Determination and speciation of arsenic in drinking water samples by X-ray spectrometry technique.

Arsenic is ranked as the first compound in the Substance Priority List 2023 by the Agency for Toxic Substances and Disease Registry (ATSDR). The most prominent entrance to the human body is through drinking water wherein the predominant species are arsenite and arsenate. The more toxic As(III) has rigorously threatened human health worldwide; hence, speciation and separation are the need of the hour. In this article, we have reported a simple method of arsenic speciation by wavelength dispersive X-ray fluorescence (WD-XRF) spectrometer. Valence to core (VtC) electronic transitions, i.e., AsKß2,5 fluorescence lines were used for arsenic speciation. This speciation study by WD-XRF entails direct measurement of activated alumina pellets containing arsenate and arsenite species adsorbed from water sample without separation of the trivalent and pentavalent species. This is the first report wherein the X-ray technique has been explored for speciation analysis of arsenic and the biggest advantage of the method lies in its applicability to direct analysis of synthesized nanotubes or other solid-phase extraction sorbents entrapping both the arsenic species. For determination of total arsenic using activated alumina as adsorbent, the most intense AsKα1,2 analytical lines were used and the instrumental limit of detection and the lower limit of quantification were 0.23 µg/L and 0.89 µg/L, respectively. For speciation, these limits were calculated to be 50 µg/L and 200 µg/L, respectively.

Removal of Aqueous Uranyl and Arsenate Mixtures after Reaction with Limestone, PO43-, and Ca2.

The co-occurrence of uranyl and arsenate in contaminated water caused by natural processes and mining is a concern for impacted communities, including in Native American lands in the U.S. Southwest. We investigated the simultaneous removal of aqueous uranyl and arsenate after the reaction with limestone and precipitated hydroxyapatite (HAp, Ca10(PO4)6(OH)2). In benchtop experiments with an initial pH of 3.0 and initial concentrations of 1 mM U and As, uranyl and arsenate coprecipitated in the presence of 1 g L-1 limestone. However, related experiments initiated under circumneutral pH conditions showed that uranyl and arsenate remained soluble. Upon addition of 1 mM PO43- and 3 mM Ca2+ in solution (initial concentration of 0.05 mM U and As) resulted in the rapid removal of over 97% of U via Ca-U-P precipitation. In experiments with 2 mM PO43- and 10 mM Ca2+ at pH rising from 7.0 to 11.0, aqueous concentrations of As decreased (between 30 and 98%) circa pH 9. HAp precipitation in solids was confirmed by powder X-ray diffraction and scanning electron microscopy/energy dispersive X-ray. Electron microprobe analysis indicated U was coprecipitated with Ca and P, while As was mainly immobilized through HAp adsorption. The results indicate that natural materials, such as HAp and limestone, can effectively remove uranyl and arsenate mixtures.

Enhancing arsenate metabolism in Microcystis aeruginosa and relieving risks of arsenite and microcystins by nano-Fe2O3 under dissolved organic phosphorus conditions.

Little information is available on how nano-Fe2O3 substituted iron ions as a possible iron source impacting on algal growth and arsenate (As(V)) metabolism under dissolved organic phosphorus (DOP) (D-glucose-6-phosphate (GP)) conditions. We investigated the growth of Microcystis aeruginosa and As(V) metabolism together with their metabolites in As(V) aquatic environments with nano-Fe2O3 and GP as the sole iron and P sources, respectively. Results showed that nano-Fe2O3 showed inhibitory effects on M. aeruginosa growth and microcystin (MCs) release under GP conditions in As(V) polluted water. There was little influence on As species changes in GP media under different nano-Fe2O3 concentrations except for obvious total As (TAs) removal in 100.0 mg L-1 nano-Fe2O3 levels. As(V) metabolism dominated with As(V) biotransformation in algal cells was facilitated and arsenite (As(III)) releasing risk was relieved clearly by nano-Fe2O3 under GP conditions. The dissolved organic matter (DOM) in media exhibited more fatty acid analogs containing -CO, -CH2 =CH2, and -CH functional groups with increasing nano-Fe2O3 concentrations, but the fluorescent analogs were relatively reduced especially for the fluorescent DOM dominated by aromatic protein-like tryptophan which was significantly inhibited by nano-Fe2O3. Thus, As methylation that was facilitated in M. aeruginosa by nano-Fe2O3 in GP environments also caused more organic substances to release that absorb infrared spectra while reducing the release risks of As(III) and MCs as well as protein-containing tryptophan fractions. From 1H-NMR analysis, this might be caused by the increased metabolites of aromatic compounds, organic acid/amino acid, and carbohydrates/glucose in algal cells. The findings are vital for a better understanding of nano-Fe2O3 role-playing in As bioremediation by microalgae and the subsequent potential aquatic ecological risks.

