Phloem transport of arsenic species from flag leaf to grain during grain filling
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99 GENERAL AND MISCELLANEOUS↗
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GaAs(Sb) nanostructures formed by arsenic-induced in-situ etching of III-Sb surfaces.
Abstract not provided.
Addamane, Sadhvikas↗
Data for "High dopant activation in arsenic doped single-crystal CdTe thin films: Insights from MBE growth and rapid thermal processing"
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14 SOLAR ENERGY↗
Arsenic Doping of Polycrystalline CdSeTe Devices for Microsecond Life-times with High Carrier Concentrations
We report seminal advances in fabrication and understanding of group V (As) doped thin-film polycrystalline CdTe-based solar cells. The devices are fabricated using a novel approach, by sublimating layers of CdSeTe and CdSeTe:As. This new method allowed us to achieve minority carrier lifetime of over 1 μs, carrier concentration of more than 5x1015 cc-1 and external radiative efficiency of over 2% in a device configuration. We find an increase in open-circuit voltage when comparing As-doped, Cu-doped and undoped devices. The choice of CdSeTe instead of a CdTe-only absorber has been explained using first-principle density functional theory model. A SCAPS device model is used to analyze the potential causes for lower open-circuit voltage.
14 SOLAR ENERGY↗
Transcriptional Control of hgcAB by an ArsR-Like Regulator in Pseudodesulfovibrio mercurii ND132
The hgcAB gene pair encodes mercury (Hg) methylation capability in a diverse group of microorganisms, but its evolution and transcriptional regulation remain unknown. Working from the possibility that the evolutionary function of HgcAB may not be Hg methylation, we test a possible link to arsenic resistance. Using model Hg methylator Pseudodesulfovibrio mercurii ND132, we evaluated transcriptional control of hgcAB by a putative ArsR encoded upstream and cotranscribed with hgcAB. This regulator shares homology with ArsR repressors of arsenic resistance and S-adenosylhomocysteine (SAH)- responsive regulators of methionine biosynthesis but is distinct from other ArsR/SahR proteins in P. mercurii. Using quantitative PCR (qPCR) and RNA sequencing (RNA-seq) transcriptome analyses, we confirmed this ArsR regulates hgcAB transcription and is responsive to arsenic and SAH. Additionally, RNA-seq indicated a possible link between hgcAB activity and arsenic transformations, with significant upregulation of other ArsRregulated arsenic resistance operons alongside hgcAB. Interestingly, wild-type ND132 was less sensitive to As(V) (but not As(III)) than an hgcAB knockout strain, supporting the idea that hgcAB may be linked to arsenic resistance. Arsenic significantly impacted rates of Hg methylation by ND132; however, responses varied with culture conditions. Differences in growth and metabolic activity did not account for arsenic impacts on methylation. While arsenic significantly increased hgcAB expression, hgcAB gene and transcript abundance was not a good predictor of Hg methylation rates. Taken together, these results support the idea that Hg and As cycling are linked in P. mercurii ND132. Our results may hold clues to the evolution of hgcAB and the controls on Hg methylation in nature. This work reveals a link between microbial mercury methylation and arsenic resistance and may hold clues to the evolution of mercury methylation genes (hgcAB). Microbes with hgcAB produce methylmercury, a strong neurotoxin that readily accumulates in the food web. This study addresses a critical gap in our understanding about the environmental factors that control hgcAB expression. We show that hgcAB expression is controlled by an ArsR-like regulator responsive to both arsenic and S-adenosylhomocysteine in our model organism, Pseudodesulfovibrio mercurii ND132. Exposure to arsenic also significantly impacted Pseudodesulfovibrio mercurii ND132 mercury methylation rates. However, expression of hgcAB was not always a good predictor of Hg methylation rates, highlighting the roles of Hg bioavailability and other biochemical mechanisms in methylmercury production. This study improves our understanding of the controls on hgcAB expression, which is needed to better predict environmental methylmercury production
