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Sample records for respiratory arsenate reductase

  1. Respiratory arsenate reductase as a bidirectional enzyme

    SciTech Connect

    Richey, Christine; Chovanec, Peter; Hoeft, Shelley E.; Oremland, Ronald S.; Basu, Partha; Stolz, John F.

    2009-05-01

    The haloalkaliphilic bacterium Alkalilimnicola ehrlichii is capable of anaerobic chemolithoautotrophic growth by coupling the oxidation of arsenite (As(III)) to the reduction of nitrate and carbon dioxide. Analysis of its complete genome indicates that it lacks a conventional arsenite oxidase (Aox), but instead possesses two operons that each encode a putative respiratory arsenate reductase (Arr). Here we show that one homolog is expressed under chemolithoautotrophic conditions and exhibits both arsenite oxidase and arsenate reductase activity. We also demonstrate that Arr from two arsenate respiring bacteria, Alkaliphilus oremlandii and Shewanella sp. strain ANA-3, is also biochemically reversible. Thus Arr can function as a reductase or oxidase. Its physiological role in a specific organism, however, may depend on the electron potentials of the molybdenum center and [Fe-S] clusters, additional subunits, or constitution of the electron transfer chain. This versatility further underscores the ubiquity and antiquity of microbial arsenic metabolism.

  2. Respiratory arsenate reductase as a bidirectional enzyme

    USGS Publications Warehouse

    Richey, C.; Chovanec, P.; Hoeft, S.E.; Oremland, R.S.; Basu, P.; Stolz, J.F.

    2009-01-01

    The haloalkaliphilic bacterium Alkalilimnicola ehrlichii is capable of anaerobic chemolithoautotrophic growth by coupling the oxidation of arsenite (As(III)) to the reduction of nitrate and carbon dioxide. Analysis of its complete genome indicates that it lacks a conventional arsenite oxidase (Aox), but instead possesses two operons that each encode a putative respiratory arsenate reductase (Arr). Here we show that one homolog is expressed under chemolithoautotrophic conditions and exhibits both arsenite oxidase and arsenate reductase activity. We also demonstrate that Arr from two arsenate respiring bacteria, Alkaliphilus oremlandii and Shewanella sp. strain ANA-3, is also biochemically reversible. Thus Arr can function as a reductase or oxidase. Its physiological role in a specific organism, however, may depend on the electron potentials of the molybdenum center and [Fe–S] clusters, additional subunits, or constitution of the electron transfer chain. This versatility further underscores the ubiquity and antiquity of microbial arsenic metabolism.

  3. The respiratory arsenate reductase from Bacillus selenitireducens strain MLS10

    USGS Publications Warehouse

    Afkar, E.; Lisak, J.; Saltikov, C.; Basu, P.; Oremland, R.S.; Stolz, J.F.

    2003-01-01

    The respiratory arsenate reductase from the Gram-positive, haloalkaliphile, Bacillus selenitireducens strain MLS10 was purified and characterized. It is a membrane bound heterodimer (150 kDa) composed of two subunits ArrA (110 kDa) and ArrB (34 kDa), with an apparent Km for arsenate of 34 ??M and Vmax of 2.5 ??mol min-1 mg-1. Optimal activity occurred at pH 9.5 and 150 g l-1 of NaCl. Metal analysis (inductively coupled plasma mass spectrometry) of the holoenzyme and sequence analysis of the catalytic subunit (ArrA; the gene for which was cloned and sequenced) indicate it is a member of the DMSO reductase family of molybdoproteins. ?? 2003 Federation of European Microbiological Societies. Published by Elsevier B.V. All rights reserved.

  4. Diversity of Arsenate Respiratory Reductase Genes Along Gradients of Arsenate and Arsenite Within Hypersaline, Alkaline Sediments

    NASA Astrophysics Data System (ADS)

    Saltikov, C. W.; Nilsen, J.; Oremland, R. S.; Kulp, T. R.; Hoeft, S. E.; Miller, L. G.; Switzer Blum, J.; Baesman, S.; Han, S.; Lanoil, B.

    2005-12-01

    There are several soda lakes in western United States that contain high arsenic concentrations (up to 4 mM total As). Interestingly, these lakes have high rates of anaerobic arsenate reduction, which is catalyzed by arsenate respiring prokaryotes. Several cultured arsenate respiring prokaryotes have been shown to respire and reduce arsenate via a membrane-associated enzyme, ArrA. This enzyme is present in many diverse arsenate respiring prokaryotes. To investigate arsenate respiring microbial communities within these extreme environments, we used functional gene analysis to detect the presence, abundance, and diversity of the arrA gene in core samples collected from two arsenic enriched, hypersaline, alkaline lakes, Mono Lake and Searles Lake. Each sample exhibited concentration gradients for dissolved arsenic species and oxygen. Porewater arsenite concentration increased with depth and was correlated with oxygen depletion. To investigate the depth dependency of the arrA gene in these core samples we utilized the Malasarn et al. (2004) polymerase chain reaction (PCR) primers to detect a partial arrA gene fragment in nucleic acids extracted from sediment samples. The arrA gene fragment was detected only in the top 1-2 cm of the Mono Lake core and no detection was observed in the Searles Lake homogenized core. After the primers were redesigned to include the nucleotide codon bias for haloalkaliphilic archaea ( Halobacterium), the arrA gene fragments could be detected at each depth interval throughout the Mono Lake core and in the homogenized core of Searles Lake. Work is currently focused on characterizing the diversity and abundance of the arrA gene fragments obtained in each core sample and at different depths. Although no haloalkaliphilic arsenate respiring archaea have been isolated to date, these results suggest that the arrA gene fragments detected in these soda lakes may be of archaeal origins.

  5. Enzyme phylogenies as markers for the oxidation state of the environment: the case of respiratory arsenate reductase and related enzymes.

    PubMed

    Duval, Simon; Ducluzeau, Anne-Lise; Nitschke, Wolfgang; Schoepp-Cothenet, Barbara

    2008-07-16

    Phylogenies of certain bioenergetic enzymes have proved to be useful tools for deducing evolutionary ancestry of bioenergetic pathways and their relationship to geochemical parameters of the environment. Our previous phylogenetic analysis of arsenite oxidase, the molybdopterin enzyme responsible for the biological oxidation of arsenite to arsenate, indicated its probable emergence prior to the Archaea/Bacteria split more than 3 billion years ago, in line with the geochemical fact that arsenite was present in biological habitats on the early Earth. Respiratory arsenate reductase (Arr), another molybdopterin enzyme involved in microbial arsenic metabolism, serves as terminal oxidase, and is thus situated at the opposite end of bioenergetic electron transfer chains as compared to arsenite oxidase. The evolutionary history of the Arr-enzyme has not been studied in detail so far. We performed a genomic search of genes related to arrA coding for the molybdopterin subunit. The multiple alignment of the retrieved sequences served to reconstruct a neighbor-joining phylogeny of Arr and closely related enzymes. Our analysis confirmed the previously proposed proximity of Arr to the cluster of polysulfide/thiosulfate reductases but also unravels a hitherto unrecognized clade even more closely related to Arr. The obtained phylogeny strongly suggests that Arr originated after the Bacteria/Archaea divergence in the domain Bacteria, and was subsequently laterally distributed within this domain. It further more indicates that, as a result of accumulation of arsenate in the environment, an enzyme related to polysulfide reductase and not to arsenite oxidase has evolved into Arr. These findings are paleogeochemically rationalized by the fact that the accumulation of arsenate over arsenite required the increase in oxidation state of the environment brought about by oxygenic photosynthesis.

  6. Prokaryotic arsenate reductase enhances arsenate resistance in Mammalian cells.

    PubMed

    Wu, Dan; Tao, Xuanyu; Wu, Gaofeng; Li, Xiangkai; Liu, Pu

    2014-01-01

    Arsenic is a well-known heavy metal toxicant in the environment. Bioremediation of heavy metals has been proposed as a low-cost and eco-friendly method. This article described some of recent patents on transgenic plants with enhanced heavy metal resistance. Further, to test whether genetic modification of mammalian cells could render higher arsenic resistance, a prokaryotic arsenic reductase gene arsC was transfected into human liver cancer cell HepG2. In the stably transfected cells, the expression level of arsC gene was determined by quantitative real-time PCR. Results showed that arsC was expressed in HepG2 cells and the expression was upregulated by 3 folds upon arsenate induction. To further test whether arsC has function in HepG2 cells, the viability of HepG2-pCI-ArsC cells exposed to arsenite or arsenate was compared to that of HepG2-pCI cells without arsC gene. The results indicated that arsC increased the viability of HepG2 cells by 25% in arsenate, but not in arsenite. And the test of reducing ability of stably transfected cells revealed that the concentration of accumulated trivalent arsenic increased by 25% in HepG2-pCI-ArsC cells. To determine the intracellular localization of ArsC, a fusion vector with fluorescent marker pEGFP-N1-ArsC was constructed and transfected into.HepG2. Laser confocal microscopy showed that EGFP-ArsC fusion protein was distributed throughout the cells. Taken together, these results demonstrated that prokaryotic arsenic resistant gene arsC integrated successfully into HepG2 genome and enhanced arsenate resistance of HepG2, which brought new insights of arsenic detoxification in mammalian cells.

  7. Dissimilatory arsenate reductase activity and arsenate-respiring bacteria in bovine rumen fluid, hamster feces, and the termite hindgut

    USGS Publications Warehouse

    Herbel, M.J.; Switzer, Blum J.; Hoeft, S.E.; Cohen, S.M.; Arnold, L.L.; Lisak, J.; Stolz, J.F.; Oremland, R.S.

    2002-01-01

    Bovine rumen fluid and slurried hamster feces completely reduced millimolar levels of arsenate to arsenite upon incubation under anoxic conditions. This activity was strongly inhibited by autoclaving or aerobic conditions, and partially inhibited by tungstate or chloramphenicol. The rate of arsenate reduction was faster in feces from a population of arsenate-watered (100 ppm) hamsters compared to a control group watered without arsenate. Using radioisotope methods, arsenate reductase activity in hamster feces was also detected at very low concentrations of added arsenate (???10 ??M). Bacterial cultures were isolated from these materials, as well as from the termite hindgut, that grew using H2 as their electron donor, acetate as their carbon source, and arsenate as their respiratory electron acceptor. The three cultures aligned phylogenetically either with well-established enteric bacteria, or with an organism associated with feedlot fecal wastes. Because arsenite is transported across the gut epithelium more readily than arsenate, microbial dissimilatory reduction of arsenate in the gut may promote the body's absorption of arsenic and hence potentiate its toxicity. ?? 2002 Federation of European Microbiological Societies. Published by Elsevier Science B.V. All rights reserved.

  8. The arsenic hyperaccumulating Pteris vittata expresses two arsenate reductases.

    PubMed

    Cesaro, Patrizia; Cattaneo, Chiara; Bona, Elisa; Berta, Graziella; Cavaletto, Maria

    2015-09-28

    Enzymatic reduction of arsenate to arsenite is the first known step in arsenate metabolism in all organisms. Although the presence of one mRNA arsenate reductase (PvACR2) has been characterized in gametophytes of P. vittata, no arsenate reductase protein has been directly observed in this arsenic hyperaccumulating fern, yet. In order to assess the possible presence of arsenate reductase in P. vittata, two recombinant proteins, ACR2-His6 and Trx-His6-S-Pv2.5-8 were prepared in Escherichia coli, purified and used to produce polyclonal antibodies. The presence of these two enzymes was evaluated by qRT-PCR, immunoblotting and direct MS analysis. Enzymatic activity was detected in crude extracts. For the first time we detected and identified two arsenate reductase proteins (PvACR2 and Pv2.5-8) in sporophytes and gametophytes of P. vittata. Despite an increase of the mRNA levels for both proteins in roots, no difference was observed at the protein level after arsenic treatment. Overall, our data demonstrate the constitutive protein expression of PvACR2 and Pv2.5-8 in P. vittata tissues and propose their specific role in the complex metabolic network of arsenic reduction.

  9. The arsenic hyperaccumulating Pteris vittata expresses two arsenate reductases

    PubMed Central

    Cesaro, Patrizia; Cattaneo, Chiara; Bona, Elisa; Berta, Graziella; Cavaletto, Maria

    2015-01-01

    Enzymatic reduction of arsenate to arsenite is the first known step in arsenate metabolism in all organisms. Although the presence of one mRNA arsenate reductase (PvACR2) has been characterized in gametophytes of P. vittata, no arsenate reductase protein has been directly observed in this arsenic hyperaccumulating fern, yet. In order to assess the possible presence of arsenate reductase in P. vittata, two recombinant proteins, ACR2-His6 and Trx-His6-S-Pv2.5–8 were prepared in Escherichia coli, purified and used to produce polyclonal antibodies. The presence of these two enzymes was evaluated by qRT-PCR, immunoblotting and direct MS analysis. Enzymatic activity was detected in crude extracts. For the first time we detected and identified two arsenate reductase proteins (PvACR2 and Pv2.5–8) in sporophytes and gametophytes of P. vittata. Despite an increase of the mRNA levels for both proteins in roots, no difference was observed at the protein level after arsenic treatment. Overall, our data demonstrate the constitutive protein expression of PvACR2 and Pv2.5–8 in P. vittata tissues and propose their specific role in the complex metabolic network of arsenic reduction. PMID:26412036

  10. The arsenic hyperaccumulating Pteris vittata expresses two arsenate reductases

    NASA Astrophysics Data System (ADS)

    Cesaro, Patrizia; Cattaneo, Chiara; Bona, Elisa; Berta, Graziella; Cavaletto, Maria

    2015-09-01

    Enzymatic reduction of arsenate to arsenite is the first known step in arsenate metabolism in all organisms. Although the presence of one mRNA arsenate reductase (PvACR2) has been characterized in gametophytes of P. vittata, no arsenate reductase protein has been directly observed in this arsenic hyperaccumulating fern, yet. In order to assess the possible presence of arsenate reductase in P. vittata, two recombinant proteins, ACR2-His6 and Trx-His6-S-Pv2.5-8 were prepared in Escherichia coli, purified and used to produce polyclonal antibodies. The presence of these two enzymes was evaluated by qRT-PCR, immunoblotting and direct MS analysis. Enzymatic activity was detected in crude extracts. For the first time we detected and identified two arsenate reductase proteins (PvACR2 and Pv2.5-8) in sporophytes and gametophytes of P. vittata. Despite an increase of the mRNA levels for both proteins in roots, no difference was observed at the protein level after arsenic treatment. Overall, our data demonstrate the constitutive protein expression of PvACR2 and Pv2.5-8 in P. vittata tissues and propose their specific role in the complex metabolic network of arsenic reduction.

  11. Properties of the arsenate reductase of plasmid R773.

    PubMed

    Gladysheva, T B; Oden, K L; Rosen, B P

    1994-06-14

    Resistance to toxic oxyanions in Escherichia coli is conferred by the ars operon carried on plasmid R773. The gene products of this operon catalyze extrusion of antimonials and arsenicals from cells of E. coli, thus providing resistance to those toxic oxyanions. In addition, resistance to arsenate is conferred by the product of the arsC gene. In this report, purified ArsC protein was shown to catalyze reduction of arsenate to arsenite. The enzymatic activity of the ArsC protein required glutaredoxin as a source of reducing equivalents. Other reductants, including glutathione and thioredoxin, were not effective electron donors. A spectrophotometric assay was devised in which arsenate reduction was coupled to NADPH oxidation. The results obtained with the coupled assay corresponded to those found by direct reduction of radioactive arsenate to arsenite. The only substrate of the reaction was arsenate (Km = 8 mM); other oxyanions including phosphate, sulfate, and antimonate were not reduced. Phosphate and sulfate were weak inhibitors, while the product, arsenite, was a stronger inhibitor (Ki = 0.1 mM). Arsenate reductase activity exhibited a pH optimum of 6.3-6.8. These results indicate that the ArsC protein is a novel reductase, and elucidation of its enzymatic mechanism should be of interest.

  12. Response to Arsenate Treatment in Schizosaccharomyces pombe and the Role of Its Arsenate Reductase Activity

    PubMed Central

    Matia-González, Ana M.; Sotelo, Jael; Zarco-Fernández, Sonia; Muñoz-Olivas, Riansares; Cámara, Carmen; Rodríguez-Gabriel, Miguel A.

    2012-01-01

    Arsenic toxicity has been studied for a long time due to its effects in humans. Although epidemiological studies have demonstrated multiple effects in human physiology, there are many open questions about the cellular targets and the mechanisms of response to arsenic. Using the fission yeast Schizosaccharomyces pombe as model system, we have been able to demonstrate a strong activation of the MAPK Spc1/Sty1 in response to arsenate. This activation is dependent on Wis1 activation and Pyp2 phosphatase inactivation. Using arsenic speciation analysis we have also demonstrated the previously unknown capacity of S. pombe cells to reduce As (V) to As (III). Genetic analysis of several fission yeast mutants point towards the cell cycle phosphatase Cdc25 as a possible candidate to carry out this arsenate reductase activity. We propose that arsenate reduction and intracellular accumulation of arsenite are the key mechanisms of arsenate tolerance in fission yeast. PMID:22912829

  13. A Hybrid Mechanism for the Synechocystis Arsenate Reductase Revealed by Structural Snapshots during Arsenate Reduction*

    PubMed Central

    Hu, Cuiyun; Yu, Caifang; Liu, Yanhua; Hou, Xianhui; Liu, Xiaoyun; Hu, Yunfei; Jin, Changwen

    2015-01-01

    Evolution of enzymes plays a crucial role in obtaining new biological functions for all life forms. Arsenate reductases (ArsC) are several families of arsenic detoxification enzymes that reduce arsenate to arsenite, which can subsequently be extruded from cells by specific transporters. Among these, the Synechocystis ArsC (SynArsC) is structurally homologous to the well characterized thioredoxin (Trx)-coupled ArsC family but requires the glutaredoxin (Grx) system for its reactivation, therefore classified as a unique Trx/Grx-hybrid family. The detailed catalytic mechanism of SynArsC is unclear and how the “hybrid” mechanism evolved remains enigmatic. Herein, we report the molecular mechanism of SynArsC by biochemical and structural studies. Our work demonstrates that arsenate reduction is carried out via an intramolecular thiol-disulfide cascade similar to the Trx-coupled family, whereas the enzyme reactivation step is diverted to the coupling of the glutathione-Grx pathway due to the local structural difference. The current results support the hypothesis that SynArsC is likely a molecular fossil representing an intermediate stage during the evolution of the Trx-coupled ArsC family from the low molecular weight protein phosphotyrosine phosphatase (LMW-PTPase) family. PMID:26224634

  14. Hyperaccumulation of arsenic in the shoots of Arabidopsis silenced for arsenate reductase (ACR2)

    PubMed Central

    Dhankher, Om Parkash; Rosen, Barry P.; McKinney, Elizabeth C.; Meagher, Richard B.

    2006-01-01

    Endogenous plant arsenate reductase (ACR) activity converts arsenate to arsenite in roots, immobilizing arsenic below ground. By blocking this activity, we hoped to construct plants that would mobilize more arsenate aboveground. We have identified a single gene in the Arabidopsis thaliana genome, ACR2, with moderate sequence homology to yeast arsenate reductase. Expression of ACR2 cDNA in Escherichia coli complemented the arsenate-resistant and arsenate-sensitive phenotypes of various bacterial ars operon mutants. RNA interference reduced ACR2 protein expression in Arabidopsis to as low as 2% of wild-type levels. The various knockdown plant lines were more sensitive to high concentrations of arsenate, but not arsenite, than wild type. The knockdown lines accumulated 10- to 16-fold more arsenic in shoots (350–500 ppm) and retained less arsenic in roots than wild type, when grown on arsenate medium with <8 ppm arsenic. Reducing expression of ACR2 homologs in tree, shrub, and grass species should play a vital role in the phytoremediation of environmental arsenic contamination. PMID:16567632

  15. A novel arsenate reductase from the bacterium Thermus thermophilus HB27: its role in arsenic detoxification.

    PubMed

    Del Giudice, Immacolata; Limauro, Danila; Pedone, Emilia; Bartolucci, Simonetta; Fiorentino, Gabriella

    2013-10-01

    Microorganisms living in arsenic-rich geothermal environments act on arsenic with different biochemical strategies, but the molecular mechanisms responsible for the resistance to the harmful effects of the metalloid have only partially been examined. In this study, we investigated the mechanisms of arsenic resistance in the thermophilic bacterium Thermus thermophilus HB27. This strain, originally isolated from a Japanese hot spring, exhibited tolerance to concentrations of arsenate and arsenite up to 20mM and 15mM, respectively; it owns in its genome a putative chromosomal arsenate reductase (TtarsC) gene encoding a protein homologous to the one well characterized from the plasmid pI258 of the Gram+bacterium Staphylococcus aureus. Differently from the majority of microorganisms, TtarsC is part of an operon including genes not related to arsenic resistance; qRT-PCR showed that its expression was four-fold increased when arsenate was added to the growth medium. The gene cloning and expression in Escherichia coli, followed by purification of the recombinant protein, proved that TtArsC was indeed a thioredoxin-coupled arsenate reductase with a kcat/KM value of 1.2×10(4)M(-1)s(-1). It also exhibited weak phosphatase activity with a kcat/KM value of 2.7×10(-4)M(-1)s(-1). The catalytic role of the first cysteine (Cys7) was ascertained by site-directed mutagenesis. These results identify TtArsC as an important component in the arsenic resistance in T. thermophilus giving the first structural-functional characterization of a thermophilic arsenate reductase.

  16. Computational identification and analysis of arsenate reductase protein in Cronobacter sakazakii ATCC BAA-894 suggests potential microorganism for reducing arsenate.

    PubMed

    Chaturvedi, Navaneet; Singh, Vinay Kumar; Pandey, Paras Nath

    2013-06-01

    This study focuses a bioinformatics-based prediction of arsC gene product arsenate reductase (ArsC) protein in Cronobacter sakazakii BAA-894 strain. A protein structure-based study encloses three-dimensional structural modeling of target ArsC protein, was carried out by homology modeling method. Ultimately, the detection of active binding regions was carried out for characterization of functional sites in protein. The ten probable ligand binding sites were predicted for target protein structure and highlighted the common binding residues between target and template protein. It has been first time identified that modeled ArsC protein structure in C. sakazakii was structurally and functionally similar to well-characterized ArsC protein of Escherichia coli because of having same structural motifs and fold with similar protein topology and function. Investigation revealed that ArsC from C. sakazakii can play significant role during arsenic resistance and potential microorganism for bioremediation of arsenic toxicity.

  17. Adventitious Arsenate Reductase Activity of the Catalytic Domain of the Human Cdc25B and Cdc25C Phosphatases†

    PubMed Central

    Bhattacharjee, Hiranmoy; Sheng, Ju; Ajees, A. Abdul; Mukhopadhyay, Rita; Rosen, Barry P.

    2013-01-01

    A number of eukaryotic enzymes that function as arsenate reductases are homologues of the catalytic domain of the human Cdc25 phosphatase. For example, the Leishmania major enzyme LmACR2 is both a phosphatase and an arsenate reductase, and its structure bears similarity to the structure of the catalytic domain of human Cdc25 phosphatase. These reductases contain an active site C-X5-R signature motif, where C is the catalytic cysteine, the five X residues form a phosphate binding loop, and R is a highly conserved arginine, which is also present in human Cdc25 phosphatases. We therefore investigated the possibility that the three human Cdc25 isoforms might have adventitious arsenate reductase activity. The sequences for the catalytic domains of Cdc25A, -B, and -C were cloned individually into a prokaryotic expression vector, and their gene products were purified from a bacterial host using nickel affinity chromatography. While each of the three Cdc25 catalytic domains exhibited phosphatase activity, arsenate reductase activity was observed only with Cdc25B and -C. These two enzymes reduced inorganic arsenate but not methylated pentavalent arsenicals. Alteration of either the cysteine and arginine residues of the Cys-X5-Arg motif led to the loss of both reductase and phosphatase activities. Our observations suggest that Cdc25B and -C may adventitiously reduce arsenate to the more toxic arsenite and may also provide a framework for identifying other human protein tyrosine phosphatases containing the active site Cys-X5-Arg loop that might moonlight as arsenate reductases. PMID:20025242

  18. All intermediates of the arsenate reductase mechanism, including an intramolecular dynamic disulfide cascade

    PubMed Central

    Messens, Joris; Martins, José C.; Van Belle, Karolien; Brosens, Elke; Desmyter, Aline; De Gieter, Marjan; Wieruszeski, Jean-Michel; Willem, Rudolph; Wyns, Lode; Zegers, Ingrid

    2002-01-01

    The mechanism of pI258 arsenate reductase (ArsC) catalyzed arsenate reduction, involving its P-loop structural motif and three redox active cysteines, has been unraveled. All essential intermediates are visualized with x-ray crystallography, and NMR is used to map dynamic regions in a key disulfide intermediate. Steady-state kinetics of ArsC mutants gives a view of the crucial residues for catalysis. ArsC combines a phosphatase-like nucleophilic displacement reaction with a unique intramolecular disulfide bond cascade. Within this cascade, the formation of a disulfide bond triggers a reversible “conformational switch” that transfers the oxidative equivalents to the surface of the protein, while releasing the reduced substrate. PMID:12072565

  19. Genome-wide Association Mapping Identifies a New Arsenate Reductase Enzyme Critical for Limiting Arsenic Accumulation in Plants

    PubMed Central

    Chao, Dai-Yin; Chen, Yi; Chen, Jiugeng; Shi, Shulin; Chen, Ziru; Wang, Chengcheng; Danku, John M.; Zhao, Fang-Jie; Salt, David E.

    2014-01-01

    Inorganic arsenic is a carcinogen, and its ingestion through foods such as rice presents a significant risk to human health. Plants chemically reduce arsenate to arsenite. Using genome-wide association (GWA) mapping of loci controlling natural variation in arsenic accumulation in Arabidopsis thaliana allowed us to identify the arsenate reductase required for this reduction, which we named High Arsenic Content 1 (HAC1). Complementation verified the identity of HAC1, and expression in Escherichia coli lacking a functional arsenate reductase confirmed the arsenate reductase activity of HAC1. The HAC1 protein accumulates in the epidermis, the outer cell layer of the root, and also in the pericycle cells surrounding the central vascular tissue. Plants lacking HAC1 lose their ability to efflux arsenite from roots, leading to both increased transport of arsenic into the central vascular tissue and on into the shoot. HAC1 therefore functions to reduce arsenate to arsenite in the outer cell layer of the root, facilitating efflux of arsenic as arsenite back into the soil to limit both its accumulation in the root and transport to the shoot. Arsenate reduction by HAC1 in the pericycle may play a role in limiting arsenic loading into the xylem. Loss of HAC1-encoded arsenic reduction leads to a significant increase in arsenic accumulation in shoots, causing an increased sensitivity to arsenate toxicity. We also confirmed the previous observation that the ACR2 arsenate reductase in A. thaliana plays no detectable role in arsenic metabolism. Furthermore, ACR2 does not interact epistatically with HAC1, since arsenic metabolism in the acr2 hac1 double mutant is disrupted in an identical manner to that described for the hac1 single mutant. Our identification of HAC1 and its associated natural variation provides an important new resource for the development of low arsenic-containing food such as rice. PMID:25464340

  20. Genome-wide association mapping identifies a new arsenate reductase enzyme critical for limiting arsenic accumulation in plants.

    PubMed

    Chao, Dai-Yin; Chen, Yi; Chen, Jiugeng; Shi, Shulin; Chen, Ziru; Wang, Chengcheng; Danku, John M; Zhao, Fang-Jie; Salt, David E

    2014-12-01

    Inorganic arsenic is a carcinogen, and its ingestion through foods such as rice presents a significant risk to human health. Plants chemically reduce arsenate to arsenite. Using genome-wide association (GWA) mapping of loci controlling natural variation in arsenic accumulation in Arabidopsis thaliana allowed us to identify the arsenate reductase required for this reduction, which we named High Arsenic Content 1 (HAC1). Complementation verified the identity of HAC1, and expression in Escherichia coli lacking a functional arsenate reductase confirmed the arsenate reductase activity of HAC1. The HAC1 protein accumulates in the epidermis, the outer cell layer of the root, and also in the pericycle cells surrounding the central vascular tissue. Plants lacking HAC1 lose their ability to efflux arsenite from roots, leading to both increased transport of arsenic into the central vascular tissue and on into the shoot. HAC1 therefore functions to reduce arsenate to arsenite in the outer cell layer of the root, facilitating efflux of arsenic as arsenite back into the soil to limit both its accumulation in the root and transport to the shoot. Arsenate reduction by HAC1 in the pericycle may play a role in limiting arsenic loading into the xylem. Loss of HAC1-encoded arsenic reduction leads to a significant increase in arsenic accumulation in shoots, causing an increased sensitivity to arsenate toxicity. We also confirmed the previous observation that the ACR2 arsenate reductase in A. thaliana plays no detectable role in arsenic metabolism. Furthermore, ACR2 does not interact epistatically with HAC1, since arsenic metabolism in the acr2 hac1 double mutant is disrupted in an identical manner to that described for the hac1 single mutant. Our identification of HAC1 and its associated natural variation provides an important new resource for the development of low arsenic-containing food such as rice.

  1. Characterization of arsenate reductase in the extract of roots and fronds of Chinese brake fern, an arsenic hyperaccumulator.

    PubMed

    Duan, Gui-Lan; Zhu, Yong-Guan; Tong, Yi-Ping; Cai, Chao; Kneer, Ralf

    2005-05-01

    Root extracts from the arsenic (As) hyperaccumulating Chinese brake fern (Pteris vittata) were shown to be able to reduce arsenate to arsenite. An arsenate reductase (AR) in the fern showed a reaction mechanism similar to the previously reported Acr2p, an AR from yeast (Saccharomyces cerevisiae), using glutathione as the electron donor. Substrate specificity as well as sensitivity toward inhibitors for the fern AR (phosphate as a competitive inhibitor, arsenite as a noncompetitive inhibitor) was also similar to Acr2p. Kinetic analysis showed that the fern AR had a Michaelis constant value of 2.33 mM for arsenate, 15-fold lower than the purified Acr2p. The AR-specific activity of the fern roots treated with 2 mM arsenate for 9 d was at least 7 times higher than those of roots and shoots of plant species that are known not to tolerate arsenate. A T-DNA knockout mutant of Arabidopsis (Arabidopsis thaliana) with disruption in the putative Acr2 gene had no AR activity. We could not detect AR activity in shoots of the fern. These results indicate that (1) arsenite, the previously reported main storage form of As in the fern fronds, may come mainly from the reduction of arsenate in roots; and (2) AR plays an important role in the detoxification of As in the As hyperaccumulating fern.

  2. Characterization of Arsenate Reductase in the Extract of Roots and Fronds of Chinese Brake Fern, an Arsenic Hyperaccumulator1

    PubMed Central

    Duan, Gui-Lan; Zhu, Yong-Guan; Tong, Yi-Ping; Cai, Chao; Kneer, Ralf

    2005-01-01

    Root extracts from the arsenic (As) hyperaccumulating Chinese brake fern (Pteris vittata) were shown to be able to reduce arsenate to arsenite. An arsenate reductase (AR) in the fern showed a reaction mechanism similar to the previously reported Acr2p, an AR from yeast (Saccharomyces cerevisiae), using glutathione as the electron donor. Substrate specificity as well as sensitivity toward inhibitors for the fern AR (phosphate as a competitive inhibitor, arsenite as a noncompetitive inhibitor) was also similar to Acr2p. Kinetic analysis showed that the fern AR had a Michaelis constant value of 2.33 mm for arsenate, 15-fold lower than the purified Acr2p. The AR-specific activity of the fern roots treated with 2 mm arsenate for 9 d was at least 7 times higher than those of roots and shoots of plant species that are known not to tolerate arsenate. A T-DNA knockout mutant of Arabidopsis (Arabidopsis thaliana) with disruption in the putative Acr2 gene had no AR activity. We could not detect AR activity in shoots of the fern. These results indicate that (1) arsenite, the previously reported main storage form of As in the fern fronds, may come mainly from the reduction of arsenate in roots; and (2) AR plays an important role in the detoxification of As in the As hyperaccumulating fern. PMID:15834011

  3. The role of arsenate reductase and superoxide dismutase in As accumulation in four Pteris species.

    PubMed

    Liu, Y; Wang, H B; Wong, M H; Ye, Z H

    2009-04-01

    Using arsenic (As) hyperaccumulators to extract As from contaminated soils is an effective and low-cost technology. Most of the known As hyperaccumulators belong to Pteris species. The present study aims to explore the responses and role of arsenate reductase (AR) and superoxide dismutase (SOD) in As hyperaccumulating fern species (Pteris vittata, and P. multifida) and non-As hyperaccumulating species (P. ensiformis, and P. semipinnata) when grown in soils added with 0 (control), 100, and 200 mg/kg (dry weight) of arsenic as Na(2)HAsO(4).7H(2)O. The results show that AR activities of roots, SOD activities and As concentrations in both roots and fronds of the four Pteris plants increased when exposed to As-contaminated soils. AR activities of roots were much higher, but SOD activities and As concentrations of roots were lower than those of fronds. It is concluded that AR of roots and SOD of both roots and fronds may play important roles to accumulate and detoxify As in the four Pteris species.

  4. The cytochrome bd respiratory oxygen reductases.

    PubMed

    Borisov, Vitaliy B; Gennis, Robert B; Hemp, James; Verkhovsky, Michael I

    2011-11-01

    Cytochrome bd is a respiratory quinol: O₂ oxidoreductase found in many prokaryotes, including a number of pathogens. The main bioenergetic function of the enzyme is the production of a proton motive force by the vectorial charge transfer of protons. The sequences of cytochromes bd are not homologous to those of the other respiratory oxygen reductases, i.e., the heme-copper oxygen reductases or alternative oxidases (AOX). Generally, cytochromes bd are noteworthy for their high affinity for O₂ and resistance to inhibition by cyanide. In E. coli, for example, cytochrome bd (specifically, cytochrome bd-I) is expressed under O₂-limited conditions. Among the members of the bd-family are the so-called cyanide-insensitive quinol oxidases (CIO) which often have a low content of the eponymous heme d but, instead, have heme b in place of heme d in at least a majority of the enzyme population. However, at this point, no sequence motif has been identified to distinguish cytochrome bd (with a stoichiometric complement of heme d) from an enzyme designated as CIO. Members of the bd-family can be subdivided into those which contain either a long or a short hydrophilic connection between transmembrane helices 6 and 7 in subunit I, designated as the Q-loop. However, it is not clear whether there is a functional consequence of this difference. This review summarizes current knowledge on the physiological functions, genetics, structural and catalytic properties of cytochromes bd. Included in this review are descriptions of the intermediates of the catalytic cycle, the proposed site for the reduction of O₂, evidence for a proton channel connecting this active site to the bacterial cytoplasm, and the molecular mechanism by which a membrane potential is generated. 2011 Elsevier B.V. All rights reserved.

  5. The cytochrome bd respiratory oxygen reductases

    PubMed Central

    Borisov, Vitaliy B.; Gennis, Robert B.; Hemp, James; Verkhovsky, Michael I.

    2011-01-01

    Summary Cytochrome bd is a respiratory quinol:O2 oxidoreductase found in many prokaryotes, including a number of pathogens. The main bioenergetic function of the enzyme is the production of a proton motive force by the vectorial charge transfer of protons. The sequences of cytochromes bd are not homologous to those of the other respiratory oxygen reductases, i.e., the heme-copper oxygen reductases or alternative oxidases (AOX). Generally, cytochromes bd are noteworthy for their high affinity for O2 and resistance to inhibition by cyanide. In E. coli, for example, cytochrome bd (specifically, cytochrome bd-I) is expressed under O2-limited conditions. Among the members of the bd-family are the so-called cyanide-insensitive quinol oxidases (CIO) which often have a low content of the eponymous heme d but, instead, have heme b in place of heme d in at least a majority of the enzyme population. However, at this point, no sequence motif has been identified to distinguish cytochrome bd (with a stoichiometric complement of heme d) from an enzyme designated as CIO. Members of the bd-family can be subdivided into those which contain either a long or a short hydrophilic connection between transmembrane helices 6 and 7 in subunit I, designated as the Q-loop. However, it is not clear whether there is a functional consequence of this difference. This review summarizes current knowledge on the physiological functions, genetics, structural and catalytic properties of cytochromes bd. Included in this review are descriptions of the intermediates of the catalytic cycle, the proposed site for the reduction of O2, evidence for a proton channel connecting this active site to the bacterial cytoplasm, and the molecular mechanism by which a membrane potential is generated. PMID:21756872

  6. An arsenate reductase homologue possessing phosphatase activity from sweet potato (Ipomoea batatas [L.] Lam): kinetic studies and characterization.

    PubMed

    Chan, Ya-Hui; Lin, Chao-Yi; Pai, Shou-Hsiung; Huang, Jenq-Kuen; Lin, Chi-Tsai

    2011-04-13

    A cDNA encoding a putative arsenate reductase homologue (IbArsR) was cloned from sweet potato (Ib). The deduced protein showed a high level of sequence homology (16-66%) with ArsRs from other organisms. A 3-D homology structure was created based on AtArsR (PDB code 1T3K ) from Arabidopsis thaliana. The putative active site of protein tyrosine phosphatase (HC(X)(5)R) is conserved in all reported ArsRs. IbArsR was overexpressed and purified. The monomeric nature of the enzyme was confirmed by 15% SDS-PAGE and molecular mass determination of the native enzyme via ESI Q-TOF. The IbArsR lacks arsenate reductase activity but possesses phosphatase activity. The Michaelis constant (K(M)) value for p-nitrophenyl phosphate (pNPP) was 11.11 mM. The phosphatase activity was inhibited by 0.5 mM sodium arsenate [As(V)]. The protein's half-life of deactivation at 25 °C was 6.1 min, and its inactivation rate constant K(d) was 1.1 × 10(-1) min(-1). The enzyme was active in a broad pH range from 4.0 to 11.0 with optimum activity at pH 10.0. Phosphatase would remove phosphate group from nucleic acid or dephosphorylation of other enzymes as regulation signaling.

  7. Genetic identification of arsenate reductase and arsenite oxidase in redox transformations carried out by arsenic metabolising prokaryotes - A comprehensive review.

    PubMed

    Kumari, Nisha; Jagadevan, Sheeja

    2016-11-01

    Arsenic (As) contamination in water is a cause of major concern to human population worldwide, especially in Bangladesh and West Bengal, India. Arsenite (As(III)) and arsenate (As(V)) are the two common forms in which arsenic exists in soil and groundwater, the former being more mobile and toxic. A large number of arsenic metabolising microorganisms play a crucial role in microbial transformation of arsenic between its different states, thus playing a key role in remediation of arsenic contaminated water. This review focuses on advances in biochemical, molecular and genomic developments in the field of arsenic metabolising bacteria - covering recent developments in the understanding of structure of arsenate reductase and arsenite oxidase enzymes, their gene and operon structures and their mechanism of action. The genetic and molecular studies of these microbes and their proteins may lead to evolution of successful strategies for effective implementation of bioremediation programs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. OsHAC1;1 and OsHAC1;2 Function as Arsenate Reductases and Regulate Arsenic Accumulation.

    PubMed

    Shi, Shulin; Wang, Tao; Chen, Ziru; Tang, Zhong; Wu, Zhongchang; Salt, David E; Chao, Dai-Yin; Zhao, Fang-Jie

    2016-11-01

    Rice is a major dietary source of the toxic metalloid arsenic (As). Reducing its accumulation in rice (Oryza sativa) grain is of critical importance to food safety. Rice roots take up arsenate and arsenite depending on the prevailing soil conditions. The first step of arsenate detoxification is its reduction to arsenite, but the enzyme(s) catalyzing this reaction in rice remains unknown. Here, we identify OsHAC1;1 and OsHAC1;2 as arsenate reductases in rice. OsHAC1;1 and OsHAC1;2 are able to complement an Escherichia coli mutant lacking the endogenous arsenate reductase and to reduce arsenate to arsenite. OsHAC1:1 and OsHAC1;2 are predominantly expressed in roots, with OsHAC1;1 being abundant in the epidermis, root hairs, and pericycle cells while OsHAC1;2 is abundant in the epidermis, outer layers of cortex, and endodermis cells. Expression of the two genes was induced by arsenate exposure. Knocking out OsHAC1;1 or OsHAC1;2 decreased the reduction of arsenate to arsenite in roots, reducing arsenite efflux to the external medium. Loss of arsenite efflux was also associated with increased As accumulation in shoots. Greater effects were observed in a double mutant of the two genes. In contrast, overexpression of either OsHAC1;1 or OsHAC1;2 increased arsenite efflux, reduced As accumulation, and enhanced arsenate tolerance. When grown under aerobic soil conditions, overexpression of either OsHAC1;1 or OsHAC1;2 also decreased As accumulation in rice grain, whereas grain As increased in the knockout mutants. We conclude that OsHAC1;1 and OsHAC1;2 are arsenate reductases that play an important role in restricting As accumulation in rice shoots and grain.

  9. Development of a Molecular System for Studying Microbial Arsenate Respiration

    NASA Astrophysics Data System (ADS)

    Saltikov, C. W.; Newman, D. K.

    2002-12-01

    The toxic element arsenic is a major contaminant of many groundwaters and surface waters throughout the world. Arsenic enrichment is primarily of geological origin resulting from weathering processes and geothermal activity. Not surprisingly, microorganisms inhabiting anoxic arsenic-contaminated environments have evolved to exploit arsenate during respiration. Numerous bacteria have been isolated that use arsenate as a terminal electron acceptor for respiratory growth. The diversity of this metabolism appears to be widespread throughout the microbial tree of life, suggesting respiratory arsenate reduction is ancient in origin. Yet little is known about the molecular mechanisms for how these organisms respire arsenate. We have developed a model system in Shewanella trabarsenatis, strain ANA-3, a facultative anaerobe that respires arsenate and tolerates high concentrations of arsenite (10 mM). Through loss-of-function studies, we have identified genes involved in both arsenic resistance and arsenate respiration. The genes that confer resistance to arsenic are homologous to the well-characterized ars operon of E. coli. However, the respiratory arsenate reductase is predicted to encode a novel protein that shares homologous regions (~ 40 % similarity) to molybdopterin anaerobic reductases specific for DMSO, thiosulfate, nitrate, and polysulfide. I will discuss our emerging model for how strain ANA-3 respires arsenate and the relationship between arsenite resistance and arsenate respiration. I will also highlight the relevance of this type of analysis for biogeochemical studies.

  10. Solution structure of an arsenate reductase-related protein, YffB, from Brucella melitensis, the etiological agent responsible for brucellosis.

    PubMed

    Buchko, Garry W; Hewitt, Stephen N; Napuli, Alberto J; Van Voorhis, Wesley C; Myler, Peter J

    2011-09-01

    Brucella melitensis is the etiological agent responsible for brucellosis. Present in the B. melitensis genome is a 116-residue protein related to arsenate reductases (Bm-YffB; BR0369). Arsenate reductases (ArsC) convert arsenate ion (H(2)AsO(4)(-)), a compound that is toxic to bacteria, to arsenite ion (AsO(2)(-)), a product that may be efficiently exported out of the cell. Consequently, Bm-YffB is a potential drug target because if arsenate reduction is the protein's major biological function then disabling the cell's ability to reduce arsenate would make these cells more sensitive to the deleterious effects of arsenate. Size-exclusion chromatography and NMR spectroscopy indicate that Bm-YffB is a monomer in solution. The solution structure of Bm-YffB (PDB entry 2kok) shows that the protein consists of two domains: a four-stranded mixed β-sheet flanked by two α-helices on one side and an α-helical bundle. The α/β domain is characteristic of the fold of thioredoxin-like proteins and the overall structure is generally similar to those of known arsenate reductases despite the marginal sequence similarity. Chemical shift perturbation studies with (15)N-labeled Bm-YffB show that the protein binds reduced glutathione at a site adjacent to a region similar to the HX(3)CX(3)R catalytic sequence motif that is important for arsenic detoxification activity in the classical arsenate-reductase family of proteins. The latter observation supports the hypothesis that the ArsC-YffB family of proteins may function as glutathione-dependent thiol reductases. However, comparison of the structure of Bm-YffB with the structures of proteins from the classical ArsC family suggest that the mechanism and possibly the function of Bm-YffB and other related proteins (ArsC-YffB) may differ from those of the ArsC family of proteins.

  11. Solution structure of an arsenate reductase-related protein, YffB, from Brucella melitensis, the etiological agent responsible for brucellosis

    PubMed Central

    Buchko, Garry W.; Hewitt, Stephen N.; Napuli, Alberto J.; Van Voorhis, Wesley C.; Myler, Peter J.

    2011-01-01

    Brucella melitensis is the etiological agent responsible for brucellosis. Present in the B. melitensis genome is a 116-residue protein related to arsenate reductases (Bm-YffB; BR0369). Arsenate reductases (ArsC) convert arsenate ion (H2AsO4 −), a compound that is toxic to bacteria, to arsenite ion (AsO2 −), a product that may be efficiently exported out of the cell. Consequently, Bm-YffB is a potential drug target because if arsenate reduction is the protein’s major biological function then disabling the cell’s ability to reduce arsenate would make these cells more sensitive to the deleterious effects of arsenate. Size-exclusion chromatography and NMR spectroscopy indicate that Bm-YffB is a monomer in solution. The solution structure of Bm-YffB (PDB entry 2kok) shows that the protein consists of two domains: a four-stranded mixed β-sheet flanked by two α-helices on one side and an α-helical bundle. The α/β domain is characteristic of the fold of thioredoxin-like proteins and the overall structure is generally similar to those of known arsenate reductases despite the marginal sequence similarity. Chemical shift perturbation studies with 15N-labeled Bm-YffB show that the protein binds reduced glutathione at a site adjacent to a region similar to the HX 3CX 3R catalytic sequence motif that is important for arsenic detoxification activity in the classical arsenate-reductase family of proteins. The latter observation supports the hypothesis that the ArsC-YffB family of proteins may function as glutathione-dependent thiol reductases. However, comparison of the structure of Bm-YffB with the structures of proteins from the classical ArsC family suggest that the mechanism and possibly the function of Bm-YffB and other related proteins (ArsC-YffB) may differ from those of the ArsC family of proteins. PMID:21904062

  12. A SAM-dependent methyltransferase cotranscribed with arsenate reductase alters resistance to peptidyl transferase center-binding antibiotics in Azospirillum brasilense Sp7.

    PubMed

    Singh, Sudhir; Singh, Chhaya; Tripathi, Anil Kumar

    2014-05-01

    The genome of Azospirillum brasilense harbors a gene encoding S-adenosylmethionine-dependent methyltransferase, which is located downstream of an arsenate reductase gene. Both genes are cotranscribed and translationally coupled. When they were cloned and expressed individually in an arsenate-sensitive strain of Escherichia coli, arsenate reductase conferred tolerance to arsenate; however, methyltransferase failed to do so. Sequence analysis revealed that methyltransferase was more closely related to a PrmB-type N5-glutamine methyltransferase than to the arsenate detoxifying methyltransferase ArsM. Insertional inactivation of prmB gene in A. brasilense resulted in an increased sensitivity to chloramphenicol and resistance to tiamulin and clindamycin, which are known to bind at the peptidyl transferase center (PTC) in the ribosome. These observations suggested that the inability of prmB:km mutant to methylate L3 protein might alter hydrophobicity in the antibiotic-binding pocket of the PTC, which might affect the binding of chloramphenicol, clindamycin, and tiamulin differentially. This is the first report showing the role of PrmB-type N5-glutamine methyltransferases in conferring resistance to tiamulin and clindamycin in any bacterium.

  13. Hydrogen formation by an arsenate-reducing Pseudomonas putida, isolated from arsenic-contaminated groundwater in West Bengal, India.

    PubMed

    Freikowski, Dominik; Winter, Josef; Gallert, Claudia

    2010-12-01

    Anaerobic growth of a newly isolated Pseudomonas putida strain WB from an arsenic-contaminated soil in West Bengal, India on glucose, L: -lactate, and acetate required the presence of arsenate, which was reduced to arsenite. During aerobic growth in the presence of arsenite arsenate was formed. Anaerobic growth of P. putida WB on glucose was made possible presumably by the non-energy-conserving arsenate reductase ArsC with energy derived only from substrate level phosphorylation. Two moles of acetate were generated intermediarily and the reducing equivalents of glycolysis and pyruvate decarboxylation served for arsenate reduction or were released as H(2). Anaerobic growth on acetate and lactate was apparently made possible by arsenate reductase ArrA coupled to respiratory electron chain energy conservation. In the presence of arsenate, both substrates were totally oxidized to CO(2) and H(2) with part of the H(2) serving for respiratory arsenate reduction to deliver energy for growth. The growth yield for anaerobic glucose degradation to acetate was Y (Glucose) = 20 g/mol, leading to an energy coefficient of Y (ATP) = 10 g/mol adenosine-5'-triphosphate (ATP), if the Emden-Meyerhof-Parnas pathway with generation of 2 mol ATP/mol glucose was used. During growth on lactate and acetate no substrate chain phosphorylation was possible. The energy gain by reduction of arsenate was Y (Arsenate) = 6.9 g/mol, which would be little less than one ATP/mol of arsenate.

  14. Arsenate reductase from Thermus thermophilus conjugated to polyethylene glycol-stabilized gold nanospheres allow trace sensing and speciation of arsenic ions

    PubMed Central

    Politi, Jane; Spadavecchia, Jolanda; Fiorentino, Gabriella; Antonucci, Immacolata

    2016-01-01

    Water sources pollution by arsenic ions is a serious environmental problem all around the world. Arsenate reductase enzyme (TtArsC) from Thermus thermophilus extremophile bacterium, naturally binds arsenic ions, As(V) and As (III), in aqueous solutions. In this research, TtArsC enzyme adsorption onto hybrid polyethylene glycol-stabilized gold nanoparticles (AuNPs) was studied at different pH values as an innovative nanobiosystem for metal concentration monitoring. Characterizations were performed by UV/Vis and circular dichroism spectroscopies, TEM images and in terms of surface charge changes. The molecular interaction between arsenic ions and the TtArsC-AuNPs nanobiosystem was also monitored at all pH values considered by UV/Vis spectroscopy. Tests performed revealed high sensitivities and limits of detection equal to 10 ± 3 M−12 and 7.7 ± 0.3 M−12 for As(III) and As(V), respectively. PMID:27707908

  15. Glutathione-S-transferase-omega [MMA(V) reductase] knockout mice: Enzyme and arsenic species concentrations in tissues after arsenate administration

    SciTech Connect

    Chowdhury, Uttam K.; Zakharyan, Robert A.; Hernandez, Alba; Avram, Mihaela D.; Kopplin, Michael J.; Aposhian, H. Vasken . E-mail: aposhian@u.arizona.edu

    2006-11-01

    Inorganic arsenic is a human carcinogen to which millions of people are exposed via their naturally contaminated drinking water. Its molecular mechanisms of carcinogenicity have remained an enigma, perhaps because arsenate is biochemically transformed to at least five other arsenic-containing metabolites. In the biotransformation of inorganic arsenic, GSTO1 catalyzes the reduction of arsenate, MMA(V), and DMA(V) to the more toxic + 3 arsenic species. MMA(V) reductase and human (hGSTO1-1) are identical proteins. The hypothesis that GST-Omega knockout mice biotransformed inorganic arsenic differently than wild-type mice has been tested. The livers of male knockout (KO) mice, in which 222 bp of Exon 3 of the GSTO1 gene were eliminated, were analyzed by PCR for mRNA. The level of transcripts of the GSTO1 gene in KO mice was 3.3-fold less than in DBA/1lacJ wild-type (WT) mice. The GSTO2 transcripts were about two-fold less in the KO mouse. When KO and WT mice were injected intramuscularly with Na arsenate (4.16 mg As/kg body weight); tissues removed at 0.5, 1, 2, 4, 8, and 12 h after arsenate injection; and the arsenic species measured by HPLC-ICP-MS, the results indicated that the highest concentration of the recently discovered and very toxic MMA(III), a key biotransformant, was in the kidneys of both KO and WT mice. The highest concentration of DMA(III) was in the urinary bladder tissue for both the KO and WT mice. The MMA(V) reducing activity of the liver cytosol of KO mice was only 20% of that found in wild-type mice. There appears to be another enzyme(s) other than GST-O able to reduce arsenic(V) species but to a lesser extent. This and other studies suggest that each step of the biotransformation of inorganic arsenic has an alternative enzyme to biotransform the arsenic substrate.

  16. Arsenate reductase from Thermus thermophilus conjugated to polyethylene glycol-stabilized gold nanospheres allow trace sensing and speciation of arsenic ions.

    PubMed

    Politi, Jane; Spadavecchia, Jolanda; Fiorentino, Gabriella; Antonucci, Immacolata; De Stefano, Luca

    2016-10-01

    Water sources pollution by arsenic ions is a serious environmental problem all around the world. Arsenate reductase enzyme (TtArsC) from Thermus thermophilus extremophile bacterium, naturally binds arsenic ions, As(V) and As (III), in aqueous solutions. In this research, TtArsC enzyme adsorption onto hybrid polyethylene glycol-stabilized gold nanoparticles (AuNPs) was studied at different pH values as an innovative nanobiosystem for metal concentration monitoring. Characterizations were performed by UV/Vis and circular dichroism spectroscopies, TEM images and in terms of surface charge changes. The molecular interaction between arsenic ions and the TtArsC-AuNPs nanobiosystem was also monitored at all pH values considered by UV/Vis spectroscopy. Tests performed revealed high sensitivities and limits of detection equal to 10 ± 3 M(-12) and 7.7 ± 0.3 M(-12) for As(III) and As(V), respectively. © 2016 The Author(s).

  17. Crystallization and preliminary crystallographic characterization of LmACR2, an arsenate/antimonate reductase from Leishmania major

    SciTech Connect

    Bisacchi, Davide; Zhou, Yao; Rosen, Barry P.; Mukhopadhyay, Rita; Bordo, Domenico

    2006-10-01

    LmACR2 from L. major is the first rhodanese-like enzyme directly involved in the reduction of arsenate and antimonate to be crystallized. Diffraction data have been collected to 1.99 Å resolution using synchrotron X-rays. Arsenic is present in the biosphere owing either to the presence of pesticides and herbicides used in agricultural and industrial activities or to leaching from geological formations. The health effects of prolonged exposure to arsenic can be devastating and may lead to various forms of cancer. Antimony(V), which is chemically very similar to arsenic, is used instead in the treatment of leishmaniasis, an infection caused by the protozoan parasite Leishmania sp.; the reduction of pentavalent antimony contained in the drug Pentostam to the active trivalent form arises from the presence in the Leishmania genome of a gene, LmACR2, coding for the protein LmACR2 (14.5 kDa, 127 amino acids) that displays weak but significant sequence similarity to the catalytic domain of Cdc25 phosphatase and to rhodanese enzymes. For structural characterization, LmACR2 was overexpressed, purified to homogeneity and crystallized in a trigonal space group (P321 or P3{sub 1}21/P3{sub 2}21). The protein crystallized in two distinct trigonal crystal forms, with unit-cell parameters a = b = 111.0, c = 86.1 Å and a = b = 111.0, c = 175.6 Å, respectively. At a synchrotron beamline, the diffraction pattern extended to a resolution limit of 1.99 Å.

  18. Role of Campylobacter jejuni Respiratory Oxidases and Reductases in Host Colonization▿

    PubMed Central

    Weingarten, Rebecca A.; Grimes, Jesse L.; Olson, Jonathan W.

    2008-01-01

    Campylobacter jejuni is the leading cause of human food-borne bacterial gastroenteritis. The C. jejuni genome sequence predicts a branched electron transport chain capable of utilizing multiple electron acceptors. Mutants were constructed by disrupting the coding regions of the respiratory enzymes nitrate reductase (napA::Cm), nitrite reductase (nrfA::Cm), dimethyl sulfoxide, and trimethylamine N-oxide reductase (termed Cj0264::Cm) and the two terminal oxidases, a cyanide-insensitive oxidase (cydA::Cm) and cbb3-type oxidase (ccoN::Cm). Each strain was characterized for the loss of the associated enzymatic function in vitro. The strains were then inoculated into 1-week-old chicks, and the cecal contents were assayed for the presence of C. jejuni 2 weeks postinoculation. cydA::Cm and Cj0264c::Cm strains colonized as well as the wild type; napA::Cm and nrfA::Cm strains colonized at levels significantly lower than the wild type. The ccoN::Cm strain was unable to colonize the chicken; no colonies were recovered at the end of the experiment. While there appears to be a role for anaerobic respiration in host colonization, oxygen is the most important respiratory acceptor for C. jejuni in the chicken cecum. PMID:18192421

  19. Arsenic dissolution from Japanese paddy soil by a dissimilatory arsenate-reducing bacterium Geobacter sp. OR-1.

    PubMed

    Ohtsuka, Toshihiko; Yamaguchi, Noriko; Makino, Tomoyuki; Sakurai, Kazuhiro; Kimura, Kenta; Kudo, Keitaro; Homma, Eri; Dong, Dian Tao; Amachi, Seigo

    2013-06-18

    Dissimilatory As(V) (arsenate)-reducing bacteria may play an important role in arsenic release from anoxic sediments in the form of As(III) (arsenite). Although respiratory arsenate reductase genes (arrA) closely related to Geobacter species have been frequently detected in arsenic-rich sediments, it is still unclear whether they directly participate in arsenic release, mainly due to lack of pure cultures capable of arsenate reduction. In this study, we isolated a novel dissimilatory arsenate-reducing bacterium, strain OR-1, from Japanese paddy soil, and found that it was phylogenetically closely related to Geobacter pelophilus. OR-1 also utilized soluble Fe(III), ferrihydrite, nitrate, and fumarate as electron acceptors. OR-1 catalyzed dissolution of arsenic from arsenate-adsorbed ferrihydrite, while Geobacter metallireducens GS-15 did not. Furthermore, inoculation of washed cells of OR-1 into sterilized paddy soil successfully restored arsenic release. Arsenic K-edge X-ray absorption near-edge structure analysis revealed that strain OR-1 reduced arsenate directly on the soil solid phase. Analysis of putative ArrA sequences from paddy soils suggested that Geobacter-related bacteria, including those closely related to OR-1, play an important role in arsenic release from paddy soils. Our results provide direct evidence for arsenic dissolution by Geobacter species and support the hypothesis that Geobacter species play a significant role in reduction and mobilization of arsenic in flooded soils and anoxic sediments.

  20. Arsenate reduction and expression of multiple chromosomal ars operons in Geobacillus kaustophilus A1.

    PubMed

    Cuebas, Mariola; Villafane, Aramis; McBride, Michelle; Yee, Nathan; Bini, Elisabetta

    2011-07-01

    Geobacillus kaustophilus strain A1 was previously isolated from a geothermal environment for its ability to grow in the presence of high arsenate levels. In this study, the molecular mechanisms of arsenate resistance of the strain were investigated. As(V) was reduced to As(III), as shown by HPLC analysis. Consistent with the observation that the micro-organism is not capable of anaerobic growth, no respiratory arsenate reductases were identified. Using specific PCR primers based on the genome sequence of G. kaustophilus HTA426, three unlinked genes encoding detoxifying arsenate reductases were detected in strain A1. These genes were designated arsC1, arsC2 and arsC3. While arsC3 is a monocistronic locus, sequencing of the regions flanking arsC1 and arsC2 revealed the presence of additional genes encoding a putative arsenite transporter and an ArsR-like regulator upstream of each arsenate reductase, indicating the presence of sequences with putative roles in As(V) reduction, As(III) export and arsenic-responsive regulation. RT-PCR demonstrated that both sets of genes were co-transcribed. Furthermore, arsC1 and arsC2, monitored by quantitative real-time RT-PCR, were upregulated in response to As(V), while arsC3 was constitutively expressed at a low level. A mechanism for regulation of As(V) detoxification by Geobacillus that is both consistent with our findings and relevant to the biogeochemical cycle of arsenic and its mobility in the environment is proposed.

  1. Succinate-cytochrome c reductase: assessment of its value in the investigation of defects of the respiratory chain.

    PubMed

    Taylor, R W; Birch-Machin, M A; Bartlett, K; Turnbull, D M

    1993-06-19

    Defects of the respiratory chain are important causes of human disease and one of the most commonly used assays in the investigation of these patients is the measurement of succinate-cytochrome c reductase. However, this assay measures several components of the respiratory chain and the ability to detect a partial defect in one enzyme complex will depend on the amount of control exerted by that enzyme step on overall electron flux. We show that measurement of succinate-cytochrome c reductase activity may fail to detect partial defects of complex III and therefore is of limited diagnostic value in the identification of complex III defects. However, complex II is a major point of control of flux through succinate-cytochrome reductase and it is likely that measurement of the latter will detect defects of complex II.

  2. The evolution of respiratory O2/NO reductases: an out-of-the-phylogenetic-box perspective

    PubMed Central

    Ducluzeau, Anne-Lise; Schoepp-Cothenet, Barbara; van Lis, Robert; Baymann, Frauke; Russell, Michael J.; Nitschke, Wolfgang

    2014-01-01

    Complex life on our planet crucially depends on strong redox disequilibria afforded by the almost ubiquitous presence of highly oxidizing molecular oxygen. However, the history of O2-levels in the atmosphere is complex and prior to the Great Oxidation Event some 2.3 billion years ago, the amount of O2 in the biosphere is considered to have been extremely low as compared with present-day values. Therefore the evolutionary histories of life and of O2-levels are likely intricately intertwined. The obvious biological proxy for inferring the impact of changing O2-levels on life is the evolutionary history of the enzyme allowing organisms to tap into the redox power of molecular oxygen, i.e. the bioenergetic O2 reductases, alias the cytochrome and quinol oxidases. Consequently, molecular phylogenies reconstructed for this enzyme superfamily have been exploited over the last two decades in attempts to elucidate the interlocking between O2 levels in the environment and the evolution of respiratory bioenergetic processes. Although based on strictly identical datasets, these phylogenetic approaches have led to diametrically opposite scenarios with respect to the history of both the enzyme superfamily and molecular oxygen on the Earth. In an effort to overcome the deadlock of molecular phylogeny, we here review presently available structural, functional, palaeogeochemical and thermodynamic information pertinent to the evolution of the superfamily (which notably also encompasses the subfamily of nitric oxide reductases). The scenario which, in our eyes, most closely fits the ensemble of these non-phylogenetic data, sees the low O2-affinity SoxM- (or A-) type enzymes as the most recent evolutionary innovation and the high-affinity O2 reductases (SoxB or B and cbb3 or C) as arising independently from NO-reducing precursor enzymes. PMID:24968694

  3. The evolution of respiratory O2/NO reductases: an out-of-the-phylogenetic-box perspective.

    PubMed

    Ducluzeau, Anne-Lise; Schoepp-Cothenet, Barbara; van Lis, Robert; Baymann, Frauke; Russell, Michael J; Nitschke, Wolfgang

    2014-09-06

    Complex life on our planet crucially depends on strong redox disequilibria afforded by the almost ubiquitous presence of highly oxidizing molecular oxygen. However, the history of O2-levels in the atmosphere is complex and prior to the Great Oxidation Event some 2.3 billion years ago, the amount of O2 in the biosphere is considered to have been extremely low as compared with present-day values. Therefore the evolutionary histories of life and of O2-levels are likely intricately intertwined. The obvious biological proxy for inferring the impact of changing O2-levels on life is the evolutionary history of the enzyme allowing organisms to tap into the redox power of molecular oxygen, i.e. the bioenergetic O2 reductases, alias the cytochrome and quinol oxidases. Consequently, molecular phylogenies reconstructed for this enzyme superfamily have been exploited over the last two decades in attempts to elucidate the interlocking between O2 levels in the environment and the evolution of respiratory bioenergetic processes. Although based on strictly identical datasets, these phylogenetic approaches have led to diametrically opposite scenarios with respect to the history of both the enzyme superfamily and molecular oxygen on the Earth. In an effort to overcome the deadlock of molecular phylogeny, we here review presently available structural, functional, palaeogeochemical and thermodynamic information pertinent to the evolution of the superfamily (which notably also encompasses the subfamily of nitric oxide reductases). The scenario which, in our eyes, most closely fits the ensemble of these non-phylogenetic data, sees the low O2-affinity SoxM- (or A-) type enzymes as the most recent evolutionary innovation and the high-affinity O2 reductases (SoxB or B and cbb3 or C) as arising independently from NO-reducing precursor enzymes. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

  4. Crystal structures of nitric oxide reductases provide key insights into functional conversion of respiratory enzymes.

    PubMed

    Tosha, Takehiko; Shiro, Yoshitsugu

    2013-03-01

    Respiration is an essential biological process to get bioenergy, ATP, for all kingdoms of life. Cytochrome c oxidase (COX) plays central role in aerobic respiration, catalyzing the reduction of O(2) coupled with pumping proton across the biological membrane. Nitric oxide reductase (NOR) involved in anaerobic nitrate respiration is suggested to be evolutionary related to COX and share the same progenitor with COX, on the basis of the amino acid sequence homology. Contrary to COX, NOR catalyzes the reduction of nitric oxide and shows no proton pumping ability. Thus, the respiratory enzyme acquires (or loses) proton pumping ability in addition to the conversion of the catalytic property along with the environmental change on earth. Recently, we solved the structures of two types of NORs, which provides novel insights into the functional conversion of the respiratory enzymes. In this review, we focus on the structural similarities and differences between COXs and NORs and discuss possible mechanism for the functional conversion of these enzymes during molecular evolution. Copyright © 2013 International Union of Biochemistry and Molecular Biology, Inc.

  5. Identification of anaerobic arsenite-oxidizing and arsenate-reducing bacteria associated with an alkaline saline lake in Khovsgol, Mongolia.

    PubMed

    Hamamura, Natsuko; Itai, Takaaki; Liu, Yitai; Reysenbach, Anna-Louise; Damdinsuren, Narantuya; Inskeep, William P

    2014-10-01

    Microbial arsenic transformation pathways associated with a saline lake located in northern Mongolia were examined using molecular biological and culturing approaches. Bacterial 16S rRNA gene sequences recovered from saline lake sediments and soils were affiliated with haloalkaliphiles, including Bacillus and Halomonas spp. Diverse sequences of arsenate respiratory reductase (arrA) and a new group of arsenite oxidase (arxA) genes were also identified. Pure cultures of arsenate-reducing Nitrincola strain and anaerobic arsenite-oxidizing Halomonas strain were isolated. The chemoorganotrophic Halomonas strain contains arxA gene similar to that of a chemoautotrophic arsenite-oxidizing Alkalilimnicola ehrlichii strain MLHE-1. These results revealed the diversity of arsenic transformation pathways associated with a geographically distinct saline system and the potential contribution of arx-dependent arsenite oxidation by heterotrophic bacteria.

  6. Role of Respiratory Nitrate Reductase in Ability of Pseudomonas fluorescens YT101 To Colonize the Rhizosphere of Maize

    PubMed Central

    Ghiglione, Jean-François; Gourbiere, François; Potier, Patrick; Philippot, Laurent; Lensi, Robert

    2000-01-01

    Selection of the denitrifying community by plant roots (i.e., increase in the denitrifier/total heterotroph ratio in the rhizosphere) has been reported by several authors. However, very few studies to evaluate the role of the denitrifying function itself in the selection of microorganisms in the rhizosphere have been performed. In the present study, we compared the rhizosphere survival of the denitrifying Pseudomonas fluorescens YT101 strain with that of its isogenic mutant deficient in the ability to synthesize the respiratory nitrate reductase, coinoculated in nonplanted or planted soil. We demonstrated that under nonlimiting nitrate conditions, the denitrifying wild-type strain had an advantage in the ability to colonize the rhizosphere of maize. Investigations of the effect of the inoculum characteristics (density of the total inoculum and relative proportions of mutant and wild-type strains) on the outcome of the selection demonstrated that the selective effect of the plant was expressed only during the phase of bacterial multiplication and that the intensity of selection was dependent on the magnitude of this phase. Moreover, application of the de Wit replacement series technique to our results suggests that the advantage of the wild-type strain was maximal when the ratio between the two strains in the inoculum was close to 1:1. This work constitutes the first direct demonstration that the presence of a functional structural gene encoding the respiratory nitrate reductase confers higher rhizosphere competence to a microorganism. PMID:10966422

  7. Part of respiratory nitrate reductase of Klebsiella aerogenes is intimately associated with the peptidoglycan.

    PubMed

    Abraham, P R; Wientjes, F B; Nanninga, N; Van't Riet, J

    1987-02-01

    Lysozyme digestion and sonication of sodium dodecyl sulfate (SDS)-purified Klebsiella aerogenes murein sacculi resulted in the quantitative release of both subunits of nitrate reductase, as well as a number of other cytoplasmic membrane polypeptides (5.2%, by weight, of the total membrane proteins). Similar results were obtained after lysozyme digestion of SDS-prepared peptidoglycan fragments, which excluded the phenomenon of simple trapping of the polypeptides by the surrounding peptidoglycan matrix. About 28% of membrane-bound nitrate reductase appears to be tightly associated with the peptidoglycan. Additional evidence for this association was demonstrated by positive immunogold labeling of SDS-murein sacculi and thin sections of plasmolyzed bacteria. Qualitative amino acid analysis of trypsin-treated sacculi, a tryptic product of holo-nitrate reductase, and amino- and carboxypeptidase digests of both nitrate reductase subunits indicated the possible existence of a terminal anchoring peptide containing the following amino acids: (Gly)n, Trp, Ser, Pro, Ile, Leu, Phe, Cys, Tyr, Asp, and Lys.