The influences of dissolved inorganic and organic phosphorus on arsenate toxicity in marine diatom Skeletonema costatum and dinoflagellate Amphidinium carterae.

In this study, arsenate (As(V)) uptake, bioaccumulation, subcellular distribution and biotransformation were assessed in the marine diatom Skeletonema costatum and dinoflagellate Amphidinium carterae cultured in dissolved inorganic phosphorus (DIP) and dissolved organic phosphorus (DOP). The results of 3-days As(V) exposure showed that As(V) was more toxic in DOP cultures than in DIP counterparts. The higher As accumulation contributed to more severe As(V) toxicity. The 4-h As(V) uptake kinetics followed Michaelis-Menten kinetics. The maximum uptake rates were higher in DOP cultures than those in DIP counterparts. After P addition, the half-saturation constants remained constant in S. costatum (2.42-3.07 µM) but decreased in A. carterae (from 10.9 to 3.8 µM) compared with that in the respective P-depleted counterparts. During long-term As(V) exposure, A. carterae accumulated more As than S. costatum. Simultaneously, As(V) was reduced and transformed into organic As species in DIP-cultured S. costatum, which was severely inhibited in their DOP counterparts. Only As(V) reduction occurred in A. carterae. Overall, this study demonstrated species-specific effects of DOP on As(V) toxicity, and thus provide a new insight into the relationship between As contamination and eutrophication on the basis of marine microalgae.

Arsenic triggered nano-sized uranyl arsenate precipitation on the surface of Kocuria rosea.

Arsenic (As) and uranium (U) frequently occur together naturally and, in consequence, transform into cocontaminants at sites of uranium mining and processing, yet the simultaneous interaction process of arsenic and uranium has not been well documented. In the present contribution, the influence of arsenate on the removal and reduction of uranyl by the indigenous microorganism Kocuria rosea was characterized using batch experiments combined with species distribution calculation, SEM-EDS, FTIR, XRD and XPS. The results showed that the coexistence of arsenic plays an active role in Kocuria rosea growth and the removal of uranium under neutral and slightly acidic conditions. U-As complex species of UO2HAsO4 (aq) had a positive effect on uranium removal, while Kocuria rosea cells appeared to have a large specific surface area serving as attachment sites. Furthermore, a large number of nano-sized flaky precipitates, constituted by uranium and arsenic, attached to the surface of Kocuria rosea cells at pH 5 through P=O, COO-, and C=O groups in phospholipids, polysaccharides, and proteins. The biological reduction of U(VI) and As(V) took place in a successive way, and the formation of a chadwickite-like uranyl arsenate precipitate further inhibited U(VI) reduction. The results will help to design more effective bioremediation strategies for arsenic-uranium cocontamination.

Insights into the conversion of dissolved organic phosphorus favors algal bloom, arsenate biotransformation and microcystins release of Microcystis aeruginosa.