RNA-seq↗
Arsenolipids in Cultured Picocystis Strain ML and Their Occurrence in Biota and Sediment from Mono Lake, California
Primary production in Mono Lake, a hypersaline soda lake rich in dissolved inorganic arsenic, is dominated by Picocystis strain ML. We set out to determine if this photoautotrophic picoplankter could metabolize inorganic arsenic and in doing so form unusual arsenolipids (e.g., arsenic bound to 2-O-methyl ribosides) as reported in other saline ecosystems and by halophilic algae. We cultivated Picocystis strain ML on a seawater-based medium with either low (37 µM) or high (1000 µM) phosphate in the presence of arsenite (400 µM), arsenate (800 µM), or without arsenic additions (ca 0.025 µM). Cultivars formed a variety of organoarsenic compounds, including a phytyl 2-O-methyl arsenosugar, depending upon the cultivation conditions and arsenic exposure. When the cells were grown at low P, the organoarsenicals they produced when exposed to both arsenite and arsenate were primarily arsenolipids (~88%) with only a modest content of water-soluble organoarsenic compounds (e.g., arsenosugars). When grown at high P, sequestration shifted to primarily water-soluble, simple methylated arsenicals such as dimethylarsinate; arsenolipids still constituted ~32% of organoarsenic incorporated into cells exposed to arsenate but < 1% when exposed to arsenite. Curiously, Picocystis strain ML grown at low P and exposed to arsenate sequestered huge amounts of arsenic into the cells accounting for 13.3% of the dry biomass; cells grown at low P and arsenite exposure sequestered much lower amounts, equivalent to 0.35% of dry biomass. Extraction of a resistant phase with trifluoroacetate recovered most of the sequestered arsenic in the form of arsenate. Uptake of arsenate into low P-cultivated cells was confirmed by X-ray fluorescence, while XANES/EXAFS spectra indicated the sequestered arsenic was retained as an inorganic iron precipitate, similar to scorodite, rather than as an As-containing macromolecule. Samples from Mono Lake demonstrated the presence of a wide variety of organoarsenic compounds, including arsenosugar phospholipids, most prevalent in zooplankton (Artemia) and phytoplankton samples, with much lower amounts detected in the bottom sediments. These observations suggest a trophic transfer of organoarsenicals from the phytoplankton (Picocystis) to the zooplankton (Artemia) community, with efficient bacterial mineralization of any lysis-released organoarsenicals back to inorganic oxyanions before they sink to the sediments.
54 ENVIRONMENTAL SCIENCES↗
Radioarsenic: A promising theragnostic candidate for nuclear medicine
Molecular imaging is a non-invasive process that enable the visualization, characterization, and quantitation of biological processes at the molecular and cellular level. With the emergence of theragnostic agents to diagnose and treat disease for personalized medicine there is a growing need for matched pairs of isotopes. Matched pairs offer the unique opportunity to obtain patient specific information from SPECT or PET diagnostic studies to quantitate in vivo function or receptor density to inform and tailor therapeutic treatment. There are several isotopes of arsenic that have emissions suitable for either or both diagnostic imaging and radiotherapy. Their half-lives are long enough to pair them with peptides and antibodies which take longer to reach maximum uptake to facilitate improved patient pharmacokinetics and dosimetry then can be obtained with shorter lived radionuclides. Arsenic-72 even offers availability from a generator that can be shipped to remote sites and thus enhances availability. Arsenic has a long history as a diagnostic agent, but until recently has suffered from limited availability, lack of suitable chelators, and concerns about toxicity have inhibited its use in nuclear medicine. However, new production methods and novel chelators are coming online and the use of radioarsenic in the pico and nanomolar scale is well below the limits associated with toxicity. This manuscript will review the production routes, separation chemistry, radiolabeling techniques and in vitro/in vivo studies of three medically relevant isotopes of arsenic (arsenic-74, arsenic-72, and arsenic-77).