  8. Low abundance of respiratory nitrate reductase is essential for Escherichia coli in resistance to aminoglycoside and cephalosporin.

    PubMed

    Ma, Yan; Guo, Chang; Li, Hui; Peng, Xuan-Xian

    2013-07-11

    In the present study, we have characterized low abundance of NarG and NarH, two components of respiratory nitrate reductase (Nar), in streptomycin (SM)-, gentamicine (GEN)-, ceftazidime (CAZ)-, tetracycline (TET)- and nalidixic acid (NA)-resistant Escherichia coli strains using native/SDS-PAGE based proteomics. We validate the finding using Western blotting and native/SDS-PAGE upon narG and narH deletion mutants. However, further functional evidence indicates that loss of narG and narH results in two types of growth behaviors, higher and lower than control, in these antibiotic-resistant E. coli strains. Specifically, SM-, GEN- and CAZ-resistant bacteria grow faster, whereas NA- and TET-resistant E. coli strains grow slower. Our data indicate that low abundance of respiratory Nar is essential for E. coli in resistance to aminoglycoside and cephalosporin antibiotics. Meanwhile, the results show that differential mechanisms exist in different antibiotic-resistant bacteria. The reason why the reversal growths are detected in NA- and TET-resistant E. coli strains waits investigation. Our findings serve to propose novel strategies for controlling of aminoglycoside- and cephalosporin-resistant E. coli strains through elevation of respiratory Nar activity. Our data indicate that low abundance of respiratory Nar is essential for E. coli in resistance to aminoglycoside and cephalosporin antibiotics. Meanwhile, the results show that differential mechanisms exist in different antibiotic-resistant bacteria. Our findings serve to propose novel strategies for controlling of aminoglycoside- and cephalosporin-resistant E. coli strains through elevation of respiratory Nar activity. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Characterization of the nirK gene encoding the respiratory, Cu-containing nitrite reductase of Bradyrhizobium japonicum.

    PubMed

    Velasco, L; Mesa, S; Delgado, M J; Bedmar, E J

    2001-10-31

    The structural gene, nirK, for the respiratory Cu-containing nitrite reductase from Bradyrhizobium japonicum USDA110 has been isolated and sequenced. The deduced amino acid sequence exhibited a high degree of similarity to other Cu-containing nitrite reductases from various sources. The full-length protein included a signal peptide for protein export. Analysis of the sequence upstream from the structural nirK gene revealed the presence of an anaerobox located 83 base pairs from the putative translational start codon. Cells of strain GRK308, a nitrite reductase-deficient derivative of strain USDA110, were unable to grow when cultured under microaerobic conditions (1% O(2)) in the presence of either nitrate or nitrite. Maximal expression of a nirK-lacZ fusion in strain USDA110 required simultaneously both low level oxygen conditions and the presence of nitrate. Expression of beta-galactosidase activity was not detected in the B. japonicum fixL 7403, fixJ 7360 and fixK(2) 9043 mutants transformed with the nirK-lacZ fusion after incubation of the cells under oxygen-limiting conditions either with or without nitrate. Complementation of B. japonicum 9043 with the fixK(2) gene restored beta-galactosidase activity to levels similar to those found in the parental strain. These results suggest that nirK expression depends on the low-oxygen-responsive two-component regulatory system FixLJ and on the Fnr/FixK-like DNA binding protein FixK(2).

  10. Acute lead arsenate poisoning.

    PubMed

    Tallis, G A

    1989-12-01

    Three cases of acute lead arsenate poisoning which occurred in South Australia during a 12 month interval are described. The case reports demonstrate a number of features of the characteristic clinical syndrome which may follow ingestion of lead arsenate. The recommended management is immediate gastric lavage and subsequent chelation therapy with calcium EDTA and dimercaprol. Early gastric lavage may prevent significant lead absorption. However, arsenic acid (produced in the stomach when lead arsenate reacts with hydrochloric acid) is relatively water soluble and prompt gastric lavage is unlikely to prevent extensive arsenic absorption. It remains controversial as to whether chelation with dimercaprol prevents arsenical neuropathy.

  11. Development of a gene expression vector for Thermus thermophilus based on the promoter of the respiratory nitrate reductase.

    PubMed

    Moreno, Renata; Zafra, Olga; Cava, Felipe; Berenguer, José

    2003-01-01

    A specific expression system for Thermus spp. is described. Plasmid pMKE1 contains replicative origins for Escherichia coli and Thermus spp., a selection gene encoding a thermostable resistance to kanamycin, and a 720 bp DNA region containing the promoter (Pnar), and the regulatory sequences of the respiratory nitrate reductase operon of Thermus thermophilus HB8. Two genes, encoding a thermophilic beta-galactosidase and an alkaline phosphatase were cloned in pMKE1 as cytoplasmic and periplasmic reporters, respectively. The expression of the reporters was specifically induced by the combined action of nitrate and anoxia in facultative anaerobic derivatives of T. thermophilus HB27 to which the gene cluster for nitrate respiration was transferred by conjugation. Overexpressions in the range of approximately 200-fold were obtained for the cytoplasmic reporter, whereas that of the periplasmic reporter was limited to approximately 20-fold, with respect to their intrinsic respective activities. Copyright 2002 Elsevier Science (USA)

  12. Sulfide Oxidation Coupled to Arsenate Reduction by a Diverse Microbial Community in a Soda Lake†

    PubMed Central

    Hollibaugh, James T.; Budinoff, Charles; Hollibaugh, Ryan A.; Ransom, Briana; Bano, Nasreen

    2006-01-01

    We characterized the arsenate-reducing, sulfide-oxidizing population of Mono Lake, California, by analyzing the distribution and diversity of rrnA, cbbL, and dissimilatory arsenate reductase (arrA) genes in environmental DNA, arsenate-plus sulfide-amended lake water, mixed cultures, and isolates. The arsenate-reducing community was diverse. An organism represented by an rrnA sequence previously retrieved from Mono Lake and affiliated with the Desulfobulbaceae (Deltaproteobacteria) appears to be an important member of the arsenate-reducing, sulfide-oxidizing community. Sulfide oxidation coupled with arsenate reduction appears to proceed via a two-electron transfer, resulting in the production of arsenite and an intermediate S compound that is subsequently disproportionated. A realgar-like As/S mineral was formed in some experiments. PMID:16517653

  13. Sulfide oxidation coupled to arsenate reduction by a diverse microbial community in a soda lake.

    PubMed

    Hollibaugh, James T; Budinoff, Charles; Hollibaugh, Ryan A; Ransom, Briana; Bano, Nasreen

    2006-03-01

    We characterized the arsenate-reducing, sulfide-oxidizing population of Mono Lake, California, by analyzing the distribution and diversity of rrnA, cbbL, and dissimilatory arsenate reductase (arrA) genes in environmental DNA, arsenate-plus sulfide-amended lake water, mixed cultures, and isolates. The arsenate-reducing community was diverse. An organism represented by an rrnA sequence previously retrieved from Mono Lake and affiliated with the Desulfobulbaceae (Deltaproteobacteria) appears to be an important member of the arsenate-reducing, sulfide-oxidizing community. Sulfide oxidation coupled with arsenate reduction appears to proceed via a two-electron transfer, resulting in the production of arsenite and an intermediate S compound that is subsequently disproportionated. A realgar-like As/S mineral was formed in some experiments.

  14. Host dihydrofolate reductase (DHFR)-directed cycloguanil analogues endowed with activity against influenza virus and respiratory syncytial virus.

    PubMed

    Tonelli, Michele; Naesens, Lieve; Gazzarrini, Sabrina; Santucci, Matteo; Cichero, Elena; Tasso, Bruno; Moroni, Anna; Costi, Maria Paola; Loddo, Roberta

    2017-07-28

    We have identified a series of 1-aryl-4,6-diamino-1,2-dihydrotriazines, structurally related to the antimalarial drug cycloguanil, as new inhibitors of influenza A and B virus and respiratory syncytial virus (RSV) via targeting of the host dihydrofolate reductase (DHFR) enzyme. Most analogues proved active against influenza B virus in the low micromolar range, and the best compounds (11, 13, 14 and 16) even reached the sub-micromolar potency of zanamivir (EC50 = 0.060 μM), and markedly exceeded (up to 327 times) the antiviral efficacy of ribavirin. Activity was also observed for two influenza A strains, including a virus with the S31N mutant form of M2 proton channel, which is the most prevalent resistance mutation for amantadine. Importantly, the compounds displayed nanomolar activity against RSV and a superior selectivity index, since the ratio of cytotoxic to antiviral concentration was >10,000 for the three most active compounds 11, 14 and 16 (EC50 ∼0.008 μM), far surpassing the potency and safety profile of the licensed drug ribavirin (EC50 = 5.8 μM, SI > 43). Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  15. Respiratory Pathways Reconstructed by Multi-Omics Analysis in Melioribacter roseus, Residing in a Deep Thermal Aquifer of the West-Siberian Megabasin

    PubMed Central

    Gavrilov, Sergey; Podosokorskaya, Olga; Alexeev, Dmitry; Merkel, Alexander; Khomyakova, Maria; Muntyan, Maria; Altukhov, Ilya; Butenko, Ivan; Bonch-Osmolovskaya, Elizaveta; Govorun, Vadim; Kublanov, Ilya

    2017-01-01

    Melioribacter roseus, a representative of recently proposed Ignavibacteriae phylum, is a metabolically versatile thermophilic bacterium, inhabiting subsurface biosphere of the West-Siberian megabasin and capable of growing on various substrates and electron acceptors. Genomic analysis followed by inhibitor studies and membrane potential measurements of aerobically grown M. roseus cells revealed the activity of aerobic respiratory electron transfer chain comprised of respiratory complexes I and IV, and an alternative complex III. Phylogeny reconstruction revealed that oxygen reductases belonged to atypical cc(o/b)o3-type and canonical cbb3–type cytochrome oxidases. Also, two molybdoenzymes of M. roseus were affiliated either with Ttr or Psr/Phs clades, but not with typical respiratory arsenate reductases of the Arr clade. Expression profiling, both at transcripts and protein level, allowed us to assign the role of the terminal respiratory oxidase under atmospheric oxygen concentration for the cc(o/b)o3 cytochrome oxidase, previously proposed to serve for oxygen detoxification only. Transcriptomic analysis revealed the involvement of both molybdoenzymes of M. roseus in As(V) respiration, yet differences in the genomic context of their gene clusters allow to hypothesize about their distinct roles in arsenate metabolism with the ‘Psr/Phs’-type molybdoenzyme being the most probable candidate respiratory arsenate reductase. Basing on multi-omics data, the pathways for aerobic and arsenate respiration were proposed. Our results start to bridge the vigorously increasing gap between homology-based predictions and experimentally verified metabolic processes, what is especially important for understudied microorganisms of novel lineages from deep subsurface environments of Eurasia, which remained separated from the rest of the biosphere for several geological periods. PMID:28713355

  16. Respiratory Pathways Reconstructed by Multi-Omics Analysis in Melioribacter roseus, Residing in a Deep Thermal Aquifer of the West-Siberian Megabasin.

    PubMed

    Gavrilov, Sergey; Podosokorskaya, Olga; Alexeev, Dmitry; Merkel, Alexander; Khomyakova, Maria; Muntyan, Maria; Altukhov, Ilya; Butenko, Ivan; Bonch-Osmolovskaya, Elizaveta; Govorun, Vadim; Kublanov, Ilya

    2017-01-01

    Melioribacter roseus, a representative of recently proposed Ignavibacteriae phylum, is a metabolically versatile thermophilic bacterium, inhabiting subsurface biosphere of the West-Siberian megabasin and capable of growing on various substrates and electron acceptors. Genomic analysis followed by inhibitor studies and membrane potential measurements of aerobically grown M. roseus cells revealed the activity of aerobic respiratory electron transfer chain comprised of respiratory complexes I and IV, and an alternative complex III. Phylogeny reconstruction revealed that oxygen reductases belonged to atypical cc(o/b)o3 -type and canonical cbb3 -type cytochrome oxidases. Also, two molybdoenzymes of M. roseus were affiliated either with Ttr or Psr/Phs clades, but not with typical respiratory arsenate reductases of the Arr clade. Expression profiling, both at transcripts and protein level, allowed us to assign the role of the terminal respiratory oxidase under atmospheric oxygen concentration for the cc(o/b)o3 cytochrome oxidase, previously proposed to serve for oxygen detoxification only. Transcriptomic analysis revealed the involvement of both molybdoenzymes of M. roseus in As(V) respiration, yet differences in the genomic context of their gene clusters allow to hypothesize about their distinct roles in arsenate metabolism with the 'Psr/Phs'-type molybdoenzyme being the most probable candidate respiratory arsenate reductase. Basing on multi-omics data, the pathways for aerobic and arsenate respiration were proposed. Our results start to bridge the vigorously increasing gap between homology-based predictions and experimentally verified metabolic processes, what is especially important for understudied microorganisms of novel lineages from deep subsurface environments of Eurasia, which remained separated from the rest of the biosphere for several geological periods.

  17. Substrate-dependent modulation of the enzymatic catalytic activity: reduction of nitrate, chlorate and perchlorate by respiratory nitrate reductase from Marinobacter hydrocarbonoclasticus 617.

    PubMed

    Marangon, Jacopo; Paes de Sousa, Patrícia M; Moura, Isabel; Brondino, Carlos D; Moura, José J G; González, Pablo J

    2012-07-01

    The respiratory nitrate reductase complex (NarGHI) from Marinobacter hydrocarbonoclasticus 617 (Mh, formerly Pseudomonas nautica 617) catalyzes the reduction of nitrate to nitrite. This reaction is the first step of the denitrification pathway and is coupled to the quinone pool oxidation and proton translocation to the periplasm, which generates the proton motive force needed for ATP synthesis. The Mh NarGH water-soluble heterodimer has been purified and the kinetic and redox properties have been studied through in-solution enzyme kinetics, protein film voltammetry and spectropotentiometric redox titration. The kinetic parameters of Mh NarGH toward substrates and inhibitors are consistent with those reported for other respiratory nitrate reductases. Protein film voltammetry showed that at least two catalytically distinct forms of the enzyme, which depend on the applied potential, are responsible for substrate reduction. These two forms are affected differentially by the oxidizing substrate, as well as by pH and inhibitors. A new model for the potential dependence of the catalytic efficiency of Nars is proposed.

  18. ArxA, a new clade of arsenite oxidase within the DMSO reductase family of molybdenum oxidoreductases

    USGS Publications Warehouse

    Zargar, Kamrun; Conrad, Alison; Bernick, David L.; Lowe, Todd M.; Stolc, Viktor; Hoeft, Shelley; Oremland, Ronald S.; Stolz, John; Saltikov, Chad W.

    2012-01-01

    Arsenotrophy, growth coupled to autotrophic arsenite oxidation or arsenate respiratory reduction, occurs only in the prokaryotic domain of life. The enzymes responsible for arsenotrophy belong to distinct clades within the DMSO reductase family of molybdenum-containing oxidoreductases: specifically arsenate respiratory reductase, ArrA, and arsenite oxidase, AioA (formerly referred to as AroA and AoxB). A new arsenite oxidase clade, ArxA, represented by the haloalkaliphilic bacterium Alkalilimnicola ehrlichii strain MLHE-1 was also identified in the photosynthetic purple sulfur bacterium Ectothiorhodospira sp. strain PHS-1. A draft genome sequence of PHS-1 was completed and an arx operon similar to MLHE-1 was identified. Gene expression studies showed that arxA was strongly induced with arsenite. Microbial ecology investigation led to the identification of additional arxA-like sequences in Mono Lake and Hot Creek sediments, both arsenic-rich environments in California. Phylogenetic analyses placed these sequences as distinct members of the ArxA clade of arsenite oxidases. ArxA-like sequences were also identified in metagenome sequences of several alkaline microbial mat environments of Yellowstone National Park hot springs. These results suggest that ArxA-type arsenite oxidases appear to be widely distributed in the environment presenting an opportunity for further investigations of the contribution of Arx-dependent arsenotrophy to the arsenic biogeochemical cycle.

  19. Redox-dependent open and closed forms of the active site of the bacterial respiratory nitric-oxide reductase revealed by cyanide binding studies.

    PubMed

    Grönberg, Karin L C; Watmough, Nicholas J; Thomson, Andrew J; Richardson, David J; Field, Sarah J

    2004-04-23

    The bacterial respiratory nitric-oxide reductase (NOR) catalyzes the respiratory detoxification of nitric oxide in bacteria and Archaea. It is a member of the well known super-family of heme-copper oxidases but has a [heme Fe-non-heme Fe] active site rather than the [heme Fe-Cu(B)] active site normally associated with oxygen reduction. Paracoccus denitrificans NOR is spectrally characterized by a ligand-to-metal charge transfer absorption band at 595 nm, which arises from the high spin ferric heme iron of a micro-oxo-bridged [heme Fe(III)-O-Fe(III)] active site. On reduction of the nonheme iron, the micro-oxo bridge is broken, and the ferric heme iron is hydroxylated or hydrated, depending on the pH. At present, the catalytic cycle of NOR is a matter of much debate, and it is not known to which redox state(s) of the enzyme nitric oxide can bind. This study has used cyanide to probe the nature of the active site in a number of different redox states. Our observations suggest that the micro-oxo-bridged [heme Fe(III)-O-Fe(III)] active site represents a closed or resting state of NOR that can be opened by reduction of the non-heme iron.

  20. Cytochrome c Biogenesis Genes Involved in Arsenate Respiration by Shewanella trabarsenatis ANA-3

    NASA Astrophysics Data System (ADS)

    Newman, D. K.

    2002-12-01

    Arsenate can be used as a terminal electron acceptor in anaerobic respiration by diverse bacteria. The detection of these bacteria in numerous contaminated environments suggests that they are widespread and metabolically active in nature. Arsenate-respiring bacteria have been implicated in the mobilization of arsenic from arsenic-contaminated sediments. However, the enzymatic mechanisms supporting arsenate respiration are largely unknown. Here, we describe c-type cytochromes that are involved in arsenate respiration by the bacterium Shewanella trabarsenatis strain ANA-3, a facultative anaerobe that is able to use a variety of electron acceptors for growth. We performed transposon mutagenesis to study the electron transport pathway in ANA-3 during arsenate respiration. 10 arsenate-respiration deficient mutants were found after screening up to 7,000 mutants, and 4 were shown to have unique transposon insertions through Southern Blot analysis. The physiological properties of these mutants were determined, including characterization of their growth on different electron acceptors. The genes flanking the transposon insertions were sequenced for each mutant, and several were found to encode c-type cytochrome biogenesis genes. UV/VIS spectra and SDS/PAGE were used to confirm the absence of c-type cytochromes in the mutants. Based on these findings, we proposed a model for respiratory electron transport to arsenate.

  1. ARSENATE REDUCTION BY ORGANIC COMPOUNDS

    EPA Science Inventory

    Arsenic is found in a variety of forms and oxidation states depending on soil pH and redox conditions. Under oxic conditions, arsenate is thermodynamically favored but arsenite, the more toxic and mobile form of arsenic, is favored under mildly reducing conditions. In many soil...

  2. Structures of reduced and ligand-bound nitric oxide reductase provide insights into functional differences in respiratory enzymes.

    PubMed

    Sato, Nozomi; Ishii, Shoko; Sugimoto, Hiroshi; Hino, Tomoya; Fukumori, Yoshihiro; Sako, Yoshihiko; Shiro, Yoshitsugu; Tosha, Takehiko

    2014-07-01

    Nitric oxide reductase (NOR) catalyzes the generation of nitrous oxide (N2O) via the reductive coupling of two nitric oxide (NO) molecules at a heme/non-heme Fe center. We report herein on the structures of the reduced and ligand-bound forms of cytochrome c-dependent NOR (cNOR) from Pseudomonas aeruginosa at a resolution of 2.3-2.7 Å, to elucidate structure-function relationships in NOR, and compare them to those of cytochrome c oxidase (CCO) that is evolutionarily related to NOR. Comprehensive crystallographic refinement of the CO-bound form of cNOR suggested that a total of four atoms can be accommodated at the binuclear center. Consistent with this, binding of bulky acetaldoxime (CH3-CH=N-OH) to the binuclear center of cNOR was confirmed by the structural analysis. Active site reduction and ligand binding in cNOR induced only ∼0.5 Å increase in the heme/non-heme Fe distance, but no significant structural change in the protein. The highly localized structural change is consistent with the lack of proton-pumping activity in cNOR, because redox-coupled conformational changes are thought to be crucial for proton pumping in CCO. It also permits the rapid decomposition of cytotoxic NO in denitrification. In addition, the shorter heme/non-heme Fe distance even in the bulky ligand-bound form of cNOR (∼4.5 Å) than the heme/Cu distance in CCO (∼5 Å) suggests the ability of NOR to maintain two NO molecules within a short distance in the confined space of the active site, thereby facilitating N-N coupling to produce a hyponitrite intermediate for the generation of N2O.

  3. Analysis of multiple haloarchaeal genomes suggests that the quinone-dependent respiratory nitric oxide reductase is an important source of nitrous oxide in hypersaline environments.

    PubMed

    Torregrosa-Crespo, Javier; González-Torres, Pedro; Bautista, Vanesa; Esclapez, Julia M; Pire, Carmen; Camacho, Mónica; Bonete, María José; Richardson, David J; Watmough, Nicholas J; Martínez-Espinosa, Rosa María

    2017-09-19

    Microorganisms, including Bacteria and Archaea, play a key role in denitrification, which is the major mechanism by which fixed nitrogen returns to the atmosphere from soil and water. Whilst the enzymology of denitrification is well understood in Bacteria, the details of the last two reactions in this pathway, which catalyse the reduction of nitric oxide (NO) via nitrous oxide (N2 O) to nitrogen (N2 ), are little studied in Archaea, and hardly at all in haloarchaea. This work describes an extensive interspecies analysis of both complete and draft haloarchaeal genomes aimed at identifying the genes that encode respiratory nitric oxide reductases (Nors). The study revealed that the only nor gene found in haloarchaea is one that encodes a single subunit quinone dependent Nor homologous to the qNor found in bacteria. This surprising discovery is considered in terms of our emerging understanding of haloarchaeal bioenergetics and NO management. This article is protected by copyright. All rights reserved. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  4. The RavA-ViaA Chaperone-Like System Interacts with and Modulates the Activity of the Fumarate Reductase Respiratory Complex.

    PubMed

    Wong, Keith S; Bhandari, Vaibhav; Janga, Sarath Chandra; Houry, Walid A

    2017-01-20

    Regulatory ATPase variant A (RavA) is a MoxR AAA+ protein that functions together with a partner protein that we termed VWA interacting with AAA+ ATPase (ViaA) containing a von Willebrand Factor A domain. However, the functional role of RavA-ViaA in the cell is not yet well established. Here, we show that RavA-ViaA are functionally associated with anaerobic respiration in Escherichia coli through interactions with the fumarate reductase (Frd) electron transport complex. Expression analysis of ravA and viaA genes showed that both proteins are co-expressed with multiple anaerobic respiratory genes, many of which are regulated by the anaerobic transcriptional regulator Fnr. Consistently, the expression of both ravA and viaA was found to be dependent on Fnr in cells grown under oxygen-limiting condition. ViaA was found to physically interact with FrdA, the flavin-containing subunit of the Frd complex. Both RavA and the Fe-S-containing subunit of the Frd complex, FrdB, regulate this interaction. Importantly, Frd activity was observed to increase in the absence of RavA and ViaA. This indicates that RavA and ViaA modulate the activity of the Frd complex, signifying a potential regulatory chaperone-like function for RavA-ViaA during bacterial anaerobic respiration with fumarate as the terminal electron acceptor. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Arsenate adsorption by unsaturated alluvial sediments

    USDA-ARS?s Scientific Manuscript database

    Arsenate adsorption as a function of solution arsenic concentration and solution pH was investigated on five alluvial sediments from the Antelope Valley, Western Mojave Desert, California. Arsenate adsorption increased with increasing solution pH, exhibited a maximum around pH 4 to 5, and then decr...

  6. Nitrate and periplasmic nitrate reductases

    PubMed Central

    Sparacino-Watkins, Courtney; Stolz, John F.; Basu, Partha

    2014-01-01

    The nitrate anion is a simple, abundant and relatively stable species, yet plays a significant role in global cycling of nitrogen, global climate change, and human health. Although it has been known for quite some time that nitrate is an important species environmentally, recent studies have identified potential medical applications. In this respect the nitrate anion remains an enigmatic species that promises to offer exciting science in years to come. Many bacteria readily reduce nitrate to nitrite via nitrate reductases. Classified into three distinct types – periplasmic nitrate reductase (Nap), respiratory nitrate reductase (Nar) and assimilatory nitrate reductase (Nas), they are defined by their cellular location, operon organization and active site structure. Of these, Nap proteins are the focus of this review. Despite similarities in the catalytic and spectroscopic properties Nap from different Proteobacteria are phylogenetically distinct. This review has two major sections: in the first section, nitrate in the nitrogen cycle and human health, taxonomy of nitrate reductases, assimilatory and dissimilatory nitrate reduction, cellular locations of nitrate reductases, structural and redox chemistry are discussed. The second section focuses on the features of periplasmic nitrate reductase where the catalytic subunit of the Nap and its kinetic properties, auxiliary Nap proteins, operon structure and phylogenetic relationships are discussed. PMID:24141308

  7. Definition of cytochrome c binding domains by chemical modification: Kinetics of reaction with beef mitochondrial reductase and functional organization of the respiratory chain*

    PubMed Central

    Speck, Samuel H.; Ferguson-Miller, Shelagh; Osheroff, Neil; Margoliash, E.

    1979-01-01

    An assay has been developed to study the steady-state kinetics of the reduction of cytochrome c by purified beef heart mitochondrial cytochrome c reductase (cytochrome bc1 complex, complex III). An analogue of coenzyme Q2 (2,3-dimethoxy-5-methyl-6-decylhydroquinone) was employed as an antimycin-sensitive reductant. The kinetics of reaction of ten different mono(4-carboxy-2,6-dinitrophenyl) derivatives of horse cytochrome c were determined. The modified proteins showed higher apparent Km values than the native protein and greater sensitivity to ionic strength, defining an interaction domain on cytochrome c for purified cytochrome c reductase. This interaction site is located on the front surface of the molecule (which contains the exposed heme edge) and surrounds the point at which the positive end of the dipole axis crosses the surface of the protein. The site is similar to that previously determined for mitochondrial cytochrome c oxidase and yeast cytochrome c peroxidase, suggesting that the primary interaction with redox partners is directed by the dipolar charge distribution on cytochrome c. The extensive overlapping of the interaction domains for the mitochondrial cytochrome c oxidase and reductase indicates that cytochrome c must be mobile in order to transfer electrons between them, depending on their relative positions in the membrane. Whether such mobility is necessary in intact mitochondria depends on whether the interactions with the complete membrane-bound system are the same as with the purified components. PMID:218193

  8. Biotransformation of the pesticide sodium arsenate.

    PubMed

    Shariatpanahi, M; Anderson, A C; Abdelghani, A A; Englande, A J; Hughes, J; Wilkinson, R F

    1981-01-01

    Biotransformation is an important parameter in assessing the environmental impact and fate of pesticides since metabolites produced may be either more or less toxic than the parent compound. Sodium arsenate (+5 inorganic), the wood preservative and insecticide, may be converted to both inorganic (+3) and organic compounds (-3) by microorganisms in soil, sediment and water bodies. Biotransformation of sodium arsenate was studied in pure cultures of 5 bacterial species using a mineral salt and limited carbon source medium. Arsenate concentrations were 10 microgram/ml and 100 microgram/ml of arsenic respectively. The rate of biodegradation of the parent compound was described by a first order composite exponential equation of the form Ct = C1e-k1t+C2e-k2t. Rates of production of metabolites (arsenite, monomethylarsine, dimethylarsine and trimethylarsine) were described by a first order exponential equation of the form Ct = Co (1-e-kt).

  9. Arsenate Resistance in the Unicellular Marine Diazotroph Crocosphaera watsonii.

    PubMed

    Dyhrman, Sonya T; Haley, Sheean T

    2011-01-01

    The toxic arsenate ion can behave as a phosphate analog, and this can result in arsenate toxicity especially in areas with elevated arsenate to phosphate ratios like the surface waters of the ocean gyres. In these systems, cellular arsenate resistance strategies would allow phytoplankton to ameliorate the effects of arsenate transport into the cell. Despite the potential coupling between arsenate and phosphate cycling in oligotrophic marine waters, relatively little is known about arsenate resistance in the nitrogen-fixing marine cyanobacteria that are key components of the microbial community in low nutrient systems. The unicellular diazotroph, Crocosphaera watsonii WH8501, was able to grow at reduced rates with arsenate additions up to 30 nM, and estimated arsenate to phosphate ratios of 6:1. The genome of strain WH8501 contains homologs for arsA, arsH, arsB, and arsC, allowing for the reduction of arsenate to arsenite and the pumping of arsenite out of the cell. The short-term addition of arsenate to the growth medium had no effect on nitrogen fixation. However, arsenate addition did result in the up-regulation of the arsB gene with increasing arsenate concentrations, indicating the induction of the arsenate detoxification response. The arsB gene was also up-regulated by phosphorus stress in concert with a gene encoding the high-affinity phosphate binding protein pstS. Both genes were down-regulated when phosphate was re-fed to phosphorus-stressed cells. A field survey of surface water from the low phosphate western North Atlantic detected expression of C. watsoniiarsB, suggestive of the potential importance of arsenate resistance strategies in this and perhaps other systems.

  10. Dissolution of arsenic minerals mediated by dissimilatory arsenate reducing bacteria: estimation of the physiological potential for arsenic mobilization.

    PubMed

    Lukasz, Drewniak; Liwia, Rajpert; Aleksandra, Mantur; Aleksandra, Sklodowska

    2014-01-01

    The aim of this study was characterization of the isolated dissimilatory arsenate reducing bacteria in the context of their potential for arsenic removal from primary arsenic minerals through reductive dissolution. Four strains, Shewanella sp. OM1, Pseudomonas sp. OM2, Aeromonas sp. OM4, and Serratia sp. OM17, capable of anaerobic growth with As (V) reduction, were isolated from microbial mats from an ancient gold mine. All of the isolated strains: (i) produced siderophores that promote dissolution of minerals, (ii) were resistant to dissolved arsenic compounds, (iii) were able to use the dissolved arsenates as the terminal electron acceptor, and (iii) were able to use copper minerals containing arsenic minerals (e.g., enargite) as a respiratory substrate. Based on the results obtained in this study, we postulate that arsenic can be released from some As-bearing polymetallic minerals (such as copper ore concentrates or middlings) under reductive conditions by dissimilatory arsenate reducers in indirect processes.

  11. Dissolution of Arsenic Minerals Mediated by Dissimilatory Arsenate Reducing Bacteria: Estimation of the Physiological Potential for Arsenic Mobilization

    PubMed Central

    Lukasz, Drewniak; Liwia, Rajpert; Aleksandra, Mantur; Aleksandra, Sklodowska

    2014-01-01

    The aim of this study was characterization of the isolated dissimilatory arsenate reducing bacteria in the context of their potential for arsenic removal from primary arsenic minerals through reductive dissolution. Four strains, Shewanella sp. OM1, Pseudomonas sp. OM2, Aeromonas sp. OM4, and Serratia sp. OM17, capable of anaerobic growth with As (V) reduction, were isolated from microbial mats from an ancient gold mine. All of the isolated strains: (i) produced siderophores that promote dissolution of minerals, (ii) were resistant to dissolved arsenic compounds, (iii) were able to use the dissolved arsenates as the terminal electron acceptor, and (iii) were able to use copper minerals containing arsenic minerals (e.g., enargite) as a respiratory substrate. Based on the results obtained in this study, we postulate that arsenic can be released from some As-bearing polymetallic minerals (such as copper ore concentrates or middlings) under reductive conditions by dissimilatory arsenate reducers in indirect processes. PMID:24724102

  12. Arsenolysis and Thiol-Dependent Arsenate Reduction

    EPA Science Inventory

    Conversion of arsenate to arsenite is a critical event in the pathway that leads from inorganic arsenic to a variety of methylated metabolites. The formation of methylated metabolites influences distribution and retention of arsenic and affects the reactivity and toxicity of thes...

  13. Arsenolysis and Thiol-Dependent Arsenate Reduction

    EPA Science Inventory

    Conversion of arsenate to arsenite is a critical event in the pathway that leads from inorganic arsenic to a variety of methylated metabolites. The formation of methylated metabolites influences distribution and retention of arsenic and affects the reactivity and toxicity of thes...

  14. Functional roles of arcA, etrA, cyclic AMP (cAMP)-cAMP receptor protein, and cya in the arsenate respiration pathway in Shewanella sp. strain ANA-3.

    PubMed

    Murphy, Julie N; Durbin, K James; Saltikov, Chad W

    2009-02-01

    Microbial arsenate respiration can enhance arsenic release from arsenic-bearing minerals--a process that can cause arsenic contamination of water. In Shewanella sp. strain ANA-3, the arsenate respiration genes (arrAB) are induced under anaerobic conditions with arsenate and arsenite. Here we report how genes that encode anaerobic regulator (arcA and etrA [fnr homolog]) and carbon catabolite repression (crp and cya) proteins affect arsenate respiration in ANA-3. Transcription of arcA, etrA, and crp in ANA-3 was similar in cells grown on arsenate and cells grown under aerobic conditions. ANA-3 strains lacking arcA and etrA showed minor to moderate growth defects, respectively, with arsenate. However, crp was essential for growth on arsenate. In contrast to the wild-type strain, arrA was not induced in the crp mutant in cultures shifted from aerobic to anaerobic conditions containing arsenate. This indicated that cyclic AMP (cAMP)-cyclic AMP receptor (CRP) activates arr operon transcription. Computation analysis for genome-wide CRP binding motifs identified a putative binding motif within the arr promoter region. This was verified by electrophoretic mobility shift assays with cAMP-CRP and several DNA probes. Lastly, four putative adenylate cyclase (cya) genes were identified in the genome. One particular cya-like gene was differentially expressed under aerobic versus arsenate respiration conditions. Moreover, a double mutant lacking two of the cya-like genes could not grow with arsenate as a terminal electron acceptor; exogenous cAMP could complement growth of the double cya mutant. It is concluded that the components of the carbon catabolite repression system are essential to regulating arsenate respiratory reduction in Shewanella sp. strain ANA-3.

  15. Thioredoxin reductase.

    PubMed Central

    Mustacich, D; Powis, G

    2000-01-01

    The mammalian thioredoxin reductases (TrxRs) are a family of selenium-containing pyridine nucleotide-disulphide oxidoreductases with mechanistic and sequence identity, including a conserved -Cys-Val-Asn-Val-Gly-Cys- redox catalytic site, to glutathione reductases. TrxRs catalyse the NADPH-dependent reduction of the redox protein thioredoxin (Trx), as well as of other endogenous and exogenous compounds. The broad substrate specificity of mammalian TrxRs is due to a second redox-active site, a C-terminal -Cys-SeCys- (where SeCys is selenocysteine), that is not found in glutathione reductase or Escherichia coli TrxR. There are currently two confirmed forms of mammalian TrxRs, TrxR1 and TrxR2, and it is possible that other forms will be identified. The availability of Se is a key factor determining TrxR activity both in cell culture and in vivo, and the mechanism(s) for the incorporation of Se into TrxRs, as well as the regulation of TrxR activity, have only recently begun to be investigated. The importance of Trx to many aspects of cell function make it likely that TrxRs also play a role in protection against oxidant injury, cell growth and transformation, and the recycling of ascorbate from its oxidized form. Since TrxRs are able to reduce a number of substrates other than Trx, it is likely that additional biological effects will be discovered for TrxR. Furthermore, inhibiting TrxR with drugs may lead to new treatments for human diseases such as cancer, AIDS and autoimmune diseases. PMID:10657232

  16. Arsenate removal using a combination treatment of precipitation and nanofiltration.

    PubMed

    Chang, F F; Liu, W J

    2012-01-01

    A combination treatment of Ca-precipitation and nanofiltration membrane was studied to remove arsenate from water. The selected nanofiltration membrane was an amphoteric charged membrane, proved by the results of ATR-FTIR spectra and zeta potential. The arsenate and calcium removal efficiencies had the lowest values at the isoelectric point of the nanofiltration membrane, attributed to the loosest steric hindrance and the weakest electrostatic repulsion. Above the isoelectric point, arsenate precipitated with calcium ion to form the low solubility compound calcium arsenate, while steric hindrance was the main mechanism of arsenate removal. In contrast, below the isoelectric point, the nanofiltration membrane with positive charges rejected calcium ion by electrostatic repulsion. The high electrostatic shielding of calcium ion prevented arsenate from coming close to the NF membrane. Either high feed arsenate concentration or high calcium oxide dose improved the removal amount of arsenate during the nanofiltration membrane separation process. In addition, the arsenate removal efficiency approached the highest value at 200 μg/L of feed arsenate concentration. The optimal transmembrane pressure was in a range of 0.5-0.7 MPa to restrict the formation of fouling cake on the nanofiltration membrane surface.

  17. Dissimilatory arsenate and sulfate reduction in sediments of two hypersaline, arsenic-rich soda lakes: Mono and Searles Lakes, California

    USGS Publications Warehouse

    Kulp, T.R.; Hoeft, S.E.; Miller, L.G.; Saltikov, C.; Murphy, J.N.; Han, S.; Lanoil, B.; Oremland, R.S.

    2006-01-01

    A radioisotope method was devised to study bacterial respiratory reduction of arsenate in sediments. The following two arsenic-rich soda lakes in California were chosen for comparison on the basis of their different salinities: Mono Lake (???90 g/liter) and Searles Lake (???340 g/liter). Profiles of arsenate reduction and sulfate reduction were constructed for both lakes. Reduction of [73As] arsenate occurred at all depth intervals in the cores from Mono Lake (rate constant [k] = 0.103 to 0.04 h-1) and Searles Lake (k = 0.012 to 0.002 h-1), and the highest activities occurred in the top sections of each core. In contrast, [35S] sulfate reduction was measurable in Mono Lake (k = 7.6 ?? 104 to 3.2 ?? 10-6 h-1) but not in Searles Lake. Sediment DNA was extracted, PCR amplified, and separated by denaturing gradient gel electrophoresis (DGGE) to obtain phylogenetic markers (i.e., 16S rRNA genes) and a partial functional gene for dissimilatory arsenate reduction (arrA). The amplified arrA gene product showed a similar trend in both lakes; the signal was strongest in surface sediments and decreased to undetectable levels deeper in the sediments. More arrA gene signal was observed in Mono Lake and was detectable at a greater depth, despite the higher arsenate reduction activity observed in Searles Lake. A partial sequence (about 900 bp) was obtained for a clone (SLAS-3) that matched the dominant DGGE band found in deeper parts of the Searles Lake sample (below 3 cm), and this clone was found to be closely related to SLAS-1, a novel extremophilic arsenate respirer previously cultivated from Searles Lake. Copyright ?? 2006, American Society for Microbiology. All Rights Reserved.

  18. Dissimilatory arsenate and sulfate reduction in sediments of two hypersaline, arsenic-rich soda lakes: Mono and Searles Lakes, California.

    PubMed

    Kulp, T R; Hoeft, S E; Miller, L G; Saltikov, C; Murphy, J N; Han, S; Lanoil, B; Oremland, R S

    2006-10-01

    A radioisotope method was devised to study bacterial respiratory reduction of arsenate in sediments. The following two arsenic-rich soda lakes in California were chosen for comparison on the basis of their different salinities: Mono Lake (approximately 90 g/liter) and Searles Lake (approximately 340 g/liter). Profiles of arsenate reduction and sulfate reduction were constructed for both lakes. Reduction of [73As]arsenate occurred at all depth intervals in the cores from Mono Lake (rate constant [k] = 0.103 to 0.04 h(-1)) and Searles Lake (k = 0.012 to 0.002 h(-1)), and the highest activities occurred in the top sections of each core. In contrast, [35S]sulfate reduction was measurable in Mono Lake (k = 7.6 x10(4) to 3.2 x 10(-6) h(-1)) but not in Searles Lake. Sediment DNA was extracted, PCR amplified, and separated by denaturing gradient gel electrophoresis (DGGE) to obtain phylogenetic markers (i.e., 16S rRNA genes) and a partial functional gene for dissimilatory arsenate reduction (arrA). The amplified arrA gene product showed a similar trend in both lakes; the signal was strongest in surface sediments and decreased to undetectable levels deeper in the sediments. More arrA gene signal was observed in Mono Lake and was detectable at a greater depth, despite the higher arsenate reduction activity observed in Searles Lake. A partial sequence (about 900 bp) was obtained for a clone (SLAS-3) that matched the dominant DGGE band found in deeper parts of the Searles Lake sample (below 3 cm), and this clone was found to be closely related to SLAS-1, a novel extremophilic arsenate respirer previously cultivated from Searles Lake.

  19. Effect of sodium arsenate on microbial growth in a chemostat.

    PubMed

    Shariatpanahi, M; Anderson, A C

    1981-01-01

    Microbial transformation of sodium arsenate, the wood preservative and insecticide, is important in assessing the environmental impact of this pesticide. Recent studies using batch culture techniques have shown that arsenate is metabolized to more toxic end products. This study investigated the effect of the chemical on the microbial cells themselves using continuous flow cultures to examine the effect of arsenate on the growth and maintenance requirements of the microbes. Cell yield was lower and maintenance requirements higher at 100 micrograms/ml arsenate than at 10 micrograms/ml indicating a greater expenditure of energy by the cells to maintain homeostasis.

  20. Mobilization of arsenite by dissimilatory reduction of adsorbed arsenate

    USGS Publications Warehouse

    Zobrist, J.; Dowdle, P.R.; Davis, J.A.; Oremland, R.S.

    2000-01-01

    Sulfurospirillum barnesii is capable of anaerobic growth using ferric iron or arsenate as electron acceptors. Cell suspensions of S. barnesii were able to reduce arsenate to arsenite when the former oxyanion was dissolved in solution, or when it was adsorbed onto the surface of ferrihydrite, a common soil mineral, by a variety of mechanisms (e.g., coprecipitation, presorption). Reduction of Fe(III) in ferrihydrite to soluble Fe(II) also occurred, but dissolution of ferrihydrite was not required in order for adsorbed arsenate reduction to be achieved. This was illustrated by bacterial reduction of arsenate coprecipitated with aluminum hydroxide, a mineral that does not undergo reductive dissolution. The rate of arsenate reduction was influenced by the method in which arsenate became associated with the mineral phases and may have been strongly coupled with arsenate desorption rates. The extent of release of arsenite into solution was governed by adsorption of arsenite onto the ferrihydrite or alumina phases. The results of these experiments have interpretive significance to the mobilization of arsenic in large alluvial aquifers, such as those of the Ganges in India and Bangladesh, and in the hyporheic zones of contaminated streams.Sulfurospirillum barnesii is capable of anaerobic growth using ferric iron or arsenate as electron acceptors. Cell suspensions of S. barnesii were able to reduce arsenate to arsenite when the former oxyanion was dissolved in solution, or when it was adsorbed onto the surface of ferrihydrite a common soil mineral, by a variety of mechanisms (e.g., coprecipitation, presorption). Reduction of Fe(III) in ferrihydrite to soluble Fe(II) also occurred, but dissolution of ferrihydrite was not required in order for adsorbed arsenate reduction to be achieved. This was illustrated by bacterial reduction of arsenate coprecipitated with aluminum hydroxide, a mineral that does not undergo reductive dissolution. The rate of arsenate reduction was

  1. Elucidating the Structures of the Low- and High-pH Mo(V) Species in Respiratory Nitrate Reductase: A Combined EPR, (14,15)N HYSCORE, and DFT Study.

    PubMed

    Rendon, Julia; Biaso, Frédéric; Ceccaldi, Pierre; Toci, René; Seduk, Farida; Magalon, Axel; Guigliarelli, Bruno; Grimaldi, Stéphane

    2017-03-31

    Respiratory nitrate reductases (Nars), members of the prokaryotic Mo/W-bis Pyranopterin Guanosine dinucleotide (Mo/W-bisPGD) enzyme superfamily, are key players in nitrate respiration, a major bioenergetic pathway widely used by microorganisms to cope with the absence of dioxygen. The two-electron reduction of nitrate to nitrite takes place at their active site, where the molybdenum ion cycles between Mo(VI) and Mo(IV) states via a Mo(V) intermediate. The active site shows two distinct pH-dependent Mo(V) electron paramagnetic resonance (EPR) signals whose structure and catalytic relevance have long been debated. In this study, we use EPR and HYSCORE techniques to probe their nuclear environment in Escherichia coli Nar (EcNar). By using samples prepared at different pH and through different enrichment strategies in (98)Mo and (15)N nuclei, we demonstrate that each of the two Mo(V) species is coupled to a single nitrogen nucleus with similar quadrupole characteristics. Structure-based density functional theory calculations allow us to propose a molecular model of the low-pH Mo(V) species consistent with EPR spectroscopic data. Our results show that the metal ion is coordinated by a monodentate aspartate ligand and permit the assignment of the coupled nitrogen nuclei to the Nδ of Asn52, a residue located ∼3.9 Å to the Mo atom in the crystal structures. This is confirmed by measurements on selectively (15)N-Asn labeled EcNar. Further, we propose a Mo-O(H)···HN structure to account for the transfer of spin density onto the interacting nitrogen nucleus deduced from HYSCORE analysis. This work provides a foundation for monitoring the structure of the molybdenum active site in the presence of various substrates or inhibitors in Nars and other molybdenum enzymes.

  2. Investigation of biochemical responses of Bacopa monnieri L. upon exposure to arsenate.

    PubMed

    Mishra, Seema; Srivastava, Sudhakar; Dwivedi, Sanjay; Tripathi, Rudra Deo

    2013-08-01

    Widespread contamination of arsenic (As) is recognized as a global problem due to its well-known accumulation by edible and medicinal plants and associated health risks for the humans. In this study, phytotoxicity imposed upon exposure to arsenate [As(V); 0-250 μM for 1-7 days] and ensuing biochemical responses were investigated in a medicinal herb Bacopa monnieri L. vis-à-vis As accumulation. Plants accumulated substantial amount of As (total 768 μg g(-1) dw at 250 μM As(V) after 7 days) with the maximum As retention being in roots (60%) followed by stem (23%) and leaves (17%). The level of cysteine and total nonprotein thiols (NP-SH) increased significantly at all exposure concentrations and durations. Besides, the level of metalloid binding ligands viz., glutathione (GSH) and phytochelatins (PCs) increased significantly at the studied concentrations [50 and 250 μM As(V)] in both roots and leaves. The activities of various enzymes viz., arsenate reductase (AR), glutathione reductase (GR), superoxide dismutase (SOD), guaiacol peroxidase (GPX), ascorbate peroxidase (APX), and catalase (CAT) showed differential but coordinated stimulation in leaves and roots to help plants combat As toxicity up to moderate exposure concentrations (50 μM). However, beyond 50 μM, biomass production was found to decrease along with photosynthetic pigments and total soluble proteins, whereas lipid peroxidation increased. In conclusion, As accumulation potential of Bacopa may warrant its use as a phytoremediator but if Bacopa growing in contaminated areas is consumed by humans, it may prove to be toxic for health.

  3. WRKY6 Transcription Factor Restricts Arsenate Uptake and Transposon Activation in Arabidopsis[W

    PubMed Central

    Castrillo, Gabriel; Sánchez-Bermejo, Eduardo; de Lorenzo, Laura; Crevillén, Pedro; Fraile-Escanciano, Ana; TC, Mohan; Mouriz, Alfonso; Catarecha, Pablo; Sobrino-Plata, Juan; Olsson, Sanna; Leo del Puerto, Yolanda; Mateos, Isabel; Rojo, Enrique; Hernández, Luis E.; Jarillo, Jose A.; Piñeiro, Manuel; Paz-Ares, Javier; Leyva, Antonio

    2013-01-01

    Stress constantly challenges plant adaptation to the environment. Of all stress types, arsenic was a major threat during the early evolution of plants. The most prevalent chemical form of arsenic is arsenate, whose similarity to phosphate renders it easily incorporated into cells via the phosphate transporters. Here, we found that arsenate stress provokes a notable transposon burst in plants, in coordination with arsenate/phosphate transporter repression, which immediately restricts arsenate uptake. This repression was accompanied by delocalization of the phosphate transporter from the plasma membrane. When arsenate was removed, the system rapidly restored transcriptional expression and membrane localization of the transporter. We identify WRKY6 as an arsenate-responsive transcription factor that mediates arsenate/phosphate transporter gene expression and restricts arsenate-induced transposon activation. Plants therefore have a dual WRKY-dependent signaling mechanism that modulates arsenate uptake and transposon expression, providing a coordinated strategy for arsenate tolerance and transposon gene silencing. PMID:23922208

  4. Phytochelatins Are Involved in Differential Arsenate Tolerance in Holcus lanatus1

    PubMed Central

    Hartley-Whitaker, Jeanette; Ainsworth, Gillian; Vooijs, Riet; Bookum, Wilma Ten; Schat, Henk; Meharg, Andrew A.

    2001-01-01

    Arsenate tolerance is conferred by suppression of the high-affinity phosphate/arsenate uptake system, which greatly reduces arsenate influx in a number of higher plant species. Despite this suppressed uptake, arsenate-tolerant plants can still accumulate high levels of As over their lifetime, suggesting that constitutive detoxification mechanisms may be required. Phytochelatins are thiol-rich peptides, whose production is induced by a range of metals and metalloids including arsenate. This study provides evidence for the role of phytochelatins in the detoxification of arsenate in arsenate-tolerant Holcus lanatus. Elevated levels of phytochelatin were measured in plants with a range of tolerance to arsenate at equivalent levels of arsenate stress, measured as inhibition of root growth. The results suggest that arsenate tolerance in H. lanatus requires both adaptive suppression of the high-affinity phosphate uptake system and constitutive phytochelatin production. PMID:11351093

  5. Metabolism of arsenite and arsenate by the rat

    SciTech Connect

    Lerman, S.A.

    1982-01-01

    The metabolism of arsenite and arsenate by mice and rats was investigated. In initial studies, mice eliminated almost 100 percent of a single intraperitoneal dose (0.5 mg/kg) of sodium arsenite or arsenate. About 90 percent of the arsenic eliminated in urine by 24 hours was dimethylarsinic acid (DMA). Rats, however, eliminated only about 50 percent of the same dose of sodium arsenate and only 10 percent of the arsenic in the urine was DMA. Further studies were focused on the metabolism of arsenic by the rat. After i.v. administration of 4.8 nmole arsenite or arsenate to male Sprague-Dawley rats, blood levels of arsenic rose over four hours to about 60 percent of the initial dose of arsenite and 30 percent of the initial dose of arsenate. The predominant form of arsenic in the blood was DMA. Arsenite was rapidly distributed to both liver and kidney; arsenate was rapidly distributed to kidney only. The metabolite, DMA, appeared in the urine by one hour after administration of either form. These studies suggest that inorganic arsenic is rapidly taken up by liver and kidney, depending on the valence of the arsenic. The liver is more important in the metabolism of arsenite, but the kidney takes up and methylates both arsenite and arsenate. The DMA produced by these organs binds to the red blood cells. This binding appears to be the main difference between the rat and other mammalian species. 76 references, 33 figures, 7 tables.

  6. Uranyl and Arsenate Cosorption on Aluminum Oxide Surface

    SciTech Connect

    Tang, Y.; Reeder, R

    2009-01-01

    In this study, we examined the effects of simultaneous adsorption of aqueous arsenate and uranyl onto aluminum oxide over a range of pH and concentration conditions. Arsenate was used as a chemical analog for phosphate, and offers advantages for characterization via X-ray absorption spectroscopy. By combining batch experiments, speciation calculations, X-ray absorption spectroscopy, and X-ray diffraction, we investigated the uptake behavior of uranyl, as well as the local and long-range structure of the final sorption products. In the presence of arsenate, uranyl sorption was greatly enhanced in the acidic pH range, and the amount of enhancement is positively correlated to the initial arsenate and uranyl concentrations. At pH 4-6, U L{sub III-} and As K-edge EXAFS results suggest the formation of surface-sorbed uranyl and arsenate species as well as uranyl arsenate surface precipitate(s) that have a structure similar to tr{umlt o}gerite. Uranyl polymeric species or oxyhydroxide precipitate(s) become more important with increasing pH values. Our results provide the basis for predictive models of the uptake of uranyl by aluminum oxide in the presence of arsenate and (by analogy) phosphate, which can be especially important for understanding phosphate-based uranium remediation systems.

  7. Arsenate adsorption on ruthenium oxides: A spectroscopic and kinetic investigation

    SciTech Connect

    Luxton, Todd P.; Eick, Matthew J.; Scheckel, Kirk G.

    2008-12-08

    Arsenate adsorption on amorphous (RuO{sub 2} {center_dot} 1.1H{sub 2}O) and crystalline (RuO{sub 2}) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was used to determine the local coordination environment of adsorbed arsenate. Additionally, pressure-jump (p-jump) relaxation spectroscopy was used to investigate the kinetics of arsenate adsorption/desorption on ruthenium oxides. Chemical relaxations resulting from the induced pressure change were monitored via electrical conductivity detection. EXAFS data were collected for two initial arsenate solution concentrations, 3 and 33 mM at pH 5. The collected spectra indicated a similar coordination environment for arsenate adsorbed to RuO{sub 2} {center_dot} 1.1H{sub 2}O for both arsenate concentrations. In contrast the EXAFS spectra of RuO{sub 2} indicated differences in the local coordination environments for the crystalline material with increasing arsenate concentration. Data analysis indicated that both mono- and bidentate surfaces complexes were present on both RuO{sub 2} {center_dot} 1.1H{sub 2}O and RuO{sub 2}. Relaxation spectra from the pressure-jump experiments of both ruthenium oxides resulted in a double relaxation event. Based on the relaxation spectra, a two step reaction mechanism for arsenate adsorption is proposed resulting in the formation of a bidentate surface complex. Analysis of the kinetic and spectroscopic data suggested that while there were two relaxation events, arsenate adsorbed to ruthenium oxide surfaces through both mono- and bidentate surface complexes.

  8. Raman spectroscopy of selected arsenates--implications for soil remediation.

    PubMed

    Frost, Ray L; Kloprogge, Theo; Weier, Matthew L; Martens, Wayde N; Ding, Z; Edwards, Howell G H

    2003-08-01

    The contamination of soils with heavy metals such as As, Cr and Cu is of great importance; the remediation of such soils even more so. Arsenic compounds are prevalent in soils either through leaching of mine tailings, the use of Cu/Cr/As as a wood preservative or through the use of arsenic in cattle dips. The arsenic compounds in soils and leachates can be highly reactive and mobile, resulting in the formation of metal arsenate compounds. Of these compounds, one such set of minerals that can be formed is the vivianite arsenate minerals. Raman spectroscopy has been used to characterise the vivianite arsenates and to identify arsenic contaminants in a soil.

  9. Synthesis and thermodynamic properties of arsenate and sulfate-arsenate ettringite structure phases

    PubMed Central

    Wang, Weixing; Shao, Yan; Hou, Haobo; Zhou, Min

    2017-01-01

    Arsenic is a toxic and carcinogenic contaminant of potential concern. Ettringite [Ca6Al2(SO4)3(OH)12·26H2O] has the ability to incorporate oxyanions as a solid solution with SO42−, which could lower the soluble oxyanion concentrations. Therefore, ettringite containing SO42− and AsO43− has been synthesized. Results indicated that AsO43− could substitute for SO42− inside the channels of ettringite in the form of HAsO42−, and a linear correlation existed between Xinitial solution and Xsolid. The thermodynamic characterization of the solid samples was investigated by means of Visual MINTEQ, a freeware chemical equilibrium model, and the solubility product logK of -48.4 ± 0.4 was calculated for HAsO4–ettringite at 25°C. The Lippmann phase diagram and XHAsO4–XHAsO4,aq plot showed that the solid solution series containing arsenate has HAsO4-poor aqueous solutions in equilibrium. These findings can be helpful to arsenate solidification and arsenate leaching modeling projects. PMID:28759655

  10. An arsenate-reducing and alkane-metabolizing novel bacterium, Rhizobium arsenicireducens sp. nov., isolated from arsenic-rich groundwater.

    PubMed

    Mohapatra, Balaram; Sarkar, Angana; Joshi, Swati; Chatterjee, Atrayee; Kazy, Sufia Khannam; Maiti, Mrinal Kumar; Satyanarayana, Tulasi; Sar, Pinaki

    2017-03-01

    A novel arsenic (As)-resistant, arsenate-respiring, alkane-metabolizing bacterium KAs 5-22(T), isolated from As-rich groundwater of West Bengal was characterized by physiological and genomic properties. Cells of strain KAs 5-22(T) were Gram-stain-negative, rod-shaped, motile, and facultative anaerobic. Growth occurred at optimum of pH 6.0-7.0, temperature 30 °C. 16S rRNA gene affiliated the strain KAs 5-22(T) to the genus Rhizobium showing maximum similarity (98.4 %) with the type strain of Rhizobium naphthalenivorans TSY03b(T) followed by (98.0 % similarity) Rhizobium selenitireducens B1(T). The genomic G + C content was 59.4 mol%, and DNA-DNA relatedness with its closest phylogenetic neighbors was 50.2 %. Chemotaxonomy indicated UQ-10 as the major quinone; phosphatidylethanolamine, phosphatidylglycerol, and diphosphatidylglycerol as major polar lipids; C16:0, C17:0, 2-OH C10:0, 3-OH C16:0, and unresolved C18:1 ɷ7C/ɷ9C as predominant fatty acids. The cells were found to reduce O2, As(5+), NO3(-), SO4(2-) and Fe(3+) as alternate electron acceptors. The strain's ability to metabolize dodecane or other alkanes as sole carbon source using As(5+) as terminal electron acceptor was supported by the presence of genes encoding benzyl succinate synthase (bssA like) and molybdopterin-binding site (mopB) of As(5+) respiratory reductase (arrA). Differential phenotypic, chemotaxonomic, genotypic as well as physiological properties revealed that the strain KAs 5-22(T) is separated from its nearest recognized Rhizobium species. On the basis of the data presented, strain KAs 5-22(T) is considered to represent a novel species of the genus Rhizobium, for which the name Rhizobium arsenicireducens sp. nov. is proposed as type strain (=LMG 28795(T)=MTCC 12115(T)).

  11. Effects of maternal restraint stress and sodium arsenate in mice.

    PubMed

    Rasco, J F; Hood, R D

    1994-01-01

    Either maternal restraint stress or sodium arsenate treatment during pregnancy can cause adverse effects on the mouse conceptus. The current study assessed the effects of both factors administered concurrently. Five treatment groups were used initially: (1) vehicle (H2O) control [C], (2) feed/water deprived [FWD], (3) sodium arsenate [SA], (4) restraint only [R], and (5) sodium arsenate plus restraint [SA+R]. A sixth group, arsenate plus feed/water deprived [SA+FWD], was added later, along with (7) a concurrent arsenate-only control [SAC]. Mated female CD-1 mice in Groups 3, 5, 6, and 7 were injected ip with sodium arsenate (20 mg/kg) on gestation day (GD) 9 (plug = day 1). Group 5 mice were restrained for 12 h beginning immediately after dosing. Groups 4 and 5 were restrained in the supine position from 9:00 a.m. to 9:00 p.m. on GD 9; FWD mice were deprived during that time. All females were killed on GD 18 and subjected to teratologic examination. Significantly increased exencephaly and decreased fetal weight were seen in SA+R Group fetuses. The incidence of supernumerary ribs was significantly higher in the SA+R Group than in the SA Group but did not differ from the R Group. These results add to the evidence that maternal stress combined with a chemical teratogen may have a greater effect on the conceptus than would exposure to either agent alone.

  12. Biotransformation of arsenic by bacterial strains mediated by oxido-reductase enzyme system.

    PubMed

    Vishnoi, N; Singh, D P

    2014-12-24

    The present study deals with the enzyme mediated biotransformation of arsenic in five arsenic tolerant strains (Bacillus subtilis, Bacillus megaterium, Bacillus pumilus, Paenibacillus macerans and Escherichia coli). Biotransformation ability of these isolates was evaluated by monitoring arsenite oxidase and arsenate reductase activity. Results showed that arsenic oxidase activity was exclusively present in P. macerans and B. pumilus while B. subtilis, B. megaterium and E. coli strains showed presence of Arsenic oxido-reductase enzyme. The reversible nature of arsenic oxido- reductase suggested that same enzyme can carry out oxidation and reduction of arsenic depending upon the relative concentration of arsenic species. Lineweaver-Burk plot of the arsenite oxidase activity in P. macerans showed highest Km value (Km- 200 μM) and lower Vmax (0.012 μmol mg-1 protein min-1) indicating lowest affinity of the enzyme for arsenite. On the contrary, E. coli showed the lower Km value ( Km- 38.46 μM) and higher Vmax (0.044 μmol mg-1 protein min-1) suggesting for higher affinity for the arsenite. Lineweaver-Burk plot of arsenate reductase activity showed the presence of this enzyme in B. subtilis, B. megaterium and E. coli which were in the range of 200-360 μM Km and Vmax value between 0.256- 0.129 mmol mg-1 protein min-1. These results suggested that affinity of the as reductase enzyme is lowest for arsenate than that for the arsenite. Thus, arsenite oxidase system appears to be a predominant mechanism of cellular defense in these bacterial strains.

  13. Expression profiling of Crambe abyssinica under arsenate stress identifies genes and gene networks involved in arsenic metabolism and detoxification.

    PubMed

    Paulose, Bibin; Kandasamy, Suganthi; Dhankher, Om Parkash

    2010-06-14

    Arsenic contamination is widespread throughout the world and this toxic metalloid is known to cause cancers of organs such as liver, kidney, skin, and lung in human. In spite of a recent surge in arsenic related studies, we are still far from a comprehensive understanding of arsenic uptake, detoxification, and sequestration in plants. Crambe abyssinica, commonly known as 'abyssinian mustard', is a non-food, high biomass oil seed crop that is naturally tolerant to heavy metals. Moreover, it accumulates significantly higher levels of arsenic as compared to other species of the Brassicaceae family. Thus, C. abyssinica has great potential to be utilized as an ideal inedible crop for phytoremediation of heavy metals and metalloids. However, the mechanism of arsenic metabolism in higher plants, including C. abyssinica, remains elusive. To identify the differentially expressed transcripts and the pathways involved in arsenic metabolism and detoxification, C. abyssinica plants were subjected to arsenate stress and a PCR-Select Suppression Subtraction Hybridization (SSH) approach was employed. A total of 105 differentially expressed subtracted cDNAs were sequenced which were found to represent 38 genes. Those genes encode proteins functioning as antioxidants, metal transporters, reductases, enzymes involved in the protein degradation pathway, and several novel uncharacterized proteins. The transcripts corresponding to the subtracted cDNAs showed strong upregulation by arsenate stress as confirmed by the semi-quantitative RT-PCR. Our study revealed novel insights into the plant defense mechanisms and the regulation of genes and gene networks in response to arsenate toxicity. The differential expression of transcripts encoding glutathione-S-transferases, antioxidants, sulfur metabolism, heat-shock proteins, metal transporters, and enzymes in the ubiquitination pathway of protein degradation as well as several unknown novel proteins serve as molecular evidence for the

  14. Expression profiling of Crambe abyssinica under arsenate stress identifies genes and gene networks involved in arsenic metabolism and detoxification

    PubMed Central

    2010-01-01

    Background Arsenic contamination is widespread throughout the world and this toxic metalloid is known to cause cancers of organs such as liver, kidney, skin, and lung in human. In spite of a recent surge in arsenic related studies, we are still far from a comprehensive understanding of arsenic uptake, detoxification, and sequestration in plants. Crambe abyssinica, commonly known as 'abyssinian mustard', is a non-food, high biomass oil seed crop that is naturally tolerant to heavy metals. Moreover, it accumulates significantly higher levels of arsenic as compared to other species of the Brassicaceae family. Thus, C. abyssinica has great potential to be utilized as an ideal inedible crop for phytoremediation of heavy metals and metalloids. However, the mechanism of arsenic metabolism in higher plants, including C. abyssinica, remains elusive. Results To identify the differentially expressed transcripts and the pathways involved in arsenic metabolism and detoxification, C. abyssinica plants were subjected to arsenate stress and a PCR-Select Suppression Subtraction Hybridization (SSH) approach was employed. A total of 105 differentially expressed subtracted cDNAs were sequenced which were found to represent 38 genes. Those genes encode proteins functioning as antioxidants, metal transporters, reductases, enzymes involved in the protein degradation pathway, and several novel uncharacterized proteins. The transcripts corresponding to the subtracted cDNAs showed strong upregulation by arsenate stress as confirmed by the semi-quantitative RT-PCR. Conclusions Our study revealed novel insights into the plant defense mechanisms and the regulation of genes and gene networks in response to arsenate toxicity. The differential expression of transcripts encoding glutathione-S-transferases, antioxidants, sulfur metabolism, heat-shock proteins, metal transporters, and enzymes in the ubiquitination pathway of protein degradation as well as several unknown novel proteins serve as

  15. Structural characterization and vibrational spectroscopy of the arsenate mineral wendwilsonite.

    PubMed

    Frost, Ray L; Scholz, Ricardo; López, Andrés; Belotti, Fernanda Maria; Xi, Yunfei

    2014-01-24

    In this paper, we have investigated on the natural wendwilsonite mineral with the formulae Ca2(Mg,Co)(AsO4)2⋅2(H2O). Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the wendwilsonite arsenate mineral. A comparison is made with the roselite mineral group with formula Ca2B(AsO4)2⋅2H2O (where B may be Co, Fe(2+), Mg, Mn, Ni, Zn). The Raman spectra of the arsenate related to tetrahedral arsenate clusters with stretching region shows strong differences between that of wendwilsonite and the roselite arsenate minerals which is attributed to the cation substitution for calcium in the structure. The Raman arsenate (AsO4)(3-) stretching region shows strong differences between that of wendwilsonite and the roselite arsenate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists of multiple to tetrahedral (AsO4)(3-) clusters with antisymmetric stretching vibrations observed indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 450 cm(-1) are assigned to ν4 bending modes. Multiple bands in the 350-300 cm(-1) region assigned to ν2 bending modes provide evidence of symmetry reduction of the arsenate anion. Three broad bands for wendwilsonite found at 3332, 3119 and 3001 cm(-1) are assigned to OH stretching bands. By using a Libowitzky empirical equation, hydrogen bond distances of 2.65 and 2.75Å are estimated. Vibrational spectra enable the molecular structure of the wendwilsonite mineral to be determined and whilst similarities exist in the spectral patterns with the roselite mineral group, sufficient differences exist to be able to determine the identification of the minerals.

  16. Metabolism of arsenite and arsenate by the rat

    SciTech Connect

    Lerman, S.A.

    1983-01-01

    The metabolism of arsenite and arsenate by mice and rats was investigated. In initial studies, mice eliminated almost 100% of a single intraperitoneal dose (0.5 mg/kg) of sodium arsenite or arsenate. About 90% of the arsenic eliminated in urine by 24 hours was dimethylarsinic acid (DMA). Rats, however, eliminated only about 50% of the same dose of sodium arsenate and only 10% of the arsenic in the urine was DMA. Further studies were focused on the metabolism of arsenic by the rat. After four hours of exposure to arsenite, liver slices had taken up six times more arsenic and kidney slices two times more arsenic than after exposure to arsenate. Isolated hepatocytes took up as much as 20 times more arsenic after arsenite exposure. DMA was found in the medium of the liver slices and hepatocytes exposed to arsenite, but very little DMA was found in the medium 85%. These studies suggest that inorganic arsenic is rapidly taken up by liver and kidney, depending on the valence of the arsenic. The liver is more important in the metabolism of arsenite, but the kidney takes up and methylates both arsenite and arsenate. The DMA produced by these organs binds to the red blood cells. This binding appears to be the main difference between the rat and other mammalian species.

  17. ARSENATE CARRIER PRECIPITATION METHOD OF SEPARATING PLUTONIUM FROM NEUTRON IRRADIATED URANIUM AND RADIOACTIVE FISSION PRODUCTS

    DOEpatents

    Thompson, S.G.; Miller, D.R.; James, R.A.

    1961-06-20

    A process is described for precipitating Pu from an aqueous solution as the arsenate, either per se or on a bismuth arsenate carrier, whereby a separation from uranium and fission products, if present in solution, is accomplished.

  18. Shewanella sp. O23S as a Driving Agent of a System Utilizing Dissimilatory Arsenate-Reducing Bacteria Responsible for Self-Cleaning of Water Contaminated with Arsenic

    PubMed Central

    Drewniak, Lukasz; Stasiuk, Robert; Uhrynowski, Witold; Sklodowska, Aleksandra

    2015-01-01

    The purpose of this study was a detailed characterization of Shewanella sp. O23S, a strain involved in arsenic transformation in ancient gold mine waters contaminated with arsenic and other heavy metals. Physiological analysis of Shewanella sp. O23S showed that it is a facultative anaerobe, capable of growth using arsenate, thiosulfate, nitrate, iron or manganite as a terminal electron acceptor, and lactate or citrate as an electron donor. The strain can grow under anaerobic conditions and utilize arsenate in the respiratory process in a broad range of temperatures (10–37 °C), pH (4–8), salinity (0%–2%), and the presence of heavy metals (Cd, Co, Cr, Cu, Mn, Mo, Se, V and Zn). Under reductive conditions this strain can simultaneously use arsenate and thiosulfate as electron acceptors and produce yellow arsenic (III) sulfide (As2S3) precipitate. Simulation of As-removal from water containing arsenate (2.5 mM) and thiosulfate (5 mM) showed 82.5% efficiency after 21 days of incubation at room temperature. Based on the obtained results, we have proposed a model of a microbially mediated system for self-cleaning of mine waters contaminated with arsenic, in which Shewanella sp. O23S is the main driving agent. PMID:26121297

  19. Multiple Scattering Debye-Waller Factors for Arsenate

    NASA Astrophysics Data System (ADS)

    Kim, E.; Chen, N.; Arthur, Z.; Warner, J.; Demopoulos, G. P.; Rowson, J. W.; Jiang, D. T.