Little information is available on influences of the conversion of dissolved organic phosphorus (DOP) to inorganic phosphorus (IP) on algal growth and subsequent behaviors of arsenate (As(V)) in Microcystis aeruginosa (M. aeruginosa). In this study, the influences factors on the conversion of three typical DOP types including adenosine-5-triphosphate disodium salt (ATP), ß-glycerophosphate sodium (ßP) and D-glucose-6-phosphate disodium salt (GP) were investigated under different extracellular polymeric secretions (EPS) ratios from M. aeruginosa, and As(V) levels. Thus, algal growth, As(V) biotransformation and microcystins (MCs) release of M. aeruginosa were explored in the different converted DOP conditions compared with IP. Results showed that the three DOP to IP without EPS addition became in favor of algal growth during their conversion. Compared with IP, M. aeruginosa growth was thus facilitated in the three converted DOP conditions, subsequently resulting in potential algal bloom particularly at arsenic (As) contaminated water environment. Additionally, DOP after conversion could inhibit As accumulation in M. aeruginosa, thus intracellular As accumulation was lower in the converted DOP conditions than that in IP condition. As(V) biotransformation and MCs release in M. aeruginosa was impacted by different converted DOP with their different types. Specifically, DMA concentrations in media and As(III) ratios in algal cells were promoted in converted ßP condition, indicating that the observed dissolved organic compositions from ßP conversion could enhance As(V) reduction in M. aeruginosa and then accelerate DMA release. The obtained findings can provide better understanding of cyanobacteria blooms and As biotransformation in different DOP as the main phosphorus source.

Ecological Responses of Maize Rhizosphere to Antibiotics Entering the Agricultural System in an Area with High Arsenicals Geological Background.

Metal(loid)s can promote the spread and enrichment of antibiotic resistance in the environmental ecosystem through a co-selection effect. Little is known about the ecological effects of entering antibiotics into the environment with long-term metal(loid)s' resistance profiles. Here, cow manure containing oxytetracycline (OTC) or sulfadiazine (SA) at four concentrations (0 (as control), 1, 10, and 100 mg/kg) was loaded to a maize cropping system in an area with high a arsenicals geological background. Results showed that exogenous antibiotics entering significantly changed the nutrient conditions, such as the concentration of nitrate nitrogen, ammonium nitrogen, and available phosphorus in the maize rhizosphere soil, while total arsenic and metals did not display any differences in antibiotic treatments compared with control. Antibiotics exposure significantly influenced nitrate and nitrite reductase activities to reflect the inhibition of denitrification rates but did not affect the soil urease and acid phosphatase activities. OTC treatment also did not change soil dehydrogenase activities, while SA treatment posed promotion effects, showing a tendency to increase with exposure concentration. Both the tested antibiotics (OTC and SA) decreased the concentration of arsenite and arsenate in rhizosphere soil, but the inhibition effects of the former were higher than that of the latter. Moreover, antibiotic treatment impacted arsenite and arsenate levels in maize root tissue, with positive effects on arsenite and negative effects on arsenate. As a result, both OTC and SA treatments significantly increased bioconcentration factors and showed a tendency to first increase and then decrease with increasing concentration. In addition, the treatments decreased translocation capacity of arsenic from roots to shoots and showed a tendency to increase translocation factors with increasing concentration. Microbial communities with arsenic-resistance profiles may also be resistant to antibiotics entering.

The combined impacts of selenium and phosphorus on the fate of arsenic in rice seedlings (Oryza sativa L.).

Although the single role of selenium (Se) or phosphorus (P) in regulating the As contamination of rice plants has been reported in some studies, the combined impacts of Se and P on the fate of As and the underlying mechanisms are poorly understood. To address this knowledge gap, the uptake, translocation, and biotransformation of As mediated by Se were investigated in rice (Oryza sativa L.) seedlings hydroponically cultured with P-normal and P-deficient conditions. The results showed Se addition stimulated the uptake of arsenite and arsenate by 15.6% and 30.7%, respectively in P-normal condition, and such effect was more profound in P-deficient condition with the value of 43.8% and 70.8%. However, regardless of Se addition, P-deficiency elevated the As uptake by 47.0%-92.1% for arsenate but had no obvious effects for arsenite. Accompanying with the As transfer factorShoot/Root reduced by 74.5%-80.2% and 71.1%-85.7%, Se addition decreased the shoot As content by 65.8%-69.7% and 59.6%-73.1%, respectively, in the arsenite- and arsenate-treated rice plants. Relative to the corresponding treatments of P-normal condition, P-deficiency reduced the As transfer factorShoot/Root by 38.9%-52.5% and thus decreasing the shoot As content by 35.2%-42.5% in the arsenite-treated plants; while the opposite impacts were observed in the arsenate-treated plants, in which the shoot As content was increased by 22.4%-83.7%. The analysis results of As species showed As(III) was dominant in both shoots (68.9%-75.1%) and roots (94.9%-97.2%), and neither Se addition nor P-deficiency had obvious impacts on the interconversion between As(III) and As(V). Our results demonstrate the regulating roles of Se in As accumulation mainly depend on P regimes and the specific rice tissues, but the effects of P-deficiency on the fate of As were influenced by the form of As added to the culture.