07 ISOTOPE AND RADIATION SOURCES↗
Upcycling Metal(loid) Contaminants to Produce Critical Raw Materials: The Nexus of Water Treatment and Material Criticality
The Critical Raw Materials Act adopted by the European Commission in 2024 signals a growing shift in the societal value of many elements, which has important implications for the water treatment sector. This legislation partly aims to increase production of Critical Raw Materials (CRMs) from waste streams, with many CRMs being elements with which the water sector has decades of experience, such as the notorious contaminant and newly classified CRM, arsenic. In this Perspective, we use arsenic as a case study to explore how water treatment waste can be repurposed to contribute to CRM supply chain requirements. Combining arsenic mass balances for indicative groundwater treatment plants and EU statistics of water use and arsenic compound consumption, we propose that arsenic upcycling integrated with water treatment can help offset imports of arsenic compounds. However, research is now needed to develop more holistic treatment systems that integrate CRM upcycling with contaminant removal and to better understand the political, institutional, and social drivers that can accelerate adoption of such systems at water utilities. With this work, we intend to stimulate a discussion of water treatment as a discipline that can both improve water quality by removing metal(loid) contaminants and generate local sources of CRMs.
Arsenic↗
Intercalation And High-Pressure Effects On Structural Phase Transitions In Layered As x P 1-x Alloys
This project was aimed at understanding the role of composition, intercalation, and high pressure on the structural evolution of black phosphorous (BP) and layered arsenic phosphorous alloys, As y P 1-y . Under normal conditions, BP is the most stable phase of phosphorous, known as the α-phase, characterized by an orthorhombic honeycomb puckered crystal structure with the Cmca space group. On the other hand, the most stable phase of arsenic is its β-phase, known as gray arsenic (g-As), which has a rhombohedral buckled layered crystal structure with the R3m space group. In a wide range of compositions (y < 0.83), the arsenic phosphorous alloys form the α-phase, known as black arsenic phosphorous (b-As y P 1-y ) with a similar structure to BP. The project was aimed at the synthesis of BP and b-As y P 1-y with different compositions and at studying the structural evolution of these materials during intercalation with alkali metal (especially Li), and under high-pressure conditions. The main goals were to gain a better understanding of these processes and structural changes taking place under these conditions. In particular, the project was aimed at addressing whether such conditions could induce a structural transition between the α- and β-phases. For this, a series of systematic in-situ studies were conducted, including electrochemical lithium intercalation in an in-situ electrochemical cell, and high-pressure experiments in a diamond anvil cell (DAC). Overall, both types of experiments have shown that above a certain composition-dependent threshold level of intercalation or high pressure, the system undergoes phase segregation rather than phase transition. Specifically, the segregation of the excess arsenic was observed, and a single-phase system of b-As y P 1-y transformed into a two-phase system consisting of b-As y P 1-y and g-As, through the following process: 1∗(b-As y P 1-y ) → 1∗(b As y-δ P 1-y ) + δ∗(g-As). Also, the study showed that intercalation and high-pressure are two competing rather than synergistic processes causing at least a partial cancelation of these two factors
36 MATERIALS SCIENCE↗
Superior removal of As(III) and As(V) from water with Mn-doped β-FeOOH nanospindles on carbon foam
Arsenic pollution of water is one of the severest environmental challenges threatening human health. Iron-based nanomaterials have been demonstrated effective in arsenic removal. However, they generally suffer from low removal efficiency towards highly toxic As(III), loss of active sites owing to agglomeration, and poor reusability. Herein, we report a carbonized melamine foam supported Mn(IV)-doped β-FeOOH nanospindles(CF@Mn-FeOOH NSp) for tackling the technical hurdles. The designed CF@Mn-FeOOH NSp appears as a free-standing monolith through a low-cost and straightforward hydrothermal method. The atomic-scale integration of Mn(IV) into β-FeOOH enables an oxidation-adsorption bifunctionality, where Mn(IV) serves as oxidizer for As(III) and Fe(III) acts as adsorber for As(V). The maximal adsorption capacity for As(V) and As(III) can reach 152 and 107 mg g -1 , respectively. Meanwhile, As in simulated high arsenic groundwater can be decreased to below 10 μg L -1 within 24 h. By simple "filtrating-washing", 85% and 82% of its initial adsorption capacity for As(V) and As(III) can be easily recovered even after 5-cycles reuse. Kinetics and isotherm adsorption study indicate that the arsenic adsorption behavior is mainly through chemical bonding during single-layer adsorbing process. The as-prepared CF@Mn-FeOOH offers a scalable, efficient, and recyclable solution for arsenic removal in groundwater and wastewater from mines and industry.