    2013-04-01

    Debye-Waller factors for the As-O-O triangular multiple scattering paths within the arsenate in Na2HAsO4·7H2O are evaluated in terms of magnitude ratio with respect to the Debye-Waller factor of the nearest neighbour As-O shell (σ2As-0-0/σ2As-0). The arsenates are studied under two different levels of distortion from an ideal tetrahedron, i.e. a relatively high distortion in the powder form and a nearly ideal tetrahedron in an aqueous solution at pH 14. The Debye-Waller factor ratio σ2As-0-0/σ2As-0) is found to be 2.0 and 1.9 for the powder and liquid sample, respectively, appearing to be insensitive to the distortion of the arsenate tetrahedron.

  20. Toxicity and bioaccumulation kinetics of arsenate in two freshwater green algae under different phosphate regimes.

    PubMed

    Wang, Ning-Xin; Li, Yan; Deng, Xi-Hai; Miao, Ai-Jun; Ji, Rong; Yang, Liu-Yan

    2013-05-01

    In the present study, the toxicity and bioaccumulation kinetics of arsenate in two green algae Chlamydomonas reinhardtii and Scenedesmus obliquus under phosphate-enriched (+P) and limited (-P) conditions were investigated. P-limitation was found to aggravate arsenate toxicity and S. obliquus was more tolerant than C. reinhardtii. Such phosphate-condition-dependent or algal-species-specific toxicity difference was narrowed when the relative inhibition of cell growth was plotted against intracellular arsenate content instead of its extracellular concentration. The discrepance was further reduced when the intracellular ratio of arsenic to phosphorus was applied. It suggests that both arsenate bioaccumulation and intracellular phosphorus played an important role in arsenate toxicity. On the other hand, arsenate uptake was induced by P-limitation and its variation with ambient arsenate concentration could be well fitted to the Michaelis-Menten model. Arsenate transporters of S. obliquus were found to have a higher affinity but lower capacity than those of C. reinhardtii, which explains its better regulation of arsenate accumulation than the latter species in the toxicity experiment. Further, arsenate depuration was facilitated and more was transformed to arsenite in C. reinhardtii or under -P condition. Intracellular proportion of arsenite was also increased after the algae were transferred from the long-term uptake media to a relatively clean solution in the efflux experiment. Both phenomena imply that algae especially the sensitive species could make physiological adjustments to alleviate the adverse effects of arsenate. Overall, our findings will facilitate the application of algae in arsenate remediation.

  1. Bridging arsenate surface complexes on the hematite (012) surface.

    SciTech Connect

    Catalano, J. G.; Zhang, Z.; Park, C.; Fenter, P.; Bedzyk, M. J.; Chemistry; Northwestern Univ.

    2007-04-15

    The fate of the oxoanion arsenate in diverse systems is strongly affected by its adsorption on the surfaces of iron (oxyhydr)oxide minerals. Predicting this behavior in the environment requires an understanding of the mechanisms of arsenate adsorption. In this study, the binding site and adsorption geometry of arsenate on the hematite (012) surface is investigated. The structure and termination of the hematite (012)-water interface were determined by high resolution X-ray reflectivity, revealing that two distinct terminations exist in a roughly 3:1 proportion. The occurrence of multiple terminations appears to be a result of sample preparation, and is not intrinsic to the hematite (012) surface. X-ray standing wave (XSW) measurements were used to determine the registry of adsorbed arsenate to the hematite structure, and thus the binding site and geometry of the resulting surface complex. Arsenate forms a bridging bidentate complex on two adjacent singly coordinated oxygen groups on each of the two distinct terminations present at the hematite surface. Although this geometry is consistent with that seen in past studies, the derived As-Fe distances are longer, the result of the topology of the FeO6 octahedra on the (012) surface. As EXAFS-derived As-Fe distances are often used to determine the adsorption mechanism in environmental samples (e.g., mine tailings, contaminated sediments), this demonstrates the importance of considering the possible sorbent surface structures and arrangements of adsorbates when interpreting such data. As multiple functional groups are present and multiple binding geometries are possible on the hematite (012) surface, the XSW data suggest that formation of bridging bidentate surface complexes on singly coordinated oxygen sites is the preferred adsorption mechanism on this and most other hematite surfaces (provided those surfaces contain adjacent singly coordinated oxygen groups). These measurements also constrain the likely reaction

  2. Dissimilatory arsenate reduction with sulfide as electron donor: experiments with mono lake water and Isolation of strain MLMS-1, a chemoautotrophic arsenate respirer.

    PubMed

    Hoeft, Shelley E; Kulp, Thomas R; Stolz, John F; Hollibaugh, James T; Oremland, Ronald S

    2004-05-01

    Anoxic bottom water from Mono Lake, California, can biologically reduce added arsenate without any addition of electron donors. Of the possible in situ inorganic electron donors present, only sulfide was sufficiently abundant to drive this reaction. We tested the ability of sulfide to serve as an electron donor for arsenate reduction in experiments with lake water. Reduction of arsenate to arsenite occurred simultaneously with the removal of sulfide. No loss of sulfide occurred in controls without arsenate or in sterilized samples containing both arsenate and sulfide. The rate of arsenate reduction in lake water was dependent on the amount of available arsenate. We enriched for a bacterium that could achieve growth with sulfide and arsenate in a defined, mineral medium and purified it by serial dilution. The isolate, strain MLMS-1, is a gram-negative, motile curved rod that grows by oxidizing sulfide to sulfate while reducing arsenate to arsenite. Chemoautotrophy was confirmed by the incorporation of H(14)CO(3)(-) into dark-incubated cells, but preliminary gene probing tests with primers for ribulose-1,5-biphosphate carboxylase/oxygenase did not yield PCR-amplified products. Alignment of 16S rRNA sequences indicated that strain MLMS-1 was in the delta-Proteobacteria, located near sulfate reducers like Desulfobulbus sp. (88 to 90% similarity) but more closely related (97%) to unidentified sequences amplified previously from Mono Lake. However, strain MLMS-1 does not grow with sulfate as its electron acceptor.

  3. Dissimilatory arsenate reduction with sulfide as electron donor: Experiments with Mono Lake water and isolation of strain MLMS-1, a chemoautotrophic arsenate respirer

    USGS Publications Warehouse

    Hoeft, S.E.; Kulp, T.R.; Stolz, J.F.; Hollibaugh, J.T.; Oremland, R.S.

    2004-01-01

    Anoxic bottom water from Mono Lake, California, can biologically reduce added arsenate without any addition of electron donors. Of the possible in situ inorganic electron donors present, only sulfide was sufficiently abundant to drive this reaction. We tested the ability of sulfide to serve as an electron donor for arsenate reduction in experiments with lake water. Reduction of arsenate to arsenite occurred simultaneously with the removal of sulfide. No loss of sulfide occurred in controls without arsenate or in sterilized samples containing both arsenate and sulfide. The rate of arsenate reduction in lake water was dependent on the amount of available arsenate. We enriched for a bacterium that could achieve growth with sulfide and arsenate in a defined, mineral medium and purified it by serial dilution. The isolate, strain MLMS-1, is a gram-negative, motile curved rod that grows by oxidizing sulfide to sulfate while reducing arsenate to arsenite. Chemoautotrophy was confirmed by the incorporation of H14CO3- into dark-incubated cells, but preliminary gene probing tests with primers for ribulose-1,5-biphosphate carboxylase/oxygenase did not yield PCR-amplified products. Alignment of 16S rRNA sequences indicated that strain MLMS-1 was in the ??-Proteobacteria, located near sulfate reducers like Desulfobulbus sp. (88 to 90% similarity) but more closely related (97%) to unidentified sequences amplified previously from Mono Lake. However, strain MLMS-1 does not grow with sulfate as its electron acceptor.

  4. Dissimilatory arsenate reduction with sulfide as the electron donor--Experiments with Mono Lake water and isolation of strain MLMS-1, a chemoautotrophic arsenate-respirer

    USGS Publications Warehouse

    Hoeft, Shelley E.; Kulp, Thomas R.; Stolz, John F.; Hollibaugh, James T.; Oremland, Ronald S.

    2004-01-01

    Anoxic bottom water from Mono Lake, California, can biologically reduce added arsenate without any addition of electron donors. Of the possible in situ inorganic electron donors present, only sulfide was sufficiently abundant to drive this reaction. We tested the ability of sulfide to serve as an electron donor for arsenate reduction in experiments with lake water. Reduction of arsenate to arsenite occurred simultaneously with the removal of sulfide. No loss of sulfide occurred in controls without arsenate or in sterilized samples containing both arsenate and sulfide. The rate of arsenate reduction in lake water was dependent on the amount of available arsenate. We enriched for a bacterium that could achieve growth with sulfide and arsenate in a defined, mineral medium and purified it by serial dilution. The isolate, strain MLMS-1, is a gram-negative, motile curved rod that grows by oxidizing sulfide to sulfate while reducing arsenate to arsenite. Chemoautotrophy was confirmed by the incorporation of H14CO3− into dark-incubated cells, but preliminary gene probing tests with primers for ribulose-1,5-biphosphate carboxylase/oxygenase did not yield PCR-amplified products. Alignment of 16S rRNA sequences indicated that strain MLMS-1 was in the δ-Proteobacteria, located near sulfate reducers like Desulfobulbus sp. (88 to 90% similarity) but more closely related (97%) to unidentified sequences amplified previously from Mono Lake. However, strain MLMS-1 does not grow with sulfate as its electron acceptor.

  5. Quinone Reductase 2 Is a Catechol Quinone Reductase

    SciTech Connect

    Fu, Yue; Buryanovskyy, Leonid; Zhang, Zhongtao

    2008-09-05

    The functions of quinone reductase 2 have eluded researchers for decades even though a genetic polymorphism is associated with various neurological disorders. Employing enzymatic studies using adrenochrome as a substrate, we show that quinone reductase 2 is specific for the reduction of adrenochrome, whereas quinone reductase 1 shows no activity. We also solved the crystal structure of quinone reductase 2 in complexes with dopamine and adrenochrome, two compounds that are structurally related to catecholamine quinones. Detailed structural analyses delineate the mechanism of quinone reductase 2 specificity toward catechol quinones in comparison with quinone reductase 1; a side-chain rotational difference between quinone reductase 1 and quinone reductase 2 of a single residue, phenylalanine 106, determines the specificity of enzymatic activities. These results infer functional differences between two homologous enzymes and indicate that quinone reductase 2 could play important roles in the regulation of catecholamine oxidation processes that may be involved in the etiology of Parkinson disease.

  6. Rice-arsenate interactions in hydroponics: whole genome transcriptional analysis.

    PubMed

    Norton, Gareth J; Lou-Hing, Daniel E; Meharg, Andrew A; Price, Adam H

    2008-01-01

    Rice (Oryza sativa) varieties that are arsenate-tolerant (Bala) and -sensitive (Azucena) were used to conduct a transcriptome analysis of the response of rice seedlings to sodium arsenate (AsV) in hydroponic solution. RNA extracted from the roots of three replicate experiments of plants grown for 1 week in phosphate-free nutrient with or without 13.3 muM AsV was used to challenge the Affymetrix (52K) GeneChip Rice Genome array. A total of 576 probe sets were significantly up-regulated at least 2-fold in both varieties, whereas 622 were down-regulated. Ontological classification is presented. As expected, a large number of transcription factors, stress proteins, and transporters demonstrated differential expression. Striking is the lack of response of classic oxidative stress-responsive genes or phytochelatin synthases/synthatases. However, the large number of responses from genes involved in glutathione synthesis, metabolism, and transport suggests that glutathione conjugation and arsenate methylation may be important biochemical responses to arsenate challenge. In this report, no attempt is made to dissect differences in the response of the tolerant and sensitive variety, but analysis in a companion article will link gene expression to the known tolerance loci available in the BalaxAzucena mapping population.

  7. Lowered dietary phosphate increases oral bioavailability of arsenate in mice

    EPA Science Inventory

    Arsenate (iAsv), an inorganic oxyanionic species, has physicochemical properties similar to inorganic phosphate (iP). There is evidence that iAsv competes with iP for transmembrane carriers that mediate iP uptake. Thus, it is possible that altered dietary intake of iP could modif...

  8. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  9. Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

    EPA Science Inventory

    Arsenate adsorption on amorphous (RuO2•1.1H2O) and crystalline (RuO2) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

  10. New uranium compounds. Disubstituted uranium (IV) arsenate tetrahydrate

    SciTech Connect

    Chernorvkov, N.G.; Korshunov, I.S.; Voinova, L.I.

    1986-05-01

    The authors synthesize a previously unknown uranium (IV) acid arsenate with the composition of U(HAsO/sub 4/)/sub 2/ X 4H/sub 2/O. The thermal stability of this compound is studied, the composition, x-ray diffraction and IR spectroscopic characteristics of the compound are obtained and the products of its thermal decomposition are determined.

  11. Uptake, transport and transformation of arsenate in radishes (Raphanus sativus).

    PubMed

    Smith, Paula G; Koch, Iris; Reimer, Kenneth J

    2008-02-01

    The localization and identification of arsenic compounds in terrestrial plants are important for the understanding of arsenic uptake, transformation and translocation within these organisms, and contributes to our understanding of arsenic cycling in the environment. High performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS), and X-ray absorption near-edge structure (XANES) analysis identified arsenite, arsenate and arsenic(III)-sulphur compounds in leaf, stem and root sections of Rhaphanus sativus (radish) plants grown in both arsenic contaminated mine waste, and arsenic amended liquid cultures. The total arsenic distribution was similar between the plants grown in mine waste and those grown hydroponically. Arsenate was the predominant form of arsenic available in the growth mediums, and after it was taken up by roots, X-ray absorption spectroscopy (XAS) imaging indicated that some of the arsenate was transported to the shoots via the xylem. Additionally, arsenate was reduced by the plant and arsenic(III)-sulphur compound(s) accounted for the majority of arsenic in the leaf and stem of living plants. In this study the application of synchrotron techniques permitted the identification of arsenic(III)-sulphur species which were "invisible" to conventional HPLC-ICP-MS analysis.

  12. Rice–arsenate interactions in hydroponics: whole genome transcriptional analysis

    PubMed Central

    Norton, Gareth J.; Lou-Hing, Daniel E.; Meharg, Andrew A.; Price, Adam H.

    2008-01-01

    Rice (Oryza sativa) varieties that are arsenate-tolerant (Bala) and -sensitive (Azucena) were used to conduct a transcriptome analysis of the response of rice seedlings to sodium arsenate (AsV) in hydroponic solution. RNA extracted from the roots of three replicate experiments of plants grown for 1 week in phosphate-free nutrient with or without 13.3 μM AsV was used to challenge the Affymetrix (52K) GeneChip Rice Genome array. A total of 576 probe sets were significantly up-regulated at least 2-fold in both varieties, whereas 622 were down-regulated. Ontological classification is presented. As expected, a large number of transcription factors, stress proteins, and transporters demonstrated differential expression. Striking is the lack of response of classic oxidative stress-responsive genes or phytochelatin synthases/synthatases. However, the large number of responses from genes involved in glutathione synthesis, metabolism, and transport suggests that glutathione conjugation and arsenate methylation may be important biochemical responses to arsenate challenge. In this report, no attempt is made to dissect differences in the response of the tolerant and sensitive variety, but analysis in a companion article will link gene expression to the known tolerance loci available in the Bala×Azucena mapping population. PMID:18453530

  13. Lowered dietary phosphate increases oral bioavailability of arsenate in mice

    EPA Science Inventory

    Arsenate (iAsv), an inorganic oxyanionic species, has physicochemical properties similar to inorganic phosphate (iP). There is evidence that iAsv competes with iP for transmembrane carriers that mediate iP uptake. Thus, it is possible that altered dietary intake of iP could modif...

  14. Alternatives to chromated copper arsenate (CCA) for residential construction.

    Treesearch

    Stan. Lebow

    2004-01-01

    For decades chromated copper arsenate (CCA) was the primary preservative for treated wood used in residential construction. However, recent label changes submitted by CCA registrants will withdraw CCA from most residential applications. This action has increased interest in arsenic-free preservative systems that have been standardized by the American Wood Preservers’...

  15. Alternatives to chromated copper arsenate for residential construction

    Treesearch

    Stan T. Lebow

    2004-01-01

    For decades chromated copper arsenate (CCA) was the primary preservative for treated wood used in residential construction. However, recent label changes submitted by CCA registrants will withdraw CCA from most residential applications. This action has increased interest in arsenic free preservative systems that have been standardized by the American Wood Preservers...

  16. Arsenate adsorption onto iron oxide amended rice husk char.

    PubMed

    Cope, Christopher O; Webster, Damon S; Sabatini, David A

    2014-08-01

    In this study, rice husks were charred at 550 °C in a partially sealed ceramic vessel for 30minutes to create a high specific surface area (SSA) rice husk char (RHC). The RHC was then amended with iron oxides using dissolved ferric nitrate, Fe(NO3)3⋅9H2O, to provide a surface chemistry conducive to arsenic adsorption. The 550 °C iron oxide amended rice husk char's (550 IOA-RHC's) SSA was nearly 2.5 orders of magnitude higher and the arsenate adsorptive level was nearly 2 orders of magnitude higher than those reported for iron oxide amended sand, thus indicating a positive relationship between post-amendment SSA and arsenate adsorptive levels. Rice husks were then charred at temperatures ranging from 450 °C to 1050 °C to create an even higher SSA material, which might further increase arsenate adsorptive levels. The 950 °C RHC was chosen for amendment due to its high SSA and feasibility of being produced in the field. Once amended, the 950 °C iron oxide amended rice husk char (950 IOA-RHC) improved the arsenate adsorption capacity by thus confirming a positive relationship, though not a linear relationship, between post-amendment SSA and arsenic adsorptive capacity. Further study demonstrated that post-amendment mesoporous volume and mesoporous surface area appear to be better indicators of arsenic adsorptive capacity than SSA or iron content.

  17. Dielectric and structural properties of ferroelectric betaine arsenate films

    NASA Astrophysics Data System (ADS)

    Balashova, E. V.; Krichevtsov, B. B.; Zaitseva, N. V.; Yurko, E. I.; Svinarev, F. B.

    2014-12-01

    Ferroelectric films of betaine arsenate and partially deuterated betaine arsenate have been grown by evaporation on LiNbO3, α-Al2O3, and NdGaO3 substrates with a preliminarily deposited structure of interdigitated electrodes, as well as on the Al/glass substrate. This paper presents the results of the examination of the block structure of the films in a polarizing microscope, the X-ray diffraction analysis of their crystal structure, and the investigation of the dielectric properties in a measuring field oriented both parallel and perpendicular to the plane of the film. The transition of the films to the ferroelectric state at T = T c is accompanied by anomalies of the capacitance of the structure, an increase in the dielectric loss, and the appearance of dielectric hysteresis loops. The growth of the films from a solution of betaine arsenate in a heavy water leads to an increase in the ferroelectric transition temperature from T c = 119 K in the films without deuterium to T c = 149 K, which corresponds to the degree of deuteration of approximately 60-70%. The dielectric and structural properties of the films are compared with those of the betaine arsenate single crystals and the previously studied films of betaine phosphite and glycine phosphite.

  18. Chromate Reduction by a Pseudomonad Isolated from a Site Contaminated with Chromated Copper Arsenate

    PubMed Central

    McLean, Jeff; Beveridge, Terry J.

    2001-01-01

    A pseudomonad (CRB5) isolated from a decommissioned wood preservation site reduced toxic chromate [Cr(VI)] to an insoluble Cr(III) precipitate under aerobic and anaerobic conditions. CRB5 tolerated up to 520 mg of Cr(VI) liter−1 and reduced chromate in the presence of copper and arsenate. Under anaerobic conditions it also reduced Co(III) and U(VI), partially internalizing each metal. Metal precipitates were also found on the surface of the outer membrane and (sometimes) on a capsule. The results showed that chromate reduction by CRB5 was mediated by a soluble enzyme that was largely contained in the cytoplasm but also found outside of the cells. The crude reductase activity in the soluble fraction showed a Km of 23 mg liter−1 (437 μM) and a Vmax of 0.98 mg of Cr h−1 mg of protein−1 (317 nmol min−1 mg of protein−1). Minor membrane-associated Cr(VI) reduction under anaerobiosis may account for anaerobic reduction of chromate under nongrowth conditions with an organic electron donor present. Chromate reduction under both aerobic and anaerobic conditions may be a detoxification strategy for the bacterium which could be exploited to bioremediate chromate-contaminated or other toxic heavy metal-contaminated environments. PMID:11229894

  19. Use of drinking water treatment solids for arsenate removal from desalination concentrate.

    PubMed

    Xu, Xuesong; Lin, Lu; Papelis, Charalambos; Myint, Maung; Cath, Tzahi Y; Xu, Pei

    2015-05-01

    Desalination of impaired water can be hindered by the limited options for concentrate disposal. Selective removal of specific contaminants using inexpensive adsorbents is an attractive option to address the challenges of concentrate management. In this study, two types of ferric-based drinking water treatment solids (DWTS) were examined for arsenate removal from reverse osmosis concentrate during continuous-flow once-through column experiments. Arsenate sorption was investigated under different operating conditions including pH, arsenate concentration, hydraulic retention time, loading rate, temperature, and moisture content of the DWTS. Arsenate removal by the DWTS was affected primarily by surface complexation, electrostatic interactions, and arsenate speciation. Results indicated that arsenate sorption was highly dependent on initial pH and initial arsenate concentration. Acidic conditions enhanced arsenate sorption as a result of weaker electrostatic repulsion between predominantly monovalent H2AsO4(-) and negatively charged particles in the DWTS. High initial arsenate concentration increased the driving force for arsenate sorption to the DWTS surface. Tests revealed that the potential risks associated with the use of DWTS include the leaching of organic contaminants and ammonia, which can be alleviated by using wet DWTS or discarding the initially treated effluent that contains high organic concentration.

  20. Mobilization and re-adsorption of arsenate on ferrihydrite and hematite in the presence of oxalate.

    PubMed

    Yu, Bo; Jia, Shao-Yi; Liu, Yong; Wu, Song-Hai; Han, Xu

    2013-11-15

    In this study, mobilization and re-adsorption of arsenate on 2-line ferrihydrite and hematite in the presence of oxalate was investigated. Our results showed that arsenate could be mobilized during the dissolution of ferrihydrite and hematite. After reaching the maximum values, the released arsenate could re-adsorb on the residual ferrihydrite, whereas such an observation was not significant in hematite system. More reactive sites exposed during the dissolution of ferrihydrite could contribute to the re-adsorption of the released arsenate at pH 3.0, while the insignificant re-adsorption of arsenate on hematite could be explained by the inhibitory adsorption effect of oxalate on arsenate. Although dissolution rates of iron oxides decreased with the increase of arsenate on both ferrihydrite and hematite, dissolution rate was mainly determined by the reactivity of iron oxides, and ferrihydrite showed a higher reactivity than hematite in the presence of oxalate. Mathematic model proposed in our study further indicated that arsenate loading showed a more significant effect on arsenate mobilization in hematite system, while it was more effective in arsenate re-adsorption in ferrihydrite system. Copyright © 2013 Elsevier B.V. All rights reserved.

  1. Microbial Reduction of Ferrous Arsenate: Biogeochemical Implications for Arsenic Mobilization

    SciTech Connect

    Babechuk, M.; Weisener, C.G.; Fryer, B.; Paktunc, D.; Maunders, C.

    2010-11-12

    In reduced aqueous environments, the presence of As in solution is a function of both biotic and abiotic mechanisms. Recent studies have demonstrated a significant release of As(III) through the microbial reduction of dissolved and mineral-bound As(V), which raises health concerns when the greater comparative mobility and toxicity of As(III) is considered. These release mechanisms do not operate in isolation but occur in concert with a number of removal processes, including secondary mineralization and sorption to other natural substrates. Thermodynamic and applied experimental studies have shown that ferrous arsenates, such as symplesite [Fe(II){sub 3}(As(V)O{sub 4}){sub 2} {center_dot} 8H{sub 2}O], may provide a significant sink for Fe(II) and As(V). In this study, the stability of a representative ferrous arsenate phase in the presence of the arsenate-reducing bacterium Shewanella sp. strain ANA-3 is examined. The reduction of ferrous arsenate by ANA-3 results in the release of aqueous As(III) and, subsequently, the progressive nucleation of a biogenic ferrous arsenite phase proximal to the microbial cells. The valence states of secondary solid-phase products were verified using X-ray absorption spectroscopy (XAS). Electron microscopy reveals that nucleation occurs on cellular exudates which may imply a role of extracellular reduction through c-type cytochromes as investigated in recent literature. These observations provide new insights into the reduction mechanisms of ANA-3 and the biogeochemical cycling of As(III) in natural systems.

  2. Arsenate transport by sodium/phosphate cotransporter type IIb

    SciTech Connect

    Villa-Bellosta, Ricardo; Sorribas, Victor

    2010-08-15

    Arsenic is a metalloid that causes the dysfunction of critical enzymes, oxidative stress, and malignancies. In recent years several transporters of As{sup III} have been identified, including aquaglyceroporins (AQP) and multidrug resistance proteins (MRP). As{sup V} transport, however, has not been sufficiently studied because it has been assumed that arsenate is taken up by mammalian cells through inorganic phosphate (Pi) transporters. In this paper we have analyzed the role of Pi transporters in the uptake of arsenate by directly using {sup 73}As{sup V} as a radiotracer in phosphate transporter-expressing Xenopus laevis oocytes. The affinities of Pi transporters for H{sub 3}AsO{sub 4} were lower than the affinities for Pi. NaPiIIa, NaPiIIc, Pit1, and Pit2 showed a K{sub m} for arsenate that was > 1 mM (i.e., at least ten times lower than the affinities for Pi). The NaPiIIb isoform showed the highest affinity for As{sup V} in mouse (57 {mu}M), rat (51 {mu}M), and human (9.7 {mu}M), which are very similar to the affinities for Pi. Therefore, NaPiIIb can have a prominent role in the toxicokinetics of arsenic following oral exposure to freshwater or food contaminated with As{sup V}.

  3. The molecular basis of phosphate discrimination in arsenate-rich environments.

    PubMed

    Elias, Mikael; Wellner, Alon; Goldin-Azulay, Korina; Chabriere, Eric; Vorholt, Julia A; Erb, Tobias J; Tawfik, Dan S

    2012-11-01

    Arsenate and phosphate are abundant on Earth and have striking similarities: nearly identical pK(a) values, similarly charged oxygen atoms, and thermochemical radii that differ by only 4% (ref. 3). Phosphate is indispensable and arsenate is toxic, but this extensive similarity raises the question whether arsenate may substitute for phosphate in certain niches. However, whether it is used or excluded, discriminating phosphate from arsenate is a paramount challenge. Enzymes that utilize phosphate, for example, have the same binding mode and kinetic parameters as arsenate, and the latter's presence therefore decouples metabolism. Can proteins discriminate between these two anions, and how would they do so? In particular, cellular phosphate uptake systems face a challenge in arsenate-rich environments. Here we describe a molecular mechanism for this process. We examined the periplasmic phosphate-binding proteins (PBPs) of the ABC-type transport system that mediates phosphate uptake into bacterial cells, including two PBPs from the arsenate-rich Mono Lake Halomonas strain GFAJ-1. All PBPs tested are capable of discriminating phosphate over arsenate at least 500-fold. The exception is one of the PBPs of GFAJ-1 that shows roughly 4,500-fold discrimination and its gene is highly expressed under phosphate-limiting conditions. Sub-ångström-resolution structures of Pseudomonas fluorescens PBP with both arsenate and phosphate show a unique mode of binding that mediates discrimination. An extensive network of dipole-anion interactions, and of repulsive interactions, results in the 4% larger arsenate distorting a unique low-barrier hydrogen bond. These features enable the phosphate transport system to bind phosphate selectively over arsenate (at least 10(3) excess) even in highly arsenate-rich environments.

  4. Possible roles of plant sulfurtransferases in detoxification of cyanide, reactive oxygen species, selected heavy metals and arsenate.

    PubMed

    Most, Parvin; Papenbrock, Jutta

    2015-01-14

    Plants and animals have evolved various potential mechanisms to surmount the adverse effects of heavy metal toxicity. Plants possess low molecular weight compounds containing sulfhydryl groups (-SH) that actively react with toxic metals. For instance, glutathione (γ-Glu-Cys-Gly) is a sulfur-containing tripeptide thiol and a substrate of cysteine-rich phytochelatins (γ-Glu-Cys)2-11-Gly (PCs). Phytochelatins react with heavy metal ions by glutathione S-transferase in the cytosol and afterwards they are sequestered into the vacuole for degradation. Furthermore, heavy metals induce reactive oxygen species (ROS), which directly or indirectly influence metabolic processes. Reduced glutathione (GSH) attributes as an antioxidant and participates to control ROS during stress. Maintenance of the GSH/GSSG ratio is important for cellular redox balance, which is crucial for the survival of the plants. In this context, sulfurtransferases (Str), also called rhodaneses, comprise a group of enzymes widely distributed in all phyla, paving the way for the transfer of a sulfur atom from suitable sulfur donors to nucleophilic sulfur acceptors, at least in vitro. The best characterized in vitro reaction is the transfer of a sulfane sulfur atom from thiosulfate to cyanide, leading to the formation of sulfite and thiocyanate. Plants as well as other organisms have multi-protein families (MPF) of Str. Despite the presence of Str activities in many living organisms, their physiological role has not been clarified unambiguously. In mammals, these proteins are involved in the elimination of cyanide released from cyanogenic compounds. However, their ubiquity suggests additional physiological functions. Furthermore, it is speculated that a member of the Str family acts as arsenate reductase (AR) and is involved in arsenate detoxification. In summary, the role of Str in detoxification processes is still not well understood but seems to be a major function in the organism.

  5. Arsenate-induced maternal glucose intolerance and neural tube defects in a mouse model

    SciTech Connect

    Hill, Denise S.; Wlodarczyk, Bogdan J.; Mitchell, Laura E.; Finnell, Richard H.

    2009-08-15

    Background: Epidemiological studies have linked environmental arsenic (As) exposure to increased type 2 diabetes risk. Periconceptional hyperglycemia is a significant risk factor for neural tube defects (NTDs), the second most common structural birth defect. A suspected teratogen, arsenic (As) induces NTDs in laboratory animals. Objectives: We investigated whether maternal glucose homeostasis disruption was responsible for arsenate-induced NTDs in a well-established dosing regimen used in studies of arsenic's teratogenicity in early neurodevelopment. Methods: We evaluated maternal intraperitoneal (IP) exposure to As 9.6 mg/kg (as sodium arsenate) in LM/Bc/Fnn mice for teratogenicity and disruption of maternal plasma glucose and insulin levels. Selected compounds (insulin pellet, sodium selenate (SS), N-acetyl cysteine (NAC), L-methionine (L-Met), N-tert-Butyl-{alpha}-phenylnitrone (PBN)) were investigated for their potential to mitigate arsenate's effects. Results: Arsenate caused significant glucose elevation during an IP glucose tolerance test (IPGTT). Insulin levels were not different between arsenate and control dams before (arsenate, 0.55 ng/dl; control, 0.48 ng/dl) or after glucose challenge (arsenate, 1.09 ng/dl; control, 0.81 ng/dl). HOMA-IR index was higher for arsenate (3.9) vs control (2.5) dams (p = 0.0260). Arsenate caused NTDs (100%, p < 0.0001). Insulin pellet and NAC were the most successful rescue agents, reducing NTD rates to 45% and 35%. Conclusions: IPGTT, insulin assay, and HOMA-IR results suggest a modest failure of glucose stimulated insulin secretion and insulin resistance characteristic of glucose intolerance. Insulin's success in preventing arsenate-induced NTDs provides evidence that these arsenate-induced NTDs are secondary to elevated maternal glucose. The NAC rescue, which did not restore maternal glucose or insulin levels, suggests oxidative disruption plays a role.

  6. Mineral nutrition and enzymatic adaptation induced by arsenate and arsenite exposure in lettuce plants.

    PubMed

    Gusman, Grasielle S; Oliveira, Juraci A; Farnese, Fernanda S; Cambraia, José

    2013-10-01

    Arsenate (As(V)) and arsenite (As(III)) contamination is able to interfere negatively on plant metabolism, promoting a reduction of nutrients uptake and transport and also an increase of reactive oxygen species (ROS) generation. However, some plants are considered tolerant against As exposure through the activation of defense mechanisms. Therefore, this study aimed to evaluate the effects of different As(V) and As(III) concentrations (0.0, 6.6, 13.2, 26.4 and 52.8 μmol L(-1)), on mineral nutrients concentration [calcium (Ca), magnesium (Mg), phosphorous (P), iron (Fe), manganese (Mg) and copper (Cu)], on membrane lipid peroxidation and also on the enzymes belonging to the antioxidant defense system [superoxide dismutase (SOD), total peroxidase (POX), catalase (CAT), glutathione reductase (GR) and ascorbate peroxidase (APX)] of plants of Lactuca sativa L. cv Hanson. As(V) and As(III), showed, in general, the same toxic effects in leaves and roots with significant changes in essential macro- and micronutrients concentration. Lipid peroxidation of cellular membranes was also observed in tested plants, probably resulted from an action of ROS generated by this metalloid. The increase of ROS generation and their scavenge were evident since an increase of SOD, POX, CAT and APX activity in leaves, and SOD, CAT and GR activity in roots were observed. Therefore, As(V) and As(III) exposure resulted in toxic effects in leaves and roots of lettuce plants; however, this plant species was able to attenuate these potential As damages through the activation of defense mechanisms, keeping its metabolism. Arsenic-tolerant plants are considered a great risk to the public health since it results in As insertion to the food chain. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  7. SORPTION OF ARSENITE AND ARSENATE ON A HIGH AFFINITY OXIDE: MACROSCOPIC AND MICROSCOPIC STUDIES

    EPA Science Inventory

    Sorption of arsenate and arsenite was examined on a Ru compound using macroscopic and microscopic techniques. Isotherms were constructed from batch studies at pH 4 through 8. Solution As was measured by ICAP. Samples of the Ru compound were equilibrated with arsenite and arsenate...

  8. Arsenate immobilization associated with microbial oxidation of ferrous ion in complex acid sulfate water.

    PubMed

    Ma, Yingqun; Lin, Chuxia

    2012-05-30

    Chemical, XRD, SEM, RS, FTIR and XPS techniques were used to investigate arsenate immobilization associated with microbial Fe(2+) oxidation in a complex acid sulfate water system consisting of a modified 9 K solution (pH 2.0) plus As, Cu, Cd, Pb, Zn and Mn. At a 1:12.5:70 molar ratio of As:Fe:S, schweretmannite formation was impeded. This was in contrast with the predominant presence of schwertmannite when the heavy metals were absent, suggesting that a schwertmannite binding model is not valid for explaining arsenate immobilization in the complex system. In this study, arsenate was initially immobilized through co-precipitation with non-Fe metals and phosphate. Subsequently when sufficient Fe(3+) was produced from Fe(2+) oxidation, formation of a mixed iron, arsenate and phosphate phase predominated. The last stage involved surface complexation of arsenate species. Pb appeared to play an insignificant role in arsenate immobilization due to its strong affinity for sulfate to form anglesite. Phosphate strongly competed with arsenate for the available binding sites. However, As exhibited an increased capacity to compete with P and S for available binding sites from the co-precipitation to surface complexation stage. Adsorbed As tended to be in HAsO(4)(2-) form. The scavenged arsenate species was relatively stable after 2464-h aging. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Adsorption of arsenate on Cu/Mg/Fe/La layered double hydroxide from aqueous solutions.

    PubMed

    Guo, Yanwei; Zhu, Zhiliang; Qiu, Yanling; Zhao, Jianfu

    2012-11-15

    A novel layered double hydroxide containing lanthanum (Cu/Mg/Fe/La-LDH) has been synthesized and used for the removal of arsenate from aqueous solutions. The purpose of incorporation of La3+ into LDHs was tried to enhance the uptake efficiency of arsenate and broaden the application field of LDHs functional materials. Effects of various physico-chemical factors such as solution pH, adsorbent dosage, contact time and initial arsenate concentrations on the adsorption of arsenate onto Cu/Mg/Fe/La-LDH were investigated. Results showed that the removal efficiency of arsenate increased with the increment of the lanthanum content in Cu/Mg/Fe/La-LDH adsorbents, and the optimized lanthanum content was 20% of the total trivalent metals composition (Fe3+ and La3+). The adsorption isotherms can be well described by Langmuir equation, and the adsorption kinetics of arsenate followed the pseudo-second-order kinetic model. Coexistent ions such as HPO4(2-), CO3(2-), SO4(2-), Cl- and NO3- exhibited obvious competition with arsenate for the adsorption on Cu/Mg/Fe/La-LDH. The solution pH significantly affected the removal efficiency, which was closely related to the change of arsenate species distribution under different pH conditions. The predominant adsorption mechanism can be mainly attributed to the processes including ion exchange and layer ligand exchange. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Arsenic Recovery by Stinging Nettle From Lead-Arsenate Contaminated Orchard Soils

    USDA-ARS?s Scientific Manuscript database

    Soil contamination with arsenic (As) is common in orchards with a history of lead-arsenate pesticide application. This problem is prevalent in the U.S. Northeast where lead-arsenate foliar sprays were used to control codling moth (Cydia pomonella) in apple orchards. Arsenic is not easily biodegrad...

  11. SORPTION OF ARSENITE AND ARSENATE ON A HIGH AFFINITY OXIDE: MACROSCOPIC AND MICROSCOPIC STUDIES

    EPA Science Inventory

    Sorption of arsenate and arsenite was examined on a Ru compound using macroscopic and microscopic techniques. Isotherms were constructed from batch studies at pH 4 through 8. Solution As was measured by ICAP. Samples of the Ru compound were equilibrated with arsenite and arsenate...

  12. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    EPA Science Inventory

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  13. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    EPA Science Inventory

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  14. Arsenate adsorption mechanisms at the allophane - Water interface

    USGS Publications Warehouse

    Arai, Y.; Sparks, D.L.; Davis, J.A.

    2005-01-01

    We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)]0 from 50 to 1000 ??M (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0-10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline AI-As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane-water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H2PO42- and H2AsO42-) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The innersphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments. ?? 2005 American Chemical Society.

  15. Isolation of an arsenate-respiring bacterium from a redox front in an arsenic-polluted aquifer in West Bengal, Bengal Basin.

    PubMed

    Osborne, Thomas H; McArthur, John M; Sikdar, Pradip K; Santini, Joanne M

    2015-04-07

    Natural pollution of groundwater by arsenic adversely affects the health of tens of millions of people worldwide, with the deltaic aquifers of SE Asia being particularly polluted. The pollution is caused primarily by, or as a side reaction of, the microbial reduction of sedimentary Fe(III)-oxyhydroxides, but the organism(s) responsible for As release have not been isolated. Here we report the first isolation of a dissimilatory arsenate reducer from sediments of the Bengal Basin in West Bengal. The bacterium, here designated WB3, respires soluble arsenate and couples its reduction to the oxidation of acetate; WB3 is therefore implicated in the process of arsenic pollution of groundwater, which is largely by arsenite. The bacterium WB3 is also capable of reducing dissolved Fe(III) citrate, solid Fe(III)-oxyhydroxide, and elemental sulfur, using acetate as the electron donor. It is a member of the Desulfuromonas genus and possesses a dissimilatory arsenate reductase that was identified using degenerate polymerase chain reaction primers. The sediment from which WB3 was isolated was brown, Pleistocene sand at a depth of 35.2 m below ground level (mbgl). This level was some 3 cm below the boundary between the brown sands and overlying reduced, gray, Holocene aquifer sands. The color boundary is interpreted to be a reduction front that releases As for resorption downflow, yielding a high load of labile As sorbed to the sediment at a depth of 35.8 mbgl and concentrations of As in groundwater that reach >1000 μg/L.

  16. Understanding soluble arsenate removal kinetics by zerovalent iron media.

    PubMed

    Melitas, Nikos; Wang, Jianping; Conklin, Martha; O'Day, Peggy; Farrell, James

    2002-05-01

    Zerovalent iron filings have been proposed as a filter medium for removing arsenic compounds from potable water supplies. This research investigated the kinetics of arsenate removal from aqueous solutions by zerovalent iron media. Batch experiments were performed to determine the effect of the iron corrosion rate on the rate of As(V) removal. Tafel analyses were used to determine the effect of the As(V) concentration on the rate of iron corrosion in anaerobic solutions. As(V) removal in column reactors packed with iron filings was measured over a 1-year period of continuous operation. Comparison of As(V) removal by freely corroding and cathodically protected iron showed that rates of arsenate removal were dependent on the continuous generation of iron oxide adsorption sites. In addition to adsorption site availability, rates of arsenate removal were also limited by mass transfer associated with As(V) diffusion through iron corrosion products. Steady-state removal rates in the column reactor were up to 10 times faster between the inlet-end and the first sampling port than between the first sampling port and the effluent-end of the column. Faster removal near the influent-end of the column was due to a faster rate of iron oxidation in that region. The presence of 100 microg/L As(V) decreased the iron corrosion rate by up to a factor of 5 compared to a blank electrolyte solution. However, increasing the As(V) concentration from 100 to 20,000 microg/L resulted in no further decrease in the iron corrosion rate. The kinetics of arsenate removal ranged between zeroth- and first-order with respect to the aqueous As(V) concentration. The apparent reaction order was dependent on the availability of adsorption sites and on the aqueous As(V) concentration. X-ray absorption spectroscopy analyses showed the presence of iron metal, magnetite (Fe3O4), an Fe(III) oxide phase, and possibly an Fe(II,III) hydroxide phase in the reacted iron filings. These mixed valent oxide phases are

  17. Raman Investigations of Rare Earth Arsenate Single Crystals

    SciTech Connect

    Barros, G; Santos, C. C.; Ayala, A. P.; Guedes, I.; Boatner, Lynn A; Loong, C. K.

    2010-01-01

    Polarized Raman Spectroscopy was used to investigate the room-temperature phonon characteristics of a series of rare-earth arsenate (REAsO4, RE = Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, and Lu) single crystals. The Raman data were interpreted in a systematic manner based on the known tetragonal zircon structure of these compounds, and assignments and correlations were made for the observed bands. We found that the wavenumber of the internal modes of the AsO4 tetrahedron increased with increasing atomic number, and for three out of four lattice wavenumbers observed, this tendency was not nearly so marked as in the case of the internal mode wavenumber.

  18. Effect of arsenate As (V) on the biomarkers of Myriophyllum alterniflorum in oligotrophic and eutrophic conditions.

    PubMed

    Krayem, M; Deluchat, V; Rabiet, M; Cleries, K; Lenain, J F; Saad, Z; Kazpard, V; Labrousse, P

    2016-03-01

    Alternate watermilfoil, Myriophyllum alterniflorum is an aquatic macrophyte found in the Limousin rivers (France) whose potential for biomonitoring of metal pollution has been demonstrated. The objective of the present study carried out in vitro was to identify biomarkers for an early detection of the pollution by a metalloid As (V) in eutrophic and oligotrophic conditions. A synthetic medium of similar composition to the waters of the River Vienne was prepared. The morphological development of watermilfoil was monitored for 30 days, with or without contamination by 100 μg L(-1) As (V). In addition, the mineralization of plants and the analysis of biomarkers (chlorophylls, photosynthetic and respiratory intensities …) were investigated after 21 days. Our results indicated that eutrophic medium, induced a decrease in chlorophyll pigments, in growth and an increase in H2O2 compared to the oligotrophic medium. While, the presence of As (V), led to a decrease in the osmotic potential, pigment content, photosynthesis and respiration rates and an inhibition of shoot branching of plants in both conditions. However, a significant increase in H2O2 content was noted in the eutrophic medium. Finally, As (V) was found to be more accumulated in roots than shoots in both conditions but was more accumulated in oligotrophic one. Therefore, we can conclude that the water trophic level modifies the response of M. alterniflorum in presence of arsenate. Thus, M. alterniflorum shows a great promise in water-quality biomonitoring. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. ARSENATE-INDUCED MATERNAL GLUCOSE INTOLERANCE AND NEURAL TUBE DEFECTS IN A MOUSE MODEL

    PubMed Central

    Hill, Denise S.; Wlodarczyk, Bogdan J.; Mitchell, Laura E.; Finnell, Richard H.

    2009-01-01

    Background Epidemiological studies have linked environmental arsenic (As) exposure to increased type 2 diabetes risk. Periconceptional hyperglycemia is a significant risk factor for neural tube defects (NTDs), the second most common structural birth defect. A suspected teratogen, arsenic (As) induces NTDs in laboratory animals. Objectives We investigated whether maternal glucose homeostasis disruption was responsible for arsenate-induced NTDs in a well-established dosing regimen used in studies of arsenic’s teratogenicity in early neurodevelopment. Methods We evaluated maternal intraperitoneal (I.P.) exposure to As 9.6 mg/kg (as sodium arsenate) in LM/Bc/Fnn mice for teratogenicity and disruption of maternal plasma glucose and insulin levels. Selected compounds (insulin pellet, sodium selenate (SS), N-acetyl cysteine (NAC), L-methionine (L-Met), N-tert-Butyl-α-phenylnitrone (PBN)) were investigated for their potential to mitigate arsenate’s effects. Results Arsenate caused significant glucose elevation during an I.P. glucose tolerance test (IPGTT). Insulin levels were not different between arsenate and control dams before (arsenate, 0.55 ng/dl; control, 0.48 ng/dl) or after glucose challenge (arsenate, 1.09 ng/dl; control, 0.81 ng/dl). HOMA-IR index was higher for arsenate (3.9) vs control (2.5) dams (p=0.0260). Arsenate caused NTDs (100%, p<0.0001). Insulin pellet and NAC were the most successful rescue agents, reducing NTD rates to 45% and 35%. Conclusions IPGTT, insulin assay, and HOMA-IR results suggest a modest failure of glucose stimulated insulin secretion and insulin resistance characteristic of glucose intolerance. Insulin’s success in preventing arsenate-induced NTDs provides evidence that these arsenate-induced NTDs are secondary to elevated maternal glucose. The NAC rescue, which did not restore maternal glucose or insulin levels, suggests oxidative disruption plays a role. PMID:19446573

  20. Photoinduced Oxidation of Arsenite to Arsenate on Ferrihydrite

    SciTech Connect

    N Bhandari; R Reeder; D Strongin

    2011-12-31

    The photochemistry of an aqueous suspension of the iron oxyhydroxide, ferrihydrite, in the presence of arsenite has been investigated using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray absorption near edge structure (XANES), and solution phase analysis. Both ATR-FTIR and XANES show that the exposure of ferrihydrite to arsenite in the dark leads to no change in the As oxidation state, but the exposure of this arsenite-bearing surface, which is in contact with pH 5 water, to light leads to the conversion of the majority of the adsorbed arsenite to the As(V) bearing species, arsenate. Analysis of the solution phase shows that ferrous iron is released into solution during the oxidation of arsenite. The photochemical reaction, however, shows the characteristics of a self-terminating reaction in that there is a significant suppression of this redox chemistry before 10% of the total iron making up the ferrihydrite partitions into solution as ferrous iron. The self-terminating behavior exhibited by this photochemical arsenite/ferrihydrite system is likely due to the passivation of the ferrihydrite surface by the strongly bound arsenate product.

  1. Comparative proteomic analysis of rice shoots exposed to high arsenate.

    PubMed

    Liu, Yanli; Li, Ming; Han, Chao; Wu, Fengxia; Tu, Bingkun; Yang, Pingfang

    2013-10-01

    Consumption of arsenic contaminated water and cereals is a serious threat to humans all over the world. Rice (Oryza sativa "Nipponbare"), as a main cereal crop, can accumulate arsenic more than 10-fold that of in other cereals. To gain a comprehensive understanding of the response of rice subjected to 100 µM arsenate stress, a comparative proteomic analysis of rice shoots in combination with morphological and biochemical investigations have been performed in this study. The results demonstrated that arsenate suppressed the growth of rice seedlings, destroyed the cellular ultra-structure and changed the homeostasis of reactive oxygen species. Moreover, a total of 38 differentially displayed proteins, which were mainly involved in metabolism, redox and protein-metabolism, were identified. The data suggest the arsenic can inhibit rice growth through negatively affecting chloroplast structure and photosynthesis. In addition, upregulation of the proteins involved in redox and protein metabolism might help the rice to be resistant or tolerant to arsenic toxicity. In general, this study improves our understanding about the rice arsenic responsive mechanism.

  2. Arsenate removal from simulated groundwater with a Donnan dialyzer.

    PubMed

    Zhao, Bin; Zhao, Huazhang; Dockko, Seok; Ni, Jinren

    2012-05-15

    A simple point of use (POU) device based on the theory of Donnan dialysis was developed for the removal of arsenate (As(V)) in the present study. A commercial anion exchange membrane was used as a semipermeable barrier between the feed and stripping solution (As(V)-spiked groundwater and a 12gL(-1) table salt solution, respectively). The proposed POU device could be operated 26 times before replacing the stripping solution. In each batch, approximately 80% of the arsenate anions were transported across the membrane within 24h, and the arsenic concentration of the stripping solution was finally more than 180 times greater than that of the treated water. Cations were well preserved in treated water; however, a slight increase in the sodium ion concentration was observed due to electrolyte leakage. Alternatively, the chloride ion concentration significantly increased at the expense of a loss of sulfate and bicarbonate. The quality of treated water was in compliance with drinking water standards. Membrane fouling was investigated, and a reduction in the As(V) removal rates was not observed when the membrane was used repeatedly. Our results showed that the proposed Donnan dialysis POU device could effectively remove arsenic from drinking water in rural areas in a sustainable manner.

  3. Arsenate substitution in lead hydroxyl apatites: A Raman spectroscopic study.

    PubMed

    Giera, Alicja; Manecki, Maciej; Bajda, Tomasz; Rakovan, John; Kwaśniak-Kominek, Monika; Marchlewski, Tomasz

    2016-01-05

    A total of seven compounds of the hydroxylpyromorphite Pb10(PO4)6(OH)2 - hydroxylmimetite Pb10(AsO4)6(OH)2 (HPY-HMI) solid solution series were synthesized at 80°C from aqueous solutions and characterized using Raman spectroscopy. The positions of the bands in all spectra of the series depend on the content of arsenates and phosphates shifting to lower wavenumbers with substitution of (AsO4)(3-) for (PO4)(3-). This shift results from the decreasing bond strength of X-O (where X=P, As) and higher atomic mass of As than P. The position and intensity of major (PO4)(3-) and (AsO4)(3-) bands in Raman spectra exhibit linear correlation with As content, while the ratio of the intensities of these peaks shows exponential correlation. This results due to different polarizability of (PO4)(3-) and (AsO4)(3-) molecules. A small carbonate band develops with increasing As content indicating that hydroxyl lead apatites adopt the (CO3)(2-) ions, particularly at the arsenate end of the series.

  4. Derived amino acid sequences of the nosZ gene (respiratory N2O reductase) from Alcaligenes eutrophus, Pseudomonas aeruginosa and Pseudomonas stutzeri reveal potential copper-binding residues. Implications for the CuA site of N2O reductase and cytochrome-c oxidase.

    PubMed

    Zumft, W G; Dreusch, A; Löchelt, S; Cuypers, H; Friedrich, B; Schneider, B

    1992-08-15

    The nosZ genes encoding the multicopper enzyme nitrous oxide reductase of Alcaligenes eutrophus H16 and the type strain of Pseudomonas aeruginosa were cloned and sequenced for structural comparison of their gene products with the homologous product of the nosZ gene from Pseudomonas stutzeri [Viebrock, A. & Zumft, W. G. (1988) J. Bacteriol. 170, 4658-4668] and the subunit II of cytochrome-c oxidase (COII). Both types of enzymes possess the CuA binding site. The nosZ genes were identified in cosmid libraries by hybridization with an internal 1.22-kb PstI fragment (NS220) of nosZ from P. stutzeri. The derived amino acid sequences indicate unprocessed gene products of 70084 Da (A. eutrophus) and 70695 Da (P. aeruginosa). The N-terminal sequences of the NosZ proteins have the characteristics of signal peptides for transport. A homologous domain, extending over at least 50 residues, is shared among the three derived NosZ sequences and the CuA binding region of 32 COII sequences. Only three out of nine cysteine residues of the NosZ protein (P. stutzeri) are invariant. Cys618 and Cys622 are assigned to a binuclear center, A, which is thought to represent the CuA site of NosZ and is located close to the C terminus. Two conserved histidines, one methionine, one aspartate, one valine and two aromatic residues are also part of the CuA consensus sequence, which is the domain homologous between the two enzymes. The CuA consensus sequence, however, lacks four strictly conserved residues present in all COII sequences. Cys165 is likely to be a ligand of a second binuclear center, Z, for which we assume mainly histidine coordination. Of 23 histidine residues in NosZ (P. stutzeri), 14 are invariant, 7 of which are in regions with a degree of conservation well above the 50% positional identity between the Alcaligenes and Pseudomonas sequences. Conserved tryptophan residues are located close to several potential copper ligands. Trp615 may contribute to the observed quenching of

  5. Graphene oxide/ferric hydroxide composites for efficient arsenate removal from drinking water.

    PubMed

    Zhang, Kai; Dwivedi, Vineet; Chi, Chunyan; Wu, Jishan

    2010-10-15

    A series of novel composites based on graphene oxide (GO) cross-linked with ferric hydroxide was developed for effective removal of arsenate from contaminated drinking water. GO, which was used as a supporting matrix here, was firstly treated with ferrous sulfate. Then, the ferrous compound cross-linked with GO was in situ oxidized to ferric compound by hydrogen peroxide, followed by treating with ammonium hydroxide. The morphology and composition of the composites were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The ferric hydroxide was found to be homogenously impregnated onto GO sheets in amorphous form. These composites were evaluated as absorbents for arsenate removal from contaminated drinking water. For the water with arsenate concentration at 51.14 ppm, more than 95% of arsenate was absorbed by composite GO-Fe-5 with an absorption capacity of 23.78 mg arsenate/g of composite. Effective arsenate removal occurred in a wide range of pH from 4 to 9. However, the efficiency of arsenate removal was decreased when pH was increased to higher than 8.

  6. Evaluation of ferrolysis in arsenate adsorption on the paddy soil derived from an Oxisol.

    PubMed

    Jiang, Jun; Dai, Zhaoxia; Sun, Rui; Zhao, Zhenjie; Dong, Ying; Hong, Zhineng; Xu, Renkou

    2017-07-01

    Iron oxides are dominant effective adsorbents for arsenate in iron oxide-rich variable charge soils. Oxisol-derived paddy soils undergo intensive ferrolysis, which results in high leaching and transformation of iron oxides. However, little information is available concerning the effect of ferrolysis on arsenate adsorption by paddy soil and parent Oxisol. In the present study, we examined the arsenate affinity of soils using arsenate adsorption/desorption isotherms, zeta potential, adsorption kinetics, pH effect and phosphate competition experiments. Results showed that ferrolysis in an alternating flooding-drying Oxisol-derived paddy soil resulted in a significant decrease of free iron oxides and increase of amorphous iron oxides in the surface and subsurface layers. There were more reactive sites exposed on amorphous than on crystalline iron oxides. Therefore, disproportionate ratios of arsenate adsorption capacities and contents of free iron oxides were observed in the studied Oxisols compared with paddy soils. The Gibbs free energy values corroborated that both electrostatic and non-electrostatic adsorption mechanisms contributed to the arsenate adsorption by bulk soils, and the kinetic adsorption data further suggested that the rate-limiting step was chemisorption. The zeta potential of soil colloids decreased after arsenate was adsorbed on the surfaces, forming inner-sphere complexes and thus transferring their negative charges to the soil particle surfaces. The adsorption/desorption isotherms showed that non-electrostatic adsorption was the main mechanism responsible for arsenate binding to the Oxisol and derived paddy soils, representing 91.42-94.65% of the adsorption capacities. Further studies revealed that arsenate adsorption was greatly inhibited by increasing suspension pH and incorporation of phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Fate of sodium arsenate in dairy sheep and goats.

    PubMed

    Shariatpanahi, M; Anderson, A C

    1985-08-01

    This study followed the uptake, distribution, and elimination of sodium arsenate administered in a single dose and in multiple doses, respectively, to Iranian dairy sheep and goats. In the single dosing study, the blood concentration data fit an open two-compartment model of the form:C b (t)=-(A+B)e (-kat) +Ae (-αt) +Be (-βt) Absorption distribution and elimination rate constants were statistically significantly different for the two animal species. In the multiple dosing study, arsenic accumulated in the blood of both animal species, as expressed by a one compartment model of the form:C t =C ss (1-e (-kt) ) Arsenic was eliminated rapidly at the termination of dosing, with the blood washout half-life being shorter in sheep than in goats. Urinary excretion was the major elimination route from the body of both species.

  8. Synthesis of mesoporous Cu/Mg/Fe layered double hydroxide and its adsorption performance for arsenate in aqueous solutions.

    PubMed

    Guo, Yanwei; Zhu, Zhiliang; Qiu, Yanling; Zhao, Jianfu

    2013-05-01

    The mesoporous Cu/Mg/Fe layered double hydroxide (Cu/Mg/Fe-LDH) with carbonate intercalation was synthesized and used for the removal of arsenate from aqueous solutions. The Cu/Mg/Fe-LDH was characterized by Fourier transform infrared spectrometry, X-ray diffraction crystallography, scanning electron microscopy, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller. Effects of various physico-chemical parameters such as pH, adsorbent dosage, contact time and initial arsenate concentration on the adsorption of arsenate onto Cu/Mg/Fe-LDH were investigated. Results showed that it was efficient for the removal of arsenate, and the removal efficiency of arsenate increased with the increment of the adsorbent dosage, while the arsenate adsorption capacity decreased with increase of initial pH from 3 to 11. The adsorption isotherms can be well described by the Langmuir model with R2 > 0.99. Its adsorption kinetics followed the pseudo second-order kinetic model. Coexisting ions such as HPO4(2-), CO3(2-), SO4(2-) and NO3(-) could compete with arsenate for adsorption sites on the Cu/Mg/Fe-LDH. The adsorption of arsenate on the adsorbent can be mainly attributed to the ion exchange process. It was found that the synthesized Cu/Mg/Fe-LDH can reduce the arsenate concentration down to a final level of < 10 microg/L under the experimental conditions, and makes it a potential material for the decontamination of arsenate polluted water.

  9. Homology among arsenate resistance determinants of R factors in Escherichia coli.

    PubMed Central

    Mobley, H L; Silver, S; Porter, F D; Rosen, B P

    1984-01-01

    Escherichia coli bearing R factors R773 or R46 or hybrid recombinant plasmids carrying the arsenic resistance determinants derived from these plasmids synthesized inducible polypeptides of similar apparent molecular weights when exposed to arsenite salts (R773 derivative, 64,000 and 16,000; R46 derivative, 62,000, 16,500, and 13,500). In addition, both plasmids encoded energy-dependent arsenate efflux systems and demonstrated DNA sequence homology by filter blot hybridization. Human isolates of arsenate- and arsenite-resistant enterobacteria were tested for homology with the arsenate operon of R773 by colony blot hybridization. Approximately one-third of the isolates hybridized strongly, and two-thirds showed little or no evidence of homology, suggesting the presence of two or more genetically distinct arsenate resistant determinants. Images PMID:6370124

  10. ASSESSING CHILDREN'S EXPOSURES TO THE WOOD PRESERVATIVE CCA (CHROMATED COPPER ARSENATE) ON TREATED PLAYSETS AND DECKS

    EPA Science Inventory

    Concerns have been raised regarding the safety of young children contacting arsenic and chromium residues while playing on and around Chromated Copper Arsenate (CCA) treated wood playground structures and decks. Although CCA registrants voluntarily canceled treated wood for re...

  11. Coprecipitation of arsenate with metal oxides: nature, mineralogy, and reactivity of aluminum precipitates.

    PubMed

    Violante, Antonio; Ricciardella, Mariarosaria; Del Gaudio, Stefania; Pigna, Massimo

    2006-08-15

    Arsenic mobilization in soils is mainly controlled by sorption/desorption processes, but arsenic also may be coprecipitated with aluminum and/or iron in natural environments. Although coprecipitation of arsenic with aluminum and iron oxides is an effective treatment process for arsenic removal from drinking water, the nature and reactivity of aluminum- or iron-arsenic coprecipitates has received little attention. We studied the mineralogy, chemical composition, and surface properties of aluminum-arsenate coprecipitates, as well as the sorption of phosphate on and the loss of arsenate from these precipitates. Aluminum-arsenate coprecipitates were synthesized at pH 4.0, 7.0, or 10.0 and As/Al molar ratio (R) of 0, 0.01, or 0.1 and were aged 30 or 210 d at 50 degrees C. In the absence of arsenate, gibbsite (pH 4.0 or 7.0) and bayerite (pH 10.0) formed, whereas in the presence of arsenate, very poorly crystalline precipitates formed. Short-range ordered materials (mainly poorly crystalline boehmite) formed at pH 4.0 (R = 0.01 and 0.1), 7.0, and 10.0 (R= 0.1) and did not transform into Al(OH)3 polymorphs even after prolonged aging. The surface properties and chemical composition of the aluminum precipitates were affected by the initial pH, R, and aging. Chemical dissolution of the samples by 6 mol L(-1) HCl and 0.2 mol L(-1) oxalic acid/ oxalate solution indicated that arsenate was present mainly in the short-range ordered precipitates. The sorption of phosphate onto the precipitates was influenced by the nature of the samples and the amounts of arsenate present in the precipitates. Large amounts of phosphate partially replaced arsenate only from the samples formed at R = 0.1. The quantities of arsenate desorbed from these coprecipitates by phosphate increased with increasing phosphate concentration, reaction time, and precipitate age butwere always lessthan 30% of the amounts of arsenate present in the materials and were particularly low (<4%) from the sample prepared

  12. ASSESSING CHILDREN'S EXPOSURES TO THE WOOD PRESERVATIVE CCA (CHROMATED COPPER ARSENATE) ON TREATED PLAYSETS AND DECKS

    EPA Science Inventory

    Concerns have been raised regarding the safety of young children contacting arsenic and chromium residues while playing on and around Chromated Copper Arsenate (CCA) treated wood playground structures and decks. Although CCA registrants voluntarily canceled treated wood for re...

  13. Arsenate tolerance in Silene paradoxa does not rely on phytochelatin-dependent sequestration.

    PubMed

    Arnetoli, Miluscia; Vooijs, Riet; ten Bookum, Wilma; Galardi, Francesca; Gonnelli, Cristina; Gabbrielli, Roberto; Schat, Henk; Verkleij, Jos A C

    2008-04-01

    Arsenate tolerance, As accumulation and As-induced phytochelatin accumulation were compared in populations of Silene paradoxa, one from a mine site enriched in As, Cu and Zn, the other from an uncontaminated site. The mine population was significantly more arsenate-tolerant. Arsenate uptake and root-to-shoot transport were slightly but significantly higher in the non-mine plants. The difference in uptake was quantitatively insufficient to explain the difference in tolerance between the populations. As accumulation in the roots was similar in both populations, but the mine plants accumulated much less phytochelatins than the non-mine plants. The mean phytochelatin chain length, however, was higher in the mine population, possibly due to a constitutively lower cellular glutathione level. It is argued that the mine plants must possess an arsenic detoxification mechanism other than arsenate reduction and subsequent phytochelatin-based sequestration. This alternative mechanism might explain at least some part of the superior tolerance in the mine plants.

  14. Gas-bubbled nano zero-valent iron process for high concentration arsenate removal.

    PubMed

    Tanboonchuy, Visanu; Hsu, Jia-Chin; Grisdanurak, Nurak; Liao, Chih-Hsiang

    2011-02-28

    In this study, batch experiments were performed to investigate a novel process for high concentration arsenate removal in the presence of air and/or CO(2) bubbling. The pretreatment step, CO(2) bubbling at 300 mL/min for 5 min, was taken to adjust the solution pH to an acidic environment, followed by air bubbling at 300 mL/min for 10 min to increase dissolved oxygen in the solution. In the treatment period, the nano-scale zero-valent iron was applied to remove aqueous arsenate of 3000 μg/L, while the treatment system was continuously bubbled by 300 mL/min of air. Such a process resulted in outstanding performance in arsenate removal. Furthermore, in the field groundwater application, the arsenate removal rate for the proposed process was 5 times faster than the rate measured when the system was pretreated by acidic chemical species only.

  15. Synthesis and phase transformations involving scorodite, ferric arsenate and arsenical ferrihydrite: Implications for arsenic mobility

    NASA Astrophysics Data System (ADS)

    Paktunc, Dogan; Dutrizac, John; Gertsman, Valery

    2008-06-01

    Scorodite, ferric arsenate and arsenical ferrihydrite are important arsenic carriers occurring in a wide range of environments and are also common precipitates used by metallurgical industries to control arsenic in effluents. Solubility and stability of these compounds are controversial because of the complexities in their identification and characterization in heterogeneous media. To provide insights into the formation of scorodite, ferric arsenate and ferrihydrite, series of synthesis experiments were carried out at 70 °C and pH 1, 2, 3 and 4.5 from 0.2 M Fe(SO 4) 1.5 solutions also containing 0.02-0.2 M Na 2HAsO 4. The precipitates were characterized by transmission electron microscopy, X-ray diffraction and X-ray absorption fine structure techniques. Ferric arsenate, characterized by two broad diffuse peaks on the XRD pattern and having the structural formula of FeAsO 4·4-7H 2O, is a precursor to scorodite formation. As defined by As XAFS and Fe XAFS, the local structure of ferric arsenate is profoundly different than that of scorodite. It is postulated that the ferric arsenate structure is made of single chains of corner-sharing Fe(O,OH) 6 octahedra with bridging arsenate tetrahedra alternating along the chains. Scorodite was precipitated from solutions with Fe/As molar ratios of 1 over the pH range of 1-4.5. The pH strongly controls the kinetics of scorodite formation and its transformation from ferric arsenate. The scorodite crystallite size increased from 7 to 33 nm by ripening and aggregation. Precipitates, resulting from continuous synthesis at pH 4.5 from solutions having Fe/As molar ratios ranging from 1 to 4 and resembling the compounds referred to as ferric arsenate, arsenical ferrihydrite and As-rich hydrous ferric oxide in the literature, represent variable mixtures of ferric arsenate and ferrihydrite. When the Fe/As ratio increases, the proportion of ferrihydrite increases at the expense of ferric arsenate. Arsenate adsorption appears to retard

  16. Synthesis and phase transformations involving scorodite, ferric arsenate and arsenical ferrihydrite: Implications for arsenic mobility

    SciTech Connect

    Paktunc, D.; Dutrizac, J.; Gertsman, V.

    2008-07-07

    Scorodite, ferric arsenate and arsenical ferrihydrite are important arsenic carriers occurring in a wide range of environments and are also common precipitates used by metallurgical industries to control arsenic in effluents. Solubility and stability of these compounds are controversial because of the complexities in their identification and characterization in heterogeneous media. To provide insights into the formation of scorodite, ferric arsenate and ferrihydrite, series of synthesis experiments were carried out at 70 C and pH 1, 2, 3 and 4.5 from 0.2 M Fe(SO{sub 4}){sub 1.5} solutions also containing 0.02--0.2 M Na{sub 2}HAsO{sub 4}. The precipitates were characterized by transmission electron microscopy, X-ray diffraction and X-ray absorption fine structure techniques. Ferric arsenate, characterized by two broad diffuse peaks on the XRD pattern and having the structural formula of FeAsO{sub 4}{center_dot}4-7H{sub 2}O, is a precursor to scorodite formation. As defined by As XAFS, the local structure of ferric arsenate is profoundly different than that of scorodite. It is postulated that the ferric arsenate structure is made of single chains of corner-sharing Fe(O,OH){sub 6} octahedra with bridging arsenate tetrahedra alternating along the chains. Scorodite was precipitated from solutions with Fe/As molar ratios of 1 over the pH range of 1--4.5. The pH strongly controls the kinetics of scorodite formation and its transformation from ferric arsenate. The scorodite crystallite size increased from 7 to 33 nm by ripening and aggregation. Precipitates, resulting from continuous synthesis at pH 4.5 from solutions having Fe/As molar ratios ranging from 1 to 4 and resembling the compounds referred to as ferric arsenate, arsenical ferrihydrite and As-rich hydrous ferric oxide in the literature, represent variable mixtures of ferric arsenate and ferrihydrite. When the Fe/As ratio increases, the proportion of ferrihydrite increases at the expense of ferric arsenate

  17. XAFS of Synthetic Iron(III)-Arsenate Co-Precipitates and Uranium Mill Neutralized Raffinate

    SciTech Connect

    Chen, N.; Jiang, D. T.; Cutler, J.; Demopoulos, G. P.; Rowson, J. W.

    2007-02-02

    XAFS studies were carried out for chemical speciation of arsenic species in uranium mill neutralized raffinate solids. To aid the structural characterization, synthetic iron(III)-arsenate co-precipitates were prepared to mimic the actual uranium mill tailings neutralization products. The principle components analysis method was used to validate the synthetic amorphous scorodite as a primary model compound for arsenate species in the raffinate samples under the specific precipitation conditions.