Selenium Increased Arsenic Accumulation by Upregulating the Expression of Genes Responsible for Arsenic Reduction, Translocation, and Sequestration in Arsenic Hyperaccumulator Pteris vittata.

Selenate enhances arsenic (As) accumulation in As-hyperaccumulator Pteris vittata, but the associated molecular mechanisms are unclear. Here, we investigated the mechanisms of selenate-induced arsenic accumulation by exposing P. vittata to 50 µM arsenate (AsV50) and 1.25 (Se1.25) or 5 µM (Se5) selenate in hydroponics. After 2 weeks, plant biomass, plant As and Se contents, As speciation in plant and growth media, and important genes related to As detoxification in P. vittata were determined. These genes included P transporters PvPht1;3 and PvPht1;4 (AsV uptake), arsenate reductases PvHAC1 and PvHAC2 (AsV reduction), and arsenite (AsIII) antiporters PvACR3 and PvACR3;2 (AsIII translocation) in the roots, and AsIII antiporters PvACR3;1 and PvACR3;3 (AsIII sequestration) in the fronds. The results show that Se1.25 was more effective than Se5 in increasing As accumulation in both P. vittata roots and fronds, which increased by 27 and 153% to 353 and 506 mg kg-1. The As speciation analyses show that selenate increased the AsIII levels in P. vittata, with 124-282% more AsIII being translocated into the fronds. The qPCR analyses indicate that Se1.25 upregulated the gene expression of PvHAC1 by 1.2-fold, and PvACR3 and PvACR3;2 by 1.0- to 2.5-fold in the roots, and PvACR3;1 and PvACR3;3 by 0.6- to 1.1-fold in the fronds under AsV50 treatment. Though arsenate enhanced gene expression of P transporters PvPht1;3 and PvPht1;4, selenate had little effect. Our results indicate that selenate effectively increased As accumulation in P. vittata, mostly by increasing reduction of AsV to AsIII in the roots, AsIII translocation from the roots to fronds, and AsIII sequestration into the vacuoles in the fronds. The results suggest that selenate may be used to enhance phytoremediation of As-contaminated soils using P. vittata.

Trace metal content from holopelagic Sargassum spp. sampled in the tropical North Atlantic Ocean: Emphasis on spatial variation of arsenic and phosphorus.

We document for the first time, the spatial distribution at basin scale (North tropical Atlantic Ocean) of As, P and trace metal (TM) concentrations in the three morphotypes belonging to the two holopelagic species Sargassum natans and S. fluitans and three morphotypes: S. natans VIII, S. natans I and S. fluitans III. These samples collected in the North equatorial current (NEC) and in the subtropical Sargasso Sea (sSS) (∼25°N, 60°W) were also compared to coastal samples collected downwind Guadeloupe Island and on the strand of Martinique (mangrove and beach). Along the studied zonal oceanic transect, the highest values of As (range 120-240 µg g-1, dry weight, dw) were found in the sSS area where primary production is highly limited by phosphorus. At these stations, the P content of Sargassum spp. was minimal (range 500-1000 µg g-1, dw) as well as the content in Cd and Zn known for their nutrient-like oceanic behaviors and distributions very similar to P. This illustrates for the first time in the natural environment, the higher bioaccumulation of arsenic in Sargassum spp. in P-limiting conditions which is due to the competition in the phosphate transporter between arsenate and phosphate. As compared to samples collected at sea, the Sargassum spp. collected in the strand of Martinique had (1) lower As concentrations (typical range 30-45 µg g-1, dw) and (2) much higher Al, Fe, Mn, Cr and Co concentrations, showing a certain ability of Sargassum spp. to be depurated of its As content in the coastal zone following competitive exchange with terrigenous metals.

Biological effect of phosphate on the dissimilatory arsenate-respiring bacteria-catalyzed reductive mobilization of arsenic from contaminated soils.