63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
Plant Growth Study: Growth of Three Plant Species in 100-OL-1 Operable Unit Soils
Soil contamination from historical application of lead arsenate pesticides persists in the 100-OL-1 Operable Unit (OU) of the U.S. Department of Energy’s Hanford Site in Benton County, Washington. A remedial investigation used a portable X-ray fluorescence analyzer to estimate and map the concentrations of metals in surface soil in the 133 decision units comprising the OU. There is variability in lead and arsenic concentrations among the non-contiguous decision units, and an incomplete understanding of the ecological and human risks from soil contamination. While general screening criteria for lead are reported in literature, limited information is available on the impacts of heavy metals on site-specific plant and animal life. To address this information gap, a study on plant growth in Hanford soils was conducted using native bluegrass (Poa secunda), invasive cheatgrass (Bromus tectorum), and buttercrunch lettuce (Lactuca sativa). The latter is included because it is a common species used in plant growth studies. Soil samples were collected from a single general location within the 100-OL-1 OU, prepared, and categorized as having low, medium, or high concentrations of lead and arsenic, with the high concentration soil having concentrations of up to 3,400 and 790 mg/kg lead and arsenic, respectively. Additionally, a synthetic soil was prepared and used as a control, in accordance with standard plant growth protocols. Fifty-four seeds of each plant species were planted in each of the four soil types following the procedure outlined by the Washington State Department of Ecology. Germination rates and biomass measurements were recorded for 20 days. Both bluegrass and lettuce germination rates appeared to be reduced at the highest lead and arsenic concentrations (Pb: 3400 mg/kg, As: 790 mg/kg), while cheatgrass germination rates were unaffected. Total biomass for all species appeared to be related to the relative concentrations of lead and arsenic in the soil. Results of this growth study agree reasonably well with previous Hanford Site plant growth studies and provide additional data for assessing ecological risk at the Hanford Site.
54 ENVIRONMENTAL SCIENCES↗
Metalloproteomics Reveals Multi-Level Stress Response in Escherichia coli When Exposed to Arsenite
The arsRBC operon encodes a three-protein arsenic resistance system. ArsR regulates the transcription of the operon, while ArsB and ArsC are involved in exporting trivalent arsenic and reducing pentavalent arsenic, respectively. Previous research into Agrobacterium tumefaciens 5A has demonstrated that ArsR has regulatory control over a wide range of metal-related proteins and metabolic pathways. We hypothesized that ArsR has broad regulatory control in other Gram-negative bacteria and set out to test this. Here, we use differential proteomics to investigate changes caused by the presence of the arsR gene in human microbiome-relevant Escherichia coli during arsenite (AsIII) exposure. We show that ArsR has broad-ranging impacts such as the expression of TCA cycle enzymes during AsIII stress. Additionally, we found that the Isc [Fe-S] cluster and molybdenum cofactor assembly proteins are upregulated regardless of the presence of ArsR under these same conditions. An important finding from this differential proteomics analysis was the identification of response mechanisms that were strain-, ArsR-, and arsenic-specific, providing new clarity to this complex regulon. Given the widespread occurrence of the arsRBC operon, these findings should have broad applicability across microbial genera, including sensitive environments such as the human gastrointestinal tract.