  18. Concentration and chemical status of arsenic in the early placentas of arsenate-dosed hamsters

    SciTech Connect

    Hanlon, D.P.; Ferm, V.H.

    1987-04-01

    The authors determined the concentration and chemical status of arsenic in the placentas of hamsters following continuous exposure via the osmotic minipump to minimally and frankly teratogenic doses of arsenate. Close to 70% of the placental arsenic is bound to macromolecules, two-thirds of which is dialyzable. The remaining 30% of arsenic consists of low molecular weight species, predominantly inorganic arsenic. This mix is the same for minimally teratogenic and frankly teratogenic doses of arsenate.

  19. XAFS of Synthetic Iron(III)-Arsenate Co-Precipitates and Uranium Mill Neutralized Raffinate

    NASA Astrophysics Data System (ADS)

    Chen, N.; Jiang, D. T.; Cutler, J.; Demopoulos, G. P.; Rowson, J. W.

    2007-02-01

    XAFS studies were carried out for chemical speciation of arsenic species in uranium mill neutralized raffinate solids. To aid the structural characterization, synthetic iron(III)-arsenate co-precipitates were prepared to mimic the actual uranium mill tailings neutralization products. The principle components analysis method was used to validate the synthetic amorphous scorodite as a primary model compound for arsenate species in the raffinate samples under the specific precipitation conditions.

  20. Characterization of microbial arsenate reduction in the anoxic bottom waters of Mono Lake, California

    USGS Publications Warehouse

    Hoeft, S.E.; Lucas, F.; Hollibaugh, J.T.; Oremland, R.S.

    2002-01-01

    Dissimilatory reduction of arsenate (DAsR) occurs in the arsenic-rich, anoxic water column of Mono Lake, California, yet the microorganisms responsible for this observed in situ activity have not been identified. To gain insight as to which microorganisms mediate this phenomenon, as well as to some of the biogeochemical constraints on this activity, we conducted incubations of arsenate-enriched bottom water coupled with inhibition/amendment studies and Denaturing Gradient Gel Electrophoresis (DGGE) characterization techniques. DAsR was totally inhibited by filter-sterilization and by nitrate, partially inhibited (~50%) by selenate, but only slightly (~25%) inhibited by oxyanions that block sulfate-reduction (molybdate and tungstate). The apparent inhibition by nitrate, however, was not due to action as a preferred electron acceptor to arsenate. Rather, nitrate addition caused a rapid, microbial re-oxidation of arsenite to arsenate, which gave the overall appearance of no arsenate loss. A similar microbial oxidation of As(III) was also found with Fe(III), a fact that has implications for the recycling of As(V) in Mono Lake's anoxic bottom waters. DAsR could be slightly (10%) stimulated by substrate amendments of lactate, succinate, malate, or glucose, but not by acetate, suggesting that the DAsR microflora is not electron donor limited. DGGE analysis of amplified 16S rDNA gene fragments from incubated arsenate-enriched bottom waters revealed the presence of two bands that were not present in controls without added arsenate. The resolved sequences of these excised bands indicated the presence of members of the epsilon (Sulfurospirillum) and delta (Desulfovibrio) subgroups of the Proteobacteria, both of which have representative species that are capable of anaerobic growth using arsenate as their electron acceptor.

  1. Evidence for the aquatic binding of arsenate by natural organic matter-suspended Fe(III)

    USGS Publications Warehouse

    Ritter, K.; Aiken, G.R.; Ranville, J.F.; Bauer, M. E.; Macalady, D.L.

    2006-01-01

    Dialysis experiments with arsenate and three different NOM samples amended with Fe(III) showed evidence confirming the formation of aquatic arsenate-Fe(III)-NOM associations. A linear relationship was observed between the amount of complexed arsenate and the Fe(III) content of the NOM. The dialysis results were consistent with complex formation through ferric iron cations acting as bridges between the negatively charged arsenate and NOM functional groups and/or a more colloidal association, in which the arsenate is bound by suspended Fe(III)-NOM colloids. Sequential filtration experiments confirmed that a significant proportion of the iron present at all Fe/C ratios used in the dialysis experiments was colloidal in nature. These colloids may include larger NOM species that are coagulated by the presence of chelated Fe(III) and/or NOM-stabilized ferric (oxy)hydroxide colloids, and thus, the solution-phase arsenate-Fe(III)-NOM associations are at least partially colloidal in nature. ?? 2006 American Chemical Society.

  2. Synthesis and characterization of arsenate-intercalated layered double hydroxides (LDHs): prospects for arsenic mineralization.

    PubMed

    Prasanna, S V; Kamath, P Vishnu

    2009-03-15

    The arsenate-intercalated layered double hydroxide (LDH) of Mg and Al is synthesized by coprecipitation. The higher thermodynamic stability and the consequent lower solubility of the unitary arsenates preclude the formation of arsenate-intercalated LDHs of other metals directly from solution. However other M/Al-AsO(4) (M=Co, Ni, Zn) LDHs could be prepared by anion exchange, showing that arsenate intercalation proceeds topotactically. The intercalation of various species of As(V) into the interlayer of LDHs and the subsequent arsenate carrying capacity are dependent upon the pH of the solution. Upon thermal decomposition, the intercalated arsenate ion undergoes reductive deintercalation to give a mixture of As(III) and As(V) oxides. The product oxides revert back to the LDH upon soaking in water on account of the compositional and morphological metastability of the former. This is in contrast with the phosphate-intercalated LDHs, in which the reversibility is suppressed, consequent to the formation of stable metal phosphates.

  3. Comparison of arsenate and cadmium toxicity in a freshwater amphipod (Gammarus pulex).

    PubMed

    Vellinger, Céline; Parant, Marc; Rousselle, Philippe; Immel, Françoise; Wagner, Philippe; Usseglio-Polatera, Philippe

    2012-01-01

    Cadmium is largely documented on freshwater organisms while arsenic, especially arsenate, is rarely studied. The kinetic of the LC50s values for both metals was realized on Gammarus pulex. Physiological [i.e. metal concentration in body tissues, bioconcentration factor (BCF)] effects and behavioural responses (via pleopods beats) were investigated after 240-h exposure. Arsenate LC50 value was 100 fold higher than Cd-LC50 value after 240-h exposure, while concentrations in gammarids were similar for both metals at their respective LC50s. BCF decreased with increasing cadmium concentration while BCF remained stable with increasing arsenate concentration. Moreover, BCF was between 148 and 344 times lower for arsenate than cadmium. A significant hypoventilation was observed for cadmium concentrations exceeding or close to the 240h-LC50(Cd), while gammarids hyperventilated for the lowest arsenate concentrations and hypoventilated for the highest arsenate concentrations. We discussed the relationships between potential action mechanisms of these two metals and observed results.

  4. Energy-dependent arsenate efflux: the mechanism of plasmid-mediated resistance.

    PubMed Central

    Silver, S; Keach, D

    1982-01-01

    Plasmid-mediated resistance to arsenate, arsenite, and antimony(III) is coordinately induced by arsenate, arsenite, antimony(III), and bismuth(III). Resistance to arsenate was recently shown [Silver, S., Budd, K., Leahy, K.M., Shaw, W.V., Hammond, D., Novick, R.P., Willsky, G.R., Malamy, M.H. & Rosenberg, H. (1981) J. Bacteriol. 146, 983-996] to be due to decreased accumulation of arsenate by the induced resistant cells. We report here that decreased net uptake results from accelerated efflux of arsenate by induced plasmid-containing cells of Staphylococcus aureus and Escherichia coli. The efflux system in S. aureus was inhibited by nigericin, monensin, and proton-mobilizing uncouplers; efflux was unaffected by valinomycin. The mechanism of arsenate efflux in S. aureus was apparently not by chemiosmotic coupling to the membrane electrical potential or pH gradient. The intracellular efflux system was inhibited by low pH and mercurials (reversible by mercaptoethanol). The efflux rate was relatively independent of external pH or phosphate level and showed a sigmoidal pattern of concentration dependence. PMID:6755462

  5. EXAFS and DFT investigations of uranyl arsenate complexes in aqueous solution.

    PubMed

    Gezahegne, Wondemagegnehu A; Hennig, Christoph; Tsushima, Satoru; Planer-Friedrich, Britta; Scheinost, Andreas C; Merkel, Broder J

    2012-02-21

    Uranium and arsenic often co-occur in nature, for example, in acid mine drainage waters. Interaction with arsenic is thus important to understand uranium mobility in aqueous solutions. For the present study, EXAFS spectroscopy was used to investigate the formation and identify the structure of aqueous uranyl arsenate species at pH 2. The nearest U-As distance of 3.39 Å, observed in shock-frozen liquid samples, was significantly shorter than that observed in solid uranyl arsenate minerals. The shorter bond length indicated that the solution contained a bidentate-coordinated species, in contrast to the monodentate coordination in solid uranyl arsenate minerals. The U-As coordination number of 1.6 implied that two uranyl arsenate species with U:As ratios of 1:1 and 1:2 formed in nearly equal proportions and that the hydrated uranyl ion was present only as a minor component. The two uranyl arsenate species could not be differentiated spectroscopically, since their U-As distances were equal. A comparison based on DFT modeling indicated for both the 1:1 and the 1:2 species, that the bidentate arsenates were bound to uranium with one of the binding oxygen atoms being protonated. Based on the present spectroscopic study, the two species that will have to be considered in acidic uranium-arsenic-rich solutions are thus UO(2)H(2)AsO(4)(+), and UO(2)(H(2)AsO(4))(2)(0).

  6. Efficient removal of chromate and arsenate from individual and mixed system by malachite nanoparticles.

    PubMed

    Saikia, Jiban; Saha, Bedabrata; Das, Gopal

    2011-02-15

    Malachite nanoparticles of 100-150 nm have been efficiently and for the first time used as an adsorbent for the removal of toxic arsenate and chromate. We report a high adsorption capacity for chromate and arsenate on malachite nanoparticle from both individual and mixed solution in pH ∼4-5. However, the adsorption efficiency decreases with the increase of solution pH. Batch studies revealed that initial pH, temperature, malachite nanoparticles dose and initial concentration of chromate and arsenate were important parameters for the adsorption process. Thermodynamic analysis showed that adsorption of chromate and arsenate on malachite nanoparticles is endothermic and spontaneous. The adsorption of these anions has also been investigated quantitatively with the help of adsorption kinetics, isotherm, and selectivity coefficient (K) analysis. The adsorption data for both chromate and arsenate were fitted well in Langmuir isotherm and preferentially followed the second order kinetics. The binding affinity of chromate is found to be slightly higher than arsenate in a competitive adsorption process which leads to the comparatively higher adsorption of chromate on malachite nanoparticles surface.

  7. Respiratory papillomas

    PubMed Central

    Alagusundaramoorthy, Sayee Sundar; Agrawal, Abhinav

    2016-01-01

    Papillomas are known to occur in the lower respiratory tract. They are however, rare compared to their occurrence in the upper respiratory tract. These are generally exophytic tumors in the more proximal upper airways however cases with more distal location with an inverted growth pattern have also been described in the literature. These can be solitary or multiple and multifocality associated with multiple papillomas in the upper respiratory/aerodigestive tract. The four major types of respiratory papillomas are (1) Recurrent respiratory papillomas, (2) solitary squamous papillomas, (3) solitary glandular papillomas, (4) mixed papillomas. We review the incidence, etiopathology, diagnosis, and possible treatment modalities and algorithms for these respiratory papillomas. PMID:27625447

  8. Respiratory Failure

    MedlinePlus

    Respiratory failure happens when not enough oxygen passes from your lungs into your blood. Your body's organs, ... brain, need oxygen-rich blood to work well. Respiratory failure also can happen if your lungs can' ...

  9. Respiratory system

    NASA Technical Reports Server (NTRS)

    Bartlett, R. G., Jr.

    1973-01-01

    The general anatomy and function of the human respiratory system is summarized. Breathing movements, control of breathing, lung volumes and capacities, mechanical relations, and factors relevant to respiratory support and equipment design are discussed.

  10. A cytochrome cd1-type nitrite reductase mediates the first step of denitrification in Alcaligenes eutrophus.

    PubMed

    Sann, R; Kostka, S; Friedrich, B

    1994-01-01

    Respiratory nitrite reductase (NIR) has been purified from the soluble extract of denitrifying cells of Alcaligenes eutrophus strain H16 to apparent electrophoretic homogeneity. The enzyme was induced under anoxic conditions in the presence of nitrite. Purified NIR showed typical features of a cytochrome cd1-type nitrite reductase. It appeared to be a dimer of kDa subunits, its activity was only weakly inhibited by the copper chelator diethyldithiocarbamate, and spectral analysis revealed absorption maxima which were characteristic for the presence of heme c and heme d1. The isoelectric point of 8.6 was considerably higher than the pI determined for cd1 nitrite reductases from pseudomonads. Eighteen amino acids at the N-terminus of the A. eutrophus NIR, obtained by protein sequencing, showed no significant homology to the N-terminal region of nitrite reductases from Pseudomonas stutzeri and Pseudomonas aeruginosa.

  11. Coprecipitation of arsenate with metal oxides. 2. Nature, mineralogy, and reactivity of iron(III) precipitates.

    PubMed

    Violante, Antonio; Del Gaudio, Stefania; Pigna, Massimo; Ricciardella, Mariarosaria; Banerjee, Dipanjan

    2007-12-15

    Coprecipitation of arsenic with iron or aluminum occurs in natural environments and is a remediation technology used to remove this toxic metalloid from drinking water and hydrometallurgical solutions. In this work, we studied the nature, mineralogy, and reactivity toward phosphate of iron-arsenate coprecipitates formed at As(V)/Fe(III) molar ratios (R) of 0, 0.01, or 0.1 and at pH 4.0, 7.0, and 10.0 aged for 30 or 210 days at 50 degrees C and studied the desorption of arsenate. At R = 0, goethite and hematite (with ferrihydrite at pH 4.0 and 7.0) crystallized, whereas at R = 0.01, the formation of ferrihydrite increased and hematite crystallization was favored over goethite. In some samples, the morphology of hematite changed from rounded platy crystals to ellipsoids. At R = 0.1, ferrihydrite formed in all the coprecipitates and remained unchanged even after 210 days of aging. The surface area and chemical composition of the precipitates were affected by pH, R, and aging. Chemical dissolution of the samples showed that arsenate was present mainly in ferrihydrite, but at R = 0.01, it was partially incorporated into the structures of crystalline Fe oxides. The sorption of phosphate on to the coprecipitates was affected not only by the mineralogy and surface area of the samples but also by the amounts of arsenate present in the oxides. The samples formed at pH 4.0 and 7.0 and at R = 0.1 sorbed lower amounts of phosphate than the precipitates obtained at R = 0 or 0.01, despite the former having a larger surface area and showing only a presence of short-range ordered materials. This is mainly due to the fact that in the coprecipitates at R = 0.1 arsenate occupied many sorption sites, thus preventing phosphate sorption. Less than 20% of the arsenate present in the coprecipitates formed at R = 0.1 was removed by phosphate and more from the samples synthesized at pH 7.0 or 10.0 than at pH 4.0. Moreover, we found that more arsenate was desorbed by phosphate from a

  12. The use of superporous p(3-acrylamidopropyl)trimethyl ammonium chloride cryogels for removal of toxic arsenate anions.

    PubMed

    Sahiner, Nurettin; Demirci, Sahin; Sahiner, Mehtap; Yilmaz, Selahattin; Al-Lohedan, Hamad

    2015-04-01

    Poly((3-Acrylamidopropyl)trimethylammonium chloride) (p(APTMACl)) cryogels were used as a superporous polymer network for the removal of toxic arsenate anions from an aqueous medium. The fast swelling in water, in about 7 s, was shown to be very useful leading to fast arsenate adsorption by p(APTMACl) cryogels within 30 min in comparison to 12 h for bulk common p(APTMACl) hydrogels. A maximum adsorption capacity of about 120 (mg/g) arsenate was obtained for p(APTMACl) cryogels. Both the Langmuir and Freundlich adsorption isotherms were applied for adsorption of arsenate anions by p(APTMACl) cryogels, and it was observed that the adsorption of arsenate anions by p(APTMACl) cryogels are represented better via Langmuir adsorption isotherm providing the R(2) value of 0.998. Furthermore, mag-p(APTMACl) cryogels were synthesized, and shown to be very useful in the fast removal of toxic arsenate anions. The mag-p(APTMACl) cryogels including the adsorbed arsenate were removed by an externally applied magnetic field, with some reduction in the arsenate ion adsorption capacity. It was also further demonstrated that p(APTMACl) cryogels can be reused in the adsorption of arsenate 5 times from aqueous environments without significant loss of adsorption capacity, from 113.47 ± 9 to 102.67 ± 6 mg/g.

  13. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    NASA Astrophysics Data System (ADS)

    Waychunas, G. A.; Rea, B. A.; Fuller, C. C.; Davis, J. A.

    1993-05-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 ±0.01 Å) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 ± 0.02 Å). Mono-dentate arsenate linkages ( 3.60 ± 0.03 Å) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As/Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ± 0.01 Å. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As/Fe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As/Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As/Fe) indicates ferrihydrite units consisting mainly of Fe

  14. Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

    USGS Publications Warehouse

    Waychunas, G.A.; Rea, B.A.; Fuller, C.C.; Davis, J.A.

    1993-01-01

    EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, ?? (goethite), ?? (akaganeite), and ?? (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface (3.28 ??0.01 A ??) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces (3.25 ?? 0.02 A ??). Mono-dentate arsenate linkages (3.60 ?? 0.03 A ??) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 ?? 0.01 A ??. Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe ratio is increased. Coherent crystallite size is probably no more than 10 A?? in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe) indicates ferrihydrite units consisting mainly

  15. Rates of hydrous ferric oxide crystallization and the influence on coprecipitated arsenate.

    PubMed

    Ford, Robert G

    2002-06-01

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 degrees C. Comparison of extraction data and X-ray diffraction results confirmed that hematite and goethite were the primary transformation products. HFO transformation was significantly retarded at or above an arsenate solid loading of 29 455 mg As/kg HFO. However, HFO transformation proceeded at a significant rate for arsenate solid loadings of 4208 and 8416 mg As/kg HFO. At a solid loading of 8416 mg As/kg HFO, XRD results suggested arsenate primarily partitioned to hematite. Comparison of HFO transformation rates observed in this research to rates obtained from the literature at pH 6 and temperatures ranging from 24 to 70 degrees C suggests that arsenate stabilization could be realized in oxic environments with a significantfraction of iron (hydr)oxides. While this process has not been documented in natural systems, the predicted half-life for transformation of an arsenic-bearing HFO is approximately 300 days at 25 degrees C at solid loading < 8415 mg As/kg HFO. The projected time frame for arsenate stabilization indicates this process should be considered during development of conceptual and analytical models describing arsenic fate and transport in oxic systems containing reactive iron (hydr)oxides. The likelihood of this process would depend on the chemical dynamics of the soil or sediment system relative to iron (hydr)oxide precipitation-dissolution reactions and the potential retarding/competing influence of ions such as silicate and organic matter.

  16. The Pho4 transcription factor mediates the response to arsenate and arsenite in Candida albicans

    PubMed Central

    Urrialde, Verónica; Prieto, Daniel; Pla, Jesús; Alonso-Monge, Rebeca

    2015-01-01

    Arsenate (As (V)) is the dominant form of the toxic metalloid arsenic (As). Microorganisms have consequently developed mechanisms to detoxify and tolerate this kind of compounds. In the present work, we have explored the arsenate sensing and signaling mechanisms in the pathogenic fungus Candida albicans. Although mutants impaired in the Hog1 or Mkc1-mediated pathways did not show significant sensitivity to this compound, both Hog1 and Mkc1 became phosphorylated upon addition of sodium arsenate to growing cells. Hog1 phosphorylation upon arsenate challenge was shown to be Ssk1-dependent. A screening designed for the identification of transcription factors involved in the arsenate response identified Pho4, a transcription factor of the myc-family, as pho4 mutants were susceptible to As (V). The expression of PHO4 was shortly induced in the presence of sodium arsenate in a Hog1-independent manner. Pho4 level affects Hog1 phosphorylation upon As (V) challenge, suggesting an indirect relationship between Pho4 activity and signaling in C. albicans. Pho4 also mediates the response to arsenite as revealed by the fact that pho4 defective mutants are sensitive to arsenite and Pho4 becomes phosphorylated upon sodium arsenite addition. Arsenite also triggers Hog1 phosphorylation by a process that is, in this case, independent of the Ssk1 kinase. These results indicate that the HOG pathway mediates the response to arsenate and arsenite in C. albicans and that the Pho4 transcription factor can differentiate among As (III), As (V) and Pi, triggering presumably specific responses. PMID:25717325

  17. Effects of arsenate on growth and physiology in mallard ducklings

    USGS Publications Warehouse

    Camardese, M.B.; Hoffman, D.J.; LeCaptain, L.J.; Pendleton, G.W.

    1990-01-01

    Arsenic (As) has been found at elevated concentrations in irrigation drainwater and in aquatic plants utilized by waterfowl. Mallard (Anas platyrhynchos) duckings received an untreated diet (controls) or diets containing 30, 100 or 300 ppm As added as sodium arsenate. After 10 weeks blood and tissue samples were collected for biochemical and histological examination. Arsenic accumulated significantly in brain and liver of ducklings fed 100 or 300 ppm but did not result in histopathological lesions. The 300-ppm dietary As concentration decreased overall growth (weight gain) in males, whereas all concentrations of As decreased overall growth and rate of growth in females. Food consumption was less during the first three weeks in all 300-ppm group and during the second week for the 100-ppm compared to controls. Plasma sorbitol dehydrogenase activity and plasma glucose concentration were higher in the 300-ppm group compared to controls. Plasma triglyceride concentration increased in all As-treated groups. Brain ATP was lower in the 300-ppm group and sodium/potassium-dependent ATPase activity was higher in the 30- and 100-ppm groups. Hepatic glutathione peroxidase activity was lower in the 300-ppm group and malondialdehyde lower in all treatment groups. All treatment levels caused elevation in hepatic glutathione and ATP concentrations. These findings, in combination with altered duckling behavior (increased resting time) suggesting that concentrations of As that have been found in aquatic plants (up to 430 ppm dry weight) could adversely affect normal duckling development.

  18. Characterising microbial reduction of arsenate sorbed to ferrihydrite and its concurrence with iron reduction and the consequent impact on arsenic mobilisation

    NASA Astrophysics Data System (ADS)

    Huang, Jen-How

    2014-05-01

    Mobilisation of solid phase arsenic under reducing conditions involves a combination of microbial arsenate and iron reduction and is affected by secondary reactions of released products. A series of model anoxic incubations were performed to understand the concurrence between arsenate and ferrihydrite reduction by Shewanella putrefaciens strain CN-32 at different concentrations of arsenate, ferrihydrite and lactate, and with given ΔGrxn for arsenate and ferrihydrite reduction in non-growth conditions at pH 7. The reduction kinetics of arsenate sorbed to ferrihydrite is predominately controlled by the availability of dissolved arsenate, which is measured by the integral of dissolved arsenate concentrations against incubation time and shown to correlate with the first order rate constants. Thus, the mobilisation of adsorbed As(V) can be regarded as the rate determining step of microbial reduction of As(V) sorbed to ferrihydrite. High lactate concentrations slightly slowed down the rate of arsenate reduction due to the competition with arsenate for microbial contact. Under all experimental conditions, simultaneous arsenate and ferrihydrite reduction occurred following addition of S. putrefaciens inoculums and suggested no apparent competition between these two enzymatic reductions. Ferrous ions released from iron reduction might retard microbial arsenate reduction at high arsenate and ferrihydrite concentrations due to formation of ferrous arsenate. At high arsenate to ferrihydrite ratios, reductive dissolution of ferrihydrite shifted arsenate from sorption to dissolution and hence accelerated arsenate reduction. Reductive dissolution of ferrihydrite may cause additional releases of adsorbed As(V) into solution, which is especially effective at high As(V) to ferrihydrite ratios. In comparison, formation of Fe(II) secondary minerals during microbial Fe(III) reduction were responsible for trapping solution As(V) in the systems with high ferrihydrite but low As

  19. Zeatin reductase in Phaseolus embryos

    SciTech Connect

    Martin, R.C.; Mok, David, W.S.; Mok, M.C. )

    1989-04-01

    Zeatin was converted to O-xylosylzeatin in embryos of Phaseolus vulgaris . O-xylosyldihydrozeatin was also identified as a zeatin metabolite. Incubation of embryo extracts with {sup 14}C-zeatin and {sup 14}C-O-xylosylzeatin revealed that reduction preceeds the O-xylosylation of zeatin. An enzyme responsible for reducing the N{sup 6}-side chain was isolated and partially purified using ammonium sulfate fractionation and affinity, gel filtration and anion exchange chromatography. The NADPH dependent reductase was zeatin specific and did not recognize cis-zeatin, ribosylzeatin, i{sup 6}Ade or i{sup 6}Ado. Two forms of the reductase could be separated by either gel filtration or anion exchange HPLC. The HMW isozyme (Mr. 55,000) eluted from the anion exchange column later than the LMW isozyme (Mr. 25,000). Interspecific differences in zeatin reductase activity were also detected.

  20. Isolated menthone reductase and nucleic acid molecules encoding same

    DOEpatents

    Croteau, Rodney B; Davis, Edward M; Ringer, Kerry L

    2013-04-23

    The present invention provides isolated menthone reductase proteins, isolated nucleic acid molecules encoding menthone reductase proteins, methods for expressing and isolating menthone reductase proteins, and transgenic plants expressing elevated levels of menthone reductase protein.

  1. Histochemical localization of nitrate reductase.

    PubMed

    Vaughn, K C; Duke, S O

    1981-01-01

    NADH-dependent nitrate reductase (E.C. 1.6.6.1) was ultrastructurally localized in norflurazon-treated and control soybean cotyledons [Glycine max (L.) Merr.] by a method based upon the increase in osmiophilia due to the formation of an azo dye. The reaction product was observed in small vesicles throughout the cytoplasm. An apparent transport of nitrite to the plastid, the site of nitrite reduction, may occur through fusion of the nitrite-containing vesicles with the chloroplast envelope. Plants grown in tungstate lacked nitrate reductase activity as measured by standard assay procedures, and showed no increase in osmiophilia, suggesting a degree of specificity of this cytochemical procedure.

  2. Effects of pore size and dissolved organic matters on diffusion of arsenate in aqueous solution.

    PubMed

    Wang, Yulong; Wang, Shaofeng; Wang, Xin; Jia, Yongfeng

    2017-02-01

    Presented here is the influence of membrane pore size and dissolved organic matters on the diffusion coefficient (D) of aqueous arsenate, investigated by the diffusion cell method for the first time. The pH-dependent diffusion coefficient of arsenate was determined and compared with values from previous studies; the coefficient was found to decrease with increasing pH, showing the validity of our novel diffusion cell method. The D value increased dramatically as a function of membrane pore size at small pore sizes, and then increased slowly at pore sizes larger than 2.0μm. Using the ExpAssoc model, the maximum D value was determined to be 11.2565×10(-6)cm(2)/sec. The presence of dissolved organic matters led to a dramatic increase of the D of arsenate, which could be attributed to electrostatic effects and ionic effects of salts. These results improve the understanding of the diffusion behavior of arsenate, especially the important role of various environmental parameters in the study and prediction of the migration of arsenate in aquatic water systems.

  3. Edaphic factors affecting the toxicity and accumulation of arsenate in the earthworm Lumbricus terrestris

    SciTech Connect

    Meharg, A.A.; Shore, R.F.; Broadgate, K.

    1998-06-01

    The toxicity and accumulation of arsenate was determined in the earthworm Lumbricus terrestris in soil from different layers of a forest profile. Toxicity increased fourfold between 2 and 10 d. Edaphic factors (pH, soil organic matter, and depth in soil profile) also affected toxicity with a three fold decrease in the concentration that causes 50% mortality with increasing depth in soil. In a 4-d exposure study, there was no evidence of arsenic bioconcentration in earthworm tissue, although bioaccumulation was occurring. There was a considerable difference in tissue residues between living and dead earthworms, with dead worms having higher concentrations. This difference was dependent on both soil arsenate concentration and on soil type. Over a wide range of soil arsenate concentrations, earthworm arsenic residues are homeostatically maintained in living worms, but this homeostasis breaks down during death. Alternatively, equilibration with soil residues may occur via accumulation after death. In long-term accumulation studies in soils dosed with a sublethal arsenate concentration, bioconcentration of arsenate did not occur until day 12, after which earthworm concentrations rose steadily above the soil concentration, with residues in worms three fold higher than soil concentrations by the termination of the study. This bioconcentration only occurred in depurated worms over the time period of the study. Initially, depurated worms had lower arsenic concentrations than undepurated until tissue concentrations were equivalent to the soil concentration. Once tissue concentration was greater than soil concentration, depurated worms had higher arsenic residues than undepurated.

  4. Constant rate exposure of pregnant hamsters to arsenate during early gestation

    SciTech Connect

    Ferm, V.H.; Hanlon, D.P.

    1985-08-01

    The teratogenic and embryotoxic effects of constant-rate exposure of pregnant hamsters to arsenate have been examined by means of subcutaneous implants of osmotic minipumps. Different total exposure regimes were established by varying the duration of minipump implants and by varying the concentration of arsenate in the minipumps. Dams were killed on Day 13 pregnancy, 5 days after the critical stage of organogenesis. Numbers of resorptions, dead fetuses, and living fetuses were obtained. Fetal weights, crown-rump lengths, and the incidence of malformations were recorded. Control animals were treated identically with minipumps containing demineralized water. The percentage of malformations per litter, a direct measure of teratogenesis, was dependent only upon the concentration of arsenate in the minipumps. The minimum teratogenic response was achieved with a dose of 70 ..mu..mol/kg dam/24 hr during the critical stages of organogenesis. The embryotoxic (fetotoxic) indicators, fetal weight and crown-rump length, decreased with increases in exposure time and with increased concentrations of arsenate. The resorption rate also depended directly upon duration of exposure and concentration of arsenate in the mini-pump.

  5. Evaluating the performance of iron nanoparticle resin in removing arsenate from water.

    PubMed

    Boldaji, Maryam Rahmani; Nabizadeh, Ramin; Dehghani, Mohammad Hadi; Nadafi, Kazem; Mahvi, Amir Hossein

    2010-01-01

    This research was undertaken to evaluate the effectiveness of a hybrid sorbent resin (Lewatit FO36) with goethite structure for removing arsenate from water. Column experiments (with constant flow rate of 8 mL/min, corresponding to 2 min empty bed contact time (EBCT)) were conducted to evaluate the adsorption capacity of resin before and after regeneration and effects of chloride, sulfate, bicarbonate and combined competing ions for arsenate removal from water. The adsorption capacity was approximately 3.229 mg/g that was reduced to 2.826 mg/g after regeneration with 12.48% decrease, which indicates to a successful regeneration procedure. Chloride and sulfate ions had no significant effects on arsenate removal but arsenic removal decreased in the presence of bicarbonate and combined ions. This reduction may be due to the ability of bicarbonate ions in extracting and mobilizing the arsenate ions from iron oxyhydroxides. Results of this study showed that Lewatit FO36 could be developed as a suitable sorbent for arsenate removal.

  6. Respiratory alkalosis.

    PubMed

    Foster, G T; Vaziri, N D; Sassoon, C S

    2001-04-01

    Respiratory alkalosis is an extremely common and complicated problem affecting virtually every organ system in the body. This article reviews the various facets of this interesting problem. Respiratory alkalosis produces multiple metabolic abnormalities, from changes in potassium, phosphate, and calcium, to the development of a mild lactic acidosis. Renal handling of the above ions is also affected. The etiologies may be related to pulmonary or extrapulmonary disorders. Hyperventilation syndrome is a common etiology of respiratory alkalosis in the emergency department setting and is a diagnosis by exclusion. There are many cardiac effects of respiratory alkalosis, such as tachycardia, ventricular and atrial arrhythmias, and ischemic and nonischemic chest pain. In the lungs, vasodilation occurs, and in the gastrointestinal system there are changes in perfusion, motility, and electrolyte handling. Therapeutically, respiratory alkalosis is used for treatment of elevated intracranial pressure. Correction of a respiratory alkalosis is best performed by correcting the underlying etiology.

  7. Differences in the immobilization of arsenite and arsenate by calcite

    NASA Astrophysics Data System (ADS)

    Yokoyama, Yuka; Tanaka, Kazuya; Takahashi, Yoshio

    2012-08-01

    The sorption and coprecipitation experiments of arsenic (As) with calcite coupled with determinations of the chemical state of As both in the reaction fluid and in calcite were conducted to investigate the influence of the As oxidation state on its immobilization into calcite. The oxidation states of As in calcite and water were determined via As K-edge XANES and HPLC-ICP-MS analysis, respectively. The results of the sorption experiments at pH 8.2 show that only As(V) is distributed to calcite regardless of the As oxidation state in the solution. In coprecipitation experiments, As(V) is preferentially incorporated into calcite over a wide range of pH (7-12). On the other hand, the incorporation of As(III) into calcite is not observed at circumneutral pH. This difference between As(III) and As(V) is attributed to the fact that their dissolved species are neutral vs. negatively charged, respectively, at circumneutral pH (arsenite as H3AsO3; arsenate as H2AsO4- or HAsO42-). As the pH increases (>9), up to 33% of As(III)/Astotal ratio is partitioned into calcite or a precursor of calcite (metastable vaterite formed during the early stage of precipitation). The higher interaction of As with calcite at an alkaline pH compared with circumneutral pH is due to the negative charge of As(III) at alkaline pH. However, the As(III)/Astotal ratio decreases as time progresses and only As(V) can be found finally in calcite. The ratio of distribution coefficients of As(III) and As(V) into calcite (KAs(V)/KAs(III)) at pH ˜7 is larger than 2.1 × 103, suggesting that the oxidation state of As is a significant issue in considering the interaction between As and calcite in groundwater. Moreover, low KAs(III) shows that the sequestration of As via coprecipitation with calcite is not an important chemical process under reducing conditions, such as in the groundwaters in Bangladesh and other As-contaminated areas where As(III) is the dominant dissolved species of As. In the system spiked

  8. Impact of chromated copper arsenate (CCA) in wood mulch.

    PubMed

    Townsend, Timothy G; Solo-Gabriele, Helena; Tolaymat, Thabet; Stook, Kristin

    2003-06-20

    The production of landscape mulch is a major market for the recycling of yard trash and waste wood. When wood recovered from construction and demolition (C&D) debris is used as mulch, it sometimes contains chromated copper arsenate (CCA)-treated wood. The presence of CCA-treated wood may cause some potential environmental problems as a result of the chromium, copper, and arsenic present. Research was performed to examine the leachability of the three metals from a variety of processed wood mixtures in Florida. The mixtures tested included mixed wood from C&D debris recycling facilities and mulch purchased from retail outlets. The synthetic precipitation leaching procedure (SPLP) was performed to examine the leaching of chromium, copper and arsenic. Results were compared to Florida's groundwater cleanup target levels (GWCTLs). Eighteen of the 22 samples collected from C&D debris processing facilities leached arsenic at concentrations greater than Florida's GWCTL of 50 microg/l. The mean leachable arsenic concentration for the C&D debris samples was 153 microg/l with a maximum of 558 microg/l. One of the colored mulch samples purchased from a retail outlet leached arsenic above 50 microg/l, while purchased mulch samples derived from virgin materials did not leach detectable arsenic (<5 microg/l). A mass balance approach was used to compute the potential metal concentrations (mg/kg) that would result from CCA-treated wood being present in wood mulch. Less than 0.1% CCA-treated wood would cause a mulch to exceed Florida's residential clean soil guideline for arsenic (0.8 mg/kg).

  9. Combined Hydrous Ferric Oxide and Quaternary Ammonium Surfactant Tailoring of Granular Activated Carbon for Concurrent Arsenate and Perchlorate Removal

    SciTech Connect

    Jang, M.; Cannon, F; Parette, R; Yoon, S; Chen, W

    2009-01-01

    Activated carbon was tailored with both iron and quaternary ammonium surfactants so as to concurrently remove both arsenate and perchlorate from groundwater. The iron (hydr)oxide preferentially removed the arsenate oxyanion but not perchlorate; while the quaternary ammonium preferentially removed the perchlorate oxyanion, but not the arsenate. The co-sorption of two anionic oxyanions via distinct mechanisms has yielded intriguing phenomena. Rapid small-scale column tests (RSSCTs) with these dually prepared media employed synthetic waters that were concurrently spiked with arsenate and perchlorate; and these trial results showed that the quaternary ammonium surfactants enhanced arsenate removal bed life by 25-50% when compared to activated carbon media that had been preloaded merely with iron (hydr)oxide; and the surfactant also enhanced the diffusion rate of arsenate per the Donnan effect. The authors also employed natural groundwater from Rutland, MA which contained 60 microg/L As and traces of silica, and sulfate; and the authors spiked this with 40 microg/L perchlorate. When processing this water, activated carbon that had been tailored with iron and cationic surfactant could treat 12,500 bed volumes before 10 microg/L arsenic breakthrough, and 4500 bed volumes before 6 microg/L perchlorate breakthrough. Although the quaternary ammonium surfactants exhibited only a slight capacity for removing arsenate, these surfactants did facilitate a more favorably positively charged avenue for the arsenate to diffuse through the media to the iron sorption site (i.e. via the Donnan effect).

  10. Effect of flooding lead-arsenate contaminated orchard soil on growth, arsenic and lead accumulation in rice

    USDA-ARS?s Scientific Manuscript database

    Lead-arsenate has been used as a pesticide in controlling codling moth (Cydia pomonella) in apple and plum orchards from 1900-1960. As a result, many old orchards contain high levels of arsenic. Flooding soils contaminated by lead-arsenate could increase plant arsenic and lead and become a human h...

  11. Removal of arsenate from water by using an Fe-Ce oxide adsorbent: effects of coexistent fluoride and phosphate.

    PubMed

    Zhang, Yu; Dou, Xiao-Min; Yang, Min; He, Hong; Jing, Chang-Yong; Wu, Zi-Yu

    2010-07-15

    The Langmuir two-site equation, X-ray photoelectron spectroscopy, and extended X-ray absorption fine structure spectroscopy have been employed to study the competitive behaviors of fluoride (F) and phosphate (P) in relation to arsenate adsorption on an Fe-Ce adsorbent as well as the mechanisms involved. The two-site isotherm revealed the presence of two kinds of adsorption sites with different binding affinities for arsenate. Both the total and low-binding-energy maximum adsorption capacities (Q and Q(1)) of arsenate decreased significantly even at a molar ratio of As/P=1:0.1. The coexistence of F, only influenced the total Q of arsenate at high simultaneous F concentrations. The fact that Fe-Ce released 0.15-0.24 mmol sulfate for every mmol arsenate adsorbed suggested that, while sulfate groups might have played a role for adsorption, surface hydroxyl groups should be the major active sites. The XPS results indicated that arsenate and P are mainly adsorbed through the substitution of Fe surface active sites, while F is mainly adsorbed through substitution of Ce surface active sites. The As k-edge EXAFS data show that the second peak of Fe-Ce after arsenate adsorption is As-Fe shell, which further supported that arsenate adsorption occurs mainly at the Fe surface active sites. 2010 Elsevier B.V. All rights reserved.

  12. RESPIRATORY PATHWAYS IN THE MYCOPLASMA I.

    PubMed Central

    Smith, S. L.; Van Demark, P. J.; Fabricant, J.

    1963-01-01

    Smith, S. L. (Cornell University, Ithaca, N.Y.), P. J. Van Demark, and J. Fabricant. Respiratory pathways in the Mycoplasma. I. Lactate oxidation by Mycoplasma gallisepticum. J. Bacteriol. 86:893–897. 1963.—Resting cells of Mycoplasma gallisepticum 293 required the addition of nicotinamide adenine dinucleotide, thiamine pyrophosphate, and flavine mononucleotide for the maximal rate of sodium lactate oxidation. Inhibitor studies, as well as spectrophotometric and chemical assays, indicate that the pathway of electron transport to oxygen during lactate oxidation does not involve heme catalysts, and is mediated by flavin-linked enzyme systems. The presence of reduced nicotinamide adenine dinucleotide-specific lactic dehydrogenase, menadione reductase, ferricyanide reductase, and reduced nicotinamide adenine dinucleotide oxidase activities was detected in cell-free extracts. No cytochrome c reductase or reduced nicotinamide adenine dinucleotide peroxidase activity was detected in these extracts. PMID:14080798

  13. Ion chromatographic separation and determination of phosphate and arsenate in water and hair.

    PubMed

    Antony, P J; Karthikeyan, S; Iyer, C S P

    2002-02-15

    A simple and sensitive method for the sequential determination of phosphate and arsenate was developed based on initial ion chromatographic separation followed by detection as the ion-association complex formed by heteropolymolybdophosphate and arsenate with bismuth. With 200 microl sample injection and separation on a AS4A-SC column using an eluent of 3.5 mM sodium hydrogen carbonate-10.0 mM sodium hydroxide, the detection limits which are calculated as the concentration equivalent to twice the baseline noise, were found to be 0.8 microg/l and 4.2 microg/l for P and As, respectively. Spiked samples were analyzed and recoveries were found to be satisfactory in the range of 95-105% for phosphate and 90-105% for arsenate. Samples of water and hair were analyzed by the proposed method.

  14. Arsenate removal by layered double hydroxides embedded into spherical polymer beads: Batch and column studies.

    PubMed

    Nhat Ha, Ho Nguyen; Kim Phuong, Nguyen Thi; Boi An, Tran; Mai Tho, Nguyen Thi; Ngoc Thang, Tran; Quang Minh, Bui; Van Du, Cao

    2016-01-01

    In this study, the performance of poly(layered double hydroxides) [poly(LDHs)] beads as an adsorbent for arsenate removal from aqueous solution was investigated. The poly(LDHs) beads were prepared by immobilizing LDHs into spherical alginate/polyvinyl alcohol (PVA)-glutaraldehyde beads (spherical polymer beads). Batch adsorption studies were conducted to assess the effect of contact time, solution pH, initial arsenate concentrations and co-existing anions on arsenate removal performance. The potential reuse of these poly(LDHs) beads was also investigated. Approximately 79.1 to 91.2% of arsenic was removed from an arsenate solution (50 mg As L(-1)) by poly(LDHs). The adsorption data were well described by the pseudo-second-order kinetics model and the Langmuir isotherm model, and the adsorption capacities of these poly(LDHs) beads at pH 8 were from 1.64 to 1.73 mg As g(-1), as calculated from the Langmuir adsorption isotherm. The adsorption ability of the poly(LDHs) beads decreased by approximately 5-6% after 5 adsorption-desorption cycles. Phosphates markedly decreased arsenate removal. The effect of co-existing anions on the adsorption capacity declined in the following order: HPO4 (2-) > HCO3 (-) > SO4 (2-) > Cl(-). A fixed-bed column study was conducted with real-life arsenic-containing water. The breakthrough time was found to be from 7 to 10 h. Under optimized conditions, the poly(LDHs) removed more than 82% of total arsenic. The results obtained in this study will be useful for further extending the adsorbents to the field scale or for designing pilot plants in future studies. From the viewpoint of environmental friendliness, the poly(LDHs) beads are a potential cost-effective adsorbent for arsenate removal in water treatment.

  15. Adsorption of fluoride, phosphate, and arsenate ions on a new type of ion exchange fiber.

    PubMed

    Ruixia, Liu; Jinlong, Guo; Hongxiao, Tang

    2002-04-15

    A new type of ion exchange fiber for the removal of fluoride, phosphate, and arsenate ions has been developed. A batch adsorption technique for investigating adsorption kinetic and equilibrium parameters and determining pH adsorption edges is applied. It is shown that the adsorption properties of the ion exchange fiber for fluoride, phosphate, and arsenate ions depend on the pH value and anion concentration. The adsorption of arsenate on the sorbent reaches a maximum of 97.9% in the pH value range of 3.5 to 7.0. The adsorption percentage of phosphate is more than 99% in the pH range of 3.0 to 5.5. The adsorption of fluoride on the ion exchange fiber is found to be 90.4% at pH 3.0. The Freundlich model can describe the adsorption equilibrium data of fluoride, arsenate, and phosphate anions. The sorption of the three anions on the ion exchange fiber is a rapid process, and the adsorption kinetic data can be simulated very well by the pseudo-second-order rate equation. The column performance is carried out to assess the applicability of the ion exchange fiber for the removal of fluoride, phosphate, and arsenate ions from synthetic wastewaters with satisfactory removal efficiency. The desorption experiment shows that fluoride ion sorbed by the fiber column can be quantitatively desorbed with 5 mL of 0.50 mol/L NaOH at elution rate of 1 mL/min, and 30 mL of NaOH is necessary for the quantitative recovery of phosphate and arsenate ions.

  16. Effect of aqueous Fe(II) on arsenate sorption on goethite and hematite.

    PubMed

    Catalano, Jeffrey G; Luo, Yun; Otemuyiwa, Bamidele

    2011-10-15

    Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10⁻³ M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.

  17. Effect of Aqueous Fe(II) on Arsenate Sorption on Goethite and Hematite

    SciTech Connect

    Catalano, Jeffrey G.; Luo, Yun; Otemuyiwa, Bamidele

    2011-11-17

    Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10{sup -3} M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.

  18. Phosphate and arsenate removal efficiency by thermostable ferritin enzyme from Pyrococcus furiosus using radioisotopes.

    PubMed

    Sevcenco, Ana-Maria; Paravidino, Monica; Vrouwenvelder, Johannes S; Wolterbeek, Hubert Th; van Loosdrecht, Mark C M; Hagen, Wilfred R

    2015-06-01

    Oxo-anion binding properties of the thermostable enzyme ferritin from Pyrococcus furiosus were characterized with radiography. Radioisotopes (32)P and (76)As present as oxoanions were used to measure the extent and the rate of their absorption by the ferritin. Thermostable ferritin proved to be an excellent system for rapid phosphate and arsenate removal from aqueous solutions down to residual concentrations at the picomolar level. These very low concentrations make thermostable ferritin a potential tool to considerably mitigate industrial biofouling by phosphate limitation or to remove arsenate from drinking water.

  19. Lead in tissue of cats fed pine voles from lead arsenate-treated orchards

    SciTech Connect

    Gilmartin, J.E.; Alo, D.K.; Richmond, M.E.; Bache, C.A.; Lisk, D.J.

    1985-02-01

    Lead arsenate has been used for many years for control of insects in apple orchards in the United States. In an earlier study, it was shown that such orchard soils may contain very high concentrations of lead and that orchards voles and mice inhibating such soils accumulate inordinately high levels of lead. It is of interest to learn the possible extent of deposition of lead in higher carnivores that may consume such orchard animals. In the work reported, cats were fed pine voles (Microtus pinetorum) captured in lead arsenate-treated orchards located in the vicinity of New Paltz, New York. Following sacrifice, the lead content of cat tissues was determined.

  20. Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

    PubMed

    Song, Jia; Jia, Shao-Yi; Yu, Bo; Wu, Song-Hai; Han, Xu

    2015-08-30

    Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust.

  1. Perchlorate Reductase Is Distinguished by Active Site Aromatic Gate Residues*

    PubMed Central

    Youngblut, Matthew D.; Tsai, Chi-Lin; Clark, Iain C.; Carlson, Hans K.; Maglaqui, Adrian P.; Gau-Pan, Phonchien S.; Redford, Steven A.; Wong, Alan; Tainer, John A.; Coates, John D.

    2016-01-01

    Perchlorate is an important ion on both Earth and Mars. Perchlorate reductase (PcrAB), a specialized member of the dimethylsulfoxide reductase superfamily, catalyzes the first step of microbial perchlorate respiration, but little is known about the biochemistry, specificity, structure, and mechanism of PcrAB. Here we characterize the biophysics and phylogeny of this enzyme and report the 1.86-Å resolution PcrAB complex crystal structure. Biochemical analysis revealed a relatively high perchlorate affinity (Km = 6 μm) and a characteristic substrate inhibition compared with the highly similar respiratory nitrate reductase NarGHI, which has a relatively much lower affinity for perchlorate (Km = 1.1 mm) and no substrate inhibition. Structural analysis of oxidized and reduced PcrAB with and without the substrate analog SeO32− bound to the active site identified key residues in the positively charged and funnel-shaped substrate access tunnel that gated substrate entrance and product release while trapping transiently produced chlorate. The structures suggest gating was associated with shifts of a Phe residue between open and closed conformations plus an Asp residue carboxylate shift between monodentate and bidentate coordination to the active site molybdenum atom. Taken together, structural and mutational analyses of gate residues suggest key roles of these gate residues for substrate entrance and product release. Our combined results provide the first detailed structural insight into the mechanism of biological perchlorate reduction, a critical component of the chlorine redox cycle on Earth. PMID:26940877

  2. Subchronic dispositional and toxicological effects of arsenate administered in drinking water to mice.

    PubMed

    Hughes, M F; Thompson, D J

    1996-10-11

    Exposure to the drinking water contaminant arsenate is a daily occurrence and there are concerns that this exposure may lead to cancer. Although the acute dispositional effects of arsenate have been studied in detail, there is minimal information on the disposition and toxicological effects of it after continuous exposure. The objective of this study was to examine in mice the effect of a 4-wk treatment with arsenate administered in drinking water. Female B6C3F1 mice (3/cage) were housed in metabolism cages and given water and food ad libitum. Two groups (A, B) of mice were treated (4 cages/treatment/group) with distilled water (control, C) or water containing 0.025 mg/L (L) or 2.5 mg/L (H) arsenate. Group A was sacrificed on d 28 and plasma and urine samples were taken for determination of clinical chemistry parameters. Liver and kidney tissue samples were taken for histopathological analysis. The reduced nonprotein sulfhydryl (NPSH) content in several tissues was determined. Group B was gavaged with [73As]arsenate on d 28 and continued the arsenate drinking water exposure for 48 h. Excreta and tissues were collected and analyzed for 73As. Urine was further analyzed for arsenate and its metabolites. There were no effects on the mean daily amount of water and food consumed, whereas the mean daily urine volume excreted was significantly elevated by 10% in the H-treated animals compared to C and L. A dose-related hepatic vacuolar degeneration in the liver was observed, but no histological changes were evident in the kidney. Only clinical chemistry parameters in plasma were altered by the arsenate treatment. Glucose was significantly lower at the H dose compared to C and L, triglycerides were significantly greater in C than L and H, and creatinine was significantly greater in H than C. Hepatic NPSH content in the H animals was significantly lower than C and L animals, whereas no effects in lung and kidney were detected. The weights of liver, lung, and kidney, as well

  3. Non-linear optical titanyl arsenates: Crystal growth and properties

    NASA Astrophysics Data System (ADS)

    Nordborg, Jenni Eva Louise

    Crystals are appreciated not only for their appearance, but also for their unique physical properties which are utilized by the photonic industry in appliances that we come across every day. An important part of enabling the technical use of optical devices is the manufacture of crystals. This dissertation deals with a specific group of materials called the potassium titanyl phosphate (KIP) family, known for their non-linear optical and ferroelectric properties. The isomorphs vary in their linear optical and dielectric properties, which can be tuned to optimize device performance by forming solid solutions of the different materials. Titanyl arsenates have a wide range of near-infrared transmission which makes them useful for tunable infrared lasers. The isomorphs examined in the present work were primarily RbTiOASO4 (RTA) and CsTiOAsO4 (CTA) together with the mixtures RbxCs 1-xTiOAsO4 (RCTA). Large-scale crystals were grown by top seeding solution growth utilizing a three-zone furnace with excellent temperature control. Sufficiently slow cooling and constant upward lifting produced crystals with large volumes useable for technical applications. Optical quality RTA crystals up to 10 x 12 x 20 mm were grown. The greater difficulty in obtaining good crystals of CTA led to the use of mixed RCTA materials. The mixing of rubidium and cesium in RCTA is more favorable to crystal growth than the single components in pure RTA and CTA. Mixed crystals are rubidium-enriched and contain only 20-30% of the cesium concentration in the flux. The cesium atoms show a preference for the larger cation site. The network structure is very little affected by the cation substitution; consequently, the non-linear optical properties of the Rb-rich isomorphic mixtures of RTA and CTA can be expected to remain intact. Crystallographic methods utilizing conventional X-ray tubes, synchrotron radiation and neutron diffraction have been employed to investigate the properties of the atomic

  4. Nitrate reductase from Rhodopseudomonas sphaeroides.

    PubMed Central

    Kerber, N L; Cardenas, J

    1982-01-01

    The facultative phototroph Rhodopseudomonas sphaeroides DSM158 was incapable of either assimilating or dissimilating nitrate, although the organism could reduce it enzymatically to nitrite either anaerobically in the light or aerobically in the dark. Reduction of nitrate was mediated by a nitrate reductase bound to chromatophores that could be easily solubilized and functioned with chemically reduced viologens or photochemically reduced flavins as electron donors. The enzyme was solubilized, and some of its kinetic and molecular parameters were determined. It seemed to be nonadaptive, ammonia did not repress its synthesis, and its activity underwent a rapid decline when the cells entered the stationary growth phase. Studies with inhibitors and with metal antagonists indicated that molybdenum and possibly iron participate in the enzymatic reduction of nitrate. The conjectural significance of this nitrate reductase in phototrophic bacteria is discussed. PMID:6978883

  5. SORPTION OF ARSENATE AND ARSENITE ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

    EPA Science Inventory

    Sorption of arsenate and arsenite was examined on a ruthenium compound using macroscopic and microscopic techniques. Batch sorption experiments at pH 4,5,6, 7 and 8 were employed to construct constant solid solution ratio isotherms (CSI). After equilibration at the appropriate pH...

  6. SORPTION OF ARSENATE AND ARSENITE ON RUO2.XH2O: A SPECTROSCOPIC AND MACROSCOPIC STUDY

    EPA Science Inventory

    The sorption of arsenate (As(V)) and arsenite (As(III)) on RuO2 xH2O was examined using macroscopic and microscopic techniques. Constant solid:solution ratio isotherms were constructed from batch sorption experiments to study the sorption of the inorganic arsenic species on RuO2...

  7. WASTE REDUCTION PRACTICES AT TWO CHROMATED COPPER ARSENATE WOOD-TREATING PLANTS

    EPA Science Inventory

    Two chromated copper arsenate (CCA) wood-treating plants were assessed for their waste reduction practices. The objectives of this study were to estimate the amount of hazardous wastes that a well-designed and well-main- tained CCA treatment facility would generate and to iden- t...

  8. New Approach to Remove Metals from Chromated Copper Arsenate (CCA)-Treated Wood

    Treesearch

    Todd F. Shupe; Chung Y. Hse; Hui Pan

    2012-01-01

    Recovery of metals from chromated copper arsenate (CCA)-treated southern pine wood particles was investigated using binary acid solutions consisting of acetic, oxalic, and phosphoric acids in a microwave reactor. Formation of an insoluble copper oxalate complex in the binary solution containing oxalic acid was the major factor for low copper removal. Furthermore, the...

  9. SORPTION OF ARSENATE AND ARSENITE ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

    EPA Science Inventory

    Sorption of arsenate and arsenite was examined on a ruthenium compound using macroscopic and microscopic techniques. Batch sorption experiments at pH 4,5,6, 7 and 8 were employed to construct constant solid solution ratio isotherms (CSI). After equilibration at the appropriate pH...

  10. SORPTION OF ARSENATE AND ARSENITE ON RUO2.XH2O: A SPECTROSCOPIC AND MACROSCOPIC STUDY

    EPA Science Inventory

    The sorption of arsenate (As(V)) and arsenite (As(III)) on RuO2 xH2O was examined using macroscopic and microscopic techniques. Constant solid:solution ratio isotherms were constructed from batch sorption experiments to study the sorption of the inorganic arsenic species on RuO2...

  11. Microwave-assisted organic acids extraction of chromate copper arsenate (CCA)-treated southern pine

    Treesearch

    Bin Yu; Chung Y. Hse; Todd F. Shupe

    2010-01-01

    The extraction effects of acid concentration, reaction time and temperature in a microwave reactor on recovery of CCA-treated wood were evaluated. Extraction of copper, chromium, and arsenic metals from chromated copper arsenate (CCA)-treated southern pine wood samples with two different organic acids (i.e., acetic acid and oxalic acid) was investigated using a...

  12. Accumulation of lead and arsenic by lettuce grown on lead-arsenate contaminated orchard soils

    USDA-ARS?s Scientific Manuscript database

    Lead-arsenate was one of the preferred insecticides used as foliar spray to control codling moth (Cydia pomonella) in apple (Malus sylvestris Mill) orchards from the 1900's to the 1960’s. Lead and arsenic are generally immobile and remain in the surface soil. Some of these contaminated lands are now...

  13. COMPARATIVE METABOLISM OF ARSENIC IN MICE AFTER A SINGLE OR REPEATED ORAL ADMINISTRATION OF ARSENATE

    EPA Science Inventory

    COMPARATIVE METABOLISM OF ARSENIC IN MICE AFTER A SINGLE OR REPEATED ORAL ADMINISTRATION OF ARSENATE
    Michael F. Hughes*1, Elaina M. Kenyon1, Brenda C. Edwards1, Carol T. Mitchell1, Luz Maria Del Razo2 and David J. Thomas1
    1US EPA, ORD, NHEERL, ETD, PKB, Research Triangle Pa...

  14. WASTE REDUCTION PRACTICES AT TWO CHROMATED COPPER ARSENATE WOOD-TREATING PLANTS

    EPA Science Inventory

    Two chromated copper arsenate (CCA) wood-treating plants were assessed for their waste reduction practices. The objectives of this study were to estimate the amount of hazardous wastes that a well-designed and well-main- tained CCA treatment facility would generate and to iden- t...

  15. Genotoxic effects of sodium arsenite and sodium arsenate after chronic exposure of Drosophila melanogaster larvae

    SciTech Connect

    Ramos-Morales, P.; Ordaz, M.G.; Munoz, A.

    1995-11-01

    Two arsenic compounds, namely: NaAsO{sub 2} (Sodium Arsenite) and Na{sub 2}HAsO{sub 4} (Sodium Arsenate) were tested for its chronic effect in somatic cells of Drosophila melanogaster. In a previous study in Drosophila we found that both compounds induced SLRL mutations, but failed to induce sex chromosome loss. In the SMART, after acute exposure, only sodium arsenite was positive when cells of the wings were used; however, both were positives in cells of the eyes of Drosophila. The genotoxicity of both compounds localized mainly on somatic cells, in agreement with reports on the carcinogenicity potential of arsenical compounds. The Somatic mutation and recombination test (SMART) was run employing cells of the wing imaginal discs from flr{sup 3}/mwh larvae. First instar larvae (24 {plus_minus} 4 h) were treated during 96 hours with sodium arsenite [0.015-4.0 ppm], and sodium arsenate [0.2-10 ppm], negative control was treated with distilled water. The frequency of spots by wing induced by the two arsenic salts were compared with control according with Frei and Wuergler procedure. Data show that sodium arsenite tested negative at all concentrations, but sodium arsenate tested positive at 0.8, 2 and 10 ppm (P<0.05). This results were consistent with the co-mutagenic role of sodium arsenite, but show that sodium arsenate was mutagenic in Drosophila test system under chronic exposure.

  16. COMPARATIVE METABOLISM OF ARSENIC IN MICE AFTER A SINGLE OR REPEATED ORAL ADMINISTRATION OF ARSENATE

    EPA Science Inventory

    COMPARATIVE METABOLISM OF ARSENIC IN MICE AFTER A SINGLE OR REPEATED ORAL ADMINISTRATION OF ARSENATE
    Michael F. Hughes*1, Elaina M. Kenyon1, Brenda C. Edwards1, Carol T. Mitchell1, Luz Maria Del Razo2 and David J. Thomas1
    1US EPA, ORD, NHEERL, ETD, PKB, Research Triangle Pa...

  17. ACCUMULATION AND METABOLISM OF ARSENIC IN MICE AFTER REPEATED ADMINISTRATION OF ARSENATE

    EPA Science Inventory

    Accumulation and metabolism of arsenic in mice after repeated oral administration of arsenate, Hughes, M. F., Kenyon, E. M., Edwards, B. C., Mitchell, C. T., Del Razo, L. M., and Thomas,
    D. J.

    The human carcinogen inorganic arsenic (iAs) is a pervasive environmental ...

  18. Accumulation of lead and arsenic by carrots grown on four lead-arsenate contaminated orchard soils

    USDA-ARS?s Scientific Manuscript database

    Concerns have been raised about possible human food chain transfer of contaminants resulting from crops grown on orchard soils with histories of lead arsenate use. The objective of this study was to determine the uptake of arsenic and lead by three cultivars of carrots. Carrots were grown on four ...

  19. Accumulation of lead and arsenic by potato grown on lead-arsenate contaminated orchard soils

    USDA-ARS?s Scientific Manuscript database

    Concerns have been raised about the potential food chain transfer of metals in crops grown on historic orchard soils where lead arsenate pesticide was used. The objective of this study was to evaluate the uptake of lead and arsenic (As) by four potato (Solanum tuberosum L.) cultivars (Atlantic, Dar...

  20. [Removal of arsenate from drinking water by activated carbon supported nano zero-valent iron].

    PubMed

    Zhu, Hui-jie; Jia, Yong-feng; Yao, Shu-hu; Wu, Xing; Wang, Shu-ying

    2009-12-01

    A new adsorbent, activated carbon impregnated with nano zero-valent iron was prepared, which size of the needle-shaped iron particles in the pores of carbon was (30-500) nm x (1000-3000) nm and approximately 8.2% of iron was loaded onto it. The arsenate removal percentage was 99.5% by 1.5 g/L NZVI/AC in the 2 mg/L arsenic solution at pH 6.5 and (25 +/- 2) degrees C. The adsorption capacity was about 15.4 mg/g when equilibrium concentration was 1.0 mg/L. Kinetics revealed that uptake of arsenate ion by NZVI/AC was 91.4% in the first 12 h and equilibrium time was about 72 h. The intraparticle diffusion model was applied to study the mechanics of arsenate in the activated carbon. The presence of phosphate and silicate could significantly decrease arsenate removal while the effects of the other anions and cations on the arsenic removal were neglectable. NZVI/AC can be effectively regenerated when elution is done with 0.1 mol/L NaOH solution. Our results suggest that NZVI/AC is a suitable candidate for drinking water treatment due to its high reactivity.

  1. Raman and infrared spectroscopy of arsenates of the roselite and fairfieldite mineral subgroups.

    PubMed

    Frost, Ray L

    2009-01-01

    Raman spectroscopy complimented with infrared spectroscopy has been used to determine the molecular structure of the roselite arsenate minerals of the roselite and fairfieldite subgroups of formula Ca(2)B(AsO(4))(2).2H(2)O (where B may be Co, Fe(2+), Mg, Mn, Ni and Zn). The Raman arsenate (AsO(4))(2-) stretching region shows strong differences between the roselite arsenate minerals which is attributed to the cation substitution for calcium in the structure. In the infrared spectra complexity exists with multiple (AsO(4))(2-) antisymmetric stretching vibrations observed, indicating a reduction of the tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong Raman bands around 450 cm(-1) are assigned to nu(4) bending modes. Multiple bands in the 300-350 cm(-1) region assigned to nu(2) bending modes provide evidence of symmetry reduction of the arsenate anion. Three broad bands for roselite are found at 3450, 3208 and 3042 cm(-1) and are assigned to OH stretching bands. By using a Libowitzky empirical equation hydrogen bond distances of 2.75 and 2.67 A are estimated. Vibrational spectra enable the molecular structure of the roselite minerals to be determined and whilst similarities exist in the spectral patterns, sufficient differences exist to be able to determine the identification of the minerals.

  2. Bioaccumulation and oxidative stress in Daphnia magna exposed to arsenite and arsenate.

    PubMed

    Fan, Wenhong; Ren, Jinqian; Li, Xiaomin; Wei, Chaoyang; Xue, Feng; Zhang, Nan

    2015-11-01

    Arsenic pollution and its toxicity to aquatic organisms have attracted worldwide attention. The bioavailability and toxicity of arsenic are highly related to its speciation. The present study investigated the differences in bioaccumulation and oxidative stress responses in an aquatic organism, Daphnia magna, induced by 2 inorganic arsenic species (As(III) and As(V)). The bioaccumulation of arsenic, Na(+) /K(+) -adenosine triphosphatase (ATPase) activity, reactive oxygen species (ROS) content, total superoxide dismutase (SOD) activity, total antioxidative capability, and malondialdehyde content in D. magna were determined after exposure to 500 µg/L of arsenite and arsenate for 48 h. The results showed that the oxidative stress and antioxidative process in D. magna exposed to arsenite and arsenate could be divided into 3 phases, which were antioxidative response, oxidation inhibition, and antioxidative recovery. In addition, differences in bioaccumulation, Na(+) /K(+) -ATPase activity, and total SOD activity were also found in D. magna exposed to As(III) and As(V). These differences might have been the result of the high affinity of As(III) with sulfhydryl groups in enzymes and the structural similarity of As(V) to phosphate. Therefore, arsenate could be taken up by organisms through phosphate transporters, could substitute for phosphate in biochemical reactions, and could lead to a change in the bioaccumulation of arsenic and activity of enzymes. These characteristics were the possible reasons for the different toxicity mechanisms in the oxidative stress process of arsenite and arsenate.

  3. Respiratory acidosis

    MedlinePlus

    ... when the lungs cannot remove all of the carbon dioxide the body produces. This causes body fluids, especially ... Acute respiratory acidosis is a condition in which carbon dioxide builds up very quickly, before the kidneys can ...

  4. Respiratory Therapists

    MedlinePlus

    ... how to stop smoking. <- Summary Work Environment -> Work Environment About this section Respiratory therapists treat patients in ... also covers different types of occupational specialties. Work Environment The Work Environment tab includes the number of ...

  5. Competitive adsorption of arsenate and phosphate onto calcite; experimental results and modeling with CCM and CD-MUSIC

    NASA Astrophysics Data System (ADS)

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus; Larsen, Flemming

    2012-09-01

    The competitive adsorption of arsenate and phosphate onto calcite was studied in batch experiments using calcite-equilibrated solutions. The solutions had circum-neutral pH (7-8.3) and covered a wide span in the activity of Ca2+ and CO32-. The results show that the adsorption of arsenate onto calcite is strongly reduced by the presence of phosphate, whereas phosphate adsorption is only slightly reduced by arsenate addition. Simultaneous and sequential addition (3 h apart) yields the same reduction in adsorption, underlining the high reversibility of the system. The reduction in adsorption of both arsenate and phosphate is most likely due to competition for the same sorption sites at the calcite surface, considering the similarity in sorption edges, pKa's and geometry of the two anions. The strong reduction in arsenate adsorption by competition with phosphate suggests that adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately. By combining the models for single sorbate systems the competitive adsorption of phosphate and arsenate onto calcite in the binary system could be predicted. This is in contrast to the constant capacitance model (CCM) which under-predicted the competition when combining the models for single sorbate systems. This study clearly shows the importance of performing competitive adsorption studies for validation of multi-component models and for estimating the mobility of an ion in the environment.

  6. Respiratory distress.

    PubMed

    Fallot, André

    2005-11-01

    Preparation for pediatric pulmonary emergencies in the office setting includes adequate training for all medical staff, properly sized and working equipment, and medications to help alleviate respiratory distress when indicated. Status asthmaticus, viral bronchiolitis, and croup account for the vast majority of respiratory emergencies encountered in the pediatric office setting. Timely application of proven approaches to assessment and treatment of these illnesses can prevent hospitalization, decrease length of hospitalizations, and save lives.

  7. [Respiratory distress].

    PubMed

    Galili, D; Garfunkel, A; Elad, S; Zusman, S P; Malamed, S F; Findler, M; Kaufman, E

    2002-01-01

    Dental treatment is usually conducted in the oral cavity and in very close proximity to the upper respiratory airway. The possibility of unintentionally compromising this airway is high in the dental environment. The accumulation of fluid (water or blood) near to the upper respiratory airway or the loosening of teeth fragmentations and fallen dental instruments can occur. Also, some of the drugs prescribed in the dental practice are central nervous system depressants and some are direct respiratory drive depressors. For this reason, awareness of the respiratory status of the dental patient is of paramount importance. This article focuses on several of the more common causes of respiratory distress, including airway obstruction, hyperventilation, asthma, bronchospasm, pulmonary edema, pulmonary embolism and cardiac insufficiency. The common denominator to all these conditions described here is that in most instances the patient is conscious. Therefore, on the one hand, valuable information can be retrieved from the patient making diagnosis easier than when the patient is unconscious. On the other hand, the conscious patient is under extreme apprehension and stress under such situations. Respiratory depression which occurs during conscious sedation or following narcotic analgesic medication will not be dealt with in this article. Advanced pain and anxiety control techniques such as conscious sedation and general anesthesia should be confined only to operators who undergo special extended training.

  8. Denitrification by plant roots? New aspects of plant plasma membrane-bound nitrate reductase.

    PubMed

    Eick, Manuela; Stöhr, Christine

    2012-10-01

    A specific form of plasma membrane-bound nitrate reductase in plants is restricted to roots. Two peptides originated from plasma membrane integral proteins isolated from Hordeum vulgare have been assigned as homologues to the subunit NarH of respiratory nitrate reductase of Escherichia coli. Corresponding sequences have been detected for predicted proteins of Populus trichocarpa with high degree of identities for the subunits NarH (75%) and NarG (65%), however, with less accordance for the subunit NarI. These findings coincide with biochemical properties, particularly in regard to the electron donors menadione and succinate. Together with the root-specific and plasma membrane-bound nitrite/NO reductase, nitric oxide is produced under hypoxic conditions in the presence of nitrate. In this context, a possible function in nitrate respiration of plant roots and an involvement of plants in denitrification processes are discussed.