Dissimilatory arsenate-respiring prokaryotes (DARPs) are considered to be the major drive of the reductive mobilization of arsenic from solid phases. However, it is not fully understood how phosphate, a structural analog of arsenate, affects the DARPs-mediated arsenic mobilization. This work aimed to address this issue. As-contaminated soils were collected from a Shimen Realgar Mine-affected area. We identified a unique diversity of DARPs from the soils, which possess high As(V)-respiring activities using one of multiple small organic acids as the electron donor. After elimination of the desorption effect of phosphate on the As mobilization, the supplement of additional 10 mM phosphate to the active slurries markedly increased the microbial community-mediated reductive mobilization of arsenic as revealed by microcosm tests; this observation was associated to the fact that phosphate significantly increased the As(V)-respiratory reductase (Arr) gene abundances in the slurries. To confirm this finding, we further obtained a new DARP strain, Priestia sp. F01, from the samples. We found that after elimination of the chemical effect of phosphate, the supplement of 10 mM phosphate to the active slurries resulted in an 82.2% increase of the released As(III) in the solutions, which could be contributed to that excessive phosphate greatly increased the Arr gene abundance, and enhanced the transcriptional level of arrA gene and the bacterial As(V)-respiring activity of F01 cells. Considering that phosphate commonly coexists with As in the environment, and is a frequently-used fertilizer, these findings are helpful for deeply understanding why As concentrations in contaminated groundwater are dynamically fluctuated, and also provided new knowledge on the interactions between the biogeochemical processes of P and As.

Biogenesis of selenium nanospheres using Halomonas venusta strain GUSDM4 exhibiting potent environmental applications.

Selenite reducing bacterial strain (GUSDM4) isolated from Mandovi estuary of Goa, India was identified as Halomonas venusta based on 16S rRNA gene sequence analysis. Its maximum tolerance level for sodium selenite (Na2SeO3) was 100 mM. The 2, 3-diaminonaphthalene-based spectroscopic analysis demonstrated 96 and 93% reduction of 2 and 4 mM Na2SeO3 respectively to elemental selenium (Se0) during the late stationary growth phase. Biosynthesis of Se nanoparticles (SeNPs) commenced within 4 h during the log phase, which was evident from the brick red color in the growth medium and a characteristic peak at 265 nm revealed by UV-Vis spectrophotometry. The intracellular periplasmic synthesis of SeNPs in GUSDM4 was confirmed by transmission electron microscopy (TEM). Characterization of SeNPs by X-ray crystallography, TEM and energy-dispersive X-ray analysis (EDAX) clearly demonstrated spherical SeNPs of 20-80 nm diameter with hexagonal crystal lattice. SeNPs (0.8 and 1 mg/L) primed seeds under arsenate [As(V)] stress showed increase in shoot length, root length and biomass by 1.4-, 1.5- and 1.1-fold respectively, as compared to As(V) primed seeds alone. The proline and phenolic content in seeds primed with SeNPs under arsenate stress showed alleviated levels proving its ameliorative potential. SeNPs also demonstrated anti-biofilm activity at 20 µg/mL against human pathogens which was evident by scanning electron microscopic (SEM) analysis. SeNPs interestingly revealed mosquito larvicidal activity also. Therefore, these studies have clearly demonstrated amazing potential of the marine bacterium, Halomonas venusta in biosynthesis of SeNPs and their applications as ameliorative, anti-biofilm and mosquito larvicidal agents which is the first report of its kind.

Selenium alleviates physiological traits, nutrient uptake and nitrogen metabolism in rice under arsenate stress.

A green house experiment was conducted to evaluate the efficacy of soil application of selenium (Se) in modulating metabolic changes in rice under arsenic (As) stress. Rice plants were grown over soil amended with sodium arsenate (25, 50 and 100 µM kg-1 soil) with or without sodium selenate @ 0.5 and 1 mg kg-1 soil in a complete randomized experimental design, and photosynthetic efficiency, nutrient uptake and nitrogen metabolism in rice leaves were estimated at tillering and grain filling stages. Se treatments significantly improved the toxic effects of As on plant height, leaf dry weight and grain yield. Arsenate treatment reduced uptake of Na, Mg, P, K, Ca, Mn, Fe and Zn and lowered chlorophyll, carotenoids and activities of enzymes of nitrogen metabolism (nitrate reductase, nitrite reductase, glutamine synthase and glutamate synthase) in rice leaves at both the stages in a dose-dependent fashion. Se application along with As improved photosynthesis, nutrient uptake and arsenate-induced effects on activities of enzymes of nitrogen metabolism with maximum impact shown by As50 + Se1 combination. Application of Se can modulate photosynthetic efficiency, nutrient uptake and alterations in nitrogen metabolism in rice Cv PR126 due to As stress that helped plants to adapt to excess As and resulted in improved plant growth.