Biochemistry & Molecular Biology↗
Removal of As(V) from wastewaters using magnetic iron oxides formed by zero-valent iron electrocoagulation
Electrocoagulation of zero-valent iron has been widely applied to the removal of dissolved arsenic, but the solid-liquid separation of arsenic-containing precipitates remains technically challenging. In this work, zero-valent iron was electrochemically oxidized to magnetic iron oxides for the removal of As(V) from simulated and actual mining wastewaters. The results indicated that lepidocrocite was formed when zero-valent iron was oxidized by dissolved oxygen, but ferrihydrite and green rust were first formed and then transformed to magnetic iron oxides (mainly magnetite and maghemite) in the electrochemical oxidation from 0 to 0.9 V (vs. SCE), which facilitates the adsorption of As(V) and subsequent solid-liquid separation under a magnetic field. In simulated As(V)-containing solution with initial pH 7.0, zero-valent iron was electrochemically oxidized to magnetite and maghemite at 0.6 V (vs. SCE) for 2 h. The As(V) concentration first decreased from 5127.5 to 26.8 μg L -1 with a removal ratio of 99.5%. In actual mining wastewaters, zero-valent iron was electrochemically oxidized to maghemite at 0.6 V (vs. SCE) for 24 h, and the As(V) concentration decreased from 5486.4 to 3.6 μg L -1 with a removal ratio of 99.9%. The removal ratio of As(V) increased slightly with increasing potential, and increased first and then decreased with increasing initial pH. Compared with that of SO 4 2- and NO 3 - , the presence of Cl - significantly enhanced the removal of As(V). This work provides a highly efficient, facile and low-cost technique for the treatment of arsenic-containing wastewaters.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of seasonal anoxia on geochemical cycling in a stratified pond: Comparison to cooler pond conditions 40 years ago
Seasonal stratification in temperate lakes deeper than a few meters creates favorable conditions for pronounced vertical redox zones, often resulting in anaerobic hypolimnions and significant geochemical changes. Here, this study examined thermocline formation and trace element behavior in a seasonally stratified pond amid rising air temperatures. Over two years, data were collected from Pond B at the US Department of Energy Savannah River Site in Aiken, South Carolina. Pond B, a man-made monomictic reservoir, received cooling water from a nuclear reactor from 1961 to 1964. Strong thermal stratification forms a distinct thermocline in May and progresses downward until November. Compared to the 1980s, this study shows a delayed onset and extended duration of stratification. The prolonged summer stratification reduces deep water oxygen replenishment, extending hypoxic conditions. Trace and major elements sampled in the water column revealed strong correlations between As, Fe, and Mn profiles, with concentrations increasing by 1–2 orders of magnitude in the anaerobic hypolimnion. This period captured the seasonal transition from winter mixing to summer stratification to fall overturn. Under anoxic conditions, Fe(III) reduces to Fe(II) in the sediment, releasing dissolved iron into the water column. The extended anoxic periods likely promoted arsenic release from sediments. Prolonged anoxia may enhance arsenic mobilization and solubility in the lake. This study illustrates how climate-induced changes in seasonal stratification of contaminated waters can convert contaminant sinks into sources, offering insights into the cycling of arsenic and other dissolved ions in stratified lakes and their implications for water quality management.
Anoxic conditions↗
Pilot Test Remediation of a Fractured Bedrock Aquifer at the Maywood Superfund Site, Maywood, New Jersey - 20073
The U.S. Army Corps of Engineers (USACE) and Cabrera Services are conducting a Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) Pilot Test treatment of a fractured bedrock aquifer at the Formerly Utilized Sites Remedial Action Program (FUSRAP) Maywood Superfund Site (FMSS) located in Maywood, New Jersey (NJ), USA. The Maywood Chemical Company Superfund Site in Bergen County, NJ is listed on the United States Environmental Protection Agency (USEPA) Superfund National Priorities List (NPL). The National Superfund Comprehensive Environmental Response, Compensation, and Liability Information System (CERCLIS) identification number is NJD980529762. The Maywood Chemical Company Superfund Site (hereafter referred to as the FMSS) consists of 92 designated properties in the communities of Maywood, Lodi and Rochelle Park, NJ. These are collectively known as FMSS 'Vicinity Properties' and include property owned by the federal government (the Maywood Interim Storage Site, or MISS); the Stepan Company (former location of the Maywood Chemical Works, or MCW); 62 residential properties; three properties owned by the state or federal government; four municipal properties; and 21 commercial properties. The Stepan Company property includes contaminated buildings and three remediated U.S. Nuclear Regulatory Commission (NRC) licensed burial pits; the MISS also includes a contaminated building. Contamination on the FMSS is being addressed under three separate actions coordinated by the lead regulator USEPA Region 2. The USACE is addressing thorium (Th) and other wastes at the site defined as 'FUSRAP waste' in the Soils and Buildings and Groundwater Records of Decision (ROD) for the