  9. Uptake, accumulation and depuration of sodium perchlorate and sodium arsenate in zebrafish (Danio rerio).

    PubMed

    Liu, Fu-Jun; Cobb, George P; Anderson, Todd A; Cheng, Qiu-Qiong; Theodorakis, Christopher W

    2006-12-01

    In toxicokinetics studies, interactions between chemicals in mixtures has been largely neglected. This study examines a mixture of perchlorate and arsenate because (1) they have the potential to co-occur in contaminated aquatic habitats, and (2) a previous study by the authors found possible toxicological interactive effects. In the present study, zebrafish (Danio rerio) were exposed to two concentrations of sodium perchlorate (10 and 100 mg l(-1)), sodium arsenate (1 and 10 mg l(-1)), and the mixture-sodium perchlorate+sodium arsenate (10+1 mg l(-1) and 100+10 mg l(-1) Na(2)HAsO(4)-high mixture) for 90 d. Their uptake and accumulation by zebrafish was evaluated at 10, 30, 60, and 90 d. In addition, depuration was examined at 1, 3, and 5d after cessation of the exposure. The uptake of either chemical was concentration-dependent, with significantly higher uptake at high concentrations at either exposure interval. In contrast, there was no significant difference in whole body residue between single chemicals and the corresponding mixture except for 100 mg l(-1) sodium arsenate at 90 d. However, there was increasing accumulation over time at the high concentration of either chemical alone and their mixture, and this increasing trend was more pronounced in the single chemical exposures than in the mixture. At the concentrations tested in the current study, both chemicals reduced the uptake but enhanced the depuration of the other chemical from the zebrafish. This study represents the first examination of the interaction of two anions-perchlorate and arsenate with respect to toxicokinetics.

  10. Effects of sodium arsenate exposure on liver fatty acid profiles and oxidative stress in rats.

    PubMed

    Kharroubi, Wafa; Dhibi, Madiha; Haouas, Zohra; Chreif, Imed; Neffati, Fadoua; Hammami, Mohamed; Sakly, Rachid

    2014-02-01

    The present study aimed to evaluate the effect of arsenic on liver fatty acids (FA) composition, hepatotoxicity and oxidative status markers in rats. Male rats were randomly devised to six groups (n=10 per group) and exposed to sodium arsenate at a dose of 1 and 10 mg/l for 45 and 90 days. Arsenate exposure is associated with significant changes in the FA composition in liver. A significant increase of saturated fatty acids (SFA) in all treated groups (p<0.01) and trans unsaturated fatty acids (trans UFA) in rats exposed both for short term for 10 mg/l (p<0.05) and long term for 1 and 10 mg/l (p<0.001) was observed. However, the cis UFA were significantly decreased in these groups (p<0.05). A markedly increase of indicator in cell membrane viscosity expressed as SFA/UFA was reported in the treated groups (p<0.001). A significant increase in the level of malondialdehyde by 38.3 % after 90 days of exposure at 10 mg/l was observed. Compared to control rats, significant liver damage was observed at 10 mg/l of arsenate by increasing plasma marker enzymes after 90 days. It is through the histological investigations in hepatic tissues of exposed rats that these damage effects of arsenate were confirmed. The antioxidant perturbations were observed to be more important at groups treated by the high dose (p<0.05). An increase in the level of protein carbonyls was observed in all treated groups (p<0.05). The present study provides evidence for a direct effect of arsenite on FA composition disturbance causing an increase of SFA and TFAs isomers, liver dysfunction and oxidative stress. Therefore, arsenate can lead to hepatic damage and propensity towards liver cancer.

  11. Selective removal of arsenate from drinking water using a polymeric ligand exchanger.

    PubMed

    An, Byungryul; Steinwinder, Thomas R; Zhao, Dongye

    2005-12-01

    The new maximum contaminant level (MCL) of 10 microg/L for arsenic in the US drinking water will take effect on January 22, 2006. The compliance cost is estimated to be approximately dollar 600 million per year using current treatment technologies. This research aims to develop an innovative ion exchange process that may help water utilities comply with the new MCL in a more cost-effective manner. A polymeric ligand exchanger (PLE) was prepared by loading Cu2+ to a commercially available chelating ion exchange resin. Results from batch and column experiments indicated that the PLE offered unusually high selectivity for arsenate over other ubiquitous anions such as sulfate, bicarbonate and chloride. The average binary arsenate/sulfate separation factor for the PLE was determined to be 12, which were over two orders of magnitude greater than that (0.1-0.2) for commercial strong-base anion (SBA) exchangers. Because of the enhanced arsenate selectivity, the PLE was able to treat approximately 10 times more bed volumes (BVs) of water than commonly used SBA resins. The PLE can operate optimally in the neutral pH range (6.0-8.0). The exhausted PLE can be regenerated highly efficiently. More than 95% arsenate capacity can be recovered using approximately 22 BVs of 4% (w/w) NaCl at pH 9.1, and the regenerated PLE can be reused without any capacity drop. Upon treatment using FeCl3, the spent brine was recovered and reused for regeneration, which may cut down the regenerant need and reduces the volume of process waste residuals. The PLE can be used as a highly selective and reusable sorbent for removal of arsenate from drinking water.

  12. Preparative separation of arsenate from phosphate by IRA-400 (OH) for oxygen isotopic work.

    PubMed

    Tang, Xiaohui; Berner, Zsolt; Khelashvilli, Pirimze; Norra, Stefan

    2013-02-15

    The paper reports about a series of tests carried out to find out the optimal conditions for the preparative separation of arsenate and phosphate from natural waters, using the anion exchange resin Amberlite IRA-400 (OH). Freundlich isotherms have been constructed on basis of data obtained by stirring different amounts of resin (0.05-1.00 g) with solutions containing 1mg/L As and 10mg/L P in form of arsenate and phosphate and the effect of pH and P/As ratio on adsorption was investigated. It was found that at these concentrations 0.5 g of IRA-400 (OH) can adsorb quantitatively arsenate and phosphate within 1h. In a range of 3.6-11.1, pH seems to have no influence on the adsorption behavior of the resin, but at pH 1.5 the adsorption of both arsenate and phosphate drops to values close to zero. Experiments with solutions with P/As ratios in a range between 1 and 30 have shown that the concentration ratios have also little effect on adsorption. An efficient selective desorption of the anions could be achieved with 2 mol/L HNO3 or HCl, but the use of HCl is impracticable if the separation aims at precipitating arsenate for oxygen isotopic work. The reported adsorption/ desorption properties of the resin are supported also by data obtained by investigating the resin particles with a scanning electron microscope equipped with a fluorescence detection device.

  13. The importance of glutathione and phytochelatins on the selenite and arsenate detoxification in Arabidopsis thaliana.

    PubMed

    Aborode, Fatai Adigun; Raab, Andrea; Voigt, Matthias; Costa, Leticia Malta; Krupp, Eva M; Feldmann, Joerg

    2016-11-01

    We investigated the role of glutathione (GSH) and phytochelatins (PCs) on the detoxification of selenite using Arabidopsis thaliana. The wild-type (WT) of Arabidopsis thaliana and its mutants (glutathione deficient Cad 2-1 and phytochelatins deficient Cad 1-3) were separately exposed to varying concentrations of selenite and arsenate and jointly to both toxicants to determine their sensitivities. The results of the study revealed that, the mutants were about 20-fold more sensitive to arsenate than the WT, an indication that the GSH and PCs affect arsenate detoxification. On the contrary, the WT and both mutants showed a similar level of sensitivity to selenite, an indication that the GSH and PCs do not significantly affect selenite detoxification. However, the WT is about 8 times more sensitive to selenite than to arsenate, and the mutants were more resistant to selenite than arsenate by a factor of 2. This could not be explained by the accumulation of both elements in roots and shoots in exposure experiments. The co-exposure of the WT indicates a synergistic effect with regards to toxicity since selenite did not induce PCs but arsenic and selenium compete in their PC binding as revealed by speciation analysis of the root extracts using HPLC-ICP-MS/ESI-MS. In the absence of PCs an antagonistic effect has been detected which might suggest indirectly that the formation of Se glutathione complex prevent the formation of detrimental selenopeptides. This study, therefore, revealed that PC and GSH have only a subordinate role in the detoxification of selenite. Copyright © 2016. Published by Elsevier B.V.

  14. Coprecipitation of arsenate with metal oxides. 3. Nature, mineralogy, and reactivity of iron(III)-aluminum precipitates.

    PubMed

    Violante, Antonio; Pigna, Massimo; Del Gaudio, Stefania; Cozzolino, Vincenza; Banerjee, Dipanjan

    2009-03-01

    Coprecipitation involving arsenic with aluminum or iron has been studied because this technique is considered particularly efficient for removal of this toxic element from polluted waters. Coprecipitation of arsenic with mixed iron-aluminum solutions has received scant attention. In this work we studied (i)the mineralogy, surface properties, and chemical composition of mixed iron-aluminum oxides formed at initial Fe/Al molar ratio of 1.0 in the absence or presence of arsenate [As/ Fe+Al molar ratio (R) of 0, 0.01, or 0.1] and at pH 4.0, 7.0, and 10.0 and aged for 30 and 210 days at 50 degrees C and (ii) the removal of arsenate from the coprecipitates after addition of phosphate. The amounts of short-range ordered precipitates (ferrihydrite, aluminous ferrihydrite and/or poorly crystalline boehmite) were greater than those found in iron and aluminum systems (studied in previous works), due to the capacity of both aluminum and arsenate to retard or inhibitthe transformation of the initially formed precipitates into well-crystallized oxides (gibbsite, bayerite, and hematite). As a consequence, the surface areas of the iron-aluminum oxides formed in the absence or presence of arsenate were usually much larger than those of aluminum or iron oxides formed under the same conditions. Arsenate was found to be associated mainly into short-range ordered materials. Chemical composition of all samples was affected by pH, initial R, and aging. Phosphate sorption was facilitated by the presence of short-range ordered materials, mainly those richer in aluminum, but was inhibited by arsenate present in the samples. The quantities of arsenate replaced by phosphate, expressed as percentages of its total amount present in the samples, were particularly low, ranging from 10% to 26%. A comparison of the desorption of arsenate by phosphate from aluminum-arsenate and iron-arsenate (studied in previous works) and iron-aluminum-arsenate coprecipitates evidenced that phosphate has a greater

  15. Arabidopsis thaliana NIP7;1 is involved in tissue arsenic distribution and tolerance in response to arsenate.

    PubMed

    Lindsay, Emma R; Maathuis, Frans J M

    2016-03-01

    The Arabidopsis aquaglyceroporin NIP7;1 is involved in uptake and tolerance to the trivalent arsenic species arsenite. Here, we show that NIP7;1 is also involved in the response to pentavalent arsenate. Loss of function of NIP7;1 improved tolerance to arsenate and reduced arsenic levels in both the phloem and xylem, resulting in altered arsenic distribution between tissues. There was no clear correlation between growth and shoot arsenic concentration. This is the first report detailing the involvement of a NIP transporter in response to arsenate. The data suggest that these proteins are relevant targets for breeding and engineering arsenic tolerance in crops.

  16. Fatty acyl-CoA reductase

    SciTech Connect

    Reiser, Steven E.; Somerville, Chris R.

    1998-12-01

    The present invention relates to bacterial enzymes, in particular to an acyl-CoA reductase and a gene encoding an acyl-CoA reductase, the amino acid and nucleic acid sequences corresponding to the reductase polypeptide and gene, respectively, and to methods of obtaining such enzymes, amino acid sequences and nucleic acid sequences. The invention also relates to the use of such sequences to provide transgenic host cells capable of producing fatty alcohols and fatty aldehydes.

  17. Perinatal exposure to 50 ppb sodium arsenate induces Hypothalamic-Pituitary-Adrenal Axis dysregulation in male C57BL/6 mice

    PubMed Central

    Goggin, Samantha L.; Labrecque, Matthew T.; Allan, Andrea M.

    2012-01-01

    Over the past two decades, key advancements have been made in understanding the complex pathology that occurs following not only high levels of arsenic exposure (>1ppm) but also levels previously considered to be low (<100 ppb). Past studies have characterized the deleterious effects of arsenic on the various functions of cardiovascular, pulmonary, immunological, respiratory, endocrine and neurological systems. Other research has demonstrated an elevated risk of a multitude of cancers and increased rates of psychopathology, even at very low levels of arsenic exposure. The hypothalamic-pituitary-adrenal (HPA) axis represents a multisite integration center that regulates a wide scope of biological and physiological processes: breakdown within this system can generate an array of far-reaching effects, making it an intriguing candidate for arsenic-mediated damage. Using a mouse model, we examined the effects of perinatal exposure to 50 ppb sodium arsenate on the functioning of the HPA axis through the assessment of corticotrophin-releasing factor (CRF), proopiomelanocortin (Pomc) mRNA, adrenocorticotrophin hormone (ACTH), corticosterone (CORT), 11β-Hydroxysteroid Dehydrogenase Type 1 (11β-HSD 1), and glucocorticoid receptor (GR) protein and mRNA. Compared to controls, we observed that the perinatal arsenic-exposed offspring exhibit an increase in hypothalamic CRF, altered CORT secretion both at baseline and in response to a stressor, decreased hippocampal 11β-HSD 1 and altered subcellular GR distribution in the hypothalamus. These data indicate significant HPA axis impairment at post-natal day 35 resulting from perinatal exposure to 50 ppb sodium arsenate. Our findings suggest that the dysregulation of this critical regulatory axis could underlie important molecular and cognitive pathology observed following exposure to arsenic. PMID:22960421

  18. Mutational and gene expression analysis of mtrDEF, omcA and mtrCAB during arsenate and iron reduction in Shewanella sp. ANA-3.

    PubMed

    Reyes, Carolina; Murphy, Julie N; Saltikov, Chad W

    2010-07-01

    Arsenate respiration and Fe(III) reduction are important processes that influence the fate and transport of arsenic in the environment. The goal of this study was to investigate the impact of arsenate on Fe(III) reduction using arsenate and Fe(III) reduction deficient mutants of Shewanella sp. strain ANA-3. Ferrihydrite reduction in the absence of arsenate was similar for an arsenate reduction mutant (arrA and arsC deletion strain of ANA-3) compared with wild-type ANA-3. However, the presence of arsenate adsorbed onto ferrihydrite impeded Fe(III) reduction for the arsenate reduction mutant but not in the wild-type. In an Fe(III) reduction mutant (mtrDEF, omcA, mtrCAB null mutant of ANA-3), arsenate was reduced similarly to wild-type ANA-3 indicating the Fe(III) reduction pathway is not required for ferrihydrite-associated arsenate reduction. Expression analysis of the mtr/omc gene cluster of ANA-3 showed that omcA and mtrCAB were expressed under soluble Fe(III), ferrihydrite and arsenate growth conditions and not in aerobically grown cells. Expression of arrA was greater with ferrihydrite pre-adsorbed with arsenate relative to ferrihydrite only. Lastly, arrA and mtrA were simultaneously induced in cells shifted to anaerobic conditions and exposed to soluble Fe(III) and arsenate. These observations suggest that, unlike Fe(III), arsenate can co-induce operons (arr and mtr) implicated in arsenic mobilization.

  19. Preabsorptive Metabolism of Sodium Arsenate by Anaerobic Microbiota of Mouse Cecum Forms a Variety of Methylated and Thiolated Arsenicals

    EPA Science Inventory

    The conventional scheme for arsenic methylation accounts for methylated oxyarsenical production but not for thioarsenical formation. Here, we report that in vitro anaerobic microbiota of mouse cecum converts arsenate into oxy- and thio- arsenicals. Besides methylarsonic acid (MMA...

  20. Preabsorptive Metabolism of Sodium Arsenate by Anaerobic Microbiota of Mouse Cecum Forms a Variety of Methylated and Thiolated Arsenicals

    EPA Science Inventory

    The conventional scheme for arsenic methylation accounts for methylated oxyarsenical production but not for thioarsenical formation. Here, we report that in vitro anaerobic microbiota of mouse cecum converts arsenate into oxy- and thio- arsenicals. Besides methylarsonic acid (MMA...

  1. Microbial arsenic metabolism: New twists on an old poison

    USGS Publications Warehouse

    Stolz, J.F.; Basu, P.; Oremland, R.S.

    2010-01-01

    Phylogenetically diverse microorganisms metabolize arsenic despite its toxicity and are part of its robust iogeochemical cycle. Respiratory arsenate reductase is a reversible enzyme, functioning in some microbes as an arsenate reductase but in others as an arsenite oxidase. As(III) can serve as an electron donor for anoxygenic photolithoautotrophy and chemolithoautotrophy. Organoarsenicals, such as the feed additive roxarsone, can be used as a source of energy, releasing inorganic arsenic.

  2. Nitrate Reductase Regulates Expression of Nitrite Uptake and Nitrite Reductase Activities in Chlamydomonas reinhardtii 1

    PubMed Central

    Galván, Aurora; Cárdenas, Jacobo; Fernández, Emilio

    1992-01-01

    In Chlamydomonas reinhardtii mutants defective at the structural locus for nitrate reductase (nit-1) or at loci for biosynthesis of the molybdopterin cofactor (nit-3, nit-4, or nit-5 and nit-6), both nitrite uptake and nitrite reductase activities were repressed in ammonium-grown cells and expressed at high amounts in nitrogen-free media or in media containing nitrate or nitrite. In contrast, wild-type cells required nitrate induction for expression of high levels of both activities. In mutants defective at the regulatory locus for nitrate reductase (nit-2), very low levels of nitrite uptake and nitrite reductase activities were expressed even in the presence of nitrate or nitrite. Both restoration of nitrate reductase activity in mutants defective at nit-1, nit-3, and nit-4 by isolating diploid strains among them and transformation of a structural mutant upon integration of the wild-type nit-1 gene gave rise to the wild-type expression pattern for nitrite uptake and nitrite reductase activities. Conversely, inactivation of nitrate reductase by tungstate treatment in nitrate, nitrite, or nitrogen-free media made wild-type cells respond like nitrate reductase-deficient mutants with respect to the expression of nitrite uptake and nitrite reductase activities. Our results indicate that nit-2 is a regulatory locus for both the nitrite uptake system and nitrite reductase, and that the nitrate reductase enzyme plays an important role in the regulation of the expression of both enzyme activities. PMID:16668656

  3. Coprecipitated arsenate inhibits thermal transformation of 2-line ferrihydrite: implications for long-term stability of ferrihydrite.

    PubMed

    Wang, Zhaohui; Xiao, Dongxue; Bush, Richard T; Liu, Jianshe

    2015-03-01

    2-line ferrihydrite, a ubiquitous iron oxy-hydroxide found in natural and engineered systems, is an efficient sink for the toxic metalloids such as arsenic. While much is known of the excellent capacity of ferrihydrite to coprecipitate arsenate, there is little information concerning the long-term stability of arsenate-accumulated ferrihydrite. By thermal treatment methodology, the expedited transformation of ferrihydrite in the presence of coprecipitated arsenate was studied at varying As/Fe ratios (0-0.5) and different heating temperature (40, 300, 450, 600°C). Pure and transformed minerals were characterized by thermogravimetry (TG), X-ray diffraction (XRD), Electron Spin Resonance (ESR), Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDX) and Fourier Transform Infrared Spectroscopy (FTIR). Arsenate was found to retard the thermal transformation of ferrihydrite. The extents of ferrihydrite transformation to hematite decreased with increasing As/Fe ratios, but increased at a higher heating temperature. It is predicted that the coprecipitated arsenate can stabilize the amorphous iron oxides against the transformation to more crystalline solids. Arsenate concentration appears to play an important role in this predicted long-term stability.

  4. Regulation of sugar metabolism in rice (Oryza sativa L.) seedlings under arsenate toxicity and its improvement by phosphate.

    PubMed

    Choudhury, Bhaskar; Mitra, Souvik; Biswas, Asok K

    2010-01-01

    The effect of arsenate with or without phosphate on the growth and sugar metabolism in rice seedlings cv. MTU 1010 was studied. Arsenate was found to be more toxic for root growth than shoot growth and water content of the seedlings gradually decreased with increasing concentrations. Arsenate exposure at 20 μM and 100 μM resulted in an increase in reducing sugar content and decrease in non-reducing sugar content. There was a small increase in starch content, the activity of starch phosphorylase was increased but α-amylase activity was found to be decreased. Arsenate toxicity also affected the activities of different carbohydrate metabolizing enzymes. The activities of sucrose degrading enzymes viz., acid invertase and sucrose synthase were increased whereas, the activity of sucrose synthesizing enzyme, viz. sucrose phosphate synthase declined. The combined application of arsenate with phosphate exhibited significant alterations of all the parameters tested under the purview of arsenate treatment alone which was congenial to better growth and efficient sugar metabolism in rice seedlings. Thus, the use of phosphorus enriched fertilizers may serve to ensure the production of healthy rice plants in arsenic contaminated soils.

  5. Respiratory Surgery.

    PubMed

    Nichols, Sylvain

    2016-11-01

    This article is a review of the most frequent disorders affecting the upper airway of cattle that are suitable for surgery. Information regarding the clinical signs, diagnostic methods, and the chemical restraint of cattle in respiratory distress are highlighted. Surgeries that can be performed in a field setting are thoroughly described. Copyright © 2016 Elsevier Inc. All rights reserved.

  6. Growth of strain SES-3 with arsenate and other diverse electron acceptors

    USGS Publications Warehouse

    Laverman, A.M.; Blum, J.S.; Schaefer, J.K.; Phillips, E.J.P.; Lovley, D.R.; Oremland, R.S.

    1995-01-01

    The selenate-respiring bacterial strain SES-3 was able to use a variety of inorganic electron acceptors to sustain growth. SES-3 grew with the reduction of arsenate to arsenite, Fe(III) to Fe(II), or thiosulfate to sulfide. It also grew in medium in which elemental sulfur, Mn(IV), nitrite, trimethylamine N-oxide, or fumarate was provided as an electron acceptor. Growth on oxygen was microaerophilic. There was no growth with arsenite or chromate. Washed suspensions of cells grown on selenate or nitrate had a constitutive ability to reduce arsenate but were unable to reduce arsenite. These results suggest that strain SES-3 may occupy a niche as an environmental opportunist by being able to take advantage of a diversity of electron acceptors.

  7. Growth of Strain SES-3 with Arsenate and Other Diverse Electron Acceptors

    PubMed Central

    Laverman, A. M.; Blum, J. S.; Schaefer, J. K.; Phillips, E.; Lovley, D. R.; Oremland, R. S.

    1995-01-01

    The selenate-respiring bacterial strain SES-3 was able to use a variety of inorganic electron acceptors to sustain growth. SES-3 grew with the reduction of arsenate to arsenite, Fe(III) to Fe(II), or thiosulfate to sulfide. It also grew in medium in which elemental sulfur, Mn(IV), nitrite, trimethylamine N-oxide, or fumarate was provided as an electron acceptor. Growth on oxygen was microaerophilic. There was no growth with arsenite or chromate. Washed suspensions of cells grown on selenate or nitrate had a constitutive ability to reduce arsenate but were unable to reduce arsenite. These results suggest that strain SES-3 may occupy a niche as an environmental opportunist by being able to take advantage of a diversity of electron acceptors. PMID:16535143

  8. Effects of arsenate and arsenite on germination and some physiological attributes of barley Hordeum vulgare L.

    PubMed

    Sanal, Filiz; Seren, Gülay; Güner, Utku

    2014-04-01

    Arsenic (As) is toxic to plants and animals. We tested the effects of arsenite and arsenate (0-16 mg/L) on seed germination, and on relative root and shoot length, α-amylase activity, reducing sugars and soluble total protein contents, and malondialdehyde content in barley seedlings. We also measured As accumulation in barley stems and roots. The α-amylase activity, relative root and shoot length, and seed germination decreased with increasing concentrations of arsenate and arsenite. The reducing sugars content in barley seedlings increased after 4 days of growth on media containing As. In general, the protein content in roots and seedlings decreased with increasing doses of As. Arsenic in the tissues was quantified by hydride generation-atomic absorption spectrophotometry. To confirm the accuracy of the method, we analyzed the certified reference material WEPAL-IPE-168. The limit of detection was 1.2 μg/L and the relative standard deviation was <2.0 %.

  9. RESPIRATORY PATHWAYS IN THE MYCOPLASMA II.

    PubMed Central

    VanDemark, P. J.; Smith, P. F.

    1964-01-01

    VanDemark, P. J. (University of South Dakota, Vermillion), and P. F. Smith. Respiratory pathways in the Mycoplasma. II. Pathway of electron transport during oxidation of reduced nicotinamide adenine dinucleotide by Mycoplasma hominis. J. Bacteriol. 88:122–129. 1964.—Unlike the flavin-terminated respiratory pathway of the fermentative Mycoplasma, the respiratory chain of the nonfermentative M. hominis strain 07 appears to be more complex, involving quinones and cytochromes in addition to flavins. In addition to reduction by reduced nicotine adenine dinucleotide (NADH) and reduced nicotine adenine dinucleotide phosphate, nonpyridine nucleotide-linked reduction of the respiratory chain of this organism occurred with succinate, lactate, and short-chained acyl coenzyme A derivatives as electron donors. Enzymes catalyzing the oxidation of NADH included an NADH oxidase, a diaphorase, a quinone reductase, and a cytochrome c reductase. The oxidation of NADH was sensitive to a variety of inhibitors, including 10−4m Atabrine, 10−3m sodium amytal, 10−5mp-chloromercuribenzoate, 10−4m antimycin A, and 10−4m potassium cyanide. The oxidase was resolved by the addition of 5% trichloroacetic acid and reactivated by the addition of flavin adenine dinucleotide but not flavin mononucleotide. The M. hominis sonic extract contained an NADH-coenzyme Q reductase. The oxidation of NADH was stimulated by the addition of either menadione or vitamin K2 (C35). The oxidase was inactivated by extraction with ether or irradiation at 360 mμ. The ether-inactivated enzyme was partially reactivated by the addition of “lipid” extract of the enzyme and coenzyme Q6. Difference spectra of the cell extracts revealed the presence of “b” and “a” type cytochromes. These cell extracts were found to contain a cyanide-and azide-sensitive cytochrome oxidase and catalase. PMID:14197876

  10. Sr, Ba and Cd arsenates with the apatite-type structure.

    PubMed

    Dordević, Tamara; Sutović, Sabina; Stojanović, Jovica; Karanović, Ljiljana

    2008-09-01

    X-ray diffraction analysis of single crystals of three new arsenates adopting apatite-type structures yielded formula Sr(5)(AsO(4))(3)F for strontium arsenate fluoride, (I), (Sr(1.66)Ba(0.34))(Ba(2.61)Sr(0.39))(AsO(4))(3)Cl for strontium barium arsenate chloride, (II), and Cd(5)(AsO(4))(3)Cl(0.58)(OH)(0.42) for cadmium arsenate hydroxide chloride, (III). All three structures are built up of isolated slightly distorted AsO(4) tetrahedra that are bridged by Sr(2+) in (I), by Sr(2+)/Ba(2+) in (II) and by Cd(2+) in (III). Compounds (I) and (II) represent typical fluorapatites and chlorapatites, respectively, with F(-) at the 2a (0, 0, {1/4}) site and Cl(-) at the 2b (0, 0, 0) site of P6(3)/m. In contrast, in (III), due to the requirement that the smaller Cd(2+) cation is positioned closer to the channel Cl(-) anion (partially substituted by OH(-)), the anion occupies the unusual 2a (0, 0, {1/4}) site. Therefore, Cl(-) is similar to F(-) in (I), coordinated by three A2 cations, unlike the octahedrally coordinated Cl(-) in (II) and other ordinary chlorapatites. Furthermore, in (III), using FT-IR studies, we have inferred the existence of H(+) outside the channel in oxyhydroxyapatites and provided possible atomic coordinates for a H atom in HAsO(4)(2-), leading to a proposed formulation of the compound as Cd(5)(AsO(4))(3-x)(HAsO(4))(x)Cl(0.58)(OH)(0.42-x-(y/2))O(x+(y/2))(y/2).

  11. Vanadium(V) oxide arsenate(V), VOAsO4

    PubMed Central

    Ezzine Yahmed, Safa; Zid, Mohamed Faouzi; Driss, Ahmed

    2011-01-01

    The vanadyl arsenate, VOAsO4, has been isolated by a solid-state reaction. The structure consists of distorted VO6 octa­hedra and AsO4 tetra­hedra sharing corners to build up VAsO7 layers parallel to ac linked by edge-sharing of VO6 octa­hedra, forming a three-dimensional framework. PMID:21522229

  12. Arsenite-oxidizing and arsenate-reducing bacteria associated with arsenic-rich groundwater in Taiwan

    NASA Astrophysics Data System (ADS)

    Liao, Vivian Hsiu-Chuan; Chu, Yu-Ju; Su, Yu-Chen; Hsiao, Sung-Yun; Wei, Chia-Cheng; Liu, Chen-Wuing; Liao, Chung-Min; Shen, Wei-Chiang; Chang, Fi-John

    2011-04-01

    Drinking highly arsenic-contaminated groundwater is a likely cause of blackfoot disease in Taiwan, but microorganisms that potentially control arsenic mobility in the subsurface remain unstudied. The objective of this study was to investigate the relevant arsenite-oxidizing and arsenate-reducing microbial community that exists in highly arsenic-contaminated groundwater in Taiwan. We cultured and identified arsenic-transforming bacteria, analyzed arsenic resistance and transformation, and determined the presence of genetic markers for arsenic transformation. In total, 11 arsenic-transforming bacterial strains with different colony morphologies and varying arsenic transformation abilities were isolated, including 10 facultative anaerobic arsenate-reducing bacteria and one strictly aerobic arsenite-oxidizing bacterium. All of the isolates exhibited high levels of arsenic resistance with minimum inhibitory concentrations of arsenic ranging from 2 to 200 mM. Strain AR-11 was able to rapidly oxidize arsenite to arsenate at concentrations relevant to environmental groundwater samples without the addition of any electron donors or acceptors. We provide evidence that arsenic-reduction activity may be conferred by the ars operon(s) that were not amplified by the designed primers currently in use. The 16S rRNA sequence analysis grouped the isolates into the following genera: Pseudomonas, Bacillus, Psychrobacter, Vibrio, Citrobacter, Enterobacter, and Bosea. Among these genera, we present the first report of the genus Psychrobacter being involved in arsenic reduction. Our results further support the hypothesis that bacteria capable of either oxidizing arsenite or reducing arsenate coexist and are ubiquitous in arsenic-contaminated groundwater.

  13. Understanding Regeneration of Arsenate-Loaded Ferric Hydroxide-Based Adsorbents

    PubMed Central

    Chaudhary, Binod Kumar; Farrell, James

    2015-01-01

    Abstract Adsorbents comprising ferric hydroxide loaded on a variety of support materials are commonly used to remove arsenic from potable water. Although several studies have investigated the effects of support properties on arsenic adsorption, there have been no investigations of their effects on adsorbent regeneration. Furthermore, the effect of regenerant solution composition and the kinetics of regeneration have not been investigated. This research investigated the effects of adsorbent and regenerant solution properties on the kinetics and efficiency of regeneration of arsenate-loaded ferric hydroxide-based adsorbents. Solutions containing only 0.10–5.0 M NaOH or 0.10–1.0 M NaCl, as well as solutions containing both compounds, were used as regenerants. On all media, >99% of arsenate was adsorbed through complexation with ferric hydroxide. Arsenate recovery was controlled by both equilibrium and kinetic limitations. Adsorbents containing support material with weak base anion-exchange functionality or no anion-exchange functionality could be regenerated with NaOH solutions alone. Regeneration of media containing strong base anion (SBA)-exchange functionality was greatly enhanced by addition of 0.10 M NaCl to the NaOH regenerant solutions. Adsorbed silica had a significant effect on NaOH regeneration of media containing type I SBA-exchange functionality, but on other media, adsorbed silica had little impact on regeneration. On all media, 5–25% of arsenate was resistant to desorption in 1.0 M NaOH solutions. However, the use of 2.5–5.0 M NaOH solutions significantly reduced the desorption-resistant fraction. PMID:25873779

  14. Quantitative trace-level speciation of arsenite and arsenate in drinking water by ion chromatography.

    PubMed

    Johnson, Rebecca L; Aldstad, Joseph H

    2002-10-01

    We describe an improved method for the determination of inorganic arsenic in drinking water. The method is based on comprehensive optimization of the anion-exchange ion chromatographic (IC) separation of arsenite and arsenate with post-column generation and detection of the arsenate-molybdate heteropoly acid (AMHPA) complex ion. The arsenite capacity factor was improved from 0.081 to 0.13 by using a mobile phase (2.0 mL min(-1)) composed of 2.5 mM Na2CO3 and 0.91 mM NaHCO3 (pH 10.5). A post-column photo-oxidation reactor (2.5 m x 0.7 mm) was optimized (0.37 microM potassium persulfate at 0.50 mL min(-1)) such that arsenite was converted to arsenate with 99.8 +/- 4.2% efficiency. Multi-variate optimization of the complexation reaction conditions yielded the following levels: 1.3 mM ammonium molybdate, 7.7 mM ascorbic acid, 0.48 M nitric acid, 0.17 mM potassium antimony tartrate, and 1.0% (v/v) glycerol. A long-path length flow cell (Teflon AF, 100-cm) was used to measure the absorption of the AMHPA complex (818 +/- 2 nm). Figures of merit for arsenite/arsenate include: limit of detection (1.6/0.40 microg L(-1)): standard error in absorbance (5.1 x 10(-3)/3.5 x 10(-3)); and sensitivity (2.9 x 10(-3)/2.2 x 10(-3) absorbance units per ppb). Successful application of the method to fortified surface and ground waters (100 microL samples) is also described.

  15. Removal of arsenite and arsenate using hydrous ferric oxide incorporated into naturally occurring porous diatomite.

    PubMed

    Jang, Min; Min, Soo-Hong; Kim, Tak-Hyun; Park, Jae Kwang

    2006-03-01

    In this study, a simplified and effective method was tried to immobilize iron oxide onto a naturally occurring porous diatomite. Experimental resultsfor several physicochemical properties and arsenic edges revealed that iron oxide incorporated into diatomite was amorphous hydrous ferric oxide (HFO). Sorption trends of Fe (25%)-diatomite for both arsenite and arsenate were similar to those of HFO, reported by Dixit and Hering (Environ. Sci. Technol. 2003, 37, 4182-4189). The pH at which arsenite and arsenate are equally sorbed was 7.5, which corresponds to the value reported for HFO. Judging from the number of moles of iron incorporated into diatomite, the arsenic sorption capacities of Fe (25%)-diatomite were comparable to or higher than those of the reference HFO. Furthermore, the surface complexation modeling showed that the constants of [triple bond]SHAsO4- or [triple bond]SAsO4(2-) species for Fe (25%)-diatomite were larger than those reference values for HFO or goethite. Larger differences in constants of arsenate surface species might be attributed to aluminum hydroxyl ([triple bond]Al-OH) groups that can work better for arsenate removal. The pH-controlled differential column batch reactor (DCBR) and small-scale column tests demonstrated that Fe (25%)-diatomite had high sorption speeds and high sorption capacities compared to those of a conventional sorbent (AAFS-50) that is known to be the first preference for arsenic removal performance in Bangladesh. These results could be explained by the fact that Fe (25%)-diatomite contained well-dispersed HFO having a great affinity for arsenic species and well-developed macropores as shown by scanning electron microscopy (SEM) and pore size distribution (PSD) analyses.

  16. Human aldose reductase and human small intestine aldose reductase are efficient retinal reductases: consequences for retinoid metabolism.

    PubMed

    Crosas, Bernat; Hyndman, David J; Gallego, Oriol; Martras, Sílvia; Parés, Xavier; Flynn, T Geoffrey; Farrés, Jaume

    2003-08-01

    Aldo-keto reductases (AKRs) are NAD(P)H-dependent oxidoreductases that catalyse the reduction of a variety of carbonyl compounds, such as carbohydrates, aliphatic and aromatic aldehydes and steroids. We have studied the retinal reductase activity of human aldose reductase (AR), human small-intestine (HSI) AR and pig aldehyde reductase. Human AR and HSI AR were very efficient in the reduction of all- trans -, 9- cis - and 13- cis -retinal ( k (cat)/ K (m)=1100-10300 mM(-1).min(-1)), constituting the first cytosolic NADP(H)-dependent retinal reductases described in humans. Aldehyde reductase showed no activity with these retinal isomers. Glucose was a poor inhibitor ( K (i)=80 mM) of retinal reductase activity of human AR, whereas tolrestat, a classical AKR inhibitor used pharmacologically to treat diabetes, inhibited retinal reduction by human AR and HSI AR. All- trans -retinoic acid failed to inhibit both enzymes. In this paper we present the AKRs as an emergent superfamily of retinal-active enzymes, putatively involved in the regulation of retinoid biological activity through the assimilation of retinoids from beta-carotene and the control of retinal bioavailability.

  17. Perchlorate Reductase Is Distinguished by Active Site Aromatic Gate Residues.

    PubMed

    Youngblut, Matthew D; Tsai, Chi-Lin; Clark, Iain C; Carlson, Hans K; Maglaqui, Adrian P; Gau-Pan, Phonchien S; Redford, Steven A; Wong, Alan; Tainer, John A; Coates, John D

    2016-04-22

    Perchlorate is an important ion on both Earth and Mars. Perchlorate reductase (PcrAB), a specialized member of the dimethylsulfoxide reductase superfamily, catalyzes the first step of microbial perchlorate respiration, but little is known about the biochemistry, specificity, structure, and mechanism of PcrAB. Here we characterize the biophysics and phylogeny of this enzyme and report the 1.86-Å resolution PcrAB complex crystal structure. Biochemical analysis revealed a relatively high perchlorate affinity (Km = 6 μm) and a characteristic substrate inhibition compared with the highly similar respiratory nitrate reductase NarGHI, which has a relatively much lower affinity for perchlorate (Km = 1.1 mm) and no substrate inhibition. Structural analysis of oxidized and reduced PcrAB with and without the substrate analog SeO3 (2-) bound to the active site identified key residues in the positively charged and funnel-shaped substrate access tunnel that gated substrate entrance and product release while trapping transiently produced chlorate. The structures suggest gating was associated with shifts of a Phe residue between open and closed conformations plus an Asp residue carboxylate shift between monodentate and bidentate coordination to the active site molybdenum atom. Taken together, structural and mutational analyses of gate residues suggest key roles of these gate residues for substrate entrance and product release. Our combined results provide the first detailed structural insight into the mechanism of biological perchlorate reduction, a critical component of the chlorine redox cycle on Earth. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. Enhanced Arsenate Removal Performance in Aqueous Solution by Yttrium-Based Adsorbents

    PubMed Central

    Lee, Sang-Ho; Kim, Kyoung-Woong; Lee, Byung-Tae; Bang, Sunbaek; Kim, Hyunseok; Kang, Hyorang; Jang, Am

    2015-01-01

    Arsenic contamination in drinking water has become an increasingly important issue due to its high toxicity to humans. The present study focuses on the development of the yttrium-based adsorbents, with basic yttrium carbonate (BYC), Ti-loaded basic yttrium carbonate (Ti-loaded BYC) and yttrium hydroxide prepared using a co-precipitation method. The Langmuir isotherm results confirmed the maximum adsorption capacity of Ti-loaded BYC (348.5 mg/g) was 25% higher than either BYC (289.6 mg/g) or yttrium hydroxide (206.5 mg/g) due to its increased specific surface area (82 m2/g) and surface charge (PZC: 8.4). Pseudo first- and second-order kinetic models further confirmed that the arsenate removal rate of Ti-loaded BYC was faster than for BYC and yttrium hydroxide. It was subsequently posited that the dominant removal mechanism of BYC and Ti-loaded BYC was the carbonate-arsenate ion exchange process, whereas yttrium hydroxide was regarded to be a co-precipitation process. The Ti-loaded BYC also displayed the highest adsorption affinity for a wide pH range (3–11) and in the presence of coexisting anionic species such as phosphate, silicate, and bicarbonate. Therefore, it is expected that Ti-loaded BYC can be used as an effective and practical adsorbent for arsenate remediation in drinking water. PMID:26516879

  19. Uptake and biotransformation of arsenate in the lichen Hypogymnia physodes (L.) Nyl.

    PubMed

    Mrak, Tanja; Slejkovec, Zdenka; Jeran, Zvonka; Jaćimović, Radojko; Kastelec, Damijana

    2008-01-01

    The uptake and metabolism of arsenate, As(V), as a function of time and concentration were examined in the lichen Hypogymnia physodes (L.) Nyl. Lichen thalli were exposed to As(V) in the form of a solution. Exponential uptake of As(V) from 4 microg mL(-1) As(V) solution was accompanied by constant arsenite, As(III), excretion back into the solution. Arsenate taken up into the lichens from 0, 0.1, 1, 10 microg mL(-1) As(V) solutions was partially transformed into As(III), dimethylarsinic acid (DMA) and (mono)methylarsonic acid (MA). 48 h after exposure, the main arsenic compound in the lichens was DMA in 0.1, As(III) in 1 and As(V) in 10 microg mL(-1) treatment. The proportion of methylated arsenic compounds decreased with increasing arsenate concentration in the exposure solution. These results suggest that at least two types of As(V) detoxification exist in lichens; arsenite excretion and methylation.

  20. Enhanced Arsenate Removal Performance in Aqueous Solution by Yttrium-Based Adsorbents.

    PubMed

    Lee, Sang-Ho; Kim, Kyoung-Woong; Lee, Byung-Tae; Bang, Sunbaek; Kim, Hyunseok; Kang, Hyorang; Jang, Am

    2015-10-26

    Arsenic contamination in drinking water has become an increasingly important issue due to its high toxicity to humans. The present study focuses on the development of the yttrium-based adsorbents, with basic yttrium carbonate (BYC), Ti-loaded basic yttrium carbonate (Ti-loaded BYC) and yttrium hydroxide prepared using a co-precipitation method. The Langmuir isotherm results confirmed the maximum adsorption capacity of Ti-loaded BYC (348.5 mg/g) was 25% higher than either BYC (289.6 mg/g) or yttrium hydroxide (206.5 mg/g) due to its increased specific surface area (82 m²/g) and surface charge (PZC: 8.4). Pseudo first- and second-order kinetic models further confirmed that the arsenate removal rate of Ti-loaded BYC was faster than for BYC and yttrium hydroxide. It was subsequently posited that the dominant removal mechanism of BYC and Ti-loaded BYC was the carbonate-arsenate ion exchange process, whereas yttrium hydroxide was regarded to be a co-precipitation process. The Ti-loaded BYC also displayed the highest adsorption affinity for a wide pH range (3-11) and in the presence of coexisting anionic species such as phosphate, silicate, and bicarbonate. Therefore, it is expected that Ti-loaded BYC can be used as an effective and practical adsorbent for arsenate remediation in drinking water.

  1. Arsenate-induced Apoptosis in Murine Embryonic Maxillary Mesenchymal Cells via Mitochondrial Mediated Oxidative Injury

    PubMed Central

    Singh, Saurabh; Greene, Robert M.; Pisano, M. Michele

    2009-01-01

    Background Arsenic is a ubiquitous element that is a potential carcinogen and teratogen and can cause adverse developmental outcomes. Arsenic exerts its toxic effects through the generation of reactive oxygen species (ROS) that include hydrogen peroxide (H2O2), superoxide-derived hydroxyl ion, and peroxyl radicals. However, the molecular mechanisms by which arsenic induces cytotoxicity in murine embryonic maxillary mesenchymal (MEMM) cells are undefined. Methods MEMM cells in culture were treated with different concentrations of pentavalent sodium arsenate [As (V)] for 24 or 48 hours and various end points measured. Results We show that treatment of MEMM cells with the pentavalent form of inorganic arsenic resulted in caspase-mediated apoptosis, accompanied by generation of ROS and disruption of mitochondrial membrane potential. Treatment with caspase inhibitors markedly blocked apoptosis. In addition, the free radical scavenger N-acetylcysteine dramatically attenuated arsenic-mediated ROS production and apoptosis, and exposure to arsenate increased Bax and decreased Bcl protein levels in MEMM cells. Conclusions Taken together, these findings suggest that in MEMM cells, arsenate-mediated oxidative injury acts as an early and upstream initiator of the cell death cascade, triggering cytotoxicity, mitochondrial dysfunction, altered Bcl/Bax protein ratios, and activation of caspase-9. PMID:19739150

  2. Arsenate and phosphate adsorption in relation to oxides composition in soils: LCD modeling.

    PubMed

    Cui, Yanshan; Weng, Liping

    2013-07-02

    The pH dependent solid-solution distribution of arsenate and phosphate in five Dutch agricultural soil samples was measured in the pH range 4-8, and the results were interpreted using the LCD (ligand and charge distribution) adsorption modeling. The pH dependency is similar for both oxyanions, with a minimum soluble concentration observed around pH 6-8. This pH dependency can be successfully described with the LCD model and it is attributed mainly to the synergistic effects from Ca adsorption. The solubility of phosphate is much lower than that of arsenate. This big difference cannot be sufficiently explained by the reduction of small amount of As(V) into As(III), neither by slow desorption/adsorption. The difference between phosphate and arsenate in their solid-solution distribution becomes larger with the increase of aluminum (hydr)oxides (Al-oxides) contribution to the total amount of metal (Al and Fe) (hydr)oxides. The influence of Al-oxides is much larger than its relative amount extracted from the soils. When Al-oxides account for >40% of the soil oxides, the whole adsorbents behave apparently similarly to that of pure Al-oxides. These results indicated that surface coating and substitution may have modified significantly oxyanion adsorption to Fe-oxides in soils, and how to account for this complexity is a challenge for geochemical modeling.

  3. UV and arsenate toxicity: a specific and sensitive yeast bioluminescence assay.

    PubMed

    Bakhrat, Anya; Eltzov, Evgeni; Finkelstein, Yishay; Marks, Robert S; Raveh, Dina

    2011-06-01

    We describe a Saccharomyces cerevisiae bioluminescence assay for UV and arsenate in which bacterial luciferase genes are regulated by the promoter of the yeast gene, UFO1. UFO1 encodes the F-box subunit of the Skp1–Cdc53–F-box protein ubiquitin ligase complex and is induced by DNA damage and by arsenate. We engineered the UFO1 promoter into an existing yeast bioreporter that employs human genes for detection of steroid hormone-disrupting compounds in water bodies. Our analysis indicates that use of an endogenous yeast promoter in different mutant backgrounds allows discrimination between different environmental signals. The UFO1-engineered yeast give a robust bioluminescence response to UVB and can be used for evaluating UV protective sunscreens. They are also effective in detecting extremely low concentrations of arsenate, particularly in pdr5Δ mutants that lack a mechanism to extrude toxic chemicals; however, they do not respond to cadmium or mercury. Combined use of endogenous yeast promoter elements and mutants of stress response pathways may facilitate development of high-specificity yeast bioreporters able to discriminate between closely related chemicals present together in the environment.

  4. An SEM-EDX and Raman spectroscopic study of the fibrous arsenate mineral liskeardite and in comparison with other arsenates kaňkite, scorodite and yvonite.

    PubMed

    Frost, Ray L; Scholz, Ricardo; Jirásek, Jakub; Belotti, Fernanda Maria

    2015-12-05

    The mineral liskeardite, an arsenate mineral with major cations of iron and aluminium, has been studied by a combination of scanning electron microscopy with energy dispersive spectroscopy and Raman spectroscopy. The mineral shows a fibrous nature. Semi-quantitative chemical analysis shows an Al and Fe arsenate phase with minor amounts of K, Cu, S and Si. Scanning electron microscopy shows a fibrous material. Intense Raman bands at 893, 867 and 843 cm(-1) are assigned to the ν1 and ν3 AsO4(3)(-) and HOAsO3(2)(-) symmetric and antisymmetric stretching vibrations. Raman bands are observed at 514, 499, 485 and 477 cm(-1) and are assigned to the ν4 out of plane bending modes of the AsO4(3)(-) and HOAsO3(2)(-) units. The series of bands at 373, 356 and 343 cm(-1) are assigned to the ν2 symmetric bending modes. Two groups of OH stretching bands are observed and assigned to OH unit and water stretching vibrations. A comparison of the Raman spectrum of liskeardite with scorodite, kaňkite and yvonite is made.

  5. Respiratory Home Health Care

    MedlinePlus

    ... Healthy Living > Living With Lung Disease > Respiratory Home Health Care Font: Aerosol Delivery Oxygen Resources Immunizations Pollution Nutrition ... Disease Articles written by Respiratory Experts Respiratory Home Health Care Respiratory care at home can contribute to improved ...

  6. Neuroprotective role for carbonyl reductase?

    PubMed

    Maser, Edmund

    2006-02-24

    Oxidative stress is increasingly implicated in neurodegenerative disorders including Alzheimer's, Parkinson's, Huntington's, and Creutzfeld-Jakob diseases or amyotrophic lateral sclerosis. Reactive oxygen species seem to play a significant role in neuronal cell death in that they generate reactive aldehydes from membrane lipid peroxidation. Several neuronal diseases are associated with increased accumulation of abnormal protein adducts of reactive aldehydes, which mediate oxidative stress-linked pathological events, including cellular growth inhibition and apoptosis induction. Combining findings on neurodegeneration and oxidative stress in Drosophila with studies on the metabolic characteristics of the human enzyme carbonyl reductase (CR), it is clear now that CR has a potential physiological role for neuroprotection in humans. Several lines of evidence suggest that CR represents a significant pathway for the detoxification of reactive aldehydes derived from lipid peroxidation and that CR in humans is essential for neuronal cell survival and to confer protection against oxidative stress-induced brain degeneration.

  7. Respiratory Distress

    NASA Technical Reports Server (NTRS)

    1976-01-01

    The University of Miami School of Medicine asked the Research Triangle Institute for assistance in improvising the negative pressure technique to relieve respiratory distress in infants. Marshall Space Flight Center and Johnson Space Center engineers adapted this idea to the lower-body negative-pressure system seals used during the Skylab missions. Some 20,000 babies succumb to respiratory distress in the U.S. each year, a condition in which lungs progressively lose their ability to oxygenate blood. Both positive and negative pressure techniques have been used - the first to force air into lungs, the second to keep infant's lungs expanded. Negative pressure around chest helps the baby expand his lungs and maintain proper volume of air. If doctors can keep the infant alive for four days, the missing substance in the lungs will usually form in sufficient quantity to permit normal breathing. The Skylab chamber and its leakproof seals were adapted for medical use.

  8. The deep-sea bacterium Shewanella piezotolerans WP3 has two DMSO reductases in distinct subcellular locations.

    PubMed

    Xiong, Lei; Jian, Huahua; Xiao, Xiang

    2017-07-07

    Dimethyl sulfoxide (DMSO) acts as a substantial sink for dimethyl sulfide (DMS) in deep waters and is therefore considered a potential electron acceptor supporting abyssal ecosystems. Shewanella piezotolerans WP3 was isolated from west Pacific deep-sea sediments, and two functional DMSO respiratory subsystems are essential for maximum growth of WP3 under in situ conditions (4°C/20 MPa). However, the relationship between these two subsystems and the electron transport pathway underlying DMSO reduction by WP3 remain unknown. In this study, both DMSO reductases (type I and type VI) in WP3 were found to be functionally independent, despite their close evolutionary relationship. Moreover, immunogold labeling of DMSO reductase subunits revealed that the type I DMSO reductase was localized on the outer leaflet of the outer membrane, whereas the type VI DMSO reductase was located within the periplasmic space. CymA, a cytoplasmic membrane-bound tetraheme c-type cytochrome, served as a preferential electron transport protein for both the type I and type VI DMSO reductases, in which type VI accepted electrons from CymA in a DmsE- and DmsF-independent manner. Based on these results, we proposed a core electron transport model of DMSO reduction in the deep-sea bacterium S. piezotolerans WP3. These results collectively suggest that the possession of two sets of DMSO reductases with distinct subcellular localizations might be an adaptive strategy for WP3 to achieve maximum DMSO utilization in deep-sea environments.Importance: As the dominant methylated sulfur compound in deep oceanic water, dimethyl sulfoxide (DMSO) has been suggested to play an important role in the marine biogeochemical cycle of the volatile anti-greenhouse gas dimethyl sulfide (DMS). Two sets of DMSO respiratory systems in the deep-sea bacterium Shewanella piezotolerans WP3 have previously been identified to mediate DMSO reduction under in situ conditions (4°C/20 MPa). Here, we report that the two DMSO

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

    PubMed Central

    Gao, Xiaodong; Root, Robert A.; Farrell, James; Ela, Wendell; Chorover, Jon

    2014-01-01

    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

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

    PubMed

    Gao, Xiaodong; Root, Robert A; Farrell, James; Ela, Wendell; Chorover, Jon

    2013-11-01

    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

  11. Genetics Home Reference: 5-alpha reductase deficiency

    MedlinePlus

    ... About half of these individuals adopt a male gender role in adolescence or early adulthood. Related Information ... 1730-5. Citation on PubMed Cohen-Kettenis PT. Gender change in 46,XY persons with 5alpha-reductase- ...

  12. A dissimilatory nitrite reductase in Paracoccus halodenitrificans

    NASA Technical Reports Server (NTRS)

    Grant, M. A.; Hochstein, L. I.

    1984-01-01

    Paracoccus halodenitrificans produced a membrane-associated nitrite reductase. Spectrophotometric analysis showed it to be associated with a cd-cytochrome and located on the inner side of the cytoplasmic membrane. When supplied with nitrite, membrane preparations produced nitrous oxide and nitric oxide in different ratios depending on the electron donor employed. The nitrite reductase was maximally active at relatively low concentrations of sodium chloride and remained attached to the membranes at 100 mM sodium chloride.

  13. A dissimilatory nitrite reductase in Paracoccus halodenitrificans

    NASA Technical Reports Server (NTRS)

    Grant, M. A.; Hochstein, L. I.

    1984-01-01

    Paracoccus halodenitrificans produced a membrane-associated nitrite reductase. Spectrophotometric analysis showed it to be associated with a cd-cytochrome and located on the inner side of the cytoplasmic membrane. When supplied with nitrite, membrane preparations produced nitrous oxide and nitric oxide in different ratios depending on the electron donor employed. The nitrite reductase was maximally active at relatively low concentrations of sodium chloride and remained attached to the membranes at 100 mM sodium chloride.

  14. Evolutionary migration of a post-translationally modified active-site residue in the proton-pumping heme-copper oxygen reductases.

    PubMed

    Hemp, James; Robinson, Dana E; Ganesan, Krithika B; Martinez, Todd J; Kelleher, Neil L; Gennis, Robert B

    2006-12-26

    In the respiratory chains of aerobic organisms, oxygen reductase members of the heme-copper superfamily couple the reduction of O2 to proton pumping, generating an electrochemical gradient. There are three distinct families of heme-copper oxygen reductases: A, B, and C types. The A- and B-type oxygen reductases have an active-site tyrosine that forms a unique cross-linked histidine-tyrosine cofactor. In the C-type oxygen reductases (also called cbb3 oxidases), an analogous active-site tyrosine has recently been predicted by molecular modeling to be located within a different transmembrane helix in comparison to the A- and B-type oxygen reductases. In this work, Fourier-transform mass spectrometry is used to show that the predicted tyrosine forms a histidine-tyrosine cross-linked cofactor in the active site of the C-type oxygen reductases. This is the first known example of the evolutionary migration of a post-translationally modified active-site residue. It also verifies the presence of a unique cofactor in all three families of proton-pumping respiratory oxidases, demonstrating that these enzymes likely share a common reaction mechanism and that the histidine-tyrosine cofactor may be a required component for proton pumping.

  15. Nitrate reduction in Haloferax alexandrinus: the case of assimilatory nitrate reductase.

    PubMed

    Kilic, Volkan; Kilic, Gözde Aydoğan; Kutlu, Hatice Mehtap; Martínez-Espinosa, Rosa María

    2017-05-01

    Haloferax alexandrinus Strain TM JCM 10717(T) = IFO 16590(T) is an extreme halophilic archaeon able to produce significant amounts of canthaxanthin. Its genome sequence has been analysed in this work using bioinformatics tools available at Expasy in order to look for genes encoding nitrate reductase-like proteins: respiratory nitrate reductase (Nar) and/or assimilatory nitrate reductase (Nas). The ability of the cells to reduce nitrate under aerobic conditions was tested. The enzyme in charge of nitrate reduction under aerobic conditions (Nas) has been purified and characterised. It is a monomeric enzyme (72 ± 1.8 kDa) that requires high salt concentration for stability and activity. The optimum pH value for activity was 9.5. Effectiveness of different substrates, electron donors, cofactors and inhibitors was also reported. High nitrite concentrations were detected within the culture media during aerobic/microaerobic cells growth. The main conclusion from the results is that this haloarchaeon reduces nitrate aerobically thanks to Nas and may induce denitrification under anaerobic/microaerobic conditions using nitrate as electron acceptor. The study sheds light on the role played by haloarchaea in the biogeochemical cycle of nitrogen, paying special attention to nitrate reduction processes. Besides, it provides useful information for future attempts on microecological and biotechnological implications of haloarchaeal nitrate reductases.

  16. Characterization of thyroidal glutathione reductase

    SciTech Connect

    Raasch, R.J.

    1989-01-01

    Glutathione levels were determined in bovine and rat thyroid tissue by enzymatic conjugation with 1-chloro-2,4-dinitrobenzene using glutathione S-transferase. Bovine thyroid tissue contained 1.31 {+-} 0.04 mM reduced glutathione (GSH) and 0.14 {+-} 0.02 mM oxidized glutathione (GSSG). In the rat, the concentration of GSH was 2.50 {+-} 0.05 mM while GSSG was 0.21 {+-} 0.03 mM. Glutathione reductase (GR) was purified from bovine thyroid to electrophoretic homogeneity by ion exchange, affinity and molecular exclusion chromatography. A molecular weight range of 102-109 kDa and subunit size of 55 kDa were determined for GR. Thyroidal GR was shown to be a favoprotein with one FAD per subunit. The Michaelis constants of bovine thyroidal GR were determined to be 21.8 {mu}M for NADPH and 58.8 {mu}M for GSSG. The effect of thyroid stimulating hormone (TSH) and thyroxine (T{sub 4}) on in vivo levels of GR and glucose 6-phosphate dehydrogenase were determined in rat thyroid homogenates. Both enzymes were stimulated by TSH treatment and markedly reduced following T{sub 4} treatment. Lysosomal hydrolysis of ({sup 125}I)-labeled and unlabeled thyroglobulin was examined using size exclusion HPLC.

  17. Thioredoxin Reductase and its Inhibitors

    PubMed Central

    Saccoccia, Fulvio; Angelucci, Francesco; Boumis, Giovanna; Carotti, Daniela; Desiato, Gianni; Miele, Adriana E; Bellelli, Andrea

    2014-01-01

    Thioredoxin plays a crucial role in a wide number of physiological processes, which span from reduction of nucleotides to deoxyriboucleotides to the detoxification from xenobiotics, oxidants and radicals. The redox function of Thioredoxin is critically dependent on the enzyme Thioredoxin NADPH Reductase (TrxR). In view of its indirect involvement in the above mentioned physio/pathological processes, inhibition of TrxR is an important clinical goal. As a general rule, the affinities and mechanisms of binding of TrxR inhibitors to the target enzyme are known with scarce precision and conflicting results abound in the literature. A relevant analysis of published results as well as the experimental procedures is therefore needed, also in view of the critical interest of TrxR inhibitors. We review the inhibitors of TrxR and related flavoreductases and the classical treatment of reversible, competitive, non competitive and uncompetitive inhibition with respect to TrxR, and in some cases we are able to reconcile contradictory results generated by oversimplified data analysis. PMID:24875642

  18. Validation of analysis of arsenic in water samples using Wagtech Digital Arsenator.

    PubMed

    Safarzadeh-Amiri, A; Fowlie, P; Kazi, A I; Siraj, S; Ahmed, S; Akbor, A

    2011-06-01

    Groundwater, the only source of potable water for millions of people in Bangladesh during dry season, is often contaminated with arsenic (As) above the allowable drinking water limit of 50 μg/L. Testing well water--with arsenic field test kits (FTKs)--and switching to safe-wells can effectively reduce exposure to As. FTKs are low cost, provide fast results, and are commercially available. There are between 10 and 11 million shallow tubewells in Bangladesh. Approximately, 5 million have been tested using FTKs. FTKs with color comparator rely on visual identification for generating qualitative results, which may not be highly reliable at the lower range because human eyes have low sensitivity in this range and sensitivity varies from person to person. The Wagtech Digital Arsenator does not suffer from this limitation and should, in theory, be able to generate quantitative, accurate, and reliable results. The instrument has a linear range of 0-100 μg/L, an accuracy of ± 20% for the 50 μg/L quality control standards, and a detection limit of about 4.4 μg/L. All Arsenators employed in this investigation also displayed high bias for 50 μg/L arsenic standard and were calibrated in order to improve measurement accuracy and reliability. Analyses of 179 raw and 92 treated well waters in the field and in two analytical laboratories were found to be highly correlated with the Spearman rank correlation coefficient of ≥ 0.800, indicating that Arsenator results are perhaps nearly as accurate and reliable as those from analytical laboratories. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Arsenic-resistant proteobacterium from the phyllosphere of arsenic-hyperaccumulating fern (Pteris vittata L.) reduces arsenate to arsenite.

    PubMed

    Rathinasabapathi, Bala; Raman, Suresh Babu; Kertulis, Gina; Ma, Lena

    2006-07-01

    An arsenic-resistant bacterium, AsRB1, was isolated from the fronds of Pteris vittata grown in a site contaminated with copper chromium arsenate. The bacterium exhibited resistance to arsenate, arsenite, and antimony in the culture medium. AsRB1, like Pseudomonas putida, grew on MacConkey and xylose-lactose-desoxycholate agars and utilized citrate but, unlike P. putida, was positive for indole test and negative for oxidase test. A phylogenetic analysis of the 16S rRNA gene showed that AsRB1 is a proteobacterium of the beta subclass, related to Pseudomonas saccharophila and Variovorax paradoxus. Following an exogenous supply of arsenate, most arsenic occurred as arsenite in the medium and the cell extracts, suggesting reduction and extrusion of arsenic as the mechanism for arsenic resistance in AsRB1.

  20. Two- and three-dimensional open-framework uranium arsenates: synthesis, structure, and characterization.

    PubMed

    Rao, V Koteswara; Bharathi, K; Prabhu, Ramanath; Chandra, Manabendra; Natarajan, Srinivasan

    2010-03-15

    Hydrothermal reactions between uranium salts and arsenic pentoxide in the presence of two different amines yielded six new uranium arsenate phases exhibiting open-framework structures, ethylenediamine (en): [C(2)N(2)H(9)][(UO(2))(AsO(4))], I; [C(2)N(2)H(10)][(UO(2))F(HAsO(4))](2) x 4 H(2)O, II; [C(2)N(2)H(9)][U(2)F(5)(HAsO(4))(2)], III; [C(2)N(2)H(9)][UF(2)(AsO(4))], IV; diethylenetriamine (DETA), [C(4)N(3)H(16)][U(2)F(3)(AsO(4))(2)(HAsO(4))], V; and [C(4)N(3)H(16)][U(2)F(6)(AsO(4))(HAsO(4))], VI. The structures were determined using single crystal studies, which revealed two- (I, II, V) and three-dimensional (III, IV, VI) structures for the uranium arsenates. The uranium atom, in these compounds, exhibits considerable variations in the coordination (6 to 9) that appears to have some correlation with the synthetic conditions. The water molecules in [C(2)N(2)H(10)][(UO(2))F(HAsO(4))](2) x 4 H(2)O, II, could be reversibly removed, and the dehydrated phase, [C(2)N(2)H(10)][(UO(2))F(HAsO(4))](2), IIa, was also characterized using single crystal studies. The observation of many mineralogical structures in the present compounds suggests that the hydrothermal method could successfully replicate the geothermal conditions. As part of this study, we have observed autunite, Ca[(UO(2))(PO(4))](2)(H(2)O)(11), metavauxite, [Fe(H(2)O)(6)][Al(OH)(H(2)O)(PO(4))](2), linarite, PbCu(SO(4))(OH)(2), and tancoite, LiNa(2)H[Al(PO(4))(2)(OH)], structures. The repeated observation of the secondary building unit, SBU-4, in many of the uranium arsenate structures suggests that these are viable building units. Optical studies on the uranium arsenate compound, [C(4)N(3)H(16)][U(2)F(6)(AsO(4))(HAsO(4))], VI, containing uranium in the +4 oxidation state indicates a blue emission through an upconversion process. The compound also exhibits antiferromagnetic behavior.

  1. Intraparticle diffusion and adsorption of arsenate onto granular ferric hydroxide (GFH).

    PubMed

    Badruzzaman, Mohammad; Westerhoff, Paul; Knappe, Detlef R U

    2004-11-01

    Porous iron oxides are being evaluated and selected for arsenic removal in potable water systems. Granular ferric hydroxide, a typical porous iron adsorbent, is commercially available and frequently considered in evaluation of arsenic removal methods. GFH is a highly porous (micropore volume approximately 0.0394+/-0.0056 cm(3)g(-1), mesopore volume approximately 0.0995+/-0.0096 cm(3)g(-1)) adsorbent with a BET surface area of 235+/-8 m(2)g(-1). The purpose of this paper is to quantify arsenate adsorption kinetics on GFH and to determine if intraparticle diffusion is a rate-limiting step for arsenic removal in packed-bed treatment systems. Data from bottle-point isotherm and differential column batch reactor (DCBR) experiments were used to estimate Freundlich isotherm parameters (K and 1/n) as well as kinetic parameters describing mass transfer resistances due to film diffusion (k(f)) and intraparticle surface diffusion (D(s)). The pseudo-equilibrium (18 days of contact time) arsenate adsorption density at pH 7 was 8 microg As/mg dry GFH at a liquid phase arsenate concentration of 10 microg As/L. The homogeneous surface diffusion model (HSDM) was used to describe the DCBR data. A non-linear relationship (D(S)=3.0(-9) x R(p)(1.4)) was observed between D(s) and GFH particle radius (R(P)) with D(s) values ranging from 2.98 x 10(-12) cm(2)s(-1) for the smallest GFH mesh size (100 x 140) to 64 x 10(-11) cm(2)s(-1) for the largest GFH mesh size (10 x 30). The rate-limiting process of intraparticle surface diffusion for arsenate adsorption by porous iron oxides appears analogous to organic compound adsorption by activated carbon despite differences in adsorption mechanisms (inner-sphere complexes for As versus hydrophobic interactions for organic contaminants). The findings are discussed in the context of intraparticle surface diffusion affecting packed-bed treatment system design and application of rapid small-scale column tests (RSSCTs) to simulate the performance of

  2. [Respiratory allergies].

    PubMed

    Chiriac, Anca Mirela; Demoly, Pascal

    2013-04-01

    Respiratory allergies represent a global and public health problem, due to their prevalence (still increasing), morbidity, impact on the quality of life and costs for the society. They mainly concern rhinitis (or rhinoconjunctivitis) and asthma. The diagnosis of allergy is dependent on a history of symptoms on exposure to an allergen together with the detection of allergen-specific IgE. Accurate diagnosis of allergies opens up therapeutic options that are otherwise not appropriate, such as allergen immunotherapy and allergen avoidance, that are prescribed following a stepwise approach. It has been a century since the first trial in specific immunotherapy was performed and this still remains the only disease modifying treatment for allergic individuals. In terms of route of administration, sublingual immunotherapy represents a good alternative to subcutaneous immunotherapy, considering its proven efficacy and better safety profile.

  3. The aldo-keto reductase superfamily homepage.

    PubMed

    Hyndman, David; Bauman, David R; Heredia, Vladi V; Penning, Trevor M

    2003-02-01

    The aldo-keto reductases (AKRs) are one of the three enzyme superfamilies that perform oxidoreduction on a wide variety of natural and foreign substrates. A systematic nomenclature for the AKR superfamily was adopted in 1996 and was updated in September 2000 (visit www.med.upenn.edu/akr). Investigators have been diligent in submitting sequences of functional proteins to the Web site. With the new additions, the superfamily contains 114 proteins expressed in prokaryotes and eukaryotes that are distributed over 14 families (AKR1-AKR14). The AKR1 family contains the aldose reductases, the aldehyde reductases, the hydroxysteroid dehydrogenases and steroid 5beta-reductases, and is the largest. Other families of interest include AKR6, which includes potassium channel beta-subunits, and AKR7 the aflatoxin aldehyde reductases. Two new families include AKR13 (yeast aldose reductase) and AKR14 (Escherichia coli aldehyde reductase). Crystal structures of many AKRs and their complexes with ligands are available in the PDB and accessible through the Web site. Each structure has the characteristic (alpha/beta)(8)-barrel motif of the superfamily, a conserved cofactor binding site and a catalytic tetrad, and variable loop structures that define substrate specificity. Although the majority of AKRs are monomeric proteins of about 320 amino acids in length, the AKR2, AKR6 and AKR7 family may form multimers. To expand the nomenclature to accommodate multimers, we recommend that the composition and stoichiometry be listed. For example, AKR7A1:AKR7A4 (1:3) would designate a tetramer of the composition indicated. The current nomenclature is recognized by the Human Genome Project (HUGO) and the Web site provides a link to genomic information including chromosomal localization, gene boundaries, human ESTs and SNPs and much more.

