provide an understanding of the predominant redox processes accompanying Cr(VI) reduction. Results of our study indicate that the injection of an electron donor caused a sharp decrease of Cr(VI) concentration from ~ 32 to ~ 10 nM. Cr(VI) reduction was associated with a decrease in the concentration of carboxylic acids, such as lactate (~ 6 mM to undetectable), propionate (~ 9 mM to undetectable), and acetate (~ 6 mM to undetectable), as well as dissolved inorganic carbon (30 to 10 mM C). Carbon isotope data indicate carbon transfers from the original substrate to organic byproducts and mineralized carbon. Concentrations of metabolites and stable isotope data as well as carbon isotope mass balance calculations were used to monitor biologically mediated reduction of Cr(VI).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

GaAs solar cells grown on intentionally contaminated GaAs substrates

III-V materials such as GaAs and GaInP have some of the best electronic and optical properties of any semiconductor materials, but deposition of these materials relies on high-quality single crystal GaAs substrates for their superior performance. Unfortunately, the cost of these substrates makes these high-efficiency devices only accessible in high-value or niche markets. In this study, we explore the effect of growing bulk GaAs crystals with lower purity input materials in order to reduce their cost. We observe that intentional impurities added to the melt before the crystal growth occurs segregate to the top of the boule. Single junction GaAs solar cells grown on substrates made from contaminated boules showed no performance degradation compared to a high-purity control substrate. These results suggest that lower purity Ga and As source materials can be used during crystal growth to reduce the cost of substrates.

36 MATERIALS SCIENCE↗

Post-remediation geophysical assessment: Investigating long-term electrical geophysical signatures resulting from bioremediation at a chlorinated solvent contaminated site

There is a growing need to assess long-term impacts of active remediation strategies on treated aquifers. A variety of biogeochemical alterations can result from interactions of the amendment with the aquifer, conceivably leading to a geophysical footprint of the long-term alteration of an aquifer. This concept of post-remediation geophysical assessment was investigated in a shallow, chlorinated solvent-contaminated aquifer six to eight years after amendment delivery. Surface resistivity imaging and cross-borehole resistivity and induced polarization (IP) imaging were performed on a transect that spanned treated and untreated zones of the aquifer. Established relationships between IP parameters and surface electrical conductivity were used to predict vertical profiles of electrolytic conductivity and surface conductivity from the inverted cross-borehole images. Aqueous geochemistry data, along with natural gamma and magnetic susceptibility logs, were used to constrain the interpretation. The electrical conductivity structure determined from surface and borehole imaging was foremost controlled by the electrolytic conductivity of the interconnected pore space, being linearly related to fluid specific conductance. The electrolytic conductivity (and thus the conductivity images alone) did not discriminate between treated and untreated zones of the aquifer. In contrast, inverted phase angles and surface conductivities did discriminate between treated and untreated zones of the aquifer, with the treated zone being up to an order of magnitude more polarizable in places. Supporting aqueous chemistry and borehole logging datasets indicate that this geophysical footprint of the long-term impact of the remediation on the aquifer is most likely associated with the formation of polarizable, dispersed iron sulfide minerals. The study opens the door to the possibility of employing time-lapse electrical geophysical measurements to assist with long-term environmental stewardship of legacy sites undergoing active remediation.

bioremediation↗

Uptake and elimination of 137Cs in aquatic biota inhabiting a contaminated effluent canal