FMSS. Stepan Company is addressing other chemical wastes (non-FUSRAP waste) at the FMSS. The Groundwater ROD [1] was signed into agreement by USACE Division Commander in June 2012 and USEPA Region 2 Administrator in July 2012 and presents the selected remedial actions for Operable Unit (OU) 2 groundwater at the MISS and adjacent properties. The selected remedial action is removal of non-radiologically contaminated soils on the MISS containing arsenic, lithium, and benzene with concentrations above cleanup levels, and monitored natural attenuation (MNA) of arsenic, lithium, and benzene in groundwater. In situ treatment of arsenic in the overburden aquifer using oxidation reduction (redox) alteration will also be performed if needed to meet the groundwater cleanup levels after the source soil is removed. The need for in situ treatment will be determined during the Groundwater ROD review at least three to four years after the contaminated source soil removal is completed. The third action addressing non-FUSRAP chemical wastes will be the responsibility of the Stepan Company as a primary responsible party in this action. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
A hybrid topological quantum state in an elemental solid
Topology and interactions are foundational concepts in the modern understanding of quantum matter. Their nexus yields three important research directions: (1) the competition between distinct interactions, as in several intertwined phases, (2) the interplay between interactions and topology that drives the phenomena in twisted layered materials and topological magnets, and (3) the coalescence of several topological orders to generate distinct novel phases. The first two examples have grown into major areas of research, although the last example remains mostly unexplored, mainly because of the lack of a material platform for experimental studies. Here, using tunnelling microscopy, photoemission spectroscopy and a theoretical analysis, we unveil a ‘hybrid’ topological phase of matter in the simple elemental-solid arsenic. Through a unique bulk-surface-edge correspondence, we uncover that arsenic features a conjoined strong and higher-order topology that stabilizes a hybrid topological phase. Although momentum-space spectroscopy measurements show signs of topological surface states, real-space microscopy measurements unravel a unique geometry of topologically induced step-edge conduction channels revealed on various natural nanostructures on the surface. Using theoretical models, we show that the existence of gapless step-edge states in arsenic relies on the simultaneous presence of both a non-trivial strong Z 2 invariant and a non-trivial higher-order topological invariant, which provide experimental evidence for hybrid topology. Finally, our study highlights pathways for exploring the interplay of different band topologies and harnessing the associated topological conduction channels in engineered quantum or nano-devices.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Emitter Reconstruction for Cleaved CdSexTe1-x Devices with Cu vs. As Doping
CdTe absorbers have had historically low carrier densities of ~10^14 cm-3 due to the self-compensating nature of copper dopants. Recent advances in group-V (e.g., arsenic) doping have increased this to 10^16-10^17 cm-3, but modeling suggests that the front interface and emitter properties become limiting in this case. By cleaving arsenic- and copper-doped CdTe device stacks at the emitter/absorber interface, we gain the ability to reconstruct emitters with known properties, which will not change during subsequent device processing, and directly test the modeling. By doing so, we find a much larger performance drop in arsenic devices; this is attributed to insufficient electron density in the emitter and increased sensitivity to interface changes due to collapsed depletion width. This work can help guide emitter engineering for highly-doped CdTe devices in both the as-grown-superstrate- and cleaved-substrate configurations.
As-doped↗
Guanidinium-Based Ionic Covalent-Organic Nanosheets for Sequestration of Cr(VI) and As(V) Oxoanions in Water
Chromium- and arsenic-based oxoanions are among the major highly toxic and carcinogenic inorganic pollutants present in groundwater, demanding fast and selective sequestration. Efficient capturing and removal of these highly mobile oxometallates at neutral pH presents a great challenge in groundwater cleanup. In this report, a series of guanidinium-based ionic organic covalent nanosheets (iCONs) with varying hydrogen bonding, steric, and electronic properties was studied to examine the structure–activity relationship in the adsorption and removal of chromium- and arsenic-based oxoanions in water. Structural modulations in iCONs were found to alter the guanidinium acidity, thus regulating the oxoanion uptake limits via ion exchange. The hydrogen bonding, steric, and electrostatic interactions at/near the guanidinium-based anion binding site in iCONs exerted heavy influences on the uptake efficiency and selectivity of arsenate but not on those of chromate. Further analyses revealed that the parallel bidentate hydrogen bonding interactions play a key role in the weak binding of arsenate to the protonated/positively charged guanidine motifs, whereas the strong ion–ion interactions between chromate and guanidinium appear to be more tolerant to the geometric and structural perturbation.
36 MATERIALS SCIENCE↗