  4. Chicken muscle aldose reductase: purification, properties and relationship to other chicken aldo/keto reductases.

    PubMed

    Murphy, D G; Davidson, W S

    1986-01-01

    An enzyme that catalyzes the NADPH-dependent reduction of a wide range of aromatic and hydroxy-aliphatic aldehydes was purified from chicken breast muscle. This enzyme shares many properties with mammalian aldose reductases including molecular weight, relative substrate specificity, Michaelis constants, an inhibitor specificity. Therefore, it seems appropriate to call this enzyme an aldose reductase (EC 1.1.1.21). Chicken muscle aldose reductase appears to be kinetically identical to an aldose reductase that has been purified from chicken kidney (Hara et al., Eur. J. Biochem. 133, 207-214) and to hen muscle L-glycol dehydrogenase (Bernado et al., Biochim. biophys. Acta 659, 189-198). The association of this aldose reductase with muscular dystrophy in the chick is discussed.

  5. Molecular characterization of nosRZDFYLX genes coding for denitrifying nitrous oxide reductase of Bradyrhizobium japonicum.

    PubMed

    Velasco, Leonardo; Mesa, Socorro; Xu, Chang-Ai; Delgado, María J; Bedmar, Eulogio J

    2004-04-01

    The nosRZDFYLX gene cluster for the respiratory nitrous oxide reductase from Bradyrhizobium japonicum strain USDA110 has been cloned and sequenced. Seven protein coding regions corresponding to nosR, nosZ, the structural gene, nosD, nosF, nosY, nosL, and nosX were detected. The deduced amino acid sequence exhibited a high degree of similarity to other nitrous oxide reductases from various sources. The NosZ protein included a signal peptide for protein export. Mutant strains carrying either a nosZ or a nosR mutation accumulated nitrous oxide when cultured microaerobically in the presence of nitrate. Maximal expression of a P nosZ-lacZ fusion in strain USDA110 required simultaneously both low level oxygen conditions and the presence of nitrate. Microaerobic activation of the fusion required FixLJ and FixK(2).

  6. A QM/MM study to investigate selectivity of nanoporous graphene membrane for arsenate and chromate removal from water

    NASA Astrophysics Data System (ADS)

    Riyaz, Mohd; Goel, Neetu

    2017-10-01

    Density functional calculations have been performed within the QM/MM approach to investigate the permeability and selectivity of N-passivated nanoporous graphene towards chromate and arsenate removal from water. The passage of three target molecules namely water, arsenate and chromate from the four different sized nanoporous sheet has been elucidated in detail by treating the porous area of the sheet within the formalism of DFT, while molecular mechanics has been applied to the remaining sheet. The selectivity of the nanoporous sheet towards the passage of target molecules has been measured in terms of their diffusion energy barrier.

  7. Fluorescence sensing of arsenate at nanomolar level in a greener way: naphthalene based probe for living cell imaging.

    PubMed

    Sahana, Animesh; Banerjee, Arnab; Lohar, Sisir; Panja, Sukanya; Mukhopadhyay, Subhra Kanti; Matalobos, Jesús Sanmartín; Das, Debasis

    2013-08-21

    Naphthalene-salisaldehyde conjugate (NAPSAL) is established as a novel arsenate (H2AsO4(-)) selective 'turn-on' fluorescence probe. It can detect as low as 5 × 10(-9) M H2AsO4(-) in HEPES buffered EtOH : water (0.1 M, 1 : 9, v/v, pH 7.4). Trace level H2AsO4(-) in drinking water samples is measured using standard addition method. Intracellular arsenate in Candida albicans, grown in arsenic contaminated water of Purbasthali has successfully been detected under fluorescence microscope.

  8. The cymA Gene, Encoding a Tetraheme c-Type Cytochrome, Is Required for Arsenate Respiration in Shewanella Species▿

    PubMed Central

    Murphy, Julie N.; Saltikov, Chad W.

    2007-01-01

    In Shewanella sp. strain ANA-3, utilization of arsenate as a terminal electron acceptor is conferred by a two-gene operon, arrAB, which lacks a gene encoding a membrane-anchoring subunit for the soluble ArrAB protein complex. Analysis of the genome sequence of Shewanella putrefaciens strain CN-32 showed that it also contained the same arrAB operon with 100% nucleotide identity. Here, we report that CN-32 respires arsenate and that this metabolism is dependent on arrA and an additional gene encoding a membrane-associated tetraheme c-type cytochrome, cymA. Deletion of cymA in ANA-3 also eliminated growth on and reduction of arsenate. The ΔcymA strains of CN-32 and ANA-3 negatively affected the reduction of Fe(III) and Mn(IV) but not growth on nitrate. Unlike the CN-32 ΔcymA strain, growth on fumarate was absent in the ΔcymA strain of ANA-3. Both homologous and heterologous complementation of cymA in trans restored growth on arsenate in ΔcymA strains of both CN-32 and ANA-3. Transcription patterns of cymA showed that it was induced under anaerobic conditions in the presence of fumarate and arsenate. Nitrate-grown cells exhibited the greatest level of cymA expression in both wild-type strains. Lastly, site-directed mutagenesis of the first Cys to Ser in each of the four CXXCH c-heme binding motifs of the CN-32 CymA nearly eliminated growth on and reduction of arsenate. Together, these results indicate that the biochemical mechanism of arsenate respiration and reduction requires the interactions of ArrAB with a membrane-associated tetraheme cytochrome, which in the non-arsenate-respiring Shewanella species Shewanella oneidensis strain MR-1, has pleiotropic effects on Fe(III), Mn(IV), dimethyl sulfoxide, nitrate, nitrite, and fumarate respiration. PMID:17209025

  9. Lungs and Respiratory System

    MedlinePlus

    ... Your 1- to 2-Year-Old Lungs and Respiratory System KidsHealth > For Parents > Lungs and Respiratory System A ... ll have taken at least 600 million breaths. Respiratory System Basics All of this breathing couldn't happen ...

  10. Chemical Speciation and Bioaccessibility of Arsenic and Chromiumin Chromated Copper Arsenate-Treated Wood and Soils

    SciTech Connect

    Nico, Peter S.; Ruby, Michael V.; Lowney, Yvette W.; Holm,Stewart E.

    2005-10-12

    This research compares the As and Cr chemistry ofdislodgeable residues from Chromated Copper Arsenate (CCA)-treated woodcollected by two different techniques (directly from the board surfaceeither by rubbing with a soft bristle brush or from human hands aftercontact with CCA-treated wood), and demonstrates that these materials areequivalent in terms of the chemical form and bonding of As and Cr and interms of the As leaching behavior. This finding links the extensivechemical characterization and bioavailability testing that has been donepreviously on the brush-removed residue to a material that is derivedfrom human skin contact with CCA-treated wood. Additionally, thisresearch characterizes the arsenic present in biological fluids (sweatand simulated gastric fluid) following contact with these residues. Thedata demonstrate that in biological fluids, the arsenic is presentprimarily as free arsenate ions.Arsenic-containing soils were alsoextracted into human sweat to evaluate the potential for arsenicdissolution from soils at the skin surface. For soils from field sites,only a small fraction of the total arsenic is soluble in sweat. Based oncomparisons to reference materials that have been used in in vivo dermalabsorption studies, these findings suggest that the actual relativebioavailability via dermal absorption of As from CCA-residues and soilmay be well below the current default value of 3 percent used by U.S.EPA.

  11. Complexation at the edges of hydrotalcite: the cases of arsenate and chromate.

    PubMed

    Jobbágy, Matías; Regazzoni, Alberto E

    2013-03-01

    Sorption of CrO(4)(2-) and HAsO(4)(2-) by hydrotalcite, in its chloride form, was studied as a function of anion concentration. In both cases, the shape of the isotherms is langmuirian. The maximum uptake of CrO(4)(2-) equals the ion-exchange capacity of the solid, whereas sorption of HAsO(4)(2-) saturates at a higher value. Chloride ions inhibit the uptake of both anions, the amount of sorbed CrO(4)(2-) declining rapidly to zero. The uptake of HAsO(4)(2-), however, attains a constant value at high chloride concentrations. The excess of arsenate uptake follows, at constant pH, a langmuirian dependence with equilibrium concentration and decreases with increasing pH, depicting a marked change in slope at pH≈pQ(a3). CrO(4)(2-) and HAsO(4)(2-) have notable, albeit different, effects on the electrophoretic behavior of hydrotalcite; the positive particle charge is screened almost completely by CrO(4)(2-), whereas sorption of HAsO(4)(2-) produces charge reversal. These results reflect the formation of inner-sphere arsenate surface complexes at the edges of hydrotalcite particles. The underlying rationale is discussed in terms of the crystal structure of hydrotalcite surfaces. Copyright © 2012 Elsevier Inc. All rights reserved.

  12. Bioaccumulation Dynamics of Arsenate at the Base of Aquatic Food Webs.

    PubMed

    Lopez, Adeline R; Hesterberg, Dean R; Funk, David H; Buchwalter, David B

    2016-06-21

    Periphyton is an important food source at the base of freshwater ecosystems that tends to bioconcentrate trace elements making them trophically available. The potential for arsenic-a trace element of particular concern due to its widespread occurrence, toxicity, and carcinogenicity-to bioconcentrate in periphyton and thus be available to benthic grazers is less well characterized. To better understand arsenate bioaccumulation dynamics in lotic food webs, we used a radiotracer approach to characterize accumulation in periphyton and subsequent trophic transfer to benthic grazers. Periphyton bioconcentrated As between 3,200-9,700-fold (dry weight) over 8 days without reaching steady state, suggesting that periphyton is a major sink for arsenate. However, As-enriched periphyton as a food source for the mayfly Neocloeon triangulifer resulted in negligible As accumulation in a full lifecycle exposure. Additional studies estimate dietary assimilation efficiency in several primary consumers ranging from 22% in the mayfly N. triangulifer to 75% in the mayfly Isonychia sp. X-ray fluorescence mapping revealed that As was predominantly associated with iron oxides in periphyton. We speculate that As adsorption to Fe in periphyton may play a role in reducing dietary bioavailability. Together, these results suggest that trophic movement of As in lotic food webs is relatively low, though species differences in bioaccumulation patterns are important.

  13. Na₃Co₂(AsO₄)(As₂O₇): a new sodium cobalt arsenate.

    PubMed

    Guesmi, Abderrahmen; Driss, Ahmed

    2012-07-01

    In the title compound, tris-odium dicobalt arsenate diarsenate, Na₃Co₂AsO₄As₂O₇, the two Co atoms, one of the two As and three of the seven O atoms lie on special positions, with site symmetries 2 and m for the Co, m for the As, and 2 and twice m for the O atoms. The two Na atoms are disordered over two general and special positions [occupancies 0.72 (3):0.28 (3) and 0.940 (6):0.060 (6), respectively]. The main structural feature is the association of the CoO₆ octa-hedra in the ab plane, forming Co₄O₂₀ units, which are corner- and edge-connected via AsO₄ and As₂O₇ arsenate groups, giving rise to a complex polyhedral connectivity with small tunnels, such as those running along the b- and c-axis directions, in which the Na⁺ ions reside. The structural model is validated by both bond-valence-sum and charge-distribution methods, and the distortion of the coordination polyhedra is analyzed by means of the effective coordination number.

  14. Removing heavy metals in water: the interaction of cactus mucilage and arsenate (As (V)).

    PubMed

    Fox, Dawn I; Pichler, Thomas; Yeh, Daniel H; Alcantar, Norma A

    2012-04-17

    High concentrations of arsenic in groundwater continue to present health threats to millions of consumers worldwide. Particularly, affected communities in the developing world need accessible technologies for arsenic removal from drinking water. We explore the application of cactus mucilage, pectic polysaccharide extracts from Opuntia ficus-indica for arsenic removal. Synthetic arsenate (As (V)) solutions were treated with two extracts, a gelling extract (GE) and a nongelling extract (NE) in batch trials. The arsenic concentration at the air-water interface was measured after equilibration. The GE and NE treated solutions showed on average 14% and 9% increases in arsenic concentration at the air-water interface respectively indicating that the mucilage bonded and transported the arsenic to the air-water interface. FTIR studies showed that the -CO groups (carboxyl and carbonyl groups) and -OH (hydroxyl) functional groups of the mucilage were involved in the interaction with the arsenate. Mucilage activity was greater in weakly basic (pH 9) and weakly acidic (pH 5.5) pH. This interaction can be optimized and harnessed for the removal of arsenic from drinking water. This work breaks the ground for the application of natural pectic materials to the removal of anionic metallic species from water.

  15. Arsenate removal from water by an alumina-modified zeolite recovered from fly ash.

    PubMed

    Qiu, Wei; Zheng, Ying

    2007-09-30

    A cancrinite-type zeolite was synthesized from Class C fly ash by molten-salt method. The product (ZFA) was used as the adsorbent for the arsenate removal from water. The adsorption equilibriums of arsenate are investigated on various adsorbents. ZFA showed a higher adsorption capacity (5.1 mg g(-1)) than activated carbon (4.0 mg g(-1)), silica gel (0.46 mg g(-1)), zeolite NaY (1.4 mg g(-1)), and zeolite 5A (4.1 mg g(-1)). The relatively higher adsorption capacity of ZFA than zeolite NaY and 5A was attributed to the low Si/Al ratio and the mesoporous secondary pore structure of ZFA. However, it was found that the adsorption capacity of zeolites were generally lower than activated alumina (16.6 mg g(-1)), which is ascribed to the small pores in zeolite frameworks. The adsorption capacity of ZFA was significantly improved after loaded by alumina via a wet-impregnation method. The modified ZFA (ZFA-Al(50)) with the optimum alumina loading showed an adsorption capacity of 34.5 mg g(-1), which was 2.1 times higher than activated alumina. The Toxicity Characteristic Leaching Procedure (TCLP) leachability tests indicated that the spent ZFA and alumina-modified ZFA complied with the EPA regulations for safe disposal.

  16. Arsenate incorporation in gypsum probed by neutron, X-ray scattering and density functional theory modeling.

    PubMed

    Fernández-Martínez, Alejandro; Cuello, Gabriel J; Johnson, Mark R; Bardelli, Fabrizio; Román-Ross, Gabriela; Charlet, Laurent; Turrillas, Xavier

    2008-06-12

    The ability of gypsum, a common sulfate mineral, to host arsenic atoms in its crystalline structure, is demonstrated through experimental structural studies of the solid solutions formed upon synthetic coprecipitation of gypsum (CaSO4 x 2 H2O) and arsenic. Neutron and X-ray diffraction methods show an enlargement of the gypsum unit cell proportional to the concentration of arsenic in the solids and to the pH solution value. The substitution of sulfate ions (SO4(2-)) by arsenate ions is shown to be more likely under alkaline conditions, where the HAsO4(2-) species predominates. A theoretical Density Functional Theory model of the arsenic-doped gypsum structure reproduces the experimental volume expansion. Extended X-ray Absorption Fine Structure (EXAFS) measurements of the local structure around the arsenic atom in the coprecipitated solids confirm solid state substitution and allow some refinement of the local structure, corroborating the theoretical structure found in the simulations. The charge redistribution within the structure upon substitutions of either the protonated or the unprotonated arsenate species studied by means of Mulliken Population Analyses demonstrates an increase in the covalency in the interaction between Ca(2+) and AsO4(3-), whereas the interaction between Ca(2+) and HAsO4(2-) remains predominantly ionic.

  17. Facile synthesis of highly active hydrated yttrium oxide towards arsenate adsorption.

    PubMed

    Yu, Yang; Yu, Ling; Sun, Min; Paul Chen, J

    2016-07-15

    A novel hydrated yttrium oxide adsorbent with high capacity towards the arsenate (As(V)) adsorption was fabricated by a one-step hydrothermal process. Structure analysis identified the hydrated yttrium oxide to be Y2O(OH)4·1.5H2O, which displayed as irregular rods in the range of tens to hundreds of nanometers. The adsorbent exhibited favorable As(V) adsorption efficiency in a wide pH range from 4.0 to 7.0, with the maximum adsorption capacity of 480.2mg-As/g obtained at pH 5.0. Both the kinetics and isotherm studies demonstrated that the adsorption of the As(V) was a monolayer chemical adsorption process, in which the ion exchange between the hydroxyl groups on the hydrated yttrium oxide and arsenate anions played a key role in the uptake of the As(V). During the adsorption, the As(V) anions were replaced the hydroxyl groups and bound to the hydrated yttrium oxide via the linkage of AsOY. The presence of fluoride and phosphate greatly hindered the As(V) uptake on the hydrated yttrium oxide, whereas the bicarbonate, sulfate and humic acid showed insignificant impacts on the removal.

  18. Mitochondrial fumarate reductase as a target of chemotherapy: from parasites to cancer cells.

    PubMed

    Sakai, Chika; Tomitsuka, Eriko; Esumi, Hiroyasu; Harada, Shigeharu; Kita, Kiyoshi

    2012-05-01

    Recent research on respiratory chain of the parasitic helminth, Ascaris suum has shown that the mitochondrial NADH-fumarate reductase system (fumarate respiration), which is composed of complex I (NADH-rhodoquinone reductase), rhodoquinone and complex II (rhodoquinol-fumarate reductase) plays an important role in the anaerobic energy metabolism of adult parasites inhabiting hosts. The enzymes in these parasite-specific pathways are potential target for chemotherapy. We isolated a novel compound, nafuredin, from Aspergillus niger, which inhibits NADH-fumarate reductase in helminth mitochondria at nM order. It competes for the quinone-binding site in complex I and shows high selective toxicity to the helminth enzyme. Moreover, nafuredin exerts anthelmintic activity against Haemonchus contortus in in vivo trials with sheep indicating that mitochondrial complex I is a promising target for chemotherapy. In addition to complex I, complex II is a good target because its catalytic direction is reverse of succinate-ubiquionone reductase in the host complex II. Furthermore, we found atpenin and flutolanil strongly and specifically inhibit mitochondrial complex II. Interestingly, fumarate respiration was found not only in the parasites but also in some types of human cancer cells. Analysis of the mitochondria from the cancer cells identified an anthelminthic as a specific inhibitor of the fumarate respiration. Role of isoforms of human complex II in the hypoxic condition of cancer cells and fetal tissues is a challenge. This article is part of a Special Issue entitled Biochemistry of Mitochondria, Life and Intervention 2010. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. EXAFS Analyses of Innersphere Surface Complexations of Arsenate and Silicate on Natural Hydrous Ferric Oxides

    NASA Astrophysics Data System (ADS)

    Tommaseo, C. E.; Kersten, M.

    2002-12-01

    X-ray absorption spectroscopy (EXAFS) was used to determine the near range order of three elements (Fe, As, Si) on the surface of hydrous ferric oxide (HFO) from thermal water scales. Fe K-edge EXAFS analyses of the 2nd shell show a better fit including Si as backscattering neighbor. Validation of the Si-Fe bond was obtained by Si K-edge EXAFS spectra, where the light absorber element is surrounded favourably by much heavier second-shell elements. Least-squares fitting of the second-shell Fourier-filtered EXAFS spectrum in the k-range of 5-11 Å-1 yields in a Si-Fe distance of 3.10-3.13Å, and a Si-Si distance of 3.00Å. Both these interatomic distances and the coordination number N = 2 obtained for the Si-Fe shell are consistent with the formation of a corner-bridging bidentate binuclear (2C) surface complex on the HFO surface. The Si-Si bonds and existance of a vibrational band at 964 cm-1 in the infrared spectrum indicate polymerisation of the silicate on the HFO surface (Tommaseo and Kersten). As K-edge XANES analyses showed the As present in form of arsenate scavenged by the HFO phase. As and Si K-edge EXAFS analyses revealed both elements to compete for 2C surface complexation sites. A mean As-Fe distance of 3.03Å indicate an approx. equal distribution of arsenate between 2C (3.24Å) and another 1E (bidentate mononuclear surface complexation) sites (2.84Å). The average Fe-(O,OH) bond length of 2.09Å is compatible with a high proportion of distorted surficial FeIII(O,OH)6 octahedra in the colloidal HFO precipitates of the scale deposits. The slight distortion of the FeIII(O,OH)6 octahedra is consistent with the apparent strong binding of the 1E arsenate surface complexes (Manceau, 1995). The adverse effect of silicate would therefore be overpredicted without surface complexation models constructed to account for both surface functional groups. The Si K-edge EXAFS data provide also a basis for explaining at the molecular level the poisoning of HFO particle

  20. The tyrosyl free radical in ribonucleotide reductase.

    PubMed Central

    Gräslund, A; Sahlin, M; Sjöberg, B M

    1985-01-01

    The enzyme, ribonucleotide reductase, catalyses the formation of deoxyribonucleotides from ribonucleotides, a reaction essential for DNA synthesis in all living cells. The Escherichia coli ribonucleotide reductase, which is the prototype of all known eukaryotic and virus-coded enzymes, consists of two nonidentical subunits, proteins B1 and B2. The B2 subunit contains an antiferromagnetically coupled pair of ferric ions and a stable tyrosyl free radical. EPR studies show that the tyrosyl radical, formed by loss of ferric ions and a stable tyrosyl free radical. EPR studies show that the tyrosyl radical, formed by loss of an electron, has its unpaired spin density delocalized in the aromatic ring of tyrosine. Effects of iron-radical interaction indicate a relatively close proximity between the iron center and the radical. The EPR signal of the radical can be studied directly in frozen packed cells of E. coli or mammalian origin, if the cells are made to overproduce ribonucleotide reductase. The hypothetic role of the tyrosyl free radical in the enzymatic reaction is not yet elucidated, except in the reaction with the inhibiting substrate analogue 2'-azido-CDP. In this case, the normal tyrosyl radical is destroyed with concomitant appearance of a 2'-azido-CDP-localized radical intermediate. Attempts at spin trapping of radical reaction intermediates have turned out negative. In E. coli the activity of ribonucleotide reductase may be regulated by enzymatic activities that interconvert a nonradical containing form and the fully active protein B2. In synchronized mammalian cells, however, the cell cycle variation of ribonucleotide reductase, studied by EPR, was shown to be due to de novo protein synthesis. Inhibitors of ribonucleotide reductase are of medical interest because of their ability to control DNA synthesis. One example is hydroxyurea, used in cancer therapy, which selectively destroys the tyrosyl free radical. PMID:3007085

  1. Lead and Arsenic Uptake by Carrots Grown on Five Orchard Soils With History of Lead Arsenate Used

    USDA-ARS?s Scientific Manuscript database

    Lead arsenate was used to control codling moth in apple and plum orchards from 1900 to 1960. Consequently, many orchard soils are contaminated with lead (Pb) and arsenic (As). Some of these lands are being used for urban development and vegetable crop production. Both soil Pb and As have become i...

  2. TISSUE DISTRIBUTION OF INORGANIC ARSENIC (AS) AND ITS METHYLATED METABOLITES IN MICE FOLLOWING ORAL ADMINISTRATION OF ARSENATE (ASV)

    EPA Science Inventory

    TISSUE DISTRIBUTION OF INORGANIC ARSENIC (iAs) AND ITS METHYLATED METABOLITES IN MICE FOLLOWING ORAL ADMINISTRATION OF ARSENATE (AsV). E M Kenyon1, L M Del Razo2, and M F Hughes1. 1NHEERL, ORD, US EPA, RTP, NC, USA; 2CINVESTAV-IPN, Mexico City, Mexico.

    The relationship o...

  3. Rapid microwave-assisted acid extraction of metals from chromated copper arsenate (CCA)-treated southern pine wood

    Treesearch

    Bin Yu; Chung Y. Hse; Todd F. Shupe

    2009-01-01

    The effects of acid concentration, reaction time, and temperature in a microwave reactor on recovery of CCA-treated wood were evaluated. Extraction of copper, chromium, and arsenic metals from chromated copper arsenate (CCA)-treated southern pine wood samples with three different acids (i.e., acetic acid, oxalic acid, and phosphoric acid) was investigated using in...

  4. Fate of arsenite and arsenate in flooded and not flooded soils of southwest Bangladesh irrigated with arsenic contaminated water.

    PubMed

    Martin, Maria; Violante, Antonio; Barberis, Elisabetta

    2007-10-01

    In Bangladesh and West Bengal, India, tons of arsenic are added every year to wide extensions of agricultural soils after irrigation with arsenic polluted groundwater, and the fate of the added arsenic in these water-soil environments is not yet clear. This work was aimed to investigate the accumulation and potential release of arsenite [As(III)] and arsenate [As(V)] in two adjacent soils of Bangladesh, irrigated with arsenic contaminated groundwater and cultivated under flooded or not flooded conditions. Both soils showed a scarce As accumulation, in spite of a good adsorption capacity, higher for As(III) than for As(V). The poorly ordered Fe oxides dominated As adsorption in the topsoil of the flooded soil, whereas the crystalline forms were more important in the well aerated soil. A high percentage of the native arsenic was exchangeable with phosphate and the freshly added arsenate or arsenite were even much more mobile. In our experimental conditions, the high As mobility was not dependent on the surface coverage, and, in the flooded soil, 60-70% of the freshly added arsenite or arsenate were desorbed with an infinite sink method, while in the not flooded soil arsenate was less desorbed than arsenite. Depending on their characteristics, some soils, in particular when cultivated under flooded conditions, can represent only a temporary sink for the added As, that can be easily released to waters and possibly enter the food chain from the water-soil system.

  5. A green sorbent of esterified egg-shell membrane for highly selective uptake of arsenate and speciation of inorganic arsenic.

    PubMed

    Chen, Ming-Li; Gu, Cui-Bo; Yang, Ting; Sun, Yan; Wang, Jian-Hua

    2013-11-15

    Egg-shell membrane (ESM) is a promising adsorbent for heavy metal uptake. However, carboxylic groups on ESM surface barrier arsenic adsorption. Herein, ESM is modified by esterification and the methyl esterified egg-shell membrane (MESM) possesses positive charge within pH 1-9. As a novel green sorbent material, MESM exhibits 200-fold improvement on sorption capacity of arsenate with respect to bare ESM. It presents an ultra-high selectivity of 256:1 toward arsenate against arsenite. At pH 6, 100% sorption efficiency is achieved for 2 μg L(-1) As(V) by 10 mg MESM, while virtually no adsorption of As(III) is observed. This provides great potential for selective sorption of arsenate in the presence of arsenite. By loading 4.0 mL sample within 0.05-5.00 μg L(-1) As(V) followed by elution with 300 μL HCl (1.5 mol L(-1)), a detection limit of 15 ng L(-1) is obtained along with a RSD of 3.5% at 0.5 μg L(-1). Total inorganic arsenic is achieved by converting As(III) to As(V) and following the same sorption process. This procedure is applied for arsenate determination and inorganic arsenic speciation in Hijiki and water samples. The results are confirmed by graphite furnace atomic absorption spectrometry and spiking recovery. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Genome wide analysis of DNA methylation and gene expression changes in the mouse lung following subchronic arsenate exposure

    EPA Science Inventory

    Alterations in DNA methylation have been proposed as a mechanism for the complex toxicological effects of arsenic. In this study, whole genome DNA methylation and gene expression changes were evaluated in lungs from female mice exposed for 90 days to 50 ppm arsenate (As) in drink...

  7. Desulfohalophilus alkaliarsenatis gen. nov., sp. nov., an extremely halophilic sulfate- and arsenate-respiring bacterium from Searles Lake, California

    USGS Publications Warehouse

    Blum, Jodi Switzer; Kulp, Thomas R.; Han, Sukkyun; Lanoil, Brian; Saltikov, Chad W.; Stolz, John F.; Miller, Laurence G.; Oremland, Ronald S.

    2012-01-01

    A haloalkaliphilic sulfate-respiring bacterium, strain SLSR-1, was isolated from a lactate-fed stable enrichment culture originally obtained from the extreme environment of Searles Lake, California. The isolate proved capable of growth via sulfate-reduction over a broad range of salinities (125–330 g/L), although growth was slowest at salt-saturation. Strain SLSR-1 was also capable of growth via dissimilatory arsenate-reduction and displayed an even broader range of salinity tolerance (50–330 g/L) when grown under these conditions. Strain SLSR-1 could also grow via dissimilatory nitrate reduction to ammonia. Growth experiments in the presence of high borate concentrations indicated a greater sensitivity of sulfate-reduction than arsenate-respiration to this naturally abundant anion in Searles Lake. Strain SLSR-1 contained genes involved in both sulfate-reduction (dsrAB) and arsenate respiration (arrA). Amplicons of 16S rRNA gene sequences obtained from DNA extracted from Searles Lake sediment revealed the presence of close relatives of strain SLSR-1 as part of the flora of this ecosystem despite the fact that sulfate-reduction activity could not be detected in situ. We conclude that strain SLSR-1 can only achieve growth via arsenate-reduction under the current chemical conditions prevalent at Searles Lake. Strain SLSR-1 is a deltaproteobacterium in the family Desulfohalobiacea of anaerobic, haloalkaliphilic bacteria, for which we propose the name Desulfohalophilus alkaliarsenatis gen. nov., sp. nov.

  8. Assessment of the environmental effects associated with wooden bridges preserved with creosote, pentachlorophenol, or chromated copper arsenate

    Treesearch

    Kenneth M. Brooks

    Timber bridges provide an economical alternative to concrete and steel structures, particularly in rural areas with light to moderate vehicle traffic. Wooden components of these bridges are treated with chromated copper arsenate type C (CCA), pentachlorophenol, or creosote to prolong the life of the structure from a few years to many decades. This results in reduced...

  9. Environmental concentrations of copper, chromium, and arsenic released from a chromated-copper-arsenate-(CCA-C-) treated wetland boardwalk

    Treesearch

    Stan T. Lebow; Daniel Foster

    2005-01-01

    A study was conducted to evaluate environmental accumulation and mobility of total copper, chromium, and arsenic adjacent to a chromated-copper-arsenate-(CCA-C-) treated wetland boardwalk. The study was considered a severe test because it included a large volume of treated wood in a site with high annual rainfall. Soil and sediment samples were collected before...

  10. Mechanical Performance of Nail-Laminated Posts Manufactured from Reclaimed Chromated Copper Arsenate-Treated Decking Lumber

    Treesearch

    John J. Janowiak; Robert H. Falk; Brad A. Gething; John A. Tsirigotis

    2014-01-01

    This study determined the mechanical properties of nail-laminated (nail-lam) posts manufactured from reclaimed chromated copper arsenate (CCA)–treated decking lumber. Though CCA-treated lumber is no longer accepted for use in residential applications, it is permitted in agricultural and industrial applications where health and environmental impacts are deemed to be...

  11. Role of uniform pore structure and high positive charges in the arsenate adsorption performance of Al13-modified montmorillonite.

    PubMed

    Zhao, Shou; Feng, Chenghong; Huang, Xiangning; Li, Baohua; Niu, Junfeng; Shen, Zhenyao

    2012-02-15

    Four modified montmorillonite adsorbents with varied Al(13) contents (i.e., Na-Mont, AC-Mont, PAC(20)-Mont, and Al(13)-Mont) were synthesized and characterized by N(2) adsorption/desorption, X-ray diffraction, and Fourier-transform infrared analyses. The arsenate adsorption performance of the four adsorbents were also investigated to determine the role of intercalated Al(13), especially its high purity, high positive charge (+7), and special Keggin structure. With increased Al(13) content, the physicochemical properties (e.g., surface area, structural uniformity, basal spacing, and pore volume) and adsorption performance of the modified montmorillonites were significantly but disproportionately improved. The adsorption data well fitted the Freundlich and Redlich-Peterson isotherm model, whereas the kinetic data better correlated with the pseudo-second-order kinetic model. The arsenate sorption mechanism of the montmorillonites changed from physical to chemisorption after intercalation with Al(13). Increasing charges of the intercalated ions enhanced the arsenate adsorption kinetics, but had minimal effect on the structural changes of the montmorillonites. The uniform pore structure formed by intercalation with high-purity Al(13) greatly enhanced the pore diffusion and adsorption rate of arsenate, resulting in the high adsorption performance of Al(13)-Mont.

  12. Assessing Metal Contamination in Lead Arsenate Contaminated Orchard Soils Using Near and Mid-Infrared Diffuse Reflectance Spectroscopy

    USDA-ARS?s Scientific Manuscript database

    Historic use of lead-arsenate as pesticide in apple orchards left many soils contaminated with arsenic (As) and lead (Pb). Notorious health effects and their severe soil contamination are of primary concerns for major regulatory agencies, and community at large. Wet chemistry methods for soil anal...

  13. New low temperature synthetic route to an ammonium zinc arsenate zeolite analogue with an ABW-type structure.

    PubMed

    Johnson, Christopher D; Macphee, Donald E; Feldmann, Jörg

    2002-07-15

    The synthesis and stability of zeolite analogues are of potential interest to the waste management community as waste metals may be used in the framework of these materials. A new synthetic route to an ABW-type ammonium zinc arsenate is proposed. The stability of this material is then examined in an aqueous environment by quantitative X-ray diffraction and leach testing.

  14. TISSUE DISTRIBUTION OF INORGANIC ARSENIC (AS) AND ITS METHYLATED METABOLITES IN MICE FOLLOWING ORAL ADMINISTRATION OF ARSENATE (ASV)

    EPA Science Inventory

    TISSUE DISTRIBUTION OF INORGANIC ARSENIC (iAs) AND ITS METHYLATED METABOLITES IN MICE FOLLOWING ORAL ADMINISTRATION OF ARSENATE (AsV). E M Kenyon1, L M Del Razo2, and M F Hughes1. 1NHEERL, ORD, US EPA, RTP, NC, USA; 2CINVESTAV-IPN, Mexico City, Mexico.

    The relationship o...

  15. Preconcentration of trace arsenite and arsenate with titanium dioxide nanoparticles and subsequent determination by silver diethyldithiocarbamate spectrophotometric method.

    PubMed

    Xiao, Yabing; Ling, Jie; Qian, Shahua; Lin, Anqing; Zheng, Wenjie; Xu, Weiya; Luo, Yuxuan; Zhang, Man

    2007-09-01

    A novel method of preconcentration of trace arsenite and arsenate by using titanium dioxide nanoparticles as adsorbent was described. The concentrations of preconcentrated arsenite and arsenate were determined by a silver diethyldithiocarbamate spectrophotometric method without desorption. Batch adsorption experiments were carried out as a function of the pH, contact time, amount of titanium dioxide nanoparticles, and solution volume. In the pH range 5 to 6, adsorption rates of arsenite and arsenate were higher than 98%. The calibration coefficient was 0.9991, and the linear range was 0 to 100 microg/L. The developed method was precise, with the relative standard deviation <5% at concentration level of 10 microg/L, with a detection limit (3sigma, n=6) of 0.44 microg/L. The accuracy of the method for total arsenic was validated by standard reference materials (SRM 3103a) (National Institute of Standards and Technology, Gaithersburg, Maryland). The method was also applied to the analysis of arsenite and arsenate in natural water samples to verify the accuracy. The recovery values remained in a narrow range, from 95 to 103%.

  16. Arsenate and Arsenite Sorption on Magnetite: Relations to Groundwater Arsenic Treatment Using Zerovalent Iron and Natural Attenuation

    EPA Science Inventory

    Magnetite (Fe3O4) is a zerovalent iron corrosion product; it is also formed in natural soil and sediment. Sorption of arsenate (As(V)) and arsenite (As(III)) on magnetite is an important process of arsenic removal from groundwater using zerovalent iron-based permeable reactive ba...

  17. Tissue Distribution and Urinary Excretion of Dimethylated Arsenic and Its Metabolites in Dimethylarsinic acid- or Arsenate-treated Rats - MCEARD

    EPA Science Inventory

    Adult female Fisher 344 rats received drinking water containing 0, 4, 40, 100, or 200 parts per million of dimethylarsinic acid or 100 parts per million of arsenate for 14 days. Urine was collected during the last 24 h of exposure. Tissues were then taken for analysis of dimethy...

  18. Laccase Inhibition by Arsenite/Arsenate: Determination of Inhibition Mechanism and Preliminary Application to a Self-Powered Biosensor.

    PubMed

    Wang, Tao; Milton, Ross D; Abdellaoui, Sofiene; Hickey, David P; Minteer, Shelley D

    2016-03-15

    The reversible inhibition of laccase by arsenite (As(3+)) and arsenate (As(5+)) is reported for the first time. Oxygen-reducing laccase bioelectrodes were found to be inhibited by both arsenic species for direct electron-transfer bioelectrodes (using anthracene functionalities for enzymatic orientation) and for mediated electron-transfer bioelectrodes [using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as an electron mediator]. Both arsenic species were determined to behave via a mixed inhibition model (behaving closely to that of uncompetitive inhibitors) when evaluated spectrophotometrically using ABTS as the electron donor. Finally, laccase bioelectrodes were employed within an enzymatic fuel cell, yielding a self-powered biosensor for arsenite and arsenate. This conceptual self-powered arsenic biosensor demonstrated limits of detection (LODs) of 13 μM for arsenite and 132 μM for arsenate. Further, this device possessed sensitivities of 0.91 ± 0.07 mV/mM for arsenite and 0.98 ± 0.02 mV/mM for arsenate.

  19. Synergistic interaction of glyceraldehydes-3-phosphate dehydrogenase and ArsJ, a novel organoarsenical efflux permease, confers arsenate resistance.

    PubMed

    Chen, Jian; Yoshinaga, Masafumi; Garbinski, Luis D; Rosen, Barry P

    2016-06-01

    Microbial biotransformations are major contributors to the arsenic biogeocycle. In parallel with transformations of inorganic arsenic, organoarsenicals pathways have recently been recognized as important components of global cycling of arsenic. The well-characterized pathway of resistance to arsenate is reduction coupled to arsenite efflux. Here, we describe a new pathway of arsenate resistance involving biosynthesis and extrusion of an unusual pentavalent organoarsenical. A number of arsenic resistance (ars) operons have two genes of unknown function that are linked in these operons. One, gapdh, encodes the glycolytic enzyme glyceraldehyde-3-phosphate dehydrogenase. The other, arsJ, encodes a major facilitator superfamily (MFS) protein. The two genes were cloned from the chromosome of Pseudomonas aeruginosa. When expressed together, but not alone, in Escherichia coli, gapdh and arsJ specifically conferred resistance to arsenate and decreased accumulation of As(V). Everted membrane vesicles from cells expressing arsJ accumulated As(V) in the presence of purified GAPDH, D-glceraldehylde 3-phosphate (G3P) and NAD(+) . GAPDH forms the unstable organoarsenical 1-arseno-3-phosphoglycerate (1As3PGA). We propose that ArsJ is an efflux permease that extrudes 1As3PGA from cells, where it rapidly dissociates into As(V) and 3-phosphoglycerate (3PGA), creating a novel pathway of arsenate resistance. © 2016 John Wiley & Sons Ltd.

  20. Tissue Distribution and Urinary Excretion of Dimethylated Arsenic and Its Metabolites in Dimethylarsinic acid- or Arsenate-treated Rats - MCEARD

    EPA Science Inventory

    Adult female Fisher 344 rats received drinking water containing 0, 4, 40, 100, or 200 parts per million of dimethylarsinic acid or 100 parts per million of arsenate for 14 days. Urine was collected during the last 24 h of exposure. Tissues were then taken for analysis of dimethy...

  1. Effect of weathering on chromated copper arsenate (CCA) treated wood : leaching of metal salts and change in water repellency

    Treesearch

    R. Sam Williams; Stan Lebow; Patricia Lebow

    2003-01-01

    Wood pressure-treated with chromated copper arsenate (CCA) wood preservative is commonly used for outdoor construction. Oxides of arsenic, copper, and chromium are bound in the wood by a complex series of chemical reactions, but a small percentage of these compounds are gradually released by leaching and weathering. Recent studies suggest that the release of these...

  2. Residual strength and stiffness of lumber from decommissioned chromated copper arsenate-treated southern pine utility poles

    Treesearch

    Cheng Piao; Leslie Groom

    2010-01-01

    The reusability of decommissioned treated wood is primarily dependent on the residual strength of the wood after service. Determining the residual strength can provide useful information for structural design and reuse of the decommissioned treated wood. This study evaluated the residual strength of decommissioned chromated copper arsenate–treated utility pole wood....

  3. Facile synthesis of size-tunable gold nanoparticles by pomegranate (Punica granatum) leaf extract: Applications in arsenate sensing

    SciTech Connect

    Rao, Ashit; Mahajan, Ketakee; Bankar, Ashok; Srikanth, Rapole; Kumar, Ameeta Ravi; Gosavi, Suresh; Zinjarde, Smita

    2013-03-15

    Highlights: ► Pomegranate leaf extracts mediated rapid gold nanoparticle (AuNP) synthesis. ► The phyto-inspired AuNPs were size-tuned and characterized. ► The reducing and capping agents in the extract were identified. ► The nanoparticles reacted specifically with arsenate (V) ions. - Abstract: When pomegranate leaf extracts were incubated with chloroauric acid (HAuCl{sub 4}), gold nanoparticles (AuNPs) were synthesized. These were characterized by a variety of techniques. With an increasing content of the leaf extract, a gradual decrease in size and an increase in monodispersity were observed. Transmission electron microscope (TEM) images showed that the phyto-fabricated AuNPs were surrounded by an amorphous layer. Gallic acid in the extract mediated the reduction and a natural decapeptide capped the nanostructures. Blocking of thiol groups in the decapeptide cysteine residues caused the nanoparticles to aggregate. On interaction with arsenate (V) ions, the UV–vis spectra of the nanoparticles showed a decrease in intensity and a red-shift. Energy dispersive spectra confirmed the presence of arsenate associated with the AuNPs. Thus, by using these AuNPs, a method for sensing the toxic arsenate ions could be developed.

  4. Effects of meso-2,3-dimercaptosuccinic acid (DMSA) on the teratogenicity of sodium arsenate in mice

    SciTech Connect

    Bosque, M.A.; Domingo, J.L.; Llobet, J.M. ); Corbella, J. )

    1991-11-01

    Although the effects of arsenic on mammalian development are now well established, very few data on the protective activity of different chelators against embryotoxicity and teratogenicity of arsenic are available. Chelating agents may interact with teratogen metals to augment or ameliorate their actions. Researchers demonstrated that a single dose of 2,3-dimercaptopropanol (BAL) was capable of affording a degree of protection to arsenate exposed fetal mice. Subcutaneous treatment with 50 mg/kg of BAL 4 hr after arsenate reduced the frequency or severity of malformations compared with the effects of arsenate alone. However, BAL has several drawbacks. In recent years dimercaptosuccinic acid (DMSA) is receiving growing attention in the USA and Western Europe. Results of a number of different investigations in rodents have led to the conclusion that DMSA is much less toxic than BAL. Moreover, DMSA has been reported to be effective in inducing arsenic excretion. In the present study, the protective effects of DMSA in alleviating the embryotoxic and teratogenic effects of sodium arsenate were evaluated in mice.

  5. Genome wide analysis of DNA methylation and gene expression changes in the mouse lung following subchronic arsenate exposure

    EPA Science Inventory

    Alterations in DNA methylation have been proposed as a mechanism for the complex toxicological effects of arsenic. In this study, whole genome DNA methylation and gene expression changes were evaluated in lungs from female mice exposed for 90 days to 50 ppm arsenate (As) in drink...

  6. Arsenate and Arsenite Sorption on Magnetite: Relations to Groundwater Arsenic Treatment Using Zerovalent Iron and Natural Attenuation

    EPA Science Inventory

    Magnetite (Fe3O4) is a zerovalent iron corrosion product; it is also formed in natural soil and sediment. Sorption of arsenate (As(V)) and arsenite (As(III)) on magnetite is an important process of arsenic removal from groundwater using zerovalent iron-based permeable reactive ba...

  7. Evaluation of nitrate reductase activity in Rhizobium japonicum

    SciTech Connect

    Streeter, J.G.; DeVine, P.J.

    1983-08-01

    Nitrate reductase activity was evaluated by four approaches, using four strains of Rhizobium japonicum and 11 chlorate-resistant mutants of the four strains. It was concluded that in vitro assays with bacteria or bacteroids provide the most simple and reliable assessment of the presence or absence of nitrate reductase. Nitrite reductase activity with methyl viologen and dithionite was found, but the enzyme activity does not confound the assay of nitrate reductase. 18 references

  8. Arsenate and Selenate Scavenging by Basaluminite: Insights into the Reactivity of Aluminum Phases in Acid Mine Drainage.

    PubMed

    Carrero, Sergio; Fernandez-Martinez, Alejandro; Pérez-López, Rafael; Poulain, Agnieszka; Salas-Colera, Eduardo; Nieto, José Miguel

    2017-01-03

    Basaluminite precipitation may play an important role in the behavior of trace elements in water and sediments affected by acid mine drainage and acid sulfate soils. In this study, the affinity of basaluminite and schwertmannite for arsenate and selenate is compared, and the coordination geometries of these oxyanions in both structures are reported. Batch isotherm experiments were conducted to examine the sorption capacity of synthetic schwertmannite and basaluminite and the potential competitive effect of sulfate. In addition, synchrotron-based techniques such as differential pair distribution function (d-PDF) analysis and extended X-ray absorption fine structure (EXAFS) were used to determine the local structure of As(V) and Se(VI) complexes. The results show that oxyanion exchange with structural sulfate was the main mechanism for removal of selenate, whereas arsenate was removed by a combination of surface complexes and oxyanion exchange. The arsenate adsorption capacity of basaluminite was 2 times higher than that of schwertmannite and 3 times higher than that of selenate in both phases. The sulfate:arsenate and sulfate:selenate exchange ratios were 1:2 and 1:1, respectively. High sulfate concentrations in the solutions did not show a competitive effect on arsenate sorption capacity but had a strong impact on selenate uptake, suggesting some kind of specific interaction for arsenate. Both d-PDF and EXAFS results indicated that the bidentate binuclear inner sphere was the most probable type of ligand for arsenate on both phases and for selenate on schwertmannite, whereas selenate forms outer-sphere complexes in the aluminum octahedral interlayer of basaluminite. Overall, these results show a strong affinity of poorly crystalline aluminum phases such as basaluminite for As(V) and Se(VI) oxyanions, with adsorption capacities on the same order of magnitude as those of iron oxides. The results obtained in this study are relevant to the understanding of trace

  9. Isolation, sequence identification and tissue expression profile of two novel soybean (glycine max) genes-vestitone reductase and chalcone reductase.

    PubMed

    Liu, G Y

    2009-09-01

    The complete mRNA sequences of two soybean (glycine max) genes-vestitone reductase and chalcone reductase, were amplified using the rapid amplification of cDNA ends methods. The sequence analysis of these two genes revealed that soybean vestitone reductase gene encodes a protein of 327 amino acids which has high homology with the vestitone reductase of Medicago sativa (77%). The soybean chalcone reductase gene encodes a protein of 314 amino acids that has high homology with the chalcone reductase of kudzu vine (88%) and medicago sativa (83%). The expression profiles of the soybean vestitone reductase and chalcone reductase genes were studied and the results indicated that these two soybean genes were differentially expressed in detected soybean tissues including leaves, stems, roots, inflorescences, embryos and endosperm. Our experiment established the foundation for further research on these two soybean genes.

  10. Realgar and realgar-containing Liu-Shen-Wan are less acutely toxic than arsenite and arsenate.

    PubMed

    Liu, Jie; Liang, Shi-Xia; Lu, Yuan-Fu; Miao, Jia-Wei; Wu, Qin; Shi, Jing-Shan

    2011-03-08

    Liu-Shen-Wan (LSW) is a widely-used traditional Chinese medicine containing realgar (As(4)S(4)). Realgar has been included in many traditional medicines, and is often taken as arsenite for risk assessment in realgar-containing traditional remedies. Is realgar toxicologically similar to arsenite? Mice were orally given LSW (60 and 200mg/kg; 200mg LSW contains 27 mg realgar), realgar (30 mg/kg, equivalent to 21 mg As/kg), and the equivalent As dose as sodium arsenite (NaAsO(2)), or as arsenate (Na(2)HAsO(4)). Acute toxicity and tissue As accumulation were determined 8h later. Arsenite and arsenate increased serum alanine aminotransferase (ALT) levels, indicative of liver injury; blood urea nitrogen (BUN) was also increased by arsenite and arsenate, indicative of nephrotoxicity. No elevations of ALT and BUN were observed in LSW and realgar groups. Histopathology showed more damage in arsenite- and arsenate-treated liver and kidneys, while in realgar- and LSW- treated animals, only mild alterations were seen. Hepatic and renal As contents were dramatically increased to 6200 and 3350ng/g, respectively, after arsenite, but only increased to 260 and 180 ng/g after LSW. The expressions of arsenic-sensitive stress genes, namely metallothionein-1 and heme oxygenase-1, were increased after arsenite or arsenate by 3-10-folds, but were unaltered after LWS and realgar. Realgar and LSW are much less toxic than arsenite and arenate. The use of total As content to evaluate the safety of realgar-containing traditional medicines is not scientifically sound. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  11. Tissue distribution and urinary excretion of dimethylated arsenic and its metabolites in dimethylarsinic acid- or arsenate-treated rats

    SciTech Connect

    Adair, Blakely M.; Moore, Tanya; Conklin, Sean D.; Creed, John T.; Wolf, Douglas C.; Thomas, David J. . E-mail: thomas.david@epa.gov

    2007-07-15

    Adult female Fisher 344 rats received drinking water containing 0, 4, 40, 100, or 200 parts per million of dimethylarsinic acid or 100 parts per million of arsenate for 14 days. Urine was collected during the last 24 h of exposure. Tissues were then taken for analysis of dimethylated and trimethylated arsenicals; urines were analyzed for these arsenicals and their thiolated derivatives. In dimethylarsinic acid-treated rats, highest concentrations of dimethylated arsenic were found in blood. In lung, liver, and kidney, concentrations of dimethylated arsenic exceeded those of trimethylated species; in urinary bladder and urine, trimethylated arsenic predominated. Dimethylthioarsinic acid and trimethylarsine sulfide were present in urine of dimethylarsinic acid-treated rats. Concentrations of dimethylated arsenicals were similar in most tissues of dimethylarsinic acid- and arsenate-treated rats, including urinary bladder which is the target for dimethylarsinic acid-induced carcinogenesis in the rat. Mean concentration of dimethylated arsenic was significantly higher (P < 0.05) in urine of dimethylarsinic acid-treated rats than in arsenate-treated rats, suggesting a difference between treatment groups in the flux of dimethylated arsenic through urinary bladder. Concentrations of trimethylated arsenic concentrations were consistently higher in dimethylarsinic acid-treated rats than in arsenate-treated rats; these differences were significant (P < 0.05) in liver, urinary bladder, and urine. Concentrations of dimethylthioarsinic acid and trimethylarsine sulfide were higher in urine from dimethylarsinic acid-treated rats than from arsenate-treated rats. Dimethylarsinic acid is extensively metabolized in the rat, yielding significant concentrations of trimethylated species and of thiolated derivatives. One or more of these metabolites could be the species causing alterations of cellular function that lead to tumors in the urinary bladder.

  12. Arsenate Uptake by Calcite: Macroscopic and Spectroscopic Characterization of Adsorption and Incorporation Mechanisms

    SciTech Connect

    Alexandratos,V.; Elzinga, E.; Reeder, R.

    2007-01-01

    Batch uptake experiments and X-ray element mapping and spectroscopic techniques were used to investigate As(V) (arsenate) uptake mechanisms by calcite, including adsorption and coprecipitation. Batch sorption experiments in calcite-equilibrated suspensions (pH 8.3; PCO{sub 2} = 10{sup -3.5} atm) reveal rapid initial sorption to calcite, with sorption rate gradually decreasing with time as available sorption sites decrease. An As(V)-calcite sorption isotherm determined after 24 h equilibration exhibits Langmuir-like behavior up to As concentrations of 300 {mu}M. Maximum distribution coefficient values (K{sub d}), derived from a best fit to a Langmuir model, are {approx}190 L kg{sup -1}. Calcite single crystals grown in the presence of As(V) show well-developed rhombohedral morphology with characteristic growth hillocks on (10{bar 1}4) surfaces at low As(V) concentrations ({<=}5 {mu}M), but habit modification is evident at As(V) concentrations {>=}30 {mu}M in the form of macrostep development preferentially on the - vicinal surfaces of growth hillocks. Micro-X-ray fluorescence element mapping of (10{bar 1}4) surfaces shows preferential incorporation of As in the - vicinal faces relative to + vicinals. EXAFS fit results for both adsorption and coprecipitation samples confirm that As occurs in the 5+ oxidation state in tetrahedral coordination with oxygen, i.e., as arsenate. For adsorption samples, As(V) forms inner-sphere surface complexes via corner-sharing with Ca octahedra. As(V) coprecipitated with calcite substitutes in carbonate sites but with As off-centered, as indicated by two Ca shells, and with likely disruption of local structure. The results indicate that As(V) interacts strongly with the calcite surface, similar to often-cited analog phosphate, and uptake can occur via both adsorption and coprecipitation reactions. Therefore, calcite may be effective for partial removal of dissolved arsenate from aquatic and soil systems.

  13. Syntheses, crystal structures and characterizations of new vanadium arsenites and arsenates

    SciTech Connect

    Liu Junhui; He Zhangzhen; Kong Fang; Xu Xiang; Sun Chuanfu; Mao Jianggao

    2012-08-15

    Systematic explorations in vanadium arsenites and arsenates led to the isolation four new compounds, namely, {alpha}-(V{sup IV}O){sub 3}(As{sup III}O{sub 3}){sub 2} (1), {beta}-(V{sup IV}O){sub 3}(As{sup III}O{sub 3}){sub 2} (2), (V{sup IV}O)[V{sup IV}O(H{sub 2}O)]{sub 2}(As{sup V}O{sub 4}){sub 2} (3), V{sup III}V{sup IV}O{sub 2}(As{sup V}O{sub 4}) (4). Compounds 1, 2 and 4 were synthesized by standard solid-state reactions, and compound 3 is a vanadium arsenate dihydrate synthesized through hydrothermal reactions. Compounds 1 and 2 are isomers, and they represent the first examples of ternary inorganic vanadium(IV) arsenites. Single crystal X-ray diffraction analysis indicated that the four compounds display four different structural types. Magnetic property measurements for compound 1 indicated that it exhibits ferromagnetism with the Curie temperature T{sub c}=65 K. Thermal stability and optical properties for compounds 1 and 3 were also investigated. - Graphical abstract: Hydrothermal or solid state reactions of V{sub 2}O{sub 5} (or VO{sub 2}) and As{sub 2}O{sub 3} yielded four new ternary compounds with four different types of structures, namely, {alpha}-(VO){sub 3}(AsO{sub 3}){sub 2} (1), {beta}-(VO){sub 3}(AsO{sub 3}){sub 2} (2), (VO)[VO(H{sub 2}O)]{sub 2}(AsO{sub 4}){sub 2} (3), (VO){sub 2}(AsO{sub 4}) (4). {alpha}-(VO){sub 3}(AsO{sub 3}){sub 2} (1), {beta}-(VO){sub 3}(AsO{sub 3}){sub 2} (2) represent the first examples of ternary inorganic vanadium(IV) arsenites. Highlights: Black-Right-Pointing-Pointer Hydrothermal or solid state reactions of V{sub 2}O{sub 5} (or VO{sub 2}) and As{sub 2}O{sub 3} yielded two new arsenites. Black-Right-Pointing-Pointer They represent the first examples of ternary vanadium arsenites. Black-Right-Pointing-Pointer Two new ternary vanadium arsenates were also obtained. Black-Right-Pointing-Pointer They exhibit four different structural types.

  14. Fumarate Reductase Activity of Streptococcus faecalis

    PubMed Central

    Aue, B. J.; Diebel, R. H.

    1967-01-01

    Some characteristics of a fumarate reductase from Streptococcus faecalis are described. The enzyme had a pH optimum of 7.4; optimal activity was observed when the ionic strength of the phosphate buffer was adjusted to 0.088. The Km value of the enzyme for reduced flavin mononucleotide was 2 × 10−4 m as determined with a 26-fold preparation. In addition to fumarate, the enzyme reduced maleate and mesaconate. No succinate dehydrogenase activity was detected, but succinate did act as an inhibitor of the fumarate reductase activity. Other inhibitors were malonate, citraconate, and trans-, trans-muconate. Metal-chelating agents did not inhibit the enzyme. A limited inhibition by sulfhydryl-binding agents was observed, and the preparations were sensitive to air oxidation and storage. Glycine, alanine, histidine, and possibly lysine stimulated fumarate reductase activity in the cell-free extracts. However, growth in media supplemented with glycine did not enhance fumarate reductase activity. The enzymatic activity appears to be constitutive. PMID:4960892

  15. Post-translational Regulation of Nitrate Reductase

    USDA-ARS?s Scientific Manuscript database

    Nitrate reductase (NR) catalyzes the reduction of nitrate to nitrite, which is the first step in the nitrate assimilation pathway, but can also reduce nitrite to nitric oxide (NO), an important signaling molecule that is thought to mediate a wide array of of developmental and physiological processes...

  16. Synthesis of symmetric disulfides as potential alternative substrates for trypanothione reductase and glutathione reductase: Part 1.

    PubMed

    Jaouhari, R; Besheya, T; McKie, J H; Douglas, K T

    1995-12-01

    The synthesis of a series of symmetrical disulfides as potential substrates of trypanothione reductase and glutathione reductase was described. The key intermediate in the synthetic approach was the choice of S-(t)butylmercapto-L-cysteine (1). The spermidine ring in the native substrate, trypanothione disulfide (TSST), was replaced with 3-dimethyl-aminopropylamine (DMAPA), while theγ-Glu moiety was replaced by phenylalanyl or tryptophanyl residues. The same modifications in theγ-Glu moiety of glutathione disulfide (GSSG) were applied.

  17. Rice-arsenate interactions in hydroponics: a three-gene model for tolerance.

    PubMed

    Norton, Gareth J; Nigar, Meher; Williams, Paul N; Dasgupta, Tapash; Meharg, Andrew A; Price, Adam H

    2008-01-01

    In this study, the genetic mapping of the tolerance of root growth to 13.3 muM arsenate [As(V)] using the BalaxAzucena population is improved, and candidate genes for further study are identified. A remarkable three-gene model of tolerance is advanced, which appears to involve epistatic interaction between three major genes, two on chromosome 6 and one on chromosome 10. Any combination of two of these genes inherited from the tolerant parent leads to the plant having tolerance. Lists of potential positional candidate genes are presented. These are then refined using whole genome transcriptomics data and bioinformatics. Physiological evidence is also provided that genes related to phosphate transport are unlikely to be behind the genetic loci conferring tolerance. These results offer testable hypotheses for genes related to As(V) tolerance that might offer strategies for mitigating arsenic (As) accumulation in consumed rice.

  18. Chemistry and toxicology of building timbers pressure-treated with chromated copper arsenate: a review.

    PubMed

    Katz, Sidney A; Salem, Harry

    2005-01-01

    A recent agreement between the United States Environmental Protection Agency (USEPA) and the wood-treating industry will result in a phase-out of building timbers preserved with chromated copper arsenate (CCA). This agreement was motivated by a desire to reduce exposure to arsenic in the production, utilization and disposal of such material. The leaching of chromium, copper and arsenic from CCA-treated building timbers into water and soil and the subsequent environmental effects have been reviewed, as have the laboratory and epidemiological studies on the toxicology of CCA-treated building timbers. The benefits of the phase-out agreement are questionable because much arsenic will remain in the environment, and the alternatives to wood preservation with CCA are not without environmental consequences.

  19. Arsenite and arsenate removal from wastewater using cationic polymer-modified waste tyre rubber.

    PubMed

    Imyim, Apichat; Sirithaweesit, Thitayati; Ruangpornvisuti, Vithaya

    2016-01-15

    Waste tyre rubber (WTR) granulate was modified with a cationic polymer, poly(3-acrylamidopropyl)trimethylammonium chloride (p(APTMACl)). The resulting WTR/p(APTMACl) was utilized for the adsorption of arsenite, As(III) and arsenate, As(V) from aqueous medium in both batch and column methods. The level of adsorption increased gradually with increasing monomer concentration and contact time. The adsorption behavior obeyed the Freundlich model, and the rate of adsorption could be predicted by employing the pseudo-second order model. In the column method, As(V) could be adsorbed onto the sorbent more effectively than As(III). Remarkable desorption of As(III) and As(V) (99 and 92%, respectively) from the adsorbent was achieved using 0.10 M HCl as eluent. An approach of evaluation of adsorption capacity uncertainty is proposed.

  20. Rice–arsenate interactions in hydroponics: a three-gene model for tolerance

    PubMed Central

    Norton, Gareth J.; Nigar, Meher; Dasgupta, Tapash; Meharg, Andrew A.; Price, Adam H.

    2008-01-01

    In this study, the genetic mapping of the tolerance of root growth to 13.3 μM arsenate [As(V)] using the Bala×Azucena population is improved, and candidate genes for further study are identified. A remarkable three-gene model of tolerance is advanced, which appears to involve epistatic interaction between three major genes, two on chromosome 6 and one on chromosome 10. Any combination of two of these genes inherited from the tolerant parent leads to the plant having tolerance. Lists of potential positional candidate genes are presented. These are then refined using whole genome transcriptomics data and bioinformatics. Physiological evidence is also provided that genes related to phosphate transport are unlikely to be behind the genetic loci conferring tolerance. These results offer testable hypotheses for genes related to As(V) tolerance that might offer strategies for mitigating arsenic (As) accumulation in consumed rice. PMID:18453529

  1. Amino acid assisted templating synthesis of hierarchical zeolitic imidazolate framework-8 for efficient arsenate removal.

    PubMed

    Wu, Yi-nan; Zhou, Meimei; Zhang, Bingru; Wu, Baozhen; Li, Jie; Qiao, Junlian; Guan, Xiaohong; Li, Fengting

    2014-01-21

    We report the strategy of using the cationic surfactant cetyltrimethylammonium bromide (CTAB) and amino acid L-histidine (His) as co-templates to produce hierarchical ZIF-8 in an aqueous system at room temperature. The hierarchical ZIF-8 had both meso- and microporous structure, resulting in a high mesopore volume as well as specific surface area which can be controlled by the synthesis conditions. We put forward the hypothesis for the formation of a mesoporous structure and the enhancement of the porosity of ZIF-8 that the histidine plays a key role on the stabilization of CTAB micelles and avoiding the production of unexpected by-products therefore promotes the fabrication of pure phase ZIF-8 containing the mesopores interconnected with micropores. The prepared hierarchical ZIF-8 exhibited an excellent performance as a new kind of porous absorbent for efficient removal of the toxic arsenate.

  2. Expression of denitrification enzymes in response to the dissolved oxygen level and respiratory substrate in continuous culture of Pseudomonas stutzeri.

    PubMed Central

    Körner, H; Zumft, W G

    1989-01-01

    The onset and cessation of the synthesis of denitrification enzymes of Pseudomonas stutzeri were investigated by using continuous culture and defined dissolved oxygen levels covering the full range of transition from air saturation to complete anaerobiosis. Expression of nitrate reductase, nitrite reductase (cytochrome cd1), and N2O reductase was controlled by discrete oxygen levels and by the nature of the nitrogenous oxide available for respiration. N2O reductase was synthesized constitutively at a low level; for enhanced expression, oxygen concentrations were required to decrease below 5 mg of O2 per liter. The threshold values for synthesis of nitrate reductase and cytochrome cd1 in the presence of nitrate were ca. 5 and ca. 2.5 mg of O2 per liter, respectively. With nitrous oxide as the respiratory substrate, nitrite reductase was again the most sensitive to oxygen concentration; however, thresholds for all denitrification enzymes shifted to lower oxygen levels. Whereas the presence of nitrate resulted in maximum expression and nearly uniform induction of all reductases, nitrite and nitrous oxide stimulated preferably the respective enzyme catalyzing reduction. In the absence of a nitrogenous oxide, anaerobiosis did not induce enzyme synthesis to any significant degree. The accumulation of nitrite seen during both the aerobic-anaerobic and anaerobic-aerobic transition phases was caused by the differences in onset or cessation of synthesis of nitrate and nitrite reductases and an inhibitory effect of nitrate on nitrite reduction. Images PMID:2764573

  3. Purification and characterization of the membrane-bound nitrate reductase isoenzymes of Bradyrhizobium japonicum.

    PubMed

    Fernández-López, M; Olivares, J; Bedmar, E J

    1996-08-19

    Two respiratory membrane-bound nitrate reductase (NR) isoenzymes, NRI and NRII, have been purified for the first time from one single microorganism. Triton X-100-solubilized NRs were purified by a three-step procedure of differential centrifugation, Q-Sepharose chromatography, and gel filtration on Sephacryl S-300. Both isoenzymes were purified to homogeneity by the criteria of NR activity staining in polyacrylamide gels run under non-denaturating conditions and coincident staining of the protein band by silver nitrate. NRI is composed of three subunits of 116 kDa, 68 kDa, and 56 kDa, whereas NRII is composed of four subunits of 116 kDa, 68 kDa, 59 kDa, and 56 kDa. The 116-kDa subunit of NRI and the 59-kDa subunit of NRII exhibited immunological cross-reactivity with the respiratory NR of Pseudomonas stutzeri strain ZoBell.

  4. Bacterial dissimilatory reduction of arsenate and sulfate in meromictic Mono Lake, California

    USGS Publications Warehouse

    Oremland, R.S.; Dowdle, P.R.; Hoeft, S.; Sharp, J.O.; Schaefer, J.K.; Miller, L.G.; Switzer, Blum J.; Smith, R.L.; Bloom, N.S.; Wallschlaeger, D.

    2000-01-01

    The stratified (meromictic) water column of alkaline and hypersaline Mono Lake, California, contains high concentrations of dissolved inorganic arsenic (~200 ??mol/L). Arsenic speciation changes from arsenate [As (V)] to arsenite [As (III)] with the transition from oxic surface waters (misolimnion) to anoxic bottom waters (monimolimnion). A radioassay was devised to measure the reduction of 73As (V) to 73As (III) and tested using cell suspensions of the As (V)-respiring Bacillus selenitireducens, which completely reduced the 73As (V). In field experiments, no significant activity was noted in the aerobic mixolimnion waters, but reduction of 73As (V) to 73As (III) was observed in all the monimolimnion samples. Rate constants ranged from 0.02 to 0.3/day, with the highest values in the samples from the deepest depths (24 and 28 m). The highest activities occurred between 18 and 21 m, where As (V) abundant (rate, ~5.9 ??mol/L per day). In contrast, sulfate reduction occurred at depths below 21 m, with the highest rates attained at 28 m (rate, ~2.3 ??mol/L per day). These results indicate that As (V) ranks second in importance, after sulfate, as an electron acceptor for anaerobic bacterial respiration in the water column. Annual arsenate respiration may mineralize as much as 14.2% of the pelagic photosynthetic carbon fixed during meromixis. When combined with sulfate-reduction data, anaerobic respiration in the water column can mineralize 32-55% of this primary production. As lakes of this type approach salt saturation, As (V) can become the most important electron acceptor for the biogeochemical cycling of carbon. Copyright (C) 2000 Elsevier Science Ltd.

  5. Dissolved Calcium and Magnesium Carbonates Promote Arsenate Release From Ferrihydrite in Flow Systems

    NASA Astrophysics Data System (ADS)

    Saalfield, S. L.; Bostick, B. C.

    2007-12-01

    Field data from water systems around the world have shown that arsenic can reach toxic concentrations in dynamic groundwater systems. This is generally in contrast to analogous static systems at circumneutral pH, where arsenic is strongly retained by sorption to iron (hydr)oxides. Our research examines the effect of calcium and magnesium carbonates on As(V) mobility. In both dynamic flow and static experiments, arsenate was pre- sorbed to poorly crystalline iron hydroxides (1-10% sorption capacity), with varying aqueous compositions including calcium, magnesium, carbonate, sulfate, lactate, and other common groundwater species (pH 7.5-8). Thus we investigated how the dissolution of common carbonate minerals, specifically CaCO3 and MgCO3, affect arsenic behavior in the context of groundwater solutions. Under static (batch) conditions, no measurable arsenic (<10 μg/L) is released into solutions containing alkaline earth metals (AEMs) and carbonates. When elevated concentrations of AEMs and carbonate are introduced by dynamic flow, however, arsenic is mobilized at up to 500 μg/L, releasing significant proportions the total arsenic present. This is only the case when both of these species are present; with other common ion pairs, little to no arsenic is released. These results indicate that arsenate adsorption is kinetically controlled under flow conditions, resulting in very different mobility relative to otherwise equivalent static systems. Furthermore, the combination of alkaline earth metals and carbonates promotes As(V) mobility in column-based systems. We propose that these phenomena indicate a combination of physical and chemical effects by which diffusion limitation becomes dominant in limiting arsenic sorption in flow systems. Many carbonate-buffered aquifers, as well as those undergoing rapid mineralization of organic matter, could be affected by these processes of AEM-carbonate-limited sorption and increased arsenic mobility.

  6. Gallium Arsenate Dihydrate under Pressure: Elastic Properties, Compression Mechanism, and Hydrogen Bonding.

    PubMed

    Spencer, Elinor C; Soghomonian, Victoria; Ross, Nancy L

    2015-08-03

    Gallium arsenate dihydrate is a member of a class of isostructural compounds, with the general formula M(3+)AsO4·2H2O (M(3+) = Fe, Al, In, or Ga), which are being considered as potential solid-state storage media for the sequestration of toxic arsenic cations. We report the first high-pressure structural analysis of a metal arsenate dihydrate, namely, GaAsO4·2H2O. This compound crystallizes in the orthorhombic space group Pbca with Z = 8. Accurate unit cell parameters as a function of pressure were obtained by high-pressure single-crystal X-ray diffraction, and a bulk modulus of 51.1(3) GPa for GaAsO4·2H2O was determined from a third-order Birch-Murnaghan equation of state fit to the P-V data. Assessment of the pressure dependencies of the unit cell lengths showed that the compressibility of the structure along the axial directions increases in the order of [010] < [100] < [001]. This order was found to correlate well with the proposed compression mechanism for GaAsO4·2H2O, which involves deformation of the internal channel void spaces of the polyhedral helices that lie parallel to the [010] direction, and increased distortion of the GaO6 octahedra. The findings of the high-pressure diffraction experiment were further supported by the results from variable-pressure Raman analysis of GaAsO4·2H2O. Moreover, we propose a revised and more complex model for the hydrogen-bonding scheme in GaAsO4·2H2O, and on the basis of this revision, we reassigned the peaks in the OH stretching regions of previously published Raman spectra of this compound.