Radiocesium (137Cs) is among the most prevalent and concerning radionuclide released from anthropogenic activities due to its relatively slow decay time and high bioavailability. Numerous studies have reported activity concentrations of 137Cs in exposed biota, but few have assessed detailed toxicokinetics. The objective of our study was to quantify and compare the uptake and elimination of 137Cs in aquatic taxa from multiple classes with different ecological roles inhabiting a canal contaminated from nuclear production activities on the Savannah River Site in South Carolina, USA. We tracked accumulation and elimination of 137Cs in four understudied aquatic species: one aquatic macrophyte [American white water lily (Nymphae odorata), two benthic associated omnivorous species (American bullfrog (Lithobates catesbeianus) and red swamp crayfish (Procambarus clarkii), and one pelagic carnivorous fish (Eastern mosquitofish (Gambusia holbrooki)]. We monitored accumulation of 137Cs from initial exposure until equilibrium for biota restricted within the canal and subsequently tracked elimination of 137Cs over time by moving organisms from the canal to a nearby reference pond. Results indicated bullfrog tadpoles reached 95 % equilibrium in approximately 9 days, the fastest among the species evaluated. After bullfrog tadpoles, the next fastest time to equilibrium was achieved by red swamp crayfish (51 days) followed by mosquitofish (86 days). At equilibrium, bullfrog tadpoles were found to have similar 137Cs activity concentrations to mosquitofish (3.16 and 3.57 Bq/g, respectively), and both were significantly higher than red swamp crayfish (1.77 Bq/g). For elimination, we found biological half-lives to range between 8 and 43 days with bullfrog tadpoles eliminating 137Cs the fastest followed by water lilies, mosquitofish, and red swamp crayfish. Overall, we found the uptake and elimination of 137Cs to vary widely among our studied species, but benthic organisms are not at an increased risk to accumulate 137Cs compared to organisms in less frequent contact with the sediment.

Benthic organism Bioaccumulation Bioindicator Elim↗

Accumulation mechanisms for contaminants on weak-base hybrid ion exchange resins

Mechanism of hexavalent chromium removal (Cr(VI) as CrO 4 2- ) by the weak-base ion exchange (IX) resin ResinTech® SIR-700-HP (SIR-700) from simulated groundwater is assessed in the presence of radioactive contaminants iodine-129 (as IO 3 - ), uranium (U as uranyl UO 2 2+ ), and technetium-99 (as TcO 4 - ), and common environmental anions sulfate (SO 4 2- ) and chloride (Cl-). Batch tests using the acid sulfate form of SIR-700 demonstrated Cr(VI) and U(VI) removal exceeded 97%, except in the presence of high SO 4 2- concentrations (536 mg/L) where Cr(VI) and U(VI) removal decreased to ≥ 80%. However, Cr(VI) removal notably improved with co-mingled U(VI) that complexes with SO 4 2- at the protonated amine sites. These U–SO 4 2- complexes are integral to U(VI) removal, as confirmed by the decrease in U(VI) removal (<40%) when the acid chloride form of SIR-700 was used instead. Solid phase characterization revealed that CrO 4 2- is removed by IX with SO 4 2- complexes and/or reduced to amorphous Cr(III)(OH) 3 at secondary alcohol sites. Tc(VII)O 4 - and I(V)O 3 - also undergo chemical reduction, following a similar removal mechanism. Oxyanion removal preference is determined by the anion reduction potential (CrO 4 2 - >TcO 4 - >IO 3 - ), geometry, and charge density. For these reasons, 39% and 69% of TcO 4 - and 17% and 39% of IO 3 - are removed in the presence and absence of Cr(VI), respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chromium speciation and mobility in contaminated coastal urban soils affected by water salinity and redox conditions

Chromium (Cr) is a redox-sensitive element in contaminated coastal urban soils. Sea level rise (SLR) with subsequent soil inundation may facilitate Cr transformation and mobilization through alterations in local redox conditions and porewater ion composition. Here, we investigated the impact of water salinity and redox conditions on Cr chemistry in these environments. Synchrotron-based X-ray spectroscopy and wet chemical analyses revealed that the soils contained very high levels of Cr (up to 4320 mg kg -1 ) and that chromite (~52%) and Fe-Cr hydroxide coprecipitates (~44%) were the predominant Cr species. The abundance of these two components resulted in low Cr mobility under non-flooded conditions. Chromium(II) was identified in the soils, potentially derived from the waste parent material. Seawater and anoxic conditions resulted in lower Cr release compared to freshwater and aerobic conditions. Up to three to eight times more Cr was released under aerobic conditions versus anaerobic conditions in the freshwater versus saltwater, respectively, with total dissolved Cr values remaining below 0.02 mg L -1 . The decrease in Cr release was likely due to Cr reduction by Fe(II) and sulfide. This work provides important information on how salinity and redox fluctuations impact Cr cycling which is likely to occur during SLR.