Interplay between arsenic and selenium biomineralization in Shewanella sp. O23S.

Bacteria play crucial roles in the biogeochemical cycle of arsenic (As) and selenium (Se) as these elements are metabolized via detoxification, energy generation (anaerobic respiration) and biosynthesis (e.g. selenocysteine) strategies. To date, arsenic and selenium biomineralization in bacteria were studied separately. In this study, the anaerobic metabolism of As and Se in Shewanella sp. O23S was investigated separately and mixed, with an emphasis put on the biomineralization products of this process. Multiple analytical techniques including ICP-MS, TEM-EDS, XRD, Micro-Raman, spectrophotometry and surface charge (zeta potential) were employed. Shewanella sp. O23S is capable of reducing selenate (SeO42-) and selenite (SeO32-) to red Se(-S)0, and arsenate (AsO43-) to arsenite (AsO33-). The release of H2S from cysteine led to the precipitation of AsS minerals: nanorod AsS and granular As2S3. When As and Se oxyanions were mixed, both As-S and Se(-S)0 biominerals were synthesized. All biominerals were extracellular, amorphous and presented a negative surface charge (-24 to -38 mV). Kinetic analysis indicated the following reduction yields: SeO32- (90%), AsO43- (60%), and SeO42- (<10%). The mix of SeO32- with AsO43- led to a decrease in As removal to 30%, while Se reduction yield was unaffected (88%). Interestingly, SeO42- incubated with AsO43- boosted the Se removal (71%). The exclusive extracellular formation of As and Se biominerals might indicate an extracellular respiratory process characteristic of various Shewanella species and strains. This is the first study documenting a complex interplay between As and Se oxyanions: selenite decreased arsenate reduction, whereas arsenate stimulated selenate reduction. Further investigation needs to clarify whether Shewanella sp. O23S employs multi-substrate respiratory enzymes or separate, high affinity enzymes for As and Se oxyanion respiration.

Positional Assignment of C-C Double Bonds in Fatty Acyl Chains of Intact Arsenosugar Phospholipids Occurring in Seaweed Extracts by Epoxidation Reactions.

Water-soluble diacyl arsenosugar phospholipids (As-PL) are natural products widespread in marine animals and algae, including the brown alga Undaria pinnatifida, also known as wakame. The systematic recognition of As-PL has been hampered by the lack of standard and of qualitative methods to establish the carbon-carbon double bond positions of unsaturated fatty acyl chains. Here, the epoxidation reaction of fatty acyl substituents of As-PL was carried out with high selectivity by meta-chloroperoxybenzoic acid and the C-C double bond localization was established by collision-induced dissociation of epoxidized species as deprotonated molecules, [epoM - H]-. Reversed-phase liquid chromatography (RPLC) separation and a sequential triple-stage MS (i.e., MS3) analysis of unsaturated and epoxidized As-PL were very helpful to characterize the carbon-carbon double bond locations of both sn-1 and sn-2 fatty acyl chains, starting from a diagnostic product ion pair with 16.0 Da mass difference. These results indicate that intact As-PL can be annotated in terms of fatty acyl chain composition and in terms of their C-C double bond position(s). Interestingly, hexadecenoic (16:1 Δ9) and octadecenoic (18:1 Δ9) along with octadecadienoic (18:2 Δ9,12) and octadecatrienoic (18:3 Δ9,12,15) were found to be the most abundant unsaturated fatty acyl chains of As-PL in the brown alga wakame, thus confirming it as a good source of essential fatty acids with a balanced ω6/ω3 ratio. Although the toxicity of As-including metabolites of algal As-PL is still a matter of debate and needs to be studied in more detail, the described approach can be exploited to assess if As-PL could contribute to the supply of essential fatty acids related to the use of algae as nutritious food.