  7. Can arsenates replace phosphates in natural biochemical processes? A computational study.

    PubMed

    Jissy, A K; Datta, Ayan

    2013-07-18

    A bacterial strain, GFAJ-1 was recently proposed to be substituting arsenic for phosphorus to sustain its growth. We have performed theoretical calculations for analyzing this controversial hypothesis by examining the addition of phosphate to ribose and glucose. Dispersion corrected Density Functional Theory (DFT) calculations in small molecules and QM/MM calculations on clusters derived from crystal structure are performed on structures involved in phosphorylation, considering both phosphates and arsenates. The exothermicity as well as the activation barriers for phosphate and arsenate transfer were examined. Quantum mechanical studies reveal that the relative stability of the products decrease marginally with successive substitution of P with As. However, simultaneously, the transition state barriers decrease with P replacement. This indicates that, kinetically, addition of As is more facile. Pseudorotation barriers for the pentavalent intermediates formed during the nucleophilic attack are also analyzed. A monotonic increase in barriers is observed for pseudorotation with the successive replacement of phosphorus with arsenic in methyl-DHP. A glucokinase crystal structure was chosen to construct a model system for QM/MM calculations. Free energy of the reaction (ΔG) reduces by less than 2.0 kcal/mol and the activation barrier (ΔG(‡)) decreases by ∼1 kcal/mol on arsenic incorporation. Thus, both DFT and QM/MM calculations show that arsenic can readily substitute phosphorus in key biomolecules. Secondary kinetic isotope effects for phosphorylation mechanism obtained by QM/MM calculations are also reported. The solvent kinetic isotopic effects (SKIE) for ATP and ATP (As) are calculated to be 5.81 and 4.73, respectively. A difference of ∼1.0 in SKIE suggests that it should be possible to experimentally determine the As-phosphorylation process.

  8. Arsenate sorption by hydrous ferric oxide incorporated onto granular activated carbon with phenol formaldehyde resins coating.

    PubMed

    Zhuang, J M; Hobenshield, E; Walsh, T

    2008-04-01

    A simple and effective method was developed using phenol formaldehyde (PF) resins to immobilize hydrous ferric oxide (HFO) onto granular activated carbon (GAC). The resulting sorbent possesses advantages for both the ferric oxide and the GAC, such as a great As-affinity of ferric oxide, large surface area of GAC, and enhanced physical strength. The studies showed that within one hour this sorbent was able to remove 85% of As(V) from water containing an initial As(V) concentration of 1.74 mg l(-1). The As(V) adsorption onto the sorbent was found to follow a pseudo-second order kinetics model. The adsorption isotherms were interpreted in terms of the Langmuir and Freundlich models. The equilibrium data fitted very well to both models. Column tests showed that this sorbent was able to achieve residual concentrations of As(V) in a range of 0.1-2.0 microg l(-1) while continuously treating about 180 bed volume (BV, 130 ml-BV) of arsenate water with an initial As(V) concentration of 1886 microg l(-1) at a filtration rate of 13.5 ml min(-1), i.e., an empty bed contact time (EBCT) of 9.6 min and a gram sorbent contact time (GSCT) of 0.15 min. After passing 635 BV of arsenate water, the exhausted sorbent was then tested by the Toxicity Characteristic Leaching Procedure (TCLP, US EPA Method 1311) test, and classified as non-hazardous for disposal. Hence, this HFO-PF-coated GAC has the capability to remove As(V) from industrial wastewater containing As(V) levels of about 2 mg l(-1).

  9. Arsenate adsorption structures on aluminum oxide and phyllosilicate mineral surfaces in smelter-impacted soils.

    PubMed

    Beaulieu, Brett T; Savage, Kaye S

    2005-05-15

    A clearer understanding of arsenic (As) retention and transport in forest soils impacted by copper smelter emissions may reduce risks to human health and provide insight into As behavior in the vadose zone. On Vashon-Maury Island in Puget Sound, As is predominantly associated with the fine (< 63 microm) fraction of surficial soils. X-ray diffraction of oriented samples from the < 2 microm size fraction indicate that clinochlore isthe dominant phyllosilicate. X-ray absorption spectroscopy (XAS) was employed to examine As oxidation state and local coordination environment in impacted soil samples. Arsenic is present as As(V) in tetrahedral coordination with oxygen, associated with aluminum (Al) octahedra in bidentate binuclear (bridging) structures with As-Al distances of 3.15 - 3.16 angstroms. Including multiple scattering (MS) paths derived from the arsenate tetrahedron in esperanzaite significantly improved the match between XAS fine structure (EXAFS) data and models generated from theoretical phase and amplitude functions. The data are interpreted to indicate arsenate adsorption onto poorly crystalline aluminum oxyhydroxides and/or the edges of clinochlore interlayer hydroxyl sheets with constrained geometries causing MS to be important This implies that As initially released from the smelter as particulate As(III) and As(V) oxides was oxidized, dissolved, and adsorbed onto soil minerals and colloids; no evidence for relic arsenic oxide was observed. Physical transport of arsenic oxide particles and As adsorbed on soil colloids may account for limited downward migration of As within the soil column. The oxidizing and mildly acidic pH conditions in the upper vadose zone promote stable sorption complexes; barring substantial changes in soil chemistry, As is not expected to experience significant mobilization.

  10. Bio-reduction of arsenate using a hydrogen-based membrane biofilm reactor.

    PubMed

    Chung, Jinwook; Li, Xiaohao; Rittmann, Bruce E

    2006-09-01

    Arsenate (As(V)) is a carcinogen and a significant problem in groundwater in many parts of the world. Since As(III) is generally more mobile and more toxic than As(V), the reduction of As(V) to As(III) is not a conventional treatment goal. However, reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation or complexation with sulfide or by adsorption to Fe(II)-based solids. A promising approach for reducing oxidized contaminants is the H2-based membrane biofilm reactor (MBfR). In the case of arsenate, the MBfR allows bio-reduction of As(V) to As(III) and sulfate to sulfide, thereby giving the potential for As removal, such as by precipitation of As2S3(s) or formation of Fe(II)-based solids. When As(V) was added to a denitrifying MBfR, As(V) was reduced immediately to As(III). Decreasing the influent sulfate loading increased As(V) reduction for a fixed H2 pressure. A series of short-term experiments elaborated on how As(V) loading, nitrate and sulfate loadings, and H2 pressure controlled As(V) reduction. Lower nitrate loading and increased As(V) loading increased the extent of As(V) reduction, but increased H2 pressure did not increase As(V) reduction. As(V) reduction was sensitive to sulfate loading, with a maximum As(V)-removal percentage and flux with no addition of sulfate. As(III) could be precipitated with sulfide or adsorbed to Fe(II) solids, which was verified by scanning electron microscopy and energy dispersive X-ray analysis.

  11. The Interaction of Respiration and Photosynthesis in Induction of Nitrate Reductase Activity 1

    PubMed Central

    Aslam, M.; Huffaker, R. C.; Travis, R. L.

    1973-01-01

    The respiration and photosynthesis requirement for induction and maintenance of nitrate reductase activity was determined on leaves of Hordeum vulgare L. In this induction, glucose substituted for light in both dark-grown and carbohydrate-depleted green leaves. Oxygen appeared to be required for induction in all cases studied. In light and under N2, 3-(3,4-dichlorophenyl)-1,1-dimethylurea completely inhibited induction, presumably by inhibiting the production of O2, Hence, under N2 the leaves appeared to utilize both the O2 produced by photosynthesis and the CO2 produced by respiration. CO2 fixation can then produce both photosynthate to drive the induction and terminal electron acceptors to allow photosynthetic electron flow. This possibility was further suggested by the observation that CO2 was an absolute requirement for induction in carbohydrate-depleted barley leaves. Results obtained with respiratory inhibitors also indicated that respiration drove the induction of nitrate reductase. Exogenously supplied glucose also substantially slowed the loss of nitrate reductase that occurred when barley leaves were placed in darkness. It is presumed that glucose allowed the synthetic or activation phase of the induction to proceed more rapidly. Our results support the hypothesis that one of the main effects of light may be to supply photosynthate to support respiration, which then drives the induction process. PMID:16658514

  12. Control of dihydrofolate reductase messenger ribonucleic acid production

    SciTech Connect

    Leys, E.J.; Kellems, R.E.

    1981-11-01

    The authors used methotrexate-resistant mouse cells in which dihydrofolate reductase levels are approximately 500 times normal to study the effect of growth stimulation on dihydrofolate reductase gene expression. As a result of growth stimulation, the relative rate of dihydrofolate reductase protein synthesis increased threefold, reaching a maximum between 25 and 30 h after stimulation. The relative rate of dihydrofolate reductase messenger ribonucleic acid production (i.e., the appearance of dihydrofolate reductase messenger ribonucleic acid in the cytoplasm) increased threefold after growth stimulation and was accompanied by a corresponding increase in the relative steady-state level of dihydrofolate reductase ribonucleic acid in the nucleus. However, the increase in the nuclear level of dihydrofolate reductase ribonucleic acid was not accompanied by a significant increase in the relative rate of transcription of the dihydrofolate reductase genes. These data indicated that the relative rate of appearance of dihydrofolate reductase messenger ribonucleic acid in the cytoplasm depends on the relative stability of the dihydrofolate reductase ribonucleic acid sequences in the nucleus and is not dependent on the relative rate of transcription of the dihydrofolate reductase genes.

  13. Augmentation of CFTR maturation by S-nitrosoglutathione reductase

    PubMed Central

    Sawczak, Victoria; Zaidi, Atiya; Butler, Maya; Bennett, Deric; Getsy, Paulina; Zeinomar, Maryam; Greenberg, Zivi; Forbes, Michael; Rehman, Shagufta; Jyothikumar, Vinod; DeRonde, Kim; Sattar, Abdus; Smith, Laura; Corey, Deborah; Straub, Adam; Sun, Fei; Palmer, Lisa; Periasamy, Ammasi; Randell, Scott; Kelley, Thomas J.; Lewis, Stephen J.

    2015-01-01

    S-nitrosoglutathione (GSNO) reductase regulates novel endogenous S-nitrosothiol signaling pathways, and mice deficient in GSNO reductase are protected from airways hyperreactivity. S-nitrosothiols are present in the airway, and patients with cystic fibrosis (CF) tend to have low S-nitrosothiol levels that may be attributed to upregulation of GSNO reductase activity. The present study demonstrates that 1) GSNO reductase activity is increased in the cystic fibrosis bronchial epithelial (CFBE41o−) cells expressing mutant F508del-cystic fibrosis transmembrane regulator (CFTR) compared with the wild-type CFBE41o− cells, 2) GSNO reductase expression level is increased in the primary human bronchial epithelial cells expressing mutant F508del-CFTR compared with the wild-type cells, 3) GSNO reductase colocalizes with cochaperone Hsp70/Hsp90 organizing protein (Hop; Stip1) in human airway epithelial cells, 4) GSNO reductase knockdown with siRNA increases the expression and maturation of CFTR and decreases Stip1 expression in human airway epithelial cells, 5) increased levels of GSNO reductase cause a decrease in maturation of CFTR, and 6) a GSNO reductase inhibitor effectively reverses the effects of GSNO reductase on CFTR maturation. These studies provide a novel approach to define the subcellular location of the interactions between Stip1 and GSNO reductase and the role of S-nitrosothiols in these interactions. PMID:26637637

  14. Atypical features of Thermus thermophilus succinate:quinone reductase.

    PubMed

    Kolaj-Robin, Olga; Noor, Mohamed R; O'Kane, Sarah R; Baymann, Frauke; Soulimane, Tewfik

    2013-01-01

    The Thermus thermophilus succinate:quinone reductase (SQR), serving as the respiratory complex II, has been homologously produced under the control of a constitutive promoter and subsequently purified. The detailed biochemical characterization of the resulting wild type (wt-rcII) and His-tagged (rcII-His(8)-SdhB and rcII-SdhB-His(6)) complex II variants showed the same properties as the native enzyme with respect to the subunit composition, redox cofactor content and sensitivity to the inhibitors malonate, oxaloacetate, 3-nitropropionic acid and nonyl-4-hydroxyquinoline-N-oxide (NQNO). The position of the His-tag determined whether the enzyme retained its native trimeric conformation or whether it was present in a monomeric form. Only the trimer exhibited positive cooperativity at high temperatures. The EPR signal of the [2Fe-2S] cluster was sensitive to the presence of substrate and showed an increased rhombicity in the presence of succinate in the native and in all recombinant forms of the enzyme. The detailed analysis of the shape of this signal as a function of pH, substrate concentration and in the presence of various inhibitors and quinones is presented, leading to a model for the molecular mechanism that underlies the influence of succinate on the rhombicity of the EPR signal of the proximal iron-sulfur cluster.

  15. The Distribution of Arsenate and Arsenite in Shoots and Roots of Holcus lanatus is Influenced by Arsenic Tolerance and Arsenate and Phosphate Supply

    PubMed Central

    Quaghebeur, Mieke; Rengel, Zdenko

    2003-01-01

    The recent discovery that phytochelatins are important for arsenic (As) detoxification in terrestrial plants results in the necessity to understand As speciation and metabolism in plant material. A hydroponic study was therefore conducted to examine the effects of different levels of phosphate and arsenate [As(V)] on As speciation and distribution in tolerant and non-tolerant clones of Holcus lanatus. Speciation of As in tissue (using high-performance liquid chromatography-inductively coupled plasma mass spectrometry) revealed that the predominant species present were the inorganic As species (As(V) and arsenite [As(III)]), although small levels (<1%) of organic As species (dimethylarsinic acid and monomethylarsonic acid) were detected in shoot material. In roots, the proportion of total As present as As(III) generally increased with increasing levels of As(V) in the nutrient solution, whereas in shoots, the proportion of total As present as As(III) generally decreased with increasing levels of As(V). H. lanatus plants growing in the high-phosphorus (P) (100 μm) solution contained a higher proportion of As(V) (with regard to total As) in both roots and shoots than plants supplied with low P (10 μm); in addition, tolerant clones generally contained a higher proportion of As(V) with regard to total As than non-tolerant clones. The study further revealed that As(V) can be reduced to As(III) in both roots and shoots. Although the reduction capacity was limited, the reduction was closely regulated by As influx for all treatments. The results therefore provide a new understanding about As metabolism in H. lanatus. PMID:12857839

  16. The distribution of arsenate and arsenite in shoots and roots of Holcus lanatus is influenced by arsenic tolerance and arsenate and phosphate supply.

    PubMed

    Quaghebeur, Mieke; Rengel, Zdenko

    2003-07-01

    The recent discovery that phytochelatins are important for arsenic (As) detoxification in terrestrial plants results in the necessity to understand As speciation and metabolism in plant material. A hydroponic study was therefore conducted to examine the effects of different levels of phosphate and arsenate [As(V)] on As speciation and distribution in tolerant and non-tolerant clones of Holcus lanatus. Speciation of As in tissue (using high-performance liquid chromatography-inductively coupled plasma mass spectrometry) revealed that the predominant species present were the inorganic As species (As(V) and arsenite [As(III)]), although small levels (<1%) of organic As species (dimethylarsinic acid and monomethylarsonic acid) were detected in shoot material. In roots, the proportion of total As present as As(III) generally increased with increasing levels of As(V) in the nutrient solution, whereas in shoots, the proportion of total As present as As(III) generally decreased with increasing levels of As(V). H. lanatus plants growing in the high-phosphorus (P) (100 micro M) solution contained a higher proportion of As(V) (with regard to total As) in both roots and shoots than plants supplied with low P (10 micro M); in addition, tolerant clones generally contained a higher proportion of As(V) with regard to total As than non-tolerant clones. The study further revealed that As(V) can be reduced to As(III) in both roots and shoots. Although the reduction capacity was limited, the reduction was closely regulated by As influx for all treatments. The results therefore provide a new understanding about As metabolism in H. lanatus.

  17. Lungs and Respiratory System

    MedlinePlus

    ... bad cough to get rid of the mucus. Common cold . Colds are caused by over 200 different viruses ... cause inflammation in the upper respiratory tract. The common cold is the most common respiratory infection. Symptoms may ...

  18. Lungs and Respiratory System

    MedlinePlus

    ... chronic bronchitis in teens. previous continue Other Conditions Common cold . Caused by more than 200 different viruses that cause inflammation in the upper respiratory tract, the common cold is the most common respiratory infection. Symptoms may ...

  19. Avian respiratory system disorders

    USGS Publications Warehouse

    Olsen, G.H.

    1989-01-01

    Diagnosing and treating respiratory diseases in avian species requires a basic knowledge about the anatomy and physiology of this system in birds. Differences between mammalian and avian respiratory system function, diagnosis, and treatment are highlighted.

  20. MSFC Respiratory Protection Services

    NASA Technical Reports Server (NTRS)

    CoVan, James P.

    1999-01-01

    An overview of the Marshall Space Flight Center Respiratory Protection program is provided in this poster display. Respiratory protection personnel, building, facilities, equipment, customers, maintenance and operational activities, and Dynatech fit testing details are described and illustrated.

  1. Quantification of the effects of organic and carbonate buffers on arsenate and phosphate adsorption on a goethite-based granular porous adsorbent.

    PubMed

    Kanematsu, Masakazu; Young, Thomas M; Fukushi, Keisuke; Sverjensky, Dimitri A; Green, Peter G; Darby, Jeannie L

    2011-01-15

    Interest in the development of oxide-based materials for arsenate removal has led to a variety of experimental methods and conditions for determining arsenate adsorption isotherms, which hinders comparative evaluation of their adsorptive capacities. Here, we systematically investigate the effects of buffer (HEPES or carbonate), adsorbent dose, and solution pH on arsenate and phosphate adsorption isotherms for a previously well characterized goethite-based adsorbent (Bayoxide E33 (E33)). All adsorption isotherms obtained at different adsorbate/adsorbent concentrations were identical when 1 mM of HEPES (96 mg C/L) was used as a buffer. At low aqueous arsenate and phosphate concentration (∼1.3 μM), however, adsorption isotherms obtained using 10 mM of NaHCO(3) buffer, which is a reasonable carbonate concentration in groundwater, are significantly different from those obtained without buffer or with HEPES. The carbonate competitive effects were analyzed using the extended triple layer model (ETLM) with the adsorption equilibrium constant of carbonate calibrated using independent published carbonate adsorption data for pure goethite taking into consideration the different surface properties. The successful ETLM calculations of arsenate adsorption isotherms for E33 under various conditions allowed quantitative comparison of the arsenate adsorption capacity between E33 and other major adsorbents initially tested under varied experimental conditions in the literature.

  2. The removal of sulphate from mine water by precipitation as ettringite and the utilisation of the precipitate as a sorbent for arsenate removal.

    PubMed

    Tolonen, Emma-Tuulia; Hu, Tao; Rämö, Jaakko; Lassi, Ulla

    2016-10-01

    The aim of this research was to investigate sulphate removal from mine water by precipitation as ettringite (Ca6Al2(SO4)3(OH)12·26H2O) and the utilisation of the precipitate as a sorbent for arsenate removal. The mine water sulphate concentration was reduced by 85-90% from the initial 1400 mg/L during ettringite precipitation depending on the treatment method. The precipitation conditions were also simulated with MINEQL + software, and the computational results were compared with the experimental results. The precipitated solids were characterised with X-ray diffraction and a scanning electron microscope. The precipitated solids were tested as sorbents for arsenate removal from the model solution. The arsenic(V) model solution concentration reduced 86-96% from the initial 1.5 mg/L with a 1 g/L sorbent dosage. The effect of initial arsenate concentration on the sorption of arsenate on the precipitate was studied and Langmuir, Freundlich, and Langmuir-Freundlich sorption isotherm models were fitted to the experimental data. The maximum arsenate sorption capacity (qm = 11.2 ± 4.7 mg/g) of the precipitate was obtained from the Langmuir-Freundlich isotherm. The results indicate that the precipitate produced during sulphate removal from mine water by precipitation as ettringite could be further used as a sorbent for arsenate removal.

  3. FRUCTOSE-6-PHOSPHATE REDUCTASE FROM SALMONELLA GALLINARUM

    PubMed Central

    Zancan, Glaci T.; Bacila, Metry

    1964-01-01

    Zancan, Glaci T. (Universidade do Paraná, Curitiba, Paraná, Brazil), and Metry Bacila. Fructose-6-phosphate reductase from Salmonella gallinarum. J. Bacteriol. 87:614–618. 1964.—A fructose-6-phosphate reductase present in cell-free extracts of Salmonella gallinarum was purified approximately 42 times. The optimal pH for this enzyme is 8.0. The enzyme is specific for fructose-6-phosphate and reduced nicotinamide adenine dinucleotide (NADH). The dissociation constants are 1.78 × 10−4m for fructose-6-phosphate and 8.3 × 10−5m for NADH. The Q10, reaction order, and equilibrium constant were determined. The enzyme is sensitive to p-chloromercuribenzoic acid, but not to o-iodosobenzoic acid nor to N-ethylmaleimide. PMID:14127579

  4. Characterization of human platelet glutathione reductase.

    PubMed

    Moroff, G; Kosow, D P

    1978-12-08

    Glutathione reductase (NAD(P)h:oxidized glutathione oxidoreductase, EC 1.6.4.2) has been purified 1000-fold from the cytoplasmic fraction of human platelets. Salts, including the heretofore unreported effect of sodium citrate, activate the NADPH-dependent reduction of oxidized glutathione. Sodium citrate and monovalent salt activation appears to involve multiple sites having different binding affinities. At sub-saturating sodium phosphate, non-linear double reciprocal plots indicative of substrate activation by oxidized glutathione were observed. Initial velocity double reciprocal plots at sub-saturating and saturating concentrations of phosphate generate a family of converging lines. NADP+ is a partial inhibitor, indicating that the reduction of oxidized glutathione can proceed by more than one pathway. FMN, FAD, and riboflavin inhibit platelet glutathione reductase by influencing only the V while nitrofurantoin inhibition is associated with an increase Koxidized glutathione and a decreased V.

  5. Hydrogen sulfide alleviates toxic effects of arsenate in pea seedlings through up-regulation of the ascorbate-glutathione cycle: Possible involvement of nitric oxide.

    PubMed

    Singh, Vijay Pratap; Singh, Samiksha; Kumar, Jitendra; Prasad, Sheo Mohan

    2015-06-01

    In plants, hydrogen sulfide (H2S) is an emerging novel signaling molecule that is involved in growth regulation and abiotic stress responses. However, little is known about its role in the regulation of arsenate (As(V)) toxicity. Therefore, hydroponic experiments were conducted to investigate whether sodium hydrosulfide (NaHS; a source of H2S) is involved in the regulation of As(V) toxicity in pea seedlings. Results showed that As(V) caused decreases in growth, photosynthesis (measured as chlorophyll fluorescence) and nitrogen content, which was accompanied by the accumulation of As. As(V) treatment also reduced the activities of cysteine desulfhydrase and nitrate reductase, and contents of H2S and nitric oxide (NO). However, addition of NaHS ameliorated As(V) toxicity in pea seedlings, which coincided with the increased contents of H2S and NO. The cysteine level was higher under As(V) treatment in comparison to all other treatments (As-free; NaHS; As(V)+NaHS). The content of reactive oxygen species (ROS) and damage to lipids, proteins and membranes increased by As(V) while NaHS alleviated these effects. Enzymes of the ascorbate-glutathione cycle (AsA-GSH cycle) showed inhibition of their activities following As(V) treatment while their activities were increased by application of NaHS. The redox status of ascorbate and glutathione was disturbed by As(V) as indicated by a steep decline in their reduced/oxidized ratios. However, simultaneous NaHS application restored the redox status of the ascorbate and glutathione pools. The results of this study demonstrated that H2S and NO might both be involved in reducing the accumulation of As and triggering up-regulation of the AsA-GSH cycle to counterbalance ROS-mediated damage to macromolecules. Furthermore, the results suggest a crucial role of H2S in plant priming, and in particular for pea seedlings in mitigating As(V) stress. Copyright © 2015 Elsevier GmbH. All rights reserved.

  6. Characterization of erythrose reductases from filamentous fungi

    PubMed Central

    2013-01-01

    Proteins with putative erythrose reductase activity have been identified in the filamentous fungi Trichoderma reesei, Aspergillus niger, and Fusarium graminearum by in silico analysis. The proteins found in T. reesei and A. niger had earlier been characterized as glycerol dehydrogenase and aldehyde reductase, respectively. Corresponding genes from all three fungi were cloned, heterologously expressed in Escherichia coli, and purified. Subsequently, they were used to establish optimal enzyme assay conditions. All three enzymes strictly require NADPH as cofactor, whereas with NADH no activity could be observed. The enzymatic characterization of the three enzymes using ten substrates revealed high substrate specificity and activity with D-erythrose and D-threose. The enzymes from T. reesei and A. niger herein showed comparable activities, whereas the one from F. graminearum reached only about a tenth of it for all tested substrates. In order to proof in vivo the proposed enzyme function, we overexpressed the erythrose reductase-encoding gene in T. reesei. An increased production of erythritol by the recombinant strain compared to the parental strain could be detected. PMID:23924507

  7. Lungs and Respiratory System

    MedlinePlus

    ... A Week of Healthy Breakfasts Shyness Lungs and Respiratory System KidsHealth > For Teens > Lungs and Respiratory System A ... didn't breathe, you couldn't live. Lungs & Respiratory System Basics Each day we breathe about 20,000 ...

  8. Respiratory Syncytial Virus

    MedlinePlus

    ... Your 1- to 2-Year-Old Respiratory Syncytial Virus KidsHealth > For Parents > Respiratory Syncytial Virus A A A What's in this article? About ... RSV When to Call the Doctor en español Virus respiratorio sincitial About RSV Respiratory syncytial (sin-SISH- ...

  9. Cytochrome P450 3A, NADPH cytochrome P450 reductase and cytochrome b5 in the upper airways in horse.

    PubMed

    Tydén, E; Olsén, L; Tallkvist, J; Tjälve, H; Larsson, P

    2008-08-01

    Gene and protein expression as well as catalytic activity of cytochrome P450 (CYP) 3A were studied in the nasal olfactory and respiratory mucosa and the tracheal mucosa of the horse. We also examined the activity of NADPH cytochrome P450 reductase (NADPH P450 reductase), the amount of cytochrome b(5) and the total CYP content in these tissues. Comparative values for the above were obtained using liver as a control. The CYP3A related catalytic activity in the tissues of the upper airways was considerably higher than in the liver. The CYP3A gene and protein expression, on the other hand, was higher in the liver than in the upper airway tissues. Thus, the pattern of CYP3A metabolic activity does not correlate with the CYP3A gene and protein expression. Our results showed that the activity of NADPH P450 reductase and the level of cytochrome b(5) in the relation to the gene and protein expression of CYP3A were higher in the tissues of the upper airways than in the liver. It is concluded that CYP3A related metabolism in horse is not solely dependent on the expression of the enzyme but also on adequate levels of NADPH P450 reductase and cytochrome b(5).

  10. Electron transport to periplasmic nitrate reductase (NapA) of Wolinella succinogenes is independent of a NapC protein.

    PubMed

    Simon, Jörg; Sänger, Monica; Schuster, Stephan C; Gross, Roland

    2003-07-01

    The rumen bacterium Wolinella succinogenes grows by respiratory nitrate ammonification with formate as electron donor. Whereas the enzymology and coupling mechanism of nitrite respiration is well known, nitrate reduction to nitrite has not yet been examined. We report here that intact cells and cell fractions catalyse nitrate and chlorate reduction by reduced viologen dyes with high specific activities. A gene cluster encoding components of a putative periplasmic nitrate reductase system (napA, G, H, B, F, L, D) was sequenced. The napA gene was inactivated by inserting a kanamycin resistance gene cassette. The resulting mutant did not grow by nitrate respiration and did not reduce nitrate during growth by fumarate respiration, in contrast to the wild type. An antigen was detected in wild-type cells using an antiserum raised against the periplasmic nitrate reductase (NapA) from Paracoccus pantotrophus. This antigen was absent in the W. succinogenes napA mutant. It is concluded that the periplasmic nitrate reductase NapA is the only respiratory nitrate reductase in W. succinogenes, although a second nitrate-reducing enzyme is apparently induced in the napA mutant. The nap cluster of W. succinogenes lacks a napC gene whose product is thought to function in quinol oxidation and electron transfer to NapA in other bacteria. The W. succinogenes genome encodes two members of the NapC/NirT family, NrfH and FccC. Characterization of corresponding deletion mutants indicates that neither of these two proteins is required for nitrate respiration. A mutant lacking the genes encoding respiratory nitrite reductase (nrfHA) had wild-type properties with respect to nitrate respiration. A model of the electron transport chain of nitrate respiration is proposed in which one or more of the napF, G, H and L gene products mediate electron transport from menaquinol to the periplasmic NapAB complex. Inspection of the W. succinogenes genome sequence suggests that ammonia formation from

  11. Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

    USGS Publications Warehouse

    Waychunas, G.; Trainor, T.; Eng, P.; Catalano, J.; Brown, G.; Davis, J.; Rogers, J.; Bargar, J.

    2005-01-01

    X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c(0001) and r(10-12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of "edge-sharing" bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. ?? Springer-Verlag 2005.

  12. Sulphate and arsenate minerals as environmental indicators in the weathering zones of selected ore deposits, Western Sudetes, Poland

    NASA Astrophysics Data System (ADS)

    Parafiniuk, Jan; Siuda, Rafał; Borkowski, Andrzej

    2016-09-01

    The results of a complex investigation of the sulphate and arsenate assemblages forming in the weathering zone of selected ore deposits in the Sudetes are presented. The development of the weathering zone has been characterised in the polymetallic ore deposits at Miedzianka-Ciechanowice and Radzimowice, and the pyrite deposit at Wieściszowice, which differ in the chemical compositions of the ore and barren minerals and the hydrological conditions. Secondary sulphate and arsenate mineral assemblages vary significantly among the ore deposits under study. Their crystallization is discussed, taking into consideration the stability of particular minerals and the paths of their transformation. It is shown that these minerals have great potential as indicators of weathering processes. A significant role for microorganisms in the formation of the weathering zone of the ore deposits under study is also proven.

  13. Rapid microwave-assisted acid extraction of southern pine waste wood to remove metals from chromated copper arsenate (CCA) treatment

    Treesearch

    Chung-Yun Hse; Todd F. Shupe; Bin Yu

    2013-01-01

    Recovery of metals from chromated copper arsenate (CCA)-treated southern pine wood particles was investigated by extraction in a microwave reactor with binary combinations of acetic acid (AA), oxalic acid (OxA), and phosphoric acid (PhA). Use of OxA was not successful, as insoluble copper oxalate complexes impeded copper removal. The combination of OxA and AA also had...

  14. Soil and sediment concentrations of chromium, copper, and arsenic adjacent to a chromated copper arsenate-treated wetland boardwalk

    Treesearch

    Stan Lebow; Daniel Foster

    2010-01-01

    Environmental accumulation of preservative adjacent to a chromated copper arsenate (type C)–treated wetland boardwalk was evaluated. The site is considered a realistic ‘‘worst case’’ because of the large volume of treated wood, low current speeds, high annual rainfall, and environmental sensitivity. Soil and sediment samples were collected before construction and 0.5,...

  15. Different arsenate and phosphate incorporation effects on the nucleation and growth of iron(III) (Hydr)oxides on quartz.

    PubMed

    Neil, Chelsea W; Lee, Byeongdu; Jun, Young-Shin

    2014-10-21

    Iron(III) (hydr)oxides play an important role in the geochemical cycling of contaminants in natural and engineered aquatic systems. The ability of iron(III) (hydr)oxides to immobilize contaminants can be related to whether the precipitates form heterogeneously (e.g., at mineral surfaces) or homogeneously in solution. Utilizing grazing incidence small-angle X-ray scattering (GISAXS), we studied heterogeneous iron(III) (hydr)oxide nucleation and growth on quartz substrates for systems containing arsenate and phosphate anions. For the iron(III) only system, the radius of gyration (Rg) of heterogeneously formed precipitates grew from 1.5 to 2.5 (± 1.0) nm within 1 h. For the system containing 10(-5) M arsenate, Rg grew from 3.6 to 6.1 (± 0.5) nm, and for the system containing 10(-5) M phosphate, Rg grew from 2.0 to 4.0 (± 0.2) nm. While the systems containing these oxyanions had more growth, the system containing only iron(III) had the most nucleation events on substrates. Ex situ analyses of homogeneously and heterogeneously formed precipitates indicated that precipitates in the arsenate system had the highest water content and that oxyanions may bridge iron(III) hydroxide polymeric embryos to form a structure similar to ferric arsenate or ferric phosphate. These new findings are important because differences in nucleation and growth rates and particle sizes will impact the number of available reactive sites and the reactivity of newly formed particles toward aqueous contaminants.

  16. Different Arsenate and Phosphate Incorporation Effects on the Nucleation and Growth of Iron(III) (Hydr)oxides on Quartz

    SciTech Connect

    Neil, Chelsea W.; Lee, Byeongdu; Jun, Young-Shin

    2014-10-21

    Iron(III) (hydr)oxides play an important role in the geochemical cycling of contaminants in natural and engineered aquatic systems. The ability of iron(III) (hydr)oxides to immobilize contaminants can be related to whether the precipitates form heterogeneously (e.g., at mineral surfaces) or homogeneously in solution. Utilizing grazing incidence small-angle X-ray scattering (GISAXS), we studied heterogeneous iron(III) (hydr)oxide nucleation and growth on quartz substrates for systems containing arsenate and phosphate anions. For the iron(III) only system, the radius of gyration ( R g ) of heterogeneously formed precipitates grew from 1.5 to 2.5 ( ± 1.0) nm within 1 h. For the system containing 10-5 M arsenate, R g grew from 3.6 to 6.1 ( ± 0.5) nm, and for the system containing 10-5 M phosphate, R g grew from 2.0 to 4.0 ( ± 0.2) nm. While the systems containing these oxyanions had more growth, the system containing only iron(III) had the most nucleation events on substrates. Ex situ analyses of homogeneously and heterogeneously formed precipitates indicated that precipitates in the arsenate system had the highest water content and that oxyanions may bridge iron(III) hydroxide polymeric embryos to form a structure similar to ferric arsenate or ferric phosphate. These new fi ndings are important because di ff erences in nucleation and growth rates and particle sizes will impact the number of available reactive sites and the reactivity of newly formed particles toward aqueous contaminants.

  17. A Ferredoxin Disulfide Reductase Delivers Electrons to the Methanosarcina barkeri Class III Ribonucleotide Reductase

    PubMed Central

    2015-01-01

    Two subtypes of class III anaerobic ribonucleotide reductases (RNRs) studied so far couple the reduction of ribonucleotides to the oxidation of formate, or the oxidation of NADPH via thioredoxin and thioredoxin reductase. Certain methanogenic archaea contain a phylogenetically distinct third subtype of class III RNR, with distinct active-site residues. Here we report the cloning and recombinant expression of the Methanosarcina barkeri class III RNR and show that the electrons required for ribonucleotide reduction can be delivered by a [4Fe-4S] protein ferredoxin disulfide reductase, and a conserved thioredoxin-like protein NrdH present in the RNR operon. The diversity of class III RNRs reflects the diversity of electron carriers used in anaerobic metabolism. PMID:26536144

  18. Arsenic mobility controlled by solid calcium arsenates: a case study in Mexico showcasing a potentially widespread environmental problem.

    PubMed

    Martínez-Villegas, Nadia; Briones-Gallardo, Roberto; Ramos-Leal, José A; Avalos-Borja, Miguel; Castañón-Sandoval, Alan D; Razo-Flores, Elías; Villalobos, Mario

    2013-05-01

    An As-contaminated perched aquifer under an urban area affected by mining was studied over a year to determine the contamination source species and the mechanism of As mobilization. Results show that the dissolution of calcium arsenates in residues disposed on an inactive smelter has caused high levels of As pollution in the adjoining downgradient 6-km perched aquifer, reaching up to 158 mg/L of dissolved As, and releasing a total of ca. 7.5 tons of As in a year. Furthermore, free calcium ion availability was found to control As mobility in the aquifer through the diagenetic precipitation of calcium arsenates (Ca5H2(AsO4)4·cH2O) preventing further mobilization of As. Results shown here represent a model for understanding a highly underreported mechanism of retention of arsenate species likely to dominate in calcium-rich environments, such as those in calcareous sediments and soils, where the commonly reported mechanism of adsorption to iron(III) oxyhydroxides is not the dominant process. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Sorption of arsenite, arsenate, and thioarsenates to iron oxides and iron sulfides: a kinetic and spectroscopic investigation.

    PubMed

    Couture, R-M; Rose, J; Kumar, N; Mitchell, K; Wallschläger, D; Van Cappellen, P

    2013-06-04

    Sorption to iron (Fe) minerals determines the fate of the toxic metalloid arsenic (As) in many subsurface environments. Recently, thiolated As species have been shown to dominate aqueous As speciation under a range of environmentally relevant conditions, thus highlighting the need for a quantitative understanding of their sorption behavior. We conducted batch experiments to measure the time-dependent sorption of two S-substituted arsenate species, mono- and tetrathioarsenate, and compared it to the sorption of arsenite and arsenate, in suspensions containing 2-line ferrihydrite, goethite, mackinawite, or pyrite. All four As species strongly sorbed to ferrihydrite. For the other sorbents, binding of the thiolated As species was generally lower compared to arsenate and arsenite, with the exception of the near instantaneous and complete sorption of monothioarsenate to pyrite. Analysis of the X-ray absorption spectroscopy (XAS) spectra of sorbed complexes implied that monothioarsenate binds to Fe oxides as a monodentate, inner-sphere complex. In the presence of Fe sulfides, mono- and tetrathioarsenate were both unstable and partially reduced to arsenite. Adsorption of the thiolated As species to the Fe sulfide minerals also caused the substitution of surface sulfur (S) atoms by As and the formation of As-Fe bonds.

  20. Effects of Phosphate on Arsenate Uptake and Translocation in Nonmetallicolous and Metallicolous Populations of Pteris Vittata L. Under Solution Culture.

    PubMed

    Wu, Fuyong; Wu, Shengchun; Deng, Dan; Wong, Ming Hung

    2015-01-01

    An arsenic hyperaccumulator, Pteris vittata L., is common in nature and could occur either on As-contaminated soils or on uncontaminated soils. However, it is not clear whether phosphate transporter play similar roles in As uptake and translocation in nonmetallicolous and metallicolous populations of P. vittata. Five populations were used to investigate effects of phosphate on arsenate uptake and translocation in the plants growing in 1.2 L 20% modified Hoagland's nutrient solution containing either 100 μM phosphate or no phosphate and 10 μM arsenate for 1, 2, 6, 12, 24 h, respectively. The results showed that the nonmetallicolous populations accumulated apparently more As in their fronds and roots than the metallicolous populations at both P supply levels. Phosphate significantly (P < 0.01) decreased frond and root concentrations of As during short time solution culture. In addition, the effects of phosphate on As translocation in P. vittata varied among different time-points during time-course hydroponics (1-24 h). The present results indicated that the inhibitory effect of phosphate on arsenate uptake was larger in the three nonmetallicolous populations than those in the two metallicolous populations of P. vittata.

  1. The removal of arsenate from water using iron-modified diatomite (D-Fe): isotherm and column experiments.

    PubMed

    Pantoja, M L; Jones, H; Garelick, H; Mohamedbakr, H G; Burkitbayev, M

    2014-01-01

    Iron hydroxide supported onto porous diatomite (D-Fe) is a low-cost material with potential to remove arsenic from contaminated water due to its affinity for the arsenate ion. This affinity was tested under varying conditions of pH, contact time, iron content in D-Fe and the presence of competitive ions, silicate and phosphate. Batch and column experiments were conducted to derive adsorption isotherms and breakthrough behaviours (50 μg L(-1)) for an initial concentration of 1,000 μg L(-1). Maximum capacity at pH 4 and 17% iron was 18.12-40.82 mg of arsenic/g of D-Fe and at pH 4 and 10% iron was 18.48-29.07 mg of arsenic/g of D-Fe. Adsorption decreased in the presence of phosphate and silicate ions. The difference in column adsorption behaviour between 10% and 17% iron was very pronounced, outweighing the impact of all other measured parameters. There was insufficient evidence of a correlation between iron content and arsenic content in isotherm experiments, suggesting that ion exchange is a negligible process occurring in arsenate adsorption using D-Fe nor is there co-precipitation of arsenate by rising iron content of the solute above saturation.

  2. [Ethanol-induced influence on the structure and arsenate adsorption of resin-based nano-hydrated ferric oxide].

    PubMed

    Wan, Qi; Li, Xu-Chun; Pan, Bing-Cai

    2013-08-01

    Here the role of ethanol in the synthesis of a new nanocomposite (D201-HFO) was evaluated in terms of its structure variation and arsenate adsorption. Results indicated that the ethanol-induced procedure improved the dispersion of HFO inside the polymer host D201 and increased the HFO sorption capacities towards arsenate by 20%. Also, the ethanol-induced procedure resulted in the increase of pore size, pore volume, and specific surface area of D201-HFO by 52%, 65% and 28%, respectively. Nevertheless, ethanol rinsing did not affect the mechanical strength of D201-HFO and the crystal type of the immobilized HFO. Little effects of the ethanol process was observed on the pH and co-anion dependent adsorption of arsenate. Furthermore, the ethanol step posed insignificant influence on the fix-bed adsorption and the repeated use of the adsorbent. The results showed that the ethanol procedure exerted little influence on the sorption properties of D201-HFO from the viewpoint of practical application and thus, it could not be included.

  3. [Music and respiratory pathology].

    PubMed

    Herer, B

    2001-04-01

    Musical performance, especially in singers and wind instrument players, depends on an effective pulmonary function. Performing artists may be seriously impaired by respiratory diseases that, comparatively, may produce only modest inconvenience for non-musicians. The report of two cases of respiratory diseases occurring in musicians herein provides an introduction to a review of the interactions between music and the human respiratory system. The following points are considered: epidemiological data; pulmonary function in musicians; favorable effects of music on the respiratory system; description of the main respiratory problems that may affect musicians.

  4. Methionine sulfoxide reductase contributes to meeting dietary methionine requirements

    PubMed Central

    Zhao, Hang; Kim, Geumsoo; Levine, Rodney L.

    2012-01-01

    Methionine sulfoxide reductases are present in all aerobic organisms. They contribute to antioxidant defenses by reducing methionine sulfoxide in proteins back to methionine. However, the actual in vivo roles of these reductases are not well defined. Since methionine is an essential amino acid in mammals, we hypothesized that methionine sulfoxide reductases may provide a portion of the dietary methionine requirement by recycling methionine sulfoxide. We used a classical bioassay, the growth of weanling mice fed diets varying in methionine, and applied it to mice genetically engineered to alter the levels of methionine sulfoxide reductase A or B1. Mice of all genotypes were growth retarded when raised on chow containing 0.10% methionine instead of the standard 0.45% methionine. Retardation was significantly greater in knockout mice lacking both reductases. We conclude that the methionine sulfoxide reductases can provide methionine for growth in mice with limited intake of methionine, such as may occur in the wild. PMID:22521563

  5. Surface chemistry of ferrihydrite: Part 2. Kinetics of arsenate adsorption and coprecipitation

    USGS Publications Warehouse

    Fuller, C.C.; Dadis, J.A.; Waychunas, G.A.

    1993-01-01

    The kinetics of As(V) adsorption by ferrihydrite was investigated in coprecipitation and postsynthesis adsorption experiments conducted in the pH range 7.5-9.0. In coprecipitation experiments, As(V) was present in solution during the hydrolysis and precipitation of iron. In adsorption experiments, a period of rapid (<5 min) As(V) uptake from solution was followed by continued uptake for at least eight days, as As(V) diffused to adsorption sites on ferrihydrite surfaces within aggregates of colloidal particles. The time dependence of As(V) adsorption is well described by a general model for diffusion into a sphere if a subset of surface sites located near the exterior of aggregates is assumed to attain adsorptive equilibrium rapidly. The kinetics of As(V) desorption after an increase in pH were also consistent with diffusion as a rate-limiting process. Aging of pure ferrihydrite prior to As(V) adsorption caused a decrease in adsorption sites on the precipitate owing to crystallite growth. In coprecipitation experiments, the initial As(V) uptake was significantly greater than in post-synthesis adsorption experiments, and the rate of uptake was not diffusion limited because As(V) was coordinated by surface sites before crystallite growth and coagulation processes could proceed. After the initial adsorption, As(V) was slowly released from coprecipitates for at least one month, as crystallite growth caused desorption of As(V). Adsorption densities as high as 0.7 mole As(V) per mole of Fe were measured in coprecipitates, in comparison to 0.25 mole As(V) per mole of Fe in post-synthesis adsorption experiments. Despite the high Concentration of As(V) in the precipitates, EXAFS spectroscopy (Waychunas et al., 1993) showed that neither ferric arsenate nor any other As-bearing surface precipitate or solid solution was formed. The high adsorption densities are possible because the ferrihydrite particles are extremely small, approaching the size of small dioctahedral chains at

  6. Structural Elucidation of Chalcone Reductase and Implications for Deoxychalcone Biosynthesis

    PubMed Central

    Bomati, Erin K.; Austin, Michael B.; Bowman, Marianne E.; Dixon, Richard A.; Noel, Joseph P.

    2010-01-01

    4,2′,4′,6′-tetrahydroxychalcone (chalcone) and 4,2′,4′-trihydroxychalcone (deoxychalcone) serve as precursors of ecologically important flavonoids and isoflavonoids. Deoxychalcone formation depends on chalcone synthase and chalcone reductase; however, the identity of the chalcone reductase substrate out of the possible substrates formed during the multistep reaction catalyzed by chalcone synthase remains experimentally elusive. We report here the three-dimensional structure of alfalfa chalcone reductase bound to the NADP+ cofactor and propose the identity and binding mode of its substrate, namely the non-aromatized coumaryl-trione intermediate of the chalcone synthase-catalyzed cyclization of the fully extended coumaryl-tetraketide thioester intermediate. In the absence of a ternary complex, the quality of the refined NADP+-bound chalcone reductase structure serves as a template for computer-assisted docking to evaluate the likelihood of possible substrates. Interestingly, chalcone reductase adopts the three-dimensional structure of the aldo/keto reductase superfamily. The aldo/keto reductase fold is structurally distinct from all known ketoreductases of fatty acid biosynthesis, which instead belong to the short-chain dehydrogenase/reductase superfamily. The results presented here provide structural support for convergent functional evolution of these two ketoreductases that share similar roles in the biosynthesis of fatty acids/polyketides. In addition, the chalcone reductase structure represents the first protein structure of a member of the aldo/ketoreductase 4 family. Therefore, the chalcone reductase structure serves as a template for the homology modeling of other aldo/ketoreductase 4 family members, including the reductase involved in morphine biosynthesis, namely codeinone reductase. PMID:15970585

  7. Limited proteolysis of the nitrate reductase from spinach leaves.

    PubMed

    Kubo, Y; Ogura, N; Nakagawa, H

    1988-12-25

    The functional structure of assimilatory NADH-nitrate reductase from spinach leaves was studied by limited proteolysis experiments. After incubation of purified nitrate reductase with trypsin, two stable products of 59 and 45 kDa were observed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The fragment of 45 kDa was purified by Blue Sepharose chromatography. NADH-ferricyanide reductase and NADH-cytochrome c reductase activities were associated with this 45-kDa fragment which contains FAD, heme, and NADH binding fragment. After incubation of purified nitrate reductase with Staphylococcus aureus V8 protease, two major peaks were observed by high performance liquid chromatography size exclusion gel filtration. FMNH2-nitrate reductase and reduced methyl viologen-nitrate reductase activities were associated with the first peak of 170 kDa which consists of two noncovalently associated (75-90-kDa) fragments. NADH-ferricyanide reductase activity, however, was associated with the second peak which consisted of FAD and NADH binding sites. Incubation of the 45-kDa fragment with S. aureus V8 protease produced two major fragments of 28 and 14 kDa which contained FAD and heme, respectively. These results indicate that the molybdenum, heme, and FAD components of spinach nitrate reductase are contained in distinct domains which are covalently linked by exposed hinge regions. The molybdenum domain appears to be important in the maintenance of subunit interactions in the enzyme complex.

  8. Phase Coexistence in the Mixed Crystal RUBIDIUM(1-X) Ammonium(x) Dihydrogen Arsenate

    NASA Astrophysics Data System (ADS)

    Pinto, Nicholas Joaquim

    1992-01-01

    A study of the coexistence phenomenon in mixed crystals of rubidium ammonium dihydrogen arsenate has been done. Coexistence in this study refers to the simultaneous presence of ferroelectric and proton glass phases as temperature is lowered below the ferroelectric phase transition temperature T_{c}. Such coexistence is found to exist in these mixed crystals only for small ammonium concentrations. Our results show that coexistence exists for lower ammonium concentration than previously suggested. A study was also done on crystals with larger ammonium concentrations that show pure proton glass behavior and the results compared with the coexistence phenomenon. Dielectric, spontaneous polarization and nuclear magnetic resonance experiments on mixed crystals with small ammonium concentrations show that at low temperatures there exists intimate coexistence of ferroelectric clusters with proton glass clusters below the glass transition temperature T_{g}. In the proton glass phase, we observe a spread of relaxation times due to the creation and annihilation of HAsO_4 and H_3AsO_4 pairs as they diffuse through the crystal. Spin lattice relaxation times for the acid deuterons in a 10% ammoniated sample show a broad T_1 minimum near the glass transition temperature which is characteristic of proton glasses. Field-cooling experiments were also done on the pure proton glass. The results are consistent with dielectric measurements, but the remanent polarization was found to be extremely small. This polarization was found to depend on the rate of heating and cooling the sample while performing the experiment.

  9. Arsenite and arsenate impact the oxidative status and antioxidant responses in Ocimum tenuiflorum L.

    PubMed

    Siddiqui, Fauzia; Tandon, P K; Srivastava, Sudhakar

    2015-07-01

    Biochemical responses of Ocimum tenuiflorum plants were studied upon exposure to arsenite (AsIII) and arsenate (AsV) for 1 to 10 d. Plants accumulated significant amounts of As in leaves (662 μg g(-1) dry weight; DW and 412 μg g(-1) DW in response to 100 μM AsIII and AsV exposure, respectively after 10 d). Consequently, fresh weight and growth of plants declined in a concentration dependent manner. Further, total chlorophyll and carotenoid contents also declined while oxidative stress markers increased, particularly on longer durations. Various antioxidant enzymes and thiols (cysteine and glutathione; GSH) showed significant and variable increases upon exposure to AsV and AsIII with the response being comparatively better in response to AsV. Proline increased significantly upon exposure to both AsIII and AsV. Plants thus tolerated high As concentrations through induced antioxidant machinery.

  10. The effects of humic acid-arsenate complexes on human red blood cells.

    PubMed

    Hseu, You-Cheng; Yang, Hsin-Ling

    2002-06-01

    Humic acid (HA) has been proposed as factor in the cause of Blackfoot disease (BFD) among individuals who live along the southwest coast of Taiwan. In this study, the interaction of the synthetic humic acid, made from catechol, with sodium arsenate (As(V)) was investigated and assessed with respect to damage to human red blood cells. HA is characterized as phenolic and phenolic carboxylic polymer structures containing both -COOH and -OH as their main functional groups. HA and As(V) alone are able to hemolyze 60-100 and 5-20% human red blood cells at concentrations of 50-300 microg/ml and 5-100 mM, respectively, after 6 h. HA is shown to be relatively ineffective in causing ATP depletion of red blood cells. For organometallic complexes composed of HA-As(V) the inhibition effect of EDTA was completely abolished and the use of the triple complex HA-As(V)-EDTA resulted in an enhancement of hemolysis. HA caused lipid peroxidation in a concentration- and time-dependent manner. However, HA-As(V) and As(V) decreased lipid peroxidation. These results indicated that HA initiates oxidative stress on red blood cells and this results in their dysfunction. HA-chelated high-concentration metal complexes inhibited the structures containing the main functional groups involved in decreasing hemolysis, and, thus, HA may be a significant factor in the etiology of BFD.

  11. Effects of chronic exposure to arsenate on the cardiovascular function of rats.

    PubMed Central

    Carmignani, M; Boscolo, P; Iannaccone, A

    1983-01-01

    Cardiovascular function was studied in anaesthetised male rats which received 50 micrograms/ml of arsenic (as sodium arsenate) in deionised drinking water for 320 days. High urinary excretion of arsenic was found at the end of treatment and the metal accumulated considerably in the kidneys and liver, which both presented slight alterations. No histopathological modifications were evident in other organs. Base line blood pressure, cardiac inotropism, and chronotropism and cardiovascular reactivity to noradrenaline, acetylcholine, angiotensin II, bradykinin, histamine, and serotonin did not differ in exposed or in control animals. In the exposed group, however, there was potentiation of the effects of vascular beta-adrenoceptor stimulation and a reduction in the vascular responsiveness to angiotensin I. Chronic arsenic exposure did not affect the baroreflex sensitivity but was able to induce sympathetic hyperactivity or hypersensitivity, or both, possibly associated with an antivagal action. Our results might help to explain the cardiovascular alterations seen in people chronically exposed to high concentrations of arsenic. PMID:6871116

  12. Effects of Sodium Arsenite and Arsenate in Testicular Histomorphometry and Antioxidants Enzymes Activities in Rats.

    PubMed

    Souza, Ana Cláudia Ferreira; Marchesi, Sarah Cozzer; Domingues de Almeida Lima, Graziela; Ferraz, Rafael Penha; Santos, Felipe Couto; da Matta, Sérgio Luis Pinto; Machado-Neves, Mariana

    2016-06-01

    The main source of environmental arsenic exposure in most countries of the world is drinking water in which inorganic forms of arsenic predominate. The present study was aimed to test the impact of two different compounds of inorganic arsenic in histomorphometric and enzymatic parameters in the testes by oral exposition. Adult Wistar male rats were exposed to sodium arsenite and arsenate in drinking water, testing for each chemical form the concentrations of 0.01 and 10 mg/L per 56 days. The animals intoxicated with arsenic, mainly sodium arsenite, showed reduction in the percentage of seminiferous epithelium and in proportion and volume of Leydig cells. Moreover, there was an increase in the percentage of tunica propria, lumen, lymphatic space, blood vessels, and macrophages. The activity of superoxide dismutase (SOD) did not change among the groups. However, the activity of catalase (CAT) decreased in animals exposed to both arsenic compounds. In addition, the higher concentration of arsenic, mainly as sodium arsenite, caused vacuolization in the seminiferous epithelium. The body and testes weight as well as testosterone concentration remained unchanged among the groups. In conclusion, exposition to arsenic, mainly as sodium arsenite, caused alteration in histomorphometric parameters and antioxidant defense system in the testes.

  13. Arsenic and chromium partitioning in a podzolic soil contaminated by chromated copper arsenate

    SciTech Connect

    Nico, Peter; Hopp, Luisa; Nico, Peter S.; Marcus, Matthew A.; Peiffer, Stefan

    2008-06-01

    This research combined the use of selective extractions and x-ray spectroscopy to examine the fate of As and Cr in a podzolic soil contaminated by chromated copper arsenate (CCA). Iron was enriched in the upper 30 cm due to a previous one-time treatment of the soil with Fe(II). High oxalate-soluble Al concentrations in the Bs horizon of the soil and micro-XRD data indicated the presence of short-range ordered aluminosilicates (i.e. proto-imogolite allophane, PIA). In the surface layers, Cr, as Cr(III), was partitioned between a mixed Fe(III)/Cr(III) solid phase that formed upon the Fe(II) application (25-50%) and a recalcitrant phase (50-75%) likely consisting of organic material such as residual CCA-treated wood. Deeper in the profile Cr appeared to be largely in the form of extractable (hydr)oxides. Throughout the soil, As was present as As(V). In the surface layers a considerable fraction of As was also associated with a recalcitrant phase, probably CCA-treated woody debris, and the remainder was associated with (hydr)oxide-like solid phases. In the Bs horizon, however, XAS and XRF findings strongly pointed to the presence of PIA acting as an effective adsorbent for As. This research shows for the first time the relevance of PIA for the adsorption of As in natural soils.

  14. Method to recover and reuse chromated copper arsenate wood preservative from spent treated wood

    SciTech Connect

    Kazi, Feroz Kabir M.; Cooper, Paul A. . E-mail: p.cooper@utoronto.ca

    2006-07-01

    The volume of chromated copper arsenate (CCA) treated wood products coming out of service is expected to increase dramatically during the next decade. There is a need for an alternative waste management approach to landfilling. This paper investigates the variables affecting extraction of CCA components from wood particles and the potential to oxidize and reuse the recovered chemicals. Most of the CCA components could be extracted by 10% H{sub 2}O{sub 2} at 50 deg. C in 6 h with an average extraction efficiency of 95% for Cr, 94% for Cu and 98% for As. The extract containing Cr{sup III}, Cu{sup II} and As{sup V} could be oxidized in several stages by aqueous 2.5% w/w H{sub 2}O{sub 2} in less than 2 h to a condition where it was compatible with CCA treating solutions and could be reused for treating new wood. When the recovered extract was mixed with fresh CCA solution in different ratios, the mixed CCA-C solutions had similar solution stability as freshly prepared CCA-C solution and treated wood had similar leaching properties as wood treated with fresh solution.

  15. Influence of the interaction between phosphate and arsenate on periphyton's growth and its nutrient uptake capacity.

    PubMed

    Rodriguez Castro, Ma Carolina; Urrea, Gemma; Guasch, Helena

    2015-01-15

    Periphyton communities grown in microcosms were studied under the exposure to different arsenate (As) and phosphate (P) regimes with the aim of revealing the effect of chronic exposure to As on periphyton physiological and structural characteristics. Also, we aimed to study periphyton changes on sensitivity to As, exposed to different P and As regimes. As affected structural and functional parameters of periphyton communities starved of P, inhibiting algal growth, photosynthetic capacity, changing community composition and reducing the ability of the community to retain P. The effects of As on these parameters were only detected in P starved communities, showing that chronic exposure to As led to changes in the photosynthetic apparatus under the conditions of P-limitation, but not when P-availability was higher. This fact reveals a lower toxicity and/or a higher adaptation of the P-amended community. Intracellular As contents were higher in communities starved of P. However, As tolerance was only induced by the combination of As and P but not by As or P alone indicating that tolerance induction may be an ATP-dependent mechanism. This study reveals that chronic exposure of natural communities to environmentally realistic As concentrations will damage periphyton communities affecting key ecosystem processes, as P uptake, leading to changes in stream ecosystems, as these organisms play a key role in nutrient cycling through nutrient uptake and transfer to higher trophic levels. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Extraction of hexavalent chromium from chromated copper arsenate treated wood under alkaline conditions.

    PubMed

    Radivojevic, Suzana; Cooper, Paul A

    2008-05-15

    Information on chromium (Cr) oxidation states is essential for the assessment of environmental and health risks associated with the overall life-cycle of chromated copper arsenate (CCA) treated wood products because of differences in toxicity between trivalent [Cr(III)] and hexavalent [Cr(VI)] chromium compounds. Hypothetical Cr(VI) fixation products were investigated in CCA type C treated sawdust of aspen and red pine during or following preservative fixation by extraction with Cr(VI)-specific extractants. Cr(VI) was found only in alkaline extracts of treated wood. A major source of Cr(VI) was method-induced oxidation of fixed Cr(III) during alkaline extraction, as confirmed by demonstrated oxidation of Cr(III) from CrCl3 treated wood. Oxidation of nontoxic and immobile Cr(III) to toxic and mobile Cr(VI) was facilitated by the presence of wood at pH > 8.5. Thermodynamic equilibrium between Cr(III) and Cr(VI) is affected by pH, temperature, rates of dissolution of CrIII) compounds, and oxygen availability. Results of this study recommend against alkaline extraction protocols for determination of Cr(VI) in treated wood. This Cr oxidation mechanism can act as a previously unrecognized route for generation of hazardous Cr(VI) if CCA treated wood is exposed to alkaline conditions during its production, use, or waste management.

  17. No evidence for competition between arsenate and phosphate for uptake from soil by medic or barley.

    PubMed

    Christophersen, H M; Smith, S E; Pope, S; Smith, F A

    2009-04-01

    We investigated the effects of phosphorus (P) supply on the uptake and toxicity of arsenate (As(V)) in two plant species (Medicago truncatula and Hordeum vulgare) grown in soil/sand mixes. Our initial hypothesis was that competition between phosphate (Pi) and As(V) for uptake would be observed, and that this would be the basis for the 'protective' effect of P with respect to As toxicity, as shown in solution culture. Addition of P to the soil/sand mixes did not have major effects on water extractable As, or vice versa. We observed that toxic effects of As(V) on plant growth were ameliorated by increased P in both plant species. However, we found no evidence that increased P supply reduced specific uptake of As(V) on a molar basis, so that competition with Pi could not be the basis for the effect. A more complex mechanism of protection is indicated which might relate to different Pi transport systems being expressed at different P levels.

  18. Interactive effects of arsenate, selenium, and dietary protein on survival, growth, and physiology in mallard ducklings

    USGS Publications Warehouse

    Hoffman, D.J.; Sanderson, C.J.; LeCaptain, L.J.; Cromartie, E.; Pendleton, G.W.

    1992-01-01

    High concentrations of arsenic (As) and selenium (Se) have been found in aquatic food chains associated with irrigation drainwater. Total biomass of invertebrates, a maJor source of protein for wild ducklings, may vary in environments that are contaminated with selenium. Dayold mallard (Anas platyrhynchos) ducklings received an untreated diet (controls) containing 22% protein or diets containing 15 ppm Se (as selenomethionine), 60 ppm Se, 200 ppm As (as sodium arsenate), 15 ppm Se with 200 ppm As, or 60 ppm Se with 200 ppm As. In a concurrent experiment, the same sequence was repeated with a proteinrestricted (7%) but isocaloric diet. After 4 weeks, blood and tissue samples were collected for biochemical and histological examination. With 22% protein and 60 ppm Se in the diet, duckling survival and growth was reduced and livers had histopathological lesions. Arsenic alone caused some reduction in growth. Antagonistic interactive effects occurred between As and Se, including complete to partial alleviation of the following Se effects: mortality, impaired growth, hepatic lesions and lipid peroxidation, and altered glutathione and thiol status. With 7% protein, survival and growth of controls was less than that with 22% protein, Se (60 ppm) caused 100% mortality, and As (200 ppm) caused mortality, decreased growth, and liver histopathology. These findings suggest the potential for antagonistic effects of Se and As on duckling survival, growth, and physiology with adequate dietary protein but more severe toxicological effects when dietary protein is diminished.

  19. Method to recover and reuse chromated copper arsenate wood preservative from spent treated wood.

    PubMed

    Kazi, Feroz Kabir M; Cooper, Paul A

    2006-01-01

    The volume of chromated copper arsenate (CCA) treated wood products coming out of service is expected to increase dramatically during the next decade. There is a need for an alternative waste management approach to landfilling. This paper investigates the variables affecting extraction of CCA components from wood particles and the potential to oxidize and reuse the recovered chemicals. Most of the CCA components could be extracted by 10% H2O2 at 50 degrees C in 6 h with an average extraction efficiency of 95% for Cr, 94% for Cu and 98% for As. The extract containing Cr(III), Cu(II) and As(V) could be oxidized in several stages by aqueous 2.5% w/w H2O2 in less than 2 h to a condition where it was compatible with CCA treating solutions and could be reused for treating new wood. When the recovered extract was mixed with fresh CCA solution in different ratios, the mixed CCA-C solutions had similar solution stability as freshly prepared CCA-C solution and treated wood had similar leaching properties as wood treated with fresh solution.

  20. Nanoporous sorbent material as an oral phosphate binder and for aqueous phosphate, chromate, and arsenate removal

    PubMed Central

    Sangvanich, Thanapon; Ngamcherdtrakul, Worapol; Lee, Richard; Morry, Jingga; Castro, David; Fryxell, Glen E.; Yantasee, Wassana

    2014-01-01

    Phosphate removal is both biologically and environmentally important. Biologically, hyperphosphatemia is a critical condition in end-stage chronic kidney disease patients. Patients with hyperphosphatemia are treated long-term with oral phosphate binders to prevent phosphate absorption to the body by capturing phosphate in the gastrointestinal (GI) tract followed by fecal excretion. Environmentally, phosphate levels in natural water resources must be regulated according to limits set forth by the US Environmental Protection Agency. By utilizing nanotechnology and ligand design, we developed a new material to overcome limitations of traditional sorbent materials such as low phosphate binding capacity, slow binding kinetics, and negative interference by other anions. A phosphate binder based on iron-ethylenediamine on nanoporous silica (Fe-EDA-SAMMS) has been optimized for substrates and Fe(III) deposition methods. The Fe-EDA-SAMMS material had a 4-fold increase in phosphate binding capacity and a broader operating pH window compared to other reports. The material had a faster phosphate binding rate and was significantly less affected by other anions than Sevelamer HCl, the gold standard oral phosphate binder, and AG® 1-X8, a commercially available anion exchanger. It had less cytotoxicity to Caco-2 cells than lanthanum carbonate, another prescribed oral phosphate binder. The Fe-EDA-SAMMS also had high capacity for arsenate and chromate, two of the most toxic anions in natural water. PMID:25554735

  1. Modeling oxyanion adsorption on ferralic soil, part 2: chromate, selenate, molybdate, and arsenate adsorption.

    PubMed

    Pérez, Claudio; Antelo, Juan; Fiol, Sarah; Arce, Florencio

    2014-10-01

    High levels of oxyanions are found in the soil environment, often as a result of human activity. At high concentrations, oxyanions can be harmful to both humans and wildlife. Information about the interactions between oxyanions and natural samples is essential for understanding the bioavailability, toxicity, and transport of these compounds in the environment. In the present study, the authors investigated the reactivity of different oxyanions (AsO4 , MoO4 , SeO4 , and CrO4 ) at different pH values in 2 horizons of a ferralic soil. By combining available microscopic data on iron oxides with the macroscopic data obtained, the authors were able to use the charge distribution model to accurately describe the adsorption of these 4 oxyanions and thus to determine the surface speciation. The charge distribution model was previously calibrated and evaluated using phosphate adsorption/desorption data. The adsorption behavior on ferralic soil is controlled mainly by the natural iron oxides present, and it is qualitatively analogous to that exhibited by synthetic iron oxides. The highest adsorption was found for arsenate ions, whereas the lowest was found for selenate, with chromate and molybdate ions showing an intermediate behavior.

  2. Complexation of arsenate with humic substance in water extract of compost.

    PubMed

    Lin, Haw-Tarn; Wang, M C; Li, Gwo-Chen

    2004-09-01

    The interactions of environmental toxicants with organic substances affect the speciation and dynamics, and subsequent toxicity, mobility, and fate of toxicants in the environment. For the purpose of understanding the complexation of As(V) with humic substances, arsenate-containing solutions with As concentrations from 1 to 8 mgl(-1) were prepared to react with the water extract of compost (WEC). All the reaction systems including the control were incubated for 48 h at 25 degrees C. The complexation of As(V) with humic substance was examined by dialysis and ion exchange techniques. From 30% to 51% of added As(V) reacted with organic substance in WEC to form an As-metal-organic complex. This was verified as a hydrophobic organic fraction after separation of As-metal-organic complex fraction from the hydrophilic fraction by XAD-8 resin. The complex substance was also identified as a humic substance by the method of proton binding formation function determination. This suggests that cations, such as Ca and Mg, and especially Fe, Al, and Mn act in cation bridging in the complexation of As(V) with humic substance. The role of metals in the complexation of As(V) with humic substance in terrestrial and especially aquatic environments thus merits close attention.

  3. Co-adsorption of Trichloroethylene and Arsenate by Iron-Impregnated Granular Activated Carbon.

    PubMed

    Deng, Baolin; Kim, Eun-Sik

    2016-05-01

    Co-adsorption of trichloroethylene (TCE) and arsenate [As(V)] was investigated using modified granular activated carbons (GAC): untreated, sodium hypochlorite-treated (NaClO-GAC), and NaClO with iron-treated GAC (NaClO/Fe-GAC). Batch experiments of single- [TCE or As(V)] and binary- [TCE and As(V)] components solutions are evaluated through Langmuir and Freundlich isotherm models and adsorption kinetic tests. In the single-component system, the adsorption capacity of As(V) was increased by the NaClO-GAC and the NaClO/Fe-GAC. The untreated GAC showed a low adsorption capacity for As(V). Adsorption of TCE by the NaClO/Fe-GAC was maximized, with an increased Freundlich constant. Removal of TCE in the binary-component system was decreased 15% by the untreated GAC, and NaClO- and NaClO/Fe-GAC showed similar efficiency to the single-component system because of the different chemical status of the GAC surfaces. Results of the adsorption isotherms of As(V) in the binary-component system were similar to adsorption isotherms of the single-component system. The adsorption affinities of single- and binary-component systems corresponded with electron transfer, competitive adsorption, and physicochemical properties.