36 MATERIALS SCIENCE↗

Microbial reduction of low-crystallinity tripuhyite (FeSbO 4 ): Implications for Sb(V) cycling in contaminated environments

Tripuhyite (FeSbO 4 ) is an important antimony (Sb)-bearing mineral that controls Sb mobility in contaminated environments, yet its structural stability during microbial reduction remains unresolved. Understanding how FeSbO 4 behaves under anoxic conditions is therefore necessary to predict natural Sb cycling. Here, this study examined how an anaerobic microbial community interacts with FeSbO 4 and alters its structural and redox behavior. Across all conditions, FeSbO 4 released measurable Sb(V), demonstrating that the mineral undergoes partial dissolution in anoxic environment even without microbial activity. However, when extensive microbial Fe(III) reduction occurred in the presence of the electron shuttle anthraquinone-2,6-disulfonate (AQDS), the released Sb was re-immobilized. This indicates that microbial reduction processes modulate Sb mobility. Microbial community analysis showed the enrichment of acetate-utilizing Fe(III)-reducing bacteria as key drivers of Fe reduction. Although secondary Fe minerals were not detected, X-ray absorption fine structure measurements and scanning electron microscopy images revealed the formation of an Sb(III)-bearing phase consistent with valentinite (Sb 2 O 3 ) in the AQDS-amended treatment. This transformation suggests that AQDS not only enhances Fe(III) reduction but is also linked to Sb(V) reduction, and facilitates the immobilization of reduced Sb(III) as Sb 2 O 3 . Overall, this work provides the first evidence that FeSbO 4 is susceptible to microbially mediated redox transformations, and that these processes can significantly alter the mobility and speciation of Sb in reducing environments.

Electron transfer mediator↗

Brown watersnakes (Nerodia taxispilota) as bioindicators of mercury contamination in a riverine system

Herein, mercury (Hg) is a contaminant that enters the environment through natural or anthropogenic means. Ecological risk assessments have examined Hg bioaccumulation and effects in many taxa, but little is known about Hg dynamics in reptiles, or their potential use as bioindicator species for monitoring Hg in aquatic systems. Numerous snake species, like North American watersnakes (Nerodia spp.), are piscivorous and are exposed to Hg through their diet. The purpose of this study was to identify factors associated with Hg accumulation in a common watersnake species and compare Hg concentrations of the snakes to those in fish occupying the same habitats. To this end, we sampled brown watersnakes (Nerodia taxispilota) from the Savannah River, a major river system in the southeastern U.S., and compared N. taxispilota Hg accumulation trends to those of bass (Micropterus salmoides), catfish (Ictalurus and Ameiurus spp.), and panfish (Lepomis and Pomoxis spp.) collected from the same reach. Total Hg (THg) in N. taxispilota tail tips ranged from 0.020 to 0.431 mg/kg (wet weight; mean: 0.104 ± 0.008). Snake tail THg was significantly correlated with blood THg, which ranged from 0.003 to 1.140 mg/kg (0.154 ± 0.019). Snake size and site of capture were significantly associated with tail THg. Snake tail THg increased at sites along and downstream of the area of historic Hg pollution, consistent with fish THg. Snake muscle THg was predicted based on tail THg and ranged from 0.095 to 1.160 (0.352 ± 0.022). To gauge Hg biomagnification in N. taxispilota, we compared predicted snake muscle THg concentrations to THg in fish of consumable size. Average biomagnification factors for THg in N. taxispilota were 3.1 (panfish) and 5.4 (catfish), demonstrating N. taxispilota likely biomagnify Hg through their diet. These results reveal N. taxispilota to be an effective bioindicator species for monitoring Hg in aquatic environments.

54 ENVIRONMENTAL SCIENCES↗

The detrimental effect of elemental contaminants when using B additions to improve the creep properties of a Ni-based superalloy

The effect of Si contamination when using B to improve the creep properties of a Ni-based superalloy was investigated using advanced characterization techniques and first-principles simulations on alloys with high and low B levels with varying Si contents. The positive effect of B segregation along grain boundaries on the creep properties was mitigated by the presence of Si which showed a similar segregation preference. Density functional theory calculations were used for validation by calculating grain boundary cleavage energies. Silicon was shown to decrease grain boundary cohesion which offsets the positive effect of B.