Arsenic speciation analysis in porewater by a novel colorimetric assay.

Arsenic is common toxic contaminant, but tracking its mobility through submerged soils is difficult because microscale processes dictate its speciation and affinity to minerals. Analyses on environmental dissolved arsenic (As) species such as arsenate and arsenite currently require highly specialized equipment and large sample volumes. In an effort to unravel arsenic dynamics in sedimentary porewater, a novel, highly sensitive, and field-usable colorimetric assay requiring 100 µL of sample was developed. Two complementary protocols are presented, suitable for sub-micromolar and micromolar ranges. Phosphate is a main interfering substance, but can be separated by measuring phosphate and arsenate under two different acidities. Arsenite is assessed by oxidation of arsenite to arsenate in the low-acidity reagent. Optimization of the protocol and spectral analyses resulted in elimination of various interferences (silicate, iron, sulfide, sulfate), and the assay is applicable across a wide range of salinities and porewater compositions. The new assay was used to study As mobilization processes through the soil of a contaminated brook. Water column sources of arsenic were limited to a modest input by a groundwater source along the flow path. In one of the sites, the arsenite and arsenate porewater profiles showed active iron-driven As redox cycling in the soil, which may play a role in arsenic mobilization and releases arsenite and arsenate into the brook water column. Low arsenic concentrations downstream from the source sites indicated arsenic retention by soil and dilution with additional sources of water. Arsenic is thus retained by the Bossegraben before it merges with larger rivers.

The Ubiquitin E3 Ligase PRU2 Modulates Phosphate Uptake in Arabidopsis.

Phosphorus is an essential macronutrient for plants. The phosphate (Pi) concentration in soil solutions is typically low, and plants always suffer from low-Pi stress. During Pi starvation, a number of adaptive mechanisms in plants have evolved to increase Pi uptake, whereas the mechanisms are not very clear. Here, we report that an ubiquitin E3 ligase, PRU2, modulates Pi acquisition in Arabidopsis response to the low-Pi stress. The mutant pru2 showed arsenate-resistant phenotypes and reduced Pi content and Pi uptake rate. The complementation with PRU2 restored these to wild-type plants. PRU2 functioned as an ubiquitin E3 ligase, and the protein accumulation of PRU2 was elevated during Pi starvation. PRU2 interacted with a kinase CK2α1 and a ribosomal protein RPL10 and degraded CK2α1 and RPL10 under low-Pi stress. The in vitro phosphorylation assay showed that CK2α1 phosphorylated PHT1;1 at Ser-514, and prior reports demonstrated that the phosphorylation of PHT1;1 Ser-514 resulted in PHT1;1 retention in the endoplasmic reticulum. Then, the degradation of CK2α1 by PRU2 under low-Pi stress facilitated PHT1;1 to move to the plasma membrane to increase Arabidopsis Pi uptake. Taken together, this study demonstrated that the ubiquitin E3 ligase-PRU2-was an important positive regulator in modulating Pi acquisition in Arabidopsis response to low-Pi stress.

Insight into the role and mechanism of polysaccharide in polymorphous magnesium oxide nanoparticle synthesis for arsenate removal.

The low cost and non-toxic of magnesium oxides make it a potential eco-friendly material for arsenic removal. Polysaccharide is a kind of green modifier to obtain nanoscale MgO particles with a higher adsorption affinity. In this study, the impact of chain structures of polysaccharides on the morphology features and arsenate removal efficiency of MgO-NPs were investigated. Pullulan and starch facilitated the synthesis of flower-like MgO-NPs, and pectin facilitated the synthesis of plate-like ones. Although the two kinds of flower-like MgO-NPs undergone similar time to reach equilibrium, the one obtained from the starch-synthesis route showed a higher arsenate adsorption capacity (98 mg g-1), due to that their bushy and smaller petals on the surface provide more active sites for arsenic adsorption. The pectin-synthesis route also produced MgO-NPs with higher arsenate adsorption capacity (101 mg g-1), ascribed to stacking of nano-plates on their surfaces facilitated to form defect surfaces. However, due to their lower BET area, the plate-like MgO-NPs took twice times to reach equilibrium for arsenic adsorption compared with the others. In the stage for the hydrolysis of MgO, hydroxyl groups on the polymer chain provide active sites to physically trap or bond with MgO particles and then to produce hydrolyzed precursors. The poly chain containing inter- and intra-hydroxyl groups directed MgO molecular growing into hydroxide crystals with 3D frameworks during their nucleation and growth. However, pectin only provides inter-hydroxyl groups and directs to form hydroxides with 2D frameworks. Furthermore, the rapid-nucleation vs. slow-growth model in the stage of pyrolysis of hydroxide crystals successfully interprets the thinner petals and complex chemical phases of the final nanoparticles obtained from the pullulan-synthesis route. This work may provide direction and perspectives for the rational design of well-performing MgO materials for arsenate removal.

A Panax notoginseng phosphate transporter, PnPht1;3, greatly contributes to phosphate and arsenate uptake.

The crisis of arsenic (As) accumulation in rhizomes threatens the quality and safety of Panax notoginseng (Burk.) F.H. Chen, which is a well-known traditional Chinese herb with a long clinical history. The uptake of arsenate (AsV) could be suppressed by supplying phosphate (Pi), in which Pi transporters play important roles in the uptake of Pi and AsV. Herein, the P . notoginseng Pi transporter-encoding gene PnPht1;3 was identified and characterised under Pi deficiency and AsV exposure. In this study, the open reading frame (ORF) of PnPht1;3 was cloned according to RNA-seq and encoded 545 amino acids. The relative expression levels revealed that PnPht1;3 was significantly upregulated under phosphate deficiency and AsV exposure. Heterologous expression in Saccharomyces cerevisiae MB192 demonstrated that PnPht1;3 performed optimally in complementing the yeast Pi-transport defect and accumulated more As in the cells. Combined with the subcellular localisation prediction, it was concluded that PnPht1;3 encodes a functional plasma membrane-localised transporter protein that mediates putative high-affinity Pi/H+ symport activity and enhances the uptake of Pi and AsV. Therefore, a better understanding of the roles of the P . notoginseng Pi transporter could provide new insight for solving As accumulation in medicinal plants.

Selenium alleviates arsenic induced stress by modulating growth, oxidative stress, antioxidant defense and thiol metabolism in rice seedlings.

This study aims to investigate the potentiality of selenium in modulating arsenic stress in rice seedlings. Arsenate accumulation along with its transformation to arsenite was enhanced in arsenate exposed seedlings. Arsenite induced oxidative stress and severely affected the growth of the seedlings. Arsenate exposure caused an elevation in ascorbate and glutathione levels along with the activities of their metabolizing enzymes viz., ascorbate peroxidase, glutathione reductase, glutathione-S-transferase, and glutathione peroxidase. Phytochelatins content was increased under arsenic stress to subdue the toxic effects in the test seedlings. Co-application of arsenate and selenate in rice seedlings manifested pronounced alteration of oxidative stress, antioxidant defense, and thiol metabolism as compared to arsenate treatment only. ANOVA analysis (Tukey's HSD test) demonstrated the relevance of using selenate along with arsenate to maintain the normal growth and development of rice seedlings. Thus, exogenous supplementation of selenium will be a beneficial approach to cultivate rice seedlings in arsenic polluted soil.

Arsenic toxicity in the environment is a global concern, causes chronic signs of poisoning to plants and humans, leads to ecological imbalance. Selenium is known for its antagonistic characteristics and has been found to be effective in combating the adversities of arsenic at low concentrations (5 µM). The present study was performed to explore the comparative responses of rice seedlings during the joint application of selenium and arsenic in terms of growth, generation of oxidative stress, antioxidant defense, and thiol metabolism. Although the molecular basis of arsenic­selenium interaction is widely known a small number of reports were listed about the physio-chemical role of selenium against arsenic stress. Thus, we investigated the influence of selenium to alleviate arsenic-induced toxic effects by modulating the activities of antioxidant enzymes and reducing the levels of oxidative stress markers. It has been noted that selenium regulates thiol metabolism which is known to play a key role in growth preservation by restriction of arsenic translocation. The outcome from the study would be useful in field trials for sustainable agriculture in arsenic-contaminated soil.