36 MATERIALS SCIENCE↗

Water Contamination Impacts on Biodiesel Antioxidants and Storage Stability

Biodiesel (fatty acid methyl esters) can oxidize in storage to form acids and gums that negatively impact engine performance and durability. Antioxidant additives are used to increase biodiesel storage stability, and previous studies that evaluated the effectiveness of antioxidants demonstrated that more polar antioxidants tend to be the most effective (provide the largest improvement in stability per unit of antioxidant added). However, polar antioxidants have significant water solubility, and diesel fuel storage tanks are commonly contaminated with water (forming a layer of water under the fuel). This study investigates whether nonpolar antioxidants, which are less effective in dry environments, might be more effective under wet conditions simulating real-world storage. Biodiesel blends treated with polar and nonpolar antioxidants were subjected to accelerated aging using the ASTM D4625 protocol (storage at 43 °C, open to air, for up to 24 weeks) both with and without added water. Fuels treated with polar/higher-effectiveness compounds and stored in contact with water (simulating water in a storage tank) or high humidity showed accelerated loss of stability compared to dry storage. The same fuel treated with a nonpolar antioxidant and stored in the same conditions did not exhibit accelerated stability loss and thus had higher storage stability over the long term despite treatment with an initially less effective additive. Analysis of the fuels during aging showed that this loss of stability was not due to oxidation but rather extraction of the polar antioxidant into the water layer. Antioxidant additives that are incompatible with wet or humid storage conditions were found to cause faster-than-anticipated loss of stability, which was preventable with use of nonpolar additives.

09 BIOMASS FUELS↗

Mercury Removal from Contaminated Water by Wood-Based Biochar Depends on Natural Organic Matter and Ionic Composition

Biochars can remove potentially toxic elements, such as inorganic mercury [Hg(II)] from contaminated waters. However, their performance in complex water matrices is rarely investigated, and the combined roles of natural organic matter (NOM) and ionic composition in the removal of Hg(II) by biochar remain unclear. Here, we investigate the influence of NOM and major ions such as chloride (Cl – ), nitrate (NO 3 – ), calcium (Ca 2+ ), and sodium (Na + ) on Hg(II) removal by a wood-based biochar (SWP700). Multiple sorption sites containing sulfur (S) were located within the porous SWP700. In the absence of NOM, Hg(II) removal was driven by these sites. Ca 2+ bridging was important in enhancing removal of negatively charged Hg(II)-chloro complexes. In the presence of NOM, formation of soluble Hg-NOM complexes (as seen from speciation calculations), which have limited access to biochar pores, suppressed Hg(II) removal, but Cl – and Ca 2+ could still facilitate it. The ability of Ca 2+ to aggregate NOM, including Hg-NOM complexes, promoted Hg(II) removal from the dissolved fraction (<0.45 μm). Hg(II) removal in the presence of Cl – followed a stepwise mechanism. Weakly bound oxygen functional groups in NOM were outcompeted by Cl – , forming smaller-sized Hg(II)-chloro complexes, which could access additional intraparticle sorption sites. Therein, Cl – was outcompeted by S, which finally immobilized Hg(II) in SWP700 as confirmed by extended X-ray absorption fine structure spectroscopy. We conclude that in NOM containing oxic waters, with relatively high molar ratios of Cl – : NOM and Ca 2+ : NOM, Hg(II) removal can still be effective with SWP700.

54 ENVIRONMENTAL SCIENCES↗

Rapid Accumulation of Soil Inorganics on Plastics: Implications for Plastic Degradation and Contaminant Fate

As plastics degrade in the environment, chemical oxidation of the plastic surface enables inorganics to adsorb and form inorganic coatings, likely through a combination of adsorption of minerals and in situ mineral formation. The presence of inorganic coatings on aged plastics has negative implications for plastics fate, hindering our ability to recycle weathered plastics and increasing the potential for plastics to adsorb contaminants. Here, inorganic coatings formed on terrestrially weathered polyethylene were characterized using synchrotron spectroscopy and microscopy techniques across spatial scales including optical microscopy, nano-X-ray-fluorescence mapping (nano-XRF), nano-X-ray absorption near edge structure (nano-XANES), and high-energy resolution fluorescence detected-XANES (HERFD-XANES). Results indicate a heterogeneous elemental distribution and speciation which includes inorganics common to soil terrestrial environments including iron oxides and oxyhydroxides, aluminosilicates, and carbonates.

36 MATERIALS SCIENCE↗

Electrocoagulation in Water Treatment: Targeted Contaminant Removal and Laboratory Best Practices

Electrocoagulation for water treatment offers many advantages over traditional treatment technologies, including improved energy efficiency and modularity. One challenge with electrocoagulation is the lack of standardization in the methodology and reporting. This review provides a novel contribution by examining the past literature using a uniform metric (charge loading) as a basis for comparison, highlighting the importance of uniform reporting practices in this field. Furthermore, this review provides practical guidance for experimentalists in standardizing the electrocoagulation design and operating procedures. First, we present a comprehensive overview of contaminant-specific electrocoagulation as an electrochemical treatment technology for processing industrial, municipal, and agricultural water, with a focus on aluminum and iron electrocoagulation. We detail the fundamental mechanisms that allow for constituent removal during pretreatment. Specifically, we highlight electrocoagulation’s potential for organics, metalloids, microbes, and hardness remediation, examining the optimal removal conditions in terms of charge loading and current density. We conclude this work with some experimental best practices for lab-scale electrocoagulation experiments.

aluminum↗

Metal–Organic Frameworks for Per- and Polyfluoroalkyl Substances Treatment in Contaminated Water

Per- and polyfluoroalkyl substances (PFAS) are synthetic pollutants known for their chemical stability, environmental persistence, and toxicological risks. Their widespread use has led to extensive contamination, particularly in aquatic systems. Conventional treatment methods often face challenges such as high energy consumption and the production of secondary pollutants. Metal− organic frameworks (MOFs), with their high surface areas and tunable structures, have emerged as promising materials for PFAS remediation. This review summarizes recent progress in MOF-based PFAS adsorption and degradation, highlighting key frameworks such as MIL, UiO, and ZIF. Mechanistic insights into adsorption behavior and regeneration capabilities are discussed, along with the catalytic performance of MOF composites and postmodified systems in degradation pathways. The review concludes with design strategies for next-generation MOF materials aimed at efficient, sustainable PFAS removal under realistic conditions.

Adsorption↗

Microbial community dynamics and cycling of plutonium and iron in a seasonally stratified and radiologically contaminated pond

Plutonium (Pu) cycling and mobility in the environment can be impacted by the iron cycle and microbial community dynamics. We investigated the spatial and temporal changes of the microbiome in an iron (Fe)-rich, plutonium-contaminated, monomictic reservoir (Pond B, Savannah River Site, South Carolina, USA). The microbial community composition varied with depth during seasonal thermal stratification and was strongly correlated with redox. During stratification, Fe(II) oxidizers (e.g., Ferrovum, Rhodoferax, Chlorobium) were most abundant in the hypoxic/anoxic zones, while Fe(III) reducers (e.g., Geothrix, Geobacter) dominated the deep, anoxic zone. Sulfate reducers and methanogens were present in the anoxic layer, likely contributing to iron and plutonium cycling. Multinomial regression of predicted functions/pathways identified metabolisms highly associated with stratification (within the top 5%), including iron reduction, methanogenesis, C1 compound utilization, fermentation, and aromatic compound degradation. Two sediment cores collected at the Inlet and Outlet of the pond were dominated by putative fermenters and organic matter (OM) degraders. Overall, microbiome analyses revealed the potential for three microbial impacts on the plutonium and iron biogeochemical cycles: (1) plutonium bioaccumulation throughout the water column, (2) Pu–Fe-OM-aggregate formation by Fe(II) oxidizers under microaerophilic/aerobic conditions, and (3) Pu–Fe-OM-aggregate or sediment reductive dissolution and organic matter degradation in the deep, anoxic waters.

54 ENVIRONMENTAL SCIENCES↗