  4. Evolution of arsenate toxicity in nodulated white lupine in a long-term culture.

    PubMed

    Vázquez, Saúl; Esteban, Elvira; Carpena, Ramón O

    2008-09-24

    White lupine is an As-resistant legume that is of interest for phytoremediation of As-contaminated soils. To achieve successful phytoremediation, monitoring of the nutritional status of the selected plant species during the entire culture cycle is required to maintain a plant cover with high biomass production. A long-term pot experiment was carried out with nodulated lupine grown on perlite with 10 and 100 microM As concentrations. The reproductive period (from 10 weeks) was the most sensitive phenologic stage of white lupine to long-term As exposure. The 10 microM As treatment increased the uptake and translocation of micronutrients, except for Cu, mainly at flowering with As levels in pods below the statutory limit (1 mg kg (-1) fresh weight). However, the 100 microM As treatment induced significant differences compared to the control. These findings confirm the relatively high resistance of white lupine to arsenate and support the use of this species in phytoremediation and/or revegetation of As-contaminated sites, with special attention on P and Cu nutrition at flowering.

  5. Raman spectroscopy of the arsenate minerals maxwellite and in comparison with tilasite.

    PubMed

    Frost, Ray L; Scholz, Ricardo; López, Andrés; Xi, Yunfei

    2014-04-05

    Maxwellite NaFe(3+)(AsO4)F is an arsenate mineral containing fluoride and forms a continuous series with tilasite CaMg(AsO4)F. Both maxwellite and tilasite form a continuous series with durangite NaAl(3+)(AsO4)F. We have used the combination of scanning electron microscopy with EDS and vibrational spectroscopy to chemically analyse the mineral maxwellite and make an assessment of the molecular structure. Chemical analysis shows that maxwellite is composed of Fe, Na and Ca with minor amounts of Mn and Al. Raman bands for tilasite at 851 and 831cm(-1) are assigned to the Raman active ν1 symmetric stretching vibration (A1) and the Raman active triply degenerate ν3 antisymmetric stretching vibration (F2). The Raman band of maxwellite at 871cm(-1) is assigned to the ν1 symmetric stretching vibration and the Raman band at 812cm(-1) is assigned to the ν3 antisymmetric stretching vibration. The intense Raman band of tilasite at 467cm(-1) is assigned to the Raman active triply degenerate ν4 bending vibration (F2). Raman band at 331cm(-1) for tilasite is assigned to the Raman active doubly degenerate ν2 symmetric bending vibration (E). Both Raman and infrared spectroscopy do not identify any bands in the hydroxyl stretching region as is expected. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Preparation and certification of arsenate [As(V)] reference material, NMIJ CRM 7912-a.

    PubMed

    Narukawa, Tomohiro; Kuroiwa, Takayoshi; Narushima, Izumi; Jimbo, Yasujiro; Suzuki, Toshihiro; Chiba, Koichi

    2010-05-01

    Arsenate [As(V)] solution reference material, National Metrology Institute of Japan (NMIJ) certified reference material (CRM) 7912-a, for speciation of arsenic species was developed and certified by NMIJ, the National Institute of Advanced Industrial Science and Technology. High-purity As(2)O(3) reagent powder was dissolved in 0.8 M HNO(3) solution and As(III) was oxidized to As(V) with HNO(3) to prepare 100 mg kg(-1) of As(V) candidate CRM solution. The solution was bottled in 400 bottles (50 mL each). The concentration of As(V) was determined by four independent analytical techniques-inductively coupled plasma mass spectrometry, inductively coupled plasma optical emission spectrometry, graphite furnace atomic absorption spectrometry, and liquid chromatography inductively coupled plasma mass spectrometry-according to As(V) calibration solutions, which were prepared from the arsenic standard of the Japan Calibration Service system and whose species was guaranteed to be As(V) by NMIJ. The uncertainties of all the measurements and preparation procedures were evaluated. The certified value of As(V) in the CRM is (99.53 +/- 1.67) mg kg(-1) (k = 2).

  7. Tolerance, arsenic uptake, and oxidative stress in Acacia farnesiana under arsenate-stress.

    PubMed

    Alcantara-Martinez, Nemi; Guizar, Sandra; Rivera-Cabrera, Fernando; Anicacio-Acevedo, Blanca E; Buendia-Gonzalez, Leticia; Volke-Sepulveda, Tania

    2016-01-01

    Acacia farnesiana is a shrub widely distributed in soils heavily polluted with arsenic in Mexico. However, the mechanisms by which this species tolerates the phytotoxic effects of arsenic are unknown. This study aimed to investigate the tolerance and bioaccumulation of As by A. farnesiana seedlings exposed to high doses of arsenate (AsV) and the role of peroxidases (POX) and glutathione S-transferases (GST) in alleviating As-stress. For that, long-period tests were performed in vitro under different AsV treatments. A. farnesiana showed a remarkable tolerance to AsV, achieving a half-inhibitory concentration (IC50) of about 2.8 mM. Bioaccumulation reached about 940 and 4380 mg As·kg(-1) of dry weight in shoots and roots, respectively, exposed for 60 days to 0.58 mM AsV. Seedlings exposed to such conditions registered a growth delay during the first 15 days, when the fastest As uptake rate (117 mg kg(-1) day(-1)) occurred, coinciding with both the highest rate of lipid peroxidation and the strongest up-regulation of enzyme activities. GST activity showed a strong correlation with the As bioaccumulated, suggesting its role in imparting AsV tolerance. This study demonstrated that besides tolerance to AsV, A. farnesiana bioaccumulates considerable amounts of As, suggesting that it may be useful for phytostabilization purposes.

  8. Characterization of adsorption of aqueous arsenite and arsenate onto charred dolomite in microcolumn systems.

    PubMed

    Salameh, Yousef; Al-Muhtaseb, Ala'a H; Mousa, Hasan; Walker, Gavin M; Ahmad, Mohammad N M

    2014-01-01

    In this work, the removal of arsenite, As(III), and arsenate, As(V), from aqueous solutions onto thermally processed dolomite (charred dolomite) via microcolumn was evaluated. The effects of mass of adsorbent (0.5-2 g), initial arsenic concentration (50-2000 ppb) and particle size (<0.355-2 mm) on the adsorption capacity of charred dolomite in a microcolumn were investigated. It was found that the adsorption of As(V) and As(III) onto charred dolomite exhibited a characteristic 'S' shape. The adsorption capacity increased as the initial arsenic concentration increased. A slow decrease in the column adsorption capacity was noted as the particle size increased from>0.335 to 0.710-2.00 mm. For the binary system, the experimental data show that the adsorption of As(V) and As(III) was independent of both ions in solution. The experimental data obtained from the adsorption process were successfully correlated with the Thomas Model and Bed Depth Service Time Model.

  9. Structure and function of NADPH-cytochrome P450 reductase and nitric oxide synthase reductase domain

    SciTech Connect

    Iyanagi, Takashi . E-mail: iyanagi@spring8.or.jp

    2005-12-09

    NADPH-cytochrome P450 reductase (CPR) and the nitric oxide synthase (NOS) reductase domains are members of the FAD-FMN family of proteins. The FAD accepts two reducing equivalents from NADPH (dehydrogenase flavin) and FMN acts as a one-electron carrier (flavodoxin-type flavin) for the transfer from NADPH to the heme protein, in which the FMNH {sup {center_dot}}/FMNH{sub 2} couple donates electrons to cytochrome P450 at constant oxidation-reduction potential. Although the interflavin electron transfer between FAD and FMN is not strictly regulated in CPR, electron transfer is activated in neuronal NOS reductase domain upon binding calmodulin (CaM), in which the CaM-bound activated form can function by a similar mechanism to that of CPR. The oxygenated form and spin state of substrate-bound cytochrome P450 in perfused rat liver are also discussed in terms of stepwise one-electron transfer from CPR. This review provides a historical perspective of the microsomal mixed-function oxidases including CPR and P450. In addition, a new model for the redox-linked conformational changes during the catalytic cycle for both CPR and NOS reductase domain is also discussed.

  10. The orphan protein bis-γ-glutamylcystine reductase joins the pyridine nucleotide-disulfide reductase family

    PubMed Central

    Kim, Juhan; Copley, Shelley D.

    2014-01-01

    Facile DNA sequencing became possible decades after many enzymes had been purified and characterized. Consequently, there are still “orphan” enyzmes whose activity is known but the genes that encode them have not been identified. Identification of the genes encoding orphan enzymes is important because it allows correct annotation of genes of unknown function or with mis-assigned function. Bis-γ-glutamylcystine reductase (GCR) is an orphan protein that was purified in 1988. This enzyme catalyzes the reduction of bis-γ-glutamylcystine. γ-Glutamylcysteine (γ-Glu-Cys) is the major low molecular weight thiol in halobacteria. We purified GCR from Halobacterium sp. NRC-1 and identified the sequence of 23 tryptic peptides by NanoLC electrospray ionization tandem mass spectrometry. These peptides cover 62% of the protein predicted to be encoded by a gene in Halobacterium sp. NRC-1 that is annotated as mercuric reductase. GCR and mercuric reductase activities were assayed using enzyme that was expressed in E. coli and re-folded from inclusion bodies. The enzyme had robust GCR activity, but no mercuric reductase activity. The genomes of most, but not all, halobacteria for which whole genome sequences are available have close homologs of GCR, suggesting that there is more to be learned about the low molecular weight thiols used in halobacteria. PMID:23560638

  11. Nitrite Reductase NirBD Is Induced and Plays an Important Role during In Vitro Dormancy of Mycobacterium tuberculosis

    PubMed Central

    Akhtar, Shamim; Khan, Arshad; Sohaskey, Charles D.; Jagannath, Chinnaswamy

    2013-01-01

    Mycobacterium tuberculosis is one of the strongest reducers of nitrate among all mycobacteria. Reduction of nitrate to nitrite, mediated by nitrate reductase (NarGHJI) of M. tuberculosis, is induced during the dormant stage, and the enzyme has a respiratory function in the absence of oxygen. Nitrite reductase (NirBD) is also functional during aerobic growth when nitrite is the sole nitrogen source. However, the role of NirBD-mediated nitrite reduction during the dormancy is not yet characterized. Here, we analyzed nitrite reduction during aerobic growth as well as in a hypoxic dormancy model of M. tuberculosis in vitro. When nitrite was used as the sole nitrogen source in the medium, the organism grew and the reduction of nitrite was evident in both hypoxic and aerobic cultures of M. tuberculosis. Remarkably, the hypoxic culture of M. tuberculosis, compared to the aerobic culture, showed 32- and 4-fold-increased expression of nitrite reductase (NirBD) at the transcription and protein levels, respectively. More importantly, a nirBD mutant of M. tuberculosis was unable to reduce nitrite and compared to the wild-type (WT) strain had a >2-log reduction in viability after 240 h in the Wayne model of hypoxic dormancy. Dependence of M. tuberculosis on nitrite reductase (NirBD) was also seen in a human macrophage-based dormancy model where the nirBD mutant was impaired for survival compared to the WT strain. Overall, the increased expression and essentiality of nitrite reductase in the in vitro dormancy models suggested that NirBD-mediated nitrite reduction could be critical during the persistent stage of M. tuberculosis. PMID:23935045

  12. Early complications. Respiratory failure.

    PubMed

    Zwischenberger, J B; Alpard, S K; Bidani, A

    1999-08-01

    Pulmonary complications following thoracic surgery are common and associated with significant morbidity and mortality. Respiratory failure after pneumonectomy occurs in approximately 5% to 15% of cases and significantly increases patient mortality. Strategies for ventilator support are based on the nature of the underlying complication and the pathophysiology of respiratory failure. This article describes the cause and pathophysiology of respiratory failure and pulmonary embolus postpneumonectomy. Diagnosis, management, and innovative therapies are also reviewed.

  13. Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase.

    PubMed

    Wu, Sheng-Yi; Rothery, Richard A; Weiner, Joel H

    2015-10-09

    We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser(719), NarG-His(1163), and NarG-His(1184)); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His(1092) and NarG-His(1098)). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of -88 and -36 mV, respectively). Ala variants of His(1092) and His(1098) also elicit large ΔEm values of -143 and -101 mV, respectively. An Arg variant of His(1092) elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  14. Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase*

    PubMed Central

    Wu, Sheng-Yi; Rothery, Richard A.; Weiner, Joel H.

    2015-01-01

    We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser719, NarG-His1163, and NarG-His1184); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His1092 and NarG-His1098). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of −88 and −36 mV, respectively). Ala variants of His1092 and His1098 also elicit large ΔEm values of −143 and −101 mV, respectively. An Arg variant of His1092 elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. PMID:26297003

  15. Managing respiratory disease.

    PubMed

    Lunn, Sarah; Restrick, Louise; Stern, Myra

    2017-02-01

    The diverse and evolving role of a psychologist within a respiratory multidisciplinary team (MDT) is described, providing a working model for service provision. The rationale for appointing a psychologist within a respiratory MDT is presented first, citing relevant policy and research and outlining the wider psychosocial impact of respiratory disease. This is followed by an insight into the psychologist's role by highlighting important areas, including key therapy themes and the challenge of patient engagement. The way in which the psychologist supports the collective aims and aspirations of respiratory colleagues to provide a more holistic package of care is illustrated throughout.

  16. The human respiratory gate

    NASA Technical Reports Server (NTRS)

    Eckberg, Dwain L.

    2003-01-01

    Respiratory activity phasically alters membrane potentials of preganglionic vagal and sympathetic motoneurones and continuously modulates their responsiveness to stimulatory inputs. The most obvious manifestation of this 'respiratory gating' is respiratory sinus arrhythmia, the rhythmic fluctuations of electrocardiographic R-R intervals observed in healthy resting humans. Phasic autonomic motoneurone firing, reflecting the throughput of the system, depends importantly on the intensity of stimulatory inputs, such that when levels of stimulation are low (as with high arterial pressure and sympathetic activity, or low arterial pressure and vagal activity), respiratory fluctuations of sympathetic or vagal firing are also low. The respiratory gate has a finite capacity, and high levels of stimulation override the ability of respiration to gate autonomic responsiveness. Autonomic throughput also depends importantly on other factors, including especially, the frequency of breathing, the rate at which the gate opens and closes. Respiratory sinus arrhythmia is small at rapid, and large at slow breathing rates. The strong correlation between systolic pressure and R-R intervals at respiratory frequencies reflects the influence of respiration on these two measures, rather than arterial baroreflex physiology. A wide range of evidence suggests that respiratory activity gates the timing of autonomic motoneurone firing, but does not influence its tonic level. I propose that the most enduring significance of respiratory gating is its use as a precisely controlled experimental tool to tease out and better understand otherwise inaccessible human autonomic neurophysiological mechanisms.

  17. 3-Methyleneoxindole Reductase of Peas 1

    PubMed Central

    Moyed, H. S.; Williamson, Valerie

    1967-01-01

    A 100-fold purification of a reduced triphosphopyridine nucleotide/3-methyleneoxindole reductase of peas has been achieved using conventional protein fractionation procedures. Reduced diphosphopyridine nucleotide is 25-fold less effective than reduced triphosphopyridine nucleotide as the reductant. The preparation is free of other reductase activities including those linking the oxidation of reduced pyridine nucleotide coenzymes to the reduction of cytochrome c; vitamins K1, K2, and K3; O2; nitrate; oxidized glutathione; and thiazolyl blue tetrazolium. The affinity of the enzyme for 3-methyleneoxindole (Ks = 0.5 mm 3-methyleneoxindole) is relatively high. It is, therefore, reasonable to assume that 3-methyleneoxindole is the normal substrate. The enzyme is inhibited by indole-3-acetic acid, indole-3-aldehyde, and by l-naph-thaleneacetic acid. While these are not especially powerful inhibitors (K1 = 1.9-4.0 mm) the competitive relationship with 3-methyleneoxindole indicates that significant inhibition might occur at low intracellular concentrations of the substrate. PMID:6042360

  18. Enzyme toolbox: novel enantiocomplementary imine reductases.

    PubMed

    Scheller, Philipp N; Fademrecht, Silvia; Hofelzer, Sebastian; Pleiss, Jürgen; Leipold, Friedemann; Turner, Nicholas J; Nestl, Bettina M; Hauer, Bernhard

    2014-10-13

    Reducing reactions are among the most useful transformations for the generation of chiral compounds in the fine-chemical industry. Because of their exquisite selectivities, enzymatic approaches have emerged as the method of choice for the reduction of C=O and activated C=C bonds. However, stereoselective enzymatic reduction of C=N bonds is still in its infancy-it was only recently described after the discovery of enzymes capable of imine reduction. In our work, we increased the spectrum of imine-reducing enzymes by database analysis. By combining the currently available knowledge about the function of imine reductases with the experimentally uncharacterized diversity stored in protein sequence databases, three novel imine reductases with complementary enantiopreference were identified along with amino acids important for catalysis. Furthermore, their reducing capability was demonstrated by the reduction of the pharmaceutically relevant prochiral imine 2-methylpyrroline. These novel enzymes exhibited comparable to higher catalytic efficiencies than previously described enzymes, and their biosynthetic potential is highlighted by the full conversion of 2-methylpyrroline in whole cells with excellent selectivities.

  19. Soluble ascorbate free radical reductase in the human lens.

    PubMed

    Bando, M; Obazawa, H

    1994-01-01

    A major and a minor ascorbate free radical (AFR) reductase were separated from the soluble fraction in the human lens cortex by DEAE-cellulose ion-exchange column chromatography. These AFR reductases also exhibited diaphorase activity using dichlorophenolindophenol and ferricyanide as electron acceptors. The major AFR reductase was partially purified by 5'AMP-Sepharose 4B affinity column chromatography. This partially purified AFR reductase showed a single band of diaphorase activity in native polyacrylamide disc gel electrophoresis. This activity band corresponded to the major protein observed in protein staining by Coomassie Brilliant Blue. However, the protein staining by Coomassie Brilliant Blue showed this activity band surrounded by diffused staining. Molecular weight of the partially purified AFR reductase was determined to be 32 kDa by gel filtration, and the apparent Km value for AFR was about 15 microM. This major lens AFR reductase could be distinguished from soluble Neurospora, Euglena and cucumber AFR reductases, and from two ubiquitous enzymes with reduction activity of AFR and/or foreign compounds, ie, NADH-cytochrome b5 reductase and DT-diaphorase, by their molecular weights, Km values and/or ion-exchange chromatographic behaviors.

  20. Functional and Phylogenetic Divergence of Fungal Adenylate-Forming Reductases

    PubMed Central

    Kalb, Daniel; Lackner, Gerald

    2014-01-01

    A key step in fungal l-lysine biosynthesis is catalyzed by adenylate-forming l-α-aminoadipic acid reductases, organized in domains for adenylation, thiolation, and the reduction step. However, the genomes of numerous ascomycetes and basidiomycetes contain an unexpectedly large number of additional genes encoding similar but functionally distinct enzymes. Here, we describe the functional in vitro characterization of four reductases which were heterologously produced in Escherichia coli. The Ceriporiopsis subvermispora serine reductase Nps1 features a terminal ferredoxin-NADP+ reductase (FNR) domain and thus belongs to a hitherto undescribed class of fungal multidomain enzymes. The second major class is characterized by the canonical terminal short-chain dehydrogenase/reductase domain and represented by Ceriporiopsis subvermispora Nps3 as the first biochemically characterized l-α-aminoadipic acid reductase of basidiomycete origin. Aspergillus flavus l-tyrosine reductases LnaA and LnbA are members of a distinct phylogenetic clade. Phylogenetic analysis supports the view that fungal adenylate-forming reductases are more diverse than previously recognized and belong to four distinct classes. PMID:25085485

  1. Structure of an integral membrane sterol reductase from Methylomicrobium alcaliphilum

    PubMed Central

    Li, Xiaochun; Roberti, Rita; Blobel, Günter

    2014-01-01

    Sterols are essential biological molecules in the majority of life forms. Sterol reductases1 including Delta-14 sterol reductase (C14SR), 7-dehydrocholesterol reductase (DHCR7) and 24-dehydrocholesterol reductase (DHCR24) reduce specific carbon-carbon double bonds of the sterol moiety using a reducing cofactor during sterol biosynthesis. Lamin B Receptor2 (LBR), an integral inner nuclear membrane protein, also contains a functional C14SR domain. Here we report the crystal structure of a Delta-14 sterol reductase (maSR1) from the methanotrophic bacterium Methylomicrobium alcaliphilum 20Z, a homolog of human C14SR, LBR, and DHCR7, with the cofactor NADPH. The enzyme contains 10 transmembrane segments (TM). Its catalytic domain comprises the C-terminal half (containing TM6-10) and envelops two interconnected pockets, one of which faces the cytoplasm and houses NADPH, while the other one is accessible from the lipid bilayer. Comparison with a soluble steroid 5β-reductase structure3 suggests that the reducing end of NADPH meets the sterol substrate at the juncture of the two pockets. A sterol reductase activity assay proves maSR1 can reduce the double bond of a cholesterol biosynthetic intermediate demonstrating functional conservation to human C14SR. Therefore, our structure as a prototype of integral membrane sterol reductases provides molecular insight into mutations in DHCR7 and LBR for inborn human diseases. PMID:25307054

  2. Structural and biochemical characterization of cinnamoyl-coa reductases

    USDA-ARS?s Scientific Manuscript database

    Cinnamoyl-coenzyme A reductase (CCR) catalyzes the reduction of hydroxycinnamoyl-coenzyme A (CoA) esters using NADPH to produce hydroxycinnamyl aldehyde precursors in lignin synthesis. The catalytic mechanism and substrate specificity of cinnamoyl-CoA reductases from sorghum (Sorghum bicolor), a str...

  3. The role of Bradyrhizobium japonicum nitric oxide reductase in nitric oxide detoxification in soya bean root nodules.

    PubMed

    Meakin, G E; Jepson, B J N; Richardson, D J; Bedmar, E J; Delgado, M J

    2006-02-01

    The identification of nitric oxide-bound leghaemoglobin within soya bean nodules has led to the question of how Bradyrhizobium japonicum bacteroids overcome the toxicity of this nitric oxide. It has previously been shown that one candidate for nitric oxide detoxification, the respiratory nitric oxide reductase, is expressed in soya bean nodules from plants supplied with nitrate. In this paper, the role of this enzyme in nitric oxide detoxification is assessed and discussion is provided on other possible B. japonicum nitric oxide detoxification systems.

  4. Copper and arsenate co-sorption at the mineral-water interfaces of goethite and jarosite.

    PubMed

    Gräfe, Markus; Beattie, David A; Smith, Euan; Skinner, William M; Singh, Balwant

    2008-06-15

    The co-sorption reaction products of arsenate (As(V)) and copper (Cu(II)) on goethite (alpha-FeOOH) and natro-jarosite (Na(3)Fe(3)(SO(4))(2)(OH)(6)) were investigated with extended X-ray absorption fine structure (EXAFS) spectroscopy to determine if Cu(II) and As(V) would form precipitates or compete with each other for surface sites. The reaction products were prepared by mixing 250 microM Cu(SO(4)) with 10, 25, or 50 microM Na(2)HAsO(4) at pH 5.65 and allowing the mixture to react in 10 m(2) L(-1) goethite or jarosite suspensions for 12 days. In addition, EXAFS data of Cu(SO(4)) and As(V) sorbed on goethite and jarosite were collected as control species. All reaction conditions were under-saturated with respect to common copper bearing minerals: tenorite (CuO), brochantite (Cu(4)(OH)(6)SO(4)), and hydrated clinoclase (Cu(3)(AsO(4))(2)2H(2)O). The extents of the As(V) and Cu(II) surface adsorption reactions showed a strong competitive effect from Cu(II) on As(V) adsorption for a nominal Cu:As mole-ratio of 25:1. With increasing nominal As(V) concentration, As(V) sorption on goethite and jarosite increased without diminishing the amount of Cu(II) sorption. In the absence of either co-sorbate, As(V) and Cu(II) formed the expected surface adsorption species, i.e., bidentate binuclear and edge-sharing surface complexes, consistent with previously published results. In each other's presence, the local bonding environments of As(V) and Cu(II) showed that the co-sorbates form a precipitate on the goethite and jarosite surface at nominal concentrations of 10:1 and 5:1. At nominal Cu:As mole-ratios of 25:1, Cu(II) did not form significantly different surface complexes on goethite or jarosite from those in the absence of As(V), however, As K-edge EXAFS results distinctly showed Cu(II) atoms in As(V)'s local bonding environment on the goethite surface. The structures of the two precipitates were different and depended on the anion-layer structure and possibly the presence of

  5. High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of layered uranyl arsenates.

    PubMed

    Liu, Hsin-Kuan; Ramachandran, Eswaran; Chen, Yi-Hsin; Chang, Wen-Jung; Lii, Kwang-Hwa

    2014-09-02

    Five new uranyl arsenates, Na14[(UO2)5(AsO4)8]·2H2O (1), K6[(UO2)5O5(AsO4)2] (2a), K4[(UO2)3O2(AsO4)2] (2b), Rb4[(UO2)3O2(AsO4)2] (3), and Cs6[(UO2)5O2(AsO4)4] (4), were synthesized by high-temperature, high-pressure hydrothermal reactions at about 560 °C and 1440 bar and were characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and photoluminescence spectroscopy. Crystal data for compound 1: triclinic, P1, a = 7.0005(3) Å, b = 12.1324(4) Å, c = 13.7428(5) Å, α = 64.175(2)°, β = 89.092(2)°, γ = 85.548(2)°, V = 1047.26(7) Å(3), Z = 1, R1 = 0.0185; compound 2a: monoclinic, P2₁/c, a = 6.8615(3) Å, b = 24.702(1) Å, c = 7.1269(3) Å, β = 98.749(2)°, V = 1193.89(9) Å(3), Z = 2, R1 = 0.0225; compound 2b: monoclinic, P2₁/c, a = 6.7852(3) Å, b = 17.3640(8) Å, c = 7.1151(3) Å, β = 98.801(3)°, V = 828.42(6) Å(3), Z = 2, R1 = 0.0269; compound 3: monoclinic, P2₁/m, a = 6.9783(3) Å, b = 17.4513(8) Å, c = 7.0867(3) Å, β = 90.808(3)°, V = 862.94(7) Å(3), Z = 2, R1 = 0.0269; compound 4: triclinic, P1, a = 7.7628(3) Å, b = 9.3324(4) Å, c = 11.9336(4) Å, α = 75.611(2)°, β = 73.136(2)°, γ = 86.329(2)°, V = 801.37(5) Å(3), Z = 1, R1 = 0.0336. The five compounds have layer structures consisting of uranyl square, pentagonal, and hexagonal bipyramids as well as AsO4 tetrahedra. Compound 1 contains chains of discrete uranyl square and pentagonal bipyramids, 2a contains three-polyhedron-wide ribbons of edge- and corner-sharing uranyl square and pentagonal bipyramids, 2b and 3 contain dimers of edge-shairing pentagonal bipyramids that share edges with hexagonal bipyramids to form chains, and 4 contains one-polyhedron-wide zigzag chains of edge-sharing uranyl polyhedra. The double sheet structure of 1 is new, but the chain topology has been observed in an organically templated uranyl sulfate. Compound 2b is a new geometrical isomer of the phosphuranylite group. The sheet anion topologies of 2a and 4 can be obtained by

  6. Physical, chemical, and biological methods for the removal of arsenic compounds.

    PubMed

    Lim, K T; Shukor, M Y; Wasoh, H

    2014-01-01

    Arsenic is a toxic metalloid which is widely distributed in nature. It is normally present as arsenate under oxic conditions while arsenite is predominant under reducing condition. The major discharges of arsenic in the environment are mainly due to natural sources such as aquifers and anthropogenic sources. It is known that arsenite salts are more toxic than arsenate as it binds with vicinal thiols in pyruvate dehydrogenase while arsenate inhibits the oxidative phosphorylation process. The common mechanisms for arsenic detoxification are uptaken by phosphate transporters, aquaglyceroporins, and active extrusion system and reduced by arsenate reductases via dissimilatory reduction mechanism. Some species of autotrophic and heterotrophic microorganisms use arsenic oxyanions for their regeneration of energy. Certain species of microorganisms are able to use arsenate as their nutrient in respiratory process. Detoxification operons are a common form of arsenic resistance in microorganisms. Hence, the use of bioremediation could be an effective and economic way to reduce this pollutant from the environment.

  7. Physical, Chemical, and Biological Methods for the Removal of Arsenic Compounds

    PubMed Central

    Lim, K. T.; Shukor, M. Y.; Wasoh, H.

    2014-01-01

    Arsenic is a toxic metalloid which is widely distributed in nature. It is normally present as arsenate under oxic conditions while arsenite is predominant under reducing condition. The major discharges of arsenic in the environment are mainly due to natural sources such as aquifers and anthropogenic sources. It is known that arsenite salts are more toxic than arsenate as it binds with vicinal thiols in pyruvate dehydrogenase while arsenate inhibits the oxidative phosphorylation process. The common mechanisms for arsenic detoxification are uptaken by phosphate transporters, aquaglyceroporins, and active extrusion system and reduced by arsenate reductases via dissimilatory reduction mechanism. Some species of autotrophic and heterotrophic microorganisms use arsenic oxyanions for their regeneration of energy. Certain species of microorganisms are able to use arsenate as their nutrient in respiratory process. Detoxification operons are a common form of arsenic resistance in microorganisms. Hence, the use of bioremediation could be an effective and economic way to reduce this pollutant from the environment. PMID:24696853

  8. Functionalized chitosan electrospun nanofiber for effective removal of trace arsenate from water

    NASA Astrophysics Data System (ADS)

    Min, Ling-Li; Zhong, Lu-Bin; Zheng, Yu-Ming; Liu, Qing; Yuan, Zhi-Huan; Yang, Li-Ming

    2016-08-01

    An environment-friendly iron functionalized chitosan elctrospun nanofiber (ICS-ENF) was synthesized for trace arsenate removal from water. The ICS-ENF was fabricated by electrospinning a mixture of chitosan, PEO and Fe3+ followed by crosslinking with ammonia vapor. The physicochemical properties of ICS-ENF were characterized by FESEM, TEM-EDX and XRD. The ICS-ENF was found to be highly effective for As(V) adsorption at neutral pH. The As(V) adsorption occurred rapidly and achieved equilibrium within 100 min, which was well fitted by pseudo-second-order kinetics model. The As(V) adsorption decreased with increased ionic strength, suggesting an outer-sphere complexation of As(V) on ICS-ENF. Freundlich model well described the adsorption isotherm, and the maximum adsorption capacity was up to 11.2 mg/g at pH 7.2. Coexisting anions of chloride and sulfate showed negligible influence on As(V) removal, but phosphate and silicate significantly reduced As(V) adsorption by competing for adsorption sites. FTIR and XPS analysis demonstrated -NH, -OH and C-O were responsible for As(V) uptake. ICS-ENF was easily regenerated using 0.003 M NaOH, and the removal rate remained above 98% after ten successively adsorption-desorption recycles. This study extends the potential applicability of electrospun nanofibers for water purification and provides a promising approach for As(V) removal from water.

  9. The role of phosphorus in the metabolism of arsenate by a freshwater green alga, Chlorella vulgaris.

    PubMed

    Baker, Josh; Wallschläger, Dirk

    2016-11-01

    A freshwater microalga, Chlorella vulgaris, was grown in the presence of varying phosphate concentrations (<10-500μg/L P) and environmentally realistic concentrations of arsenate (As(V)) (5-50μg/L As). Arsenic speciation in the culture medium and total cellular arsenic were measured using AEC-ICP-MS and ICP-DRC-MS, respectively, to determine arsenic biotransformation and uptake in the various phosphorus scenarios. At high phosphate concentration in the culture medium, >100μg/L P, the uptake and biotransformation of As(V) was minimal and dimethylarsonate (DMAs(V)) was the dominant metabolite excreted by C. vulgaris, albeit at relatively low concentrations. At common environmental P concentrations, 0-50μg/L P, the uptake and biotransformation of As(V) increased. At these higher As-uptake levels, arsenite (As(III)) was the predominant metabolite excreted from the cell. The concentrations of As(III) in these low P conditions were much higher than the concentrations of methylated arsenicals observed at the various P concentrations studied. The switchover threshold between the (small) methylation and (large) reduction of As(V) occurred around a cellular As concentration of 1fg/cell. The observed nearly quantitative conversion of As(V) to As(III) under low phosphate conditions indicates the importance of As(V) bio-reduction at common freshwater P concentrations. These findings on the influence of phosphorus on arsenic uptake, accumulation and excretion are discussed in relation to previously published research. The impact that the two scenarios of As(V) metabolism, As(III) excretion at high As(V)-uptake and methylarsenical excretion at low As(V)-uptake, have on freshwater arsenic speciation is discussed.

  10. Functionalized chitosan electrospun nanofiber for effective removal of trace arsenate from water

    PubMed Central

    Min, Ling-Li; Zhong, Lu-Bin; Zheng, Yu-Ming; Liu, Qing; Yuan, Zhi-Huan; Yang, Li-Ming

    2016-01-01

    An environment-friendly iron functionalized chitosan elctrospun nanofiber (ICS-ENF) was synthesized for trace arsenate removal from water. The ICS-ENF was fabricated by electrospinning a mixture of chitosan, PEO and Fe3+ followed by crosslinking with ammonia vapor. The physicochemical properties of ICS-ENF were characterized by FESEM, TEM-EDX and XRD. The ICS-ENF was found to be highly effective for As(V) adsorption at neutral pH. The As(V) adsorption occurred rapidly and achieved equilibrium within 100 min, which was well fitted by pseudo-second-order kinetics model. The As(V) adsorption decreased with increased ionic strength, suggesting an outer-sphere complexation of As(V) on ICS-ENF. Freundlich model well described the adsorption isotherm, and the maximum adsorption capacity was up to 11.2 mg/g at pH 7.2. Coexisting anions of chloride and sulfate showed negligible influence on As(V) removal, but phosphate and silicate significantly reduced As(V) adsorption by competing for adsorption sites. FTIR and XPS analysis demonstrated –NH, –OH and C–O were responsible for As(V) uptake. ICS-ENF was easily regenerated using 0.003 M NaOH, and the removal rate remained above 98% after ten successively adsorption-desorption recycles. This study extends the potential applicability of electrospun nanofibers for water purification and provides a promising approach for As(V) removal from water. PMID:27572634

  11. Role of rat sodium/phosphate cotransporters in the cell membrane transport of arsenate

    SciTech Connect

    Villa-Bellosta, Ricardo Sorribas, Victor

    2008-10-01

    Inorganic arsenate (As{sup V}) is a common contaminant of underground water. Following oral exposure, it is assumed that As{sup V} is distributed and crosses cell membranes through inorganic phosphate (Pi) transporters. We have tested this hypothesis by studying the inhibition of rat Na/Pi cotransporters by As{sup V} in Xenopus laevis oocytes and in several rat tissues. The ubiquitously expressed type III Pi transporters (PiT-1 and PiT-2) showed a low affinity for As{sup V} (K{sub i} {approx} 3.8 mM), similar to the Pi transport system in aortic vascular smooth muscle cells (K{sub i} 1.5 mM). The type II renal isoforms, NaPi-IIa and NaPi-IIc, were also poorly inhibited by As{sup V} (K{sub i} {approx} 1 mM), similar to the Pi transport from kidney cortex brush-border membrane (BBM) vesicles. Conversely, the high-affinity intestinal transporter, NaPi-IIb, was very efficiently inhibited with a K{sub i} of 51 {mu}M, similar to the Pi transport from intestinal BBM vesicles. Taking into account the 1.1 mM Pi in blood and renal ultrafiltrate, and the nanomolar range of As{sup V} exposures, we have determined that the contribution by Na/Pi cotransporters to As{sup V} membrane transport is negligible, given that 10-15 mM As{sup V} would be necessary in these fluids to be significantly transported. Intestinal transport is an exception, because Pi competition is weak, thereby considering that its concentration in lumen mainly depends on low Pi levels from ingested fresh water, and because As{sup V} very efficiently inhibits Pi intestinal transport. Our data agree with current toxicokinetic knowledge, and they explain the asymmetric excretion of trivalent and pentavalent arsenic species into bile and urine.

  12. Biomineralization of Arsenate to Arsenic Sulfides is Greatly Enhanced at Mildly Acidic Conditions

    PubMed Central

    Rodriguez-Freire, Lucia; Sierra-Alvarez, Reyes; Root, Robert; Chorover, Jon; Field, James A.

    2014-01-01

    Arsenic (As) is an important water contaminant due to its high toxicity and widespread occurrence. Arsenic-sulfide minerals (ASM) are formed during microbial reduction of arsenate (AsV) and sulfate (SO42−). The objective of this research is to study the effect of the pH on the removal of As due to the formation of ASM in an iron-poor system. A series of batch experiments was used to study the reduction of SO42− and AsV by an anaerobic biofilm mixed culture in a range of pH conditions (6.1–7.2), using ethanol as the electron donor. Total soluble concentrations and speciation of S and As were monitored. Solid phase speciation of arsenic was characterized by x-ray adsorption spectroscopy (XAS). A marked decrease of the total aqueous concentrations of As and S was observed in the inoculated treatments amended with ethanol, but not in the non-inoculated controls, indicating that the As-removal was biologically mediated. The pH dramatically affected the extent and rate of As removal, as well as the stoichiometric composition of the precipitate. The amount of As removed was 2-fold higher and the rate of the As removal was up to 17-fold greater at pH 6.1 than at pH 7.2. Stoichiometric analysis and XAS results confirmed the precipitate was composed of a mixture of orpiment and realgar, and the proportion of orpiment in the sample increased with increasing pH. The results taken as a whole suggest that ASM formation is greatly enhanced at mildly acidic pH conditions. PMID:25222328

  13. Arsenic Retention in Foliage and Soil after Monosodium Methyl Arsenate (MSMA) Application to Turfgrass.

    PubMed

    Matteson, Audrey R; Gannon, Travis W; Jeffries, Matthew D; Haines, Stephanie; Lewis, Dustin F; Polizzotto, Matthew L

    2014-01-01

    Monosodium methyl arsenate (MSMA) is a commonly used herbicide for weed control in turfgrass systems. There is concern that arsenic from applied MSMA could leach to groundwater or run off into surface water, thereby threatening human and ecosystem health. The USEPA has proposed a phase-out of the herbicide but is seeking additional research about the toxicity and environmental impacts of MSMA before establishing a final ruling. Little research has systematically investigated MSMA in field-based settings; instead, risks have been inferred from isolated field measurements or model-system studies. Accordingly, the overall goal of this study was to quantify the fate of arsenic after MSMA application to a managed turfgrass system. After MSMA application to turfgrass-covered and bareground lysimeters, the majority of arsenic was retained in turfgrass foliage and soils throughout year-long experiments, with 50 to 101% of the applied arsenic recovered in turfgrass systems and 55 to 66% recovered in bareground systems. Dissolved arsenic concentrations from 76.2-cm-depth pore water in the MSMA-treated soils were consistently <2 μg L, indistinguishable from background concentrations. As measured by adsorption isotherm experiments, MSMA retention by the sandy soil from our field site was markedly less than retention by a washed sand and a clay loam. Collectively, these results suggest that under aerobic conditions, minimal arsenic leaching to groundwater would occur after a typical application of MSMA to turfgrass. However, repeated MSMA application may pose environmental risks. Additional work is needed to examine arsenic cycling near the soil surface and to define arsenic speciation changes under different soil conditions.

  14. Glutathione-supported arsenate reduction coupled to arsenolysis catalyzed by ornithine carbamoyl transferase

    SciTech Connect

    Nemeti, Balazs; Gregus, Zoltan

    2009-09-01

    Three cytosolic phosphorolytic/arsenolytic enzymes, (purine nucleoside phosphorylase [PNP], glycogen phosphorylase, glyceraldehyde-3-phosphate dehydrogenase) have been shown to mediate reduction of arsenate (AsV) to the more toxic arsenite (AsIII) in a thiol-dependent manner. With unknown mechanism, hepatic mitochondria also reduce AsV. Mitochondria possess ornithine carbamoyl transferase (OCT), which catalyzes phosphorolytic or arsenolytic citrulline cleavage; therefore, we examined if mitochondrial OCT facilitated AsV reduction in presence of glutathione. Isolated rat liver mitochondria were incubated with AsV, and AsIII formed was quantified. Glutathione-supplemented permeabilized or solubilized mitochondria reduced AsV. Citrulline (substrate for OCT-catalyzed arsenolysis) increased AsV reduction. The citrulline-stimulated AsV reduction was abolished by ornithine (OCT substrate inhibiting citrulline cleavage), phosphate (OCT substrate competing with AsV), and the OCT inhibitor norvaline or PALO, indicating that AsV reduction is coupled to OCT-catalyzed arsenolysis of citrulline. Corroborating this conclusion, purified bacterial OCT mediated AsV reduction in presence of citrulline and glutathione with similar responsiveness to these agents. In contrast, AsIII formation by intact mitochondria was unaffected by PALO and slightly stimulated by citrulline, ornithine, and norvaline, suggesting minimal role for OCT in AsV reduction in intact mitochondria. In addition to OCT, mitochondrial PNP can also mediate AsIII formation; however, its role in AsV reduction appears severely limited by purine nucleoside supply. Collectively, mitochondrial and bacterial OCT promote glutathione-dependent AsV reduction with coupled arsenolysis of citrulline, supporting the hypothesis that AsV reduction is mediated by phosphorolytic/arsenolytic enzymes. Nevertheless, because citrulline cleavage is disfavored physiologically, OCT may have little role in AsV reduction in vivo.

  15. Two Ethylenediamine-Templated Zeolite-Type Structures in Zinc Arsenate and Cobalt Phosphate Systems

    NASA Astrophysics Data System (ADS)

    Bu, Xianhui; Feng, Pingyun; Gier, Thurman E.; Stucky, Galen D.

    1998-03-01

    Hydrothermal syntheses and X-ray crystal structures of two zeolite-type structures encapsulating protonated ethylenediamine and consisting of three-dimensional 8-ring channels are presented. UCSB-3 and ACP-3 are isostructural and have zeolite-type topologies. The framework consists of cross-linked bifurcated hexagonal-square (bhs) chains, similar to that found in the zeolite-type structure, AlPO 4-D. Alternatively, like a number of zeolite structures such as ABW, gismondine, merlinoite, and phillipsite, the framework can be considered as superimposed 4.8 2nets. UCSB-3 is the only amine-templated arsenate with a zeolite-type topology. Crystal data for (H 3NCH 2CH 2NH 3) 0.5. ZnAsO 4(UCSB-3): M=235.35, space group P4 2/ n, a=10.7598(1) Å, c=9.1015(1) Å, V=1053.71(2) Å 3, Z=8, Dc=2.967 g cm -3, Mo Kα, λ=0.71073 Å, μ=10.815 mm -1, 2 θmax=56.26°, R( F)=2.67% for 84 parameters and 1262 reflections with I>2 σ( I). Crystal data for (H 3NCH 2CH 2NH 3) 0.5(1- x) . Al xCo 1- xPO 4( x≈0.15, ACP-3): space group P4 2/ n, a=10.4236(1) Å, c=8.9487(1) Å, V=972.29(2) Å 3, Z=8, Mo Kα, 2 θmax=56.52°, R( F)=3.59% for 92 parameters and 1108 reflections with I>2 σ( I).

  16. Legacy lead arsenate soil contamination at childcare centers in the Yakima Valley, Central Washington, USA.

    PubMed

    Durkee, Jenna; Bartrem, Casey; Möller, Gregory

    2017-02-01

    From the early 1900s to the 1950s, Yakima Valley orchards were commonly treated with lead arsenate (LA) insecticides. Lead (Pb) and arsenic (As) soil contamination has been identified on former orchard lands throughout Central Washington and pose a threat to human health and the environment. The levels of Pb and As in soil and interior dust at participating childcare centers in the Upper Yakima Valley (Yakima County), Washington were sampled to explore exposure potential for young children. Childcare center soils were collected from two soil depths, homogenized, and analyzed in bulk by a field-portable X-ray fluorescence spectrometer (XRF). Interior dust wipes samples were collected from at least two locations in each facility. All soil samples >250 mg/kg Pb and/or >20 As mg/kg were sieved to 250 μm, tested by XRF a second time, and analyzed via acid digestion and inductively coupled plasma mass spectrometry (ICP-MS) analysis. Bulk and sieved XRF results, as well as ICP-MS to XRF results were strongly correlated. Maximum Pb and As XRF results indicated that 4 (21%) and 8 (42%) of the 19 childcare centers surveyed exceeded the regulatory standard for Pb and As, respectively. Historic land use was significantly associated with elevated Pb and As levels. Interior dust loadings were below United States Environmental Protection Agency (EPA) guidelines. Childcare centers are areas of intensive use for children and when coupled with potential residential exposure in their homes, the total daily exposure is a potential hazard to children. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Role of rat sodium/phosphate cotransporters in the cell membrane transport of arsenate.

    PubMed

    Villa-Bellosta, Ricardo; Sorribas, Víctor

    2008-10-01

    Inorganic arsenate (As(V)) is a common contaminant of underground water. Following oral exposure, it is assumed that As(V) is distributed and crosses cell membranes through inorganic phosphate (Pi) transporters. We have tested this hypothesis by studying the inhibition of rat Na/Pi cotransporters by As(V) in Xenopus laevis oocytes and in several rat tissues. The ubiquitously expressed type III Pi transporters (PiT-1 and PiT-2) showed a low affinity for As(V) (K(i) approximately 3.8 mM), similar to the Pi transport system in aortic vascular smooth muscle cells (K(i) 1.5 mM). The type II renal isoforms, NaPi-IIa and NaPi-IIc, were also poorly inhibited by As(V) (K(i) approximately 1 mM), similar to the Pi transport from kidney cortex brush-border membrane (BBM) vesicles. Conversely, the high-affinity intestinal transporter, NaPi-IIb, was very efficiently inhibited with a K(i) of 51 microM, similar to the Pi transport from intestinal BBM vesicles. Taking into account the 1.1 mM Pi in blood and renal ultrafiltrate, and the nanomolar range of As(V) exposures, we have determined that the contribution by Na/Pi cotransporters to As(V) membrane transport is negligible, given that 10-15 mM As(V) would be necessary in these fluids to be significantly transported. Intestinal transport is an exception, because Pi competition is weak, thereby considering that its concentration in lumen mainly depends on low Pi levels from ingested fresh water, and because As(V) very efficiently inhibits Pi intestinal transport. Our data agree with current toxicokinetic knowledge, and they explain the asymmetric excretion of trivalent and pentavalent arsenic species into bile and urine.

  18. Residential arsenic and lead levels in an agricultural community with a history of lead arsenate use.

    PubMed

    Wolz, Sarah; Fenske, Richard A; Simcox, Nancy J; Palcisko, Gary; Kissel, John C

    2003-11-01

    Lead arsenate (PbHAsO4) was used as an insecticide in Washington fruit orchards from 1905 to 1947. We examined exposure potential for children living in an agricultural community with historic PbHAsO4 use. Soil and housedust samples were collected from 58 residences. Families were asked about land use history, age of home, and remodeling activities. Median concentrations of arsenic were higher in housedust than in soil (9.0 and 4.2 microg/g, respectively; P=0.05), as were lead concentrations (129 and 46 microg/g, respectively; P=0.0001). Significant associations were observed between indoor and outdoor levels of each metal, indicating track-in as an important exposure pathway. Homes on or near land use for pear or apple production between 1905 and 1947 had significantly higher soil (P=0.005) and housedust (P=0.004) lead, and soil arsenic (P=0.04) than did the other homes. Homes more than 30 years old had significantly higher soil and housedust lead than did newer homes (P=0.01). Homes remodeled within the past two years had significantly higher soil (P=0.01) and housedust (P=0.04) lead. Child doses extrapolated from these data indicate that 36% of homes had soil or dust arsenic levels above the minimum risk level estimated by the Agency for Toxic Substances and Disease Registry. None of the measured lead levels exceeded current US Environmental Protection Agency guidelines. Public health education programs focused on residential hygiene would be of value in areas of historic PbHAsO4 use.

  19. Soil pollution assessment and identification of hyperaccumulating plants in chromated copper arsenate (CCA) contaminated sites, Korea.

    PubMed

    Usman, Adel R A; Lee, Sang Soo; Awad, Yasser M; Lim, Kyoung Jae; Yang, Jae E; Ok, Yong Sik

    2012-05-01

    In recent decades, heavy metal contamination in soil adjacent to chromated copper arsenate (CCA) treated wood has received increasing attention. This study was conducted to determine the pollution level (PL) based on the concentrations of Cr, Cu and As in soils and to evaluate the remediative capacity of native plant species grown in the CCA contaminated site, Gangwon Province, Korea. The pollution index (PI), integrated pollution index (IPI), bioaccumulation factors (BAF(shoots) and BAF(roots)) and translocation factor (TF) were determined to ensure soil contamination and phytoremediation availability. The 19 soil samples from 10 locations possibly contaminated with Cr, Cu and As were collected. The concentrations of Cr, Cu and As in the soil samples ranged from 50.56-94.13 mg kg(-1), 27.78-120.83 mg kg(-1), and 0.13-9.43 mg kg(-1), respectively. Generally, the metal concentrations decreased as the distance between the CCA-treated wood structure and sampling point increased. For investigating phytoremediative capacity, the 19 native plant species were also collected in the same area with soil samples. Our results showed that only one plant species of Iris ensata, which presented the highest accumulations of Cr (1120 mg kg(-1)) in its shoot, was identified as a hyperaccumulator. Moreover, the relatively higher values of BAF(shoot) (3.23-22.10) were observed for Typha orientalis, Iris ensata and Scirpus radicans Schk, suggesting that these plant species might be applicable for selective metal extraction from the soils. For phytostabilization, the 15 plant species with BAF(root) values>1 and TF values<1 were suitable; however, Typha orientalis was the best for Cr.

  20. Adsorption kinetics and isotherms of arsenite and arsenate on hematite nanoparticles and aggregates.

    PubMed

    Dickson, Dionne; Liu, Guangliang; Cai, Yong

    2017-01-15

    Iron (Fe) nanoparticles, e.g., zerovalent iron (ZVI) and iron oxide nanoparticles (IONP), have been used for remediation and environmental management of arsenic (As) contamination. These Fe nanoparticles, although originally nanosized, tend to form aggregates, in particular in the environment. The interactions of As with both nanoparticles and micron-sized aggregates should be considered when these Fe nanomaterials are used for mitigation of As issue. The objective of this study was to compare the adsorption kinetics and isotherm of arsenite (As(III)) and arsenate (As(V)) on bare hematite nanoparticles and aggregates and how this affects the fate of arsenic in the environment. The adsorption kinetic process was investigated with regards to the aggregation of the nanoparticles and the type of sorbed species. Kinetic data were best described by a pseudo second-order model. Both As species had similar rate constants, ranging from 3.82 to 6.45 × 10(-4) g/(μg·h), as rapid adsorption occurred within the first 8 h regardless of particle size. However, hematite nanoparticles and aggregates showed a higher affinity to adsorb larger amounts of As(V) (4122 ± 62.79 μg/g) than As(III) (2899 ± 71.09 μg/g) at equilibrium. We were able to show that aggregation and sedimentation of hematite nanoparticles occurs during the adsorption process and this might cause the immobilization and reduced bioavailability of arsenic. Isotherm studies were described by the Freundlich model and it confirmed that hematite nanoparticles have a significantly higher adsorption capacity for both As(V) and As(III) than hematite aggregates. This information is useful and can assist in predicting arsenic adsorption behavior and assessing the role of iron oxide nanoparticles in the biogeochemical cycling of arsenic.

  1. Phytochelatin synthesis in Dunaliella salina induced by arsenite and arsenate under various phosphate regimes.

    PubMed

    Wang, Ya; Zhang, Chunhua; Zheng, Yanheng; Ge, Ying

    2017-02-01

    This study investigated the dynamic variations in thiol compounds, including cysteine (Cys), glutathione (GSH), and phytochelatins (PCs), in Dunaliella salina samples exposed to arsenite [As(III)] and arsenate [As(V)] under various phosphate (PO4(3-)) regimes. Our results showed that GSH was the major non-protein sulfhydryl compound in D. salina cells. As(III) and As(V) induced PC syntheses in D. salina. PC2, PC3, and PC4 were all found in algal cells; the PC concentrations decreased gradually while exposed to As for 3 d. The synthesis of PC2-3 was significantly affected by As(III) and As(V) concentrations in the cultures. More PCs were detected in the As(V)-treated algal cells compared with the As(III) treatment. PC levels increased with As(III)/As(V) amount in the medium, but remained stable after 112μgL(-1) As(V) exposure. In contrast, significant (p<0.001) positive correlations were observed between PC synthesis and intracellular As(III) content or As accumulation in As(III)-treated algal cells during the 72-h exposure. PO4(3-) had a significant influence on the PC synthesis in algal cells, irrespective of the As-treated species. Reductions in As uptake and subsequent PC synthesis by D. salina were observed as the PO4(3-) concentration in the growth medium increased. L-Buthionine sulfoximine (BSO) differentially influenced PC synthesis in As-treated D. salina under different extracellular PO4(3-) regimes. Overall, our data demonstrated that the production of GSH and PCs was affected by PO4(3-) and that these thiols played an important role in As detoxification by D. salina.

  2. Living with Respiratory Failure

    MedlinePlus

    ... smoking. Emotional Issues and Support Living with respiratory failure may cause fear, anxiety, depression, and stress. Talk about how you feel with your health care team. Talking to a professional counselor also can ... to living with respiratory failure. You can see how other people who have ...

  3. Respiratory Care Therapist.

    ERIC Educational Resources Information Center

    Ohio State Univ., Columbus. Center on Education and Training for Employment.

    This document, which is designed for use in developing a tech prep competency profile for the occupation of respiratory care therapist, lists technical competencies and competency builders for 18 units pertinent to the health technologies cluster in general as well as those specific to the occupation of respiratory care therapist. The following…

  4. Respiratory Care Therapist.

    ERIC Educational Resources Information Center

    Ohio State Univ., Columbus. Center on Education and Training for Employment.

    This document, which is designed for use in developing a tech prep competency profile for the occupation of respiratory care therapist, lists technical competencies and competency builders for 18 units pertinent to the health technologies cluster in general as well as those specific to the occupation of respiratory care therapist. The following…

  5. Determination of arsenate by sorption pre-concentration on polystyrene beads packed in a microfluidic device with chemiluminescence detection.

    PubMed

    Som-aum, Waraporn; Li, Haifang; Liu, Jiangjiang; Lin, Jin-Ming

    2008-09-01

    A highly sensitive chemiluminescence (CL) method for the determination of arsenate in water based on a simple microfluidic device was developed. The method was based on sorption pre-concentration of arsenate as a form of vanadomolybdoarsenate heteropoly acid (VMoAs-HPA) ion-paired with hexadecyltrimethylammonium bromide on the surface of polystyrene beads packed in a microfluidic device monitored by chemiluminescence detection. The composition of the VMoAs-HPA complex was studied by varying the concentrations of ammonium molybdate, ammonium vanadate and sulfuric acid with a variable-size simplex optimization process, of which the optimum concentrations were 6.3 x 10(-5), 5.0 x 10(-6) and 1.0 x 10(-2) M, respectively. In this work, 1.0 x 10(-3) M ethylenediaminetetraacetic acid was added to all work solutions to remove the interferences of the other metal ions on the CL detection. The integration of sorption pre-concentration not only increased the detection sensitivity but also eliminated the interference from phosphate and chromate. The calibration plot was linear from 1.0 x 10(-7) to 5.0 x 10(-5) M As(v). The limit of detection was 8.9 x 10(-8) M As(v) (S/N = 3). The time required for one analysis run was as short as 5 min. The relative standard deviation was 5.9% (n = 9). This method was successfully applied to the determination of arsenate in mineral-, drinking- and tap-water samples.

  6. Diacetyl/l-Xylulose Reductase Mediates Chemical Redox Cycling in Lung Epithelial Cells.

    PubMed

    Yang, Shaojun; Jan, Yi-Hua; Mishin, Vladimir; Heck, Diane E; Laskin, Debra L; Laskin, Jeffrey D

    2017-07-17

    Reactive carbonyls such as diacetyl (2,3-butanedione) and 2,3-pentanedione in tobacco and many food and consumer products are known to cause severe respiratory diseases. Many of these chemicals are detoxified by carbonyl reductases in the lung, in particular, dicarbonyl/l-xylulose reductase (DCXR), a multifunctional enzyme important in glucose metabolism. DCXR is a member of the short-chain dehydrogenase/reductase (SDR) superfamily. Using recombinant human enzyme, we discovered that DCXR mediates redox cycling of a variety of quinones generating superoxide anion, hydrogen peroxide, and, in the presence of transition metals, hydroxyl radicals. Redox cycling activity preferentially utilized NADH as a cosubstrate and was greatest for 9,10-phenanthrenequinone and 1,2-naphthoquinone, followed by 1,4-naphthoquinone and 2-methyl-1,4-naphthoquinone (menadione). Using 9,10-phenanthrenequinone as the substrate, quinone redox cycling was found to inhibit DCXR reduction of l-xylulose and diacetyl. Competitive inhibition of enzyme activity by the quinone was observed with respect to diacetyl (Ki = 190 μM) and l-xylulose (Ki = 940 μM). Abundant DCXR activity was identified in A549 lung epithelial cells when diacetyl was used as a substrate. Quinones inhibited reduction of this dicarbonyl, causing an accumulation of diacetyl in the cells and culture medium and a decrease in acetoin, the reduced product of diacetyl. The identification of DCXR as an enzyme activity mediating chemical redox cycling suggests that it may be important in generating cytotoxic reactive oxygen species in the lung. These activities, together with the inhibition of dicarbonyl/l-xylulose metabolism by redox-active chemicals, as well as consequent deficiencies in pentose metabolism, are likely to contribute to lung injury following exposure to dicarbonyls and quinones.

  7. The aldo-keto reductases (AKRs): Overview.

    PubMed

    Penning, Trevor M

    2015-06-05

    The aldo-keto reductase (AKR) protein superfamily contains >190 members that fall into 16 families and are found in all phyla. These enzymes reduce carbonyl substrates such as: sugar aldehydes; keto-steroids, keto-prostaglandins, retinals, quinones, and lipid peroxidation by-products. Exceptions include the reduction of steroid double bonds catalyzed by AKR1D enzymes (5β-reductases); and the oxidation of proximate carcinogen trans-dihydrodiol polycyclic aromatic hydrocarbons; while the β-subunits of potassium gated ion channels (AKR6 family) control Kv channel opening. AKRs are usually 37kDa monomers, have an (α/β)8-barrel motif, display large loops at the back of the barrel which govern substrate specificity, and have a conserved cofactor binding domain. AKRs catalyze an ordered bi bi kinetic mechanism in which NAD(P)H cofactor binds first and leaves last. In enzymes that favor NADPH, the rate of release of NADP(+) is governed by a slow isomerization step which places an upper limit on kcat. AKRs retain a conserved catalytic tetrad consisting of Tyr55, Asp50, Lys84, and His117 (AKR1C9 numbering). There is conservation of the catalytic mechanism with short-chain dehydrogenases/reductases (SDRs) even though they show different protein folds. There are 15 human AKRs of these AKR1B1, AKR1C1-1C3, AKR1D1, and AKR1B10 have been implicated in diabetic complications, steroid hormone dependent malignancies, bile acid deficiency and defects in retinoic acid signaling, respectively. Inhibitor programs exist world-wide to target each of these enzymes to treat the aforementioned disorders. Inherited mutations in AKR1C and AKR1D1 enzymes are implicated in defects in the development of male genitalia and bile acid deficiency, respectively, and occur in evolutionarily conserved amino acids. The human AKRs have a large number of nsSNPs and splice variants, but in many instances functional genomics is lacking. AKRs and their variants are now poised to be interrogated using

  8. Experimental and theoretical vibrational spectroscopic evaluation of arsenate coordination in aqueous solutions, solids, and at mineral-water interfaces

    NASA Astrophysics Data System (ADS)

    Myneni, Satish C. B.; Traina, Samuel J.; Waychunas, Glenn A.; Logan, Terry J.

    1998-10-01

    Arsenate (AsO 43-) is a common species in oxidizing aquatic systems and hydrothermal fluids, and its solubility and partitioning into different mineral phases are determined by the nature of AsO 43- coordination, solution pH, type of soluble cations, and H 2O structure at the mineral-fluid interfaces. While the vibrational spectroscopy has been widely used in examining the AsO 43- coordination chemistry, insufficient knowledge on the correlation of AsO 43- molecular structure and its vibrational spectra impeded the complete spectral interpretation. In this paper, we evaluated the vibrational spectroscopy of AsO 43- in solutions, crystals, and sorbed on mineral surfaces using theoretical (semiempirical, for aqueous species) and experimental studies, with emphasis on the protonation, hydration, and metal complexation influence on the As-O symmetric stretching vibrations. Theoretical predictions are in excellent agreement with the experimental studies and helped in the evaluation of vibrational modes of several arsenate-complexes and in the interpretation of experimental spectra. These vibrational spectroscopic studies (IR, Raman) suggest that the symmetry of AsO 43- polyhedron is strongly distorted, and its As-O vibrations are affected by protonation and the relative influence on AsO 43- structure decreases in the order: H + ≫ cation ≥ H 2O. For all AsO 43- complexes, the As-OX symmetric stretching (X = metal, H +, H 2O; ≤820 cm -1) shifted to lower wavenumbers when compared to that of uncomplexed AsO 43-. In addition, the As-OH symmetric stretching of protonated arsenates in aqueous solutions shift to higher energies with increasing protonation (<720, <770, <790 cm -1 for HAsO 42-, H 2AsO 4-, and H 3AsO 40, respectively). The protonated arsenates in crystalline solids show the same trend with little variation in As-OH symmetric stretching vibrations. Since metal complexation of protonated AsO 43- does not influence the As-OH vibrations significantly, deducing

  9. Selective adsorption of arsenate and the reversible structure transformation of the mesoporous metal-organic framework MIL-100(Fe).

    PubMed

    Cai, Jianhua; Wang, Xueyun; Zhou, Yue; Jiang, Li; Wang, Chunru

    2016-04-28

    Here we describe a highly porous metal-organic framework MIL-100(Fe), which is initially used as an arsenate adsorbent in water. An appropriate mesoporous size allows AsO4(3-) to enter unrestrained and then be captured successfully, furthermore resulting in the damage of long-range order of uniform mesopores. Moreover, the porous framework could also make AsO4(3-) be reversibly desorbed without structural changes and the long-range order of mesopores be recovered again.

  10. Transcripts of Anthocyanidin Reductase and Leucoanthocyanidin Reductase and Measurement of Catechin and Epicatechin in Tartary Buckwheat

    PubMed Central

    Kim, Yeon Bok; Thwe, Aye Aye; Kim, YeJi; Li, Xiaohua; Cho, Jin Woong; Park, Phun Bum; Valan Arasu, Mariadhas; Abdullah Al-Dhabi, Naif; Kim, Sun-Ju; Suzuki, Tastsuro; Hyun Jho, Kwang; Park, Sang Un

    2014-01-01

    Anthocyanidin reductase (ANR) and leucoanthocyanidin reductase (LAR) play an important role in the monomeric units biosynthesis of proanthocyanidins (PAs) such as catechin and epicatechin in several plants. The aim of this study was to clone ANR and LAR genes involved in PAs biosynthesis and examine the expression of these two genes in different organs under different growth conditions in two tartary buckwheat cultivars, Hokkai T8 and T10. Gene expression was carried out by quantitative real-time RT-PCR, and catechin and epicatechin content was analyzed by high performance liquid chromatography. The expression pattern of ANR and LAR did not match the accumulation pattern of PAs in different organs of two cultivars. Epicatechin content was the highest in the flowers of both cultivars and it was affected by light in only Hokkai T8 sprouts. ANR and LAR levels in tartary buckwheat might be regulated by different mechanisms for catechin and epicatechin biosynthesis under light and dark conditions. PMID:24605062

  11. Transcripts of anthocyanidin reductase and leucoanthocyanidin reductase and measurement of catechin and epicatechin in tartary buckwheat.

    PubMed

    Kim, Yeon Bok; Thwe, Aye Aye; Kim, Yeji; Li, Xiaohua; Cho, Jin Woong; Park, Phun Bum; Valan Arasu, Mariadhas; Abdullah Al-Dhabi, Naif; Kim, Sun-Ju; Suzuki, Tastsuro; Hyun Jho, Kwang; Park, Sang Un

    2014-01-01

    Anthocyanidin reductase (ANR) and leucoanthocyanidin reductase (LAR) play an important role in the monomeric units biosynthesis of proanthocyanidins (PAs) such as catechin and epicatechin in several plants. The aim of this study was to clone ANR and LAR genes involved in PAs biosynthesis and examine the expression of these two genes in different organs under different growth conditions in two tartary buckwheat cultivars, Hokkai T8 and T10. Gene expression was carried out by quantitative real-time RT-PCR, and catechin and epicatechin content was analyzed by high performance liquid chromatography. The expression pattern of ANR and LAR did not match the accumulation pattern of PAs in different organs of two cultivars. Epicatechin content was the highest in the flowers of both cultivars and it was affected by light in only Hokkai T8 sprouts. ANR and LAR levels in tartary buckwheat might be regulated by different mechanisms for catechin and epicatechin biosynthesis under light and dark conditions.

  12. Docking and molecular dynamics studies at trypanothione reductase and glutathione reductase active sites.

    PubMed

    Iribarne, Federico; Paulino, Margot; Aguilera, Sara; Murphy, Miguel; Tapia, Orlando

    2002-05-01

    A theoretical docking study on the active sites of trypanothione reductase (TR) and glutathione reductase (GR) with the corresponding natural substrates, trypanothione disulfide (T[S]2) and glutathione disulfide (GSSG), is reported. Molecular dynamics simulations were carried out in order to check the robustness of the docking results. The energetic results are in agreement with previous experimental findings and show the crossed complexes have lower stabilization energies than the natural ones. To test DOCK3.5, four nitro furanic compounds, previously designed as potentially active anti-chagasic molecules, were docked at the GR and TR active sites with the DOCK3.5 procedure. A good correlation was found between differential inhibitory activity and relative interaction energy (affinity). The results provide a validation test for the use of DOCK3.5 in connection with the design of anti-chagasic drugs.

  13. A high-throughput assay format for determination of nitrate reductase and nitrite reductase enzyme activities

    SciTech Connect

    McNally, N.; Liu, Xiang Yang; Choudary, P.V.

    1997-01-01

    The authors describe a microplate-based high-throughput procedure for rapid assay of the enzyme activities of nitrate reductase and nitrite reductase, using extremely small volumes of reagents. The new procedure offers the advantages of rapidity, small sample size-nanoliter volumes, low cost, and a dramatic increase in the throughput sample number that can be analyzed simultaneously. Additional advantages can be accessed by using microplate reader application software packages that permit assigning a group type to the wells, recording of the data on exportable data files and exercising the option of using the kinetic or endpoint reading modes. The assay can also be used independently for detecting nitrite residues/contamination in environmental/food samples. 10 refs., 2 figs.

  14. Expression in Escherichia coli of Cytochrome c Reductase Activity from a Maize NADH:Nitrate Reductase Complementary DNA 1

    PubMed Central

    Campbell, Wilbur H.

    1992-01-01

    A cDNA clone was isolated from a maize (Zea mays L. cv W64A×W183E) scutellum λgt11 library using maize leaf NADH:nitrate reductase Zmnr1 cDNA clone as a hybridization probe; it was designated Zmnr1S. Zmnr1S was shown to be an NADH:nitrate reductase clone by nucleotide sequencing and comparison of its deduced amino acid sequence to Zmnr1. Zmnr1S, which is 1.8 kilobases in length and contains the code for both the cytochrome b and flavin adenine dinucleotide domains of nitrate reductase, was cloned into the EcoRI site of the Escherichia coli expression vector pET5b and expressed. The cell lysate contained NADH:cytochrome c reductase activity, which is a characteristic partial activity of NADH:nitrate reductase dependent on the cytochrome b and flavin adenine dinucleotide domains. Recombinant cytochrome c reductase was purified by immunoaffinity chromatography on monoclonal antibody Zm2(69) Sepharose. The purified cytochrome c reductase, which had a major size of 43 kilodaltons, was inhibited by polyclonal antibodies for maize leaf NADH:nitrate reductase and bound these antibodies when blotted to nitrocellulose. Ultraviolet and visible spectra of oxidized and NADH-reduced recombinant cytochrome c reductase were nearly identical with those of maize leaf NADH:nitrate reductase. These two enzyme forms also had very similar kinetic properties with respect to NADH-dependent cytochrome c and ferricyanide reduction. ImagesFigure 2Figure 3 PMID:16668941

  15. Treatment of synthetic arsenate wastewater with iron-air fuel cell electrocoagulation to supply drinking water and electricity in remote areas.

    PubMed

    Kim, Jung Hwan; Maitlo, Hubdar Ali; Park, Joo Yang

    2017-05-15

    Electrocoagulation with an iron-air fuel cell is an innovative arsenate removal system that can operate without an external electricity supply. Thus, this technology is advantageous for treating wastewater in remote regions where it is difficult to supply electricity. In this study, the possibility of real applications of this system for arsenate treatment with electricity production was verified through electrolyte effect investigations using a small-scale fuel cell and performance testing of a liter-scale fuel cell stack. The electrolyte species studied were NaCl, Na2SO4, and NaHCO3. NaCl was overall the most effective electrolyte for arsenate treatment, although Na2SO4 produced the greatest electrical current and power density. In addition, although the current density and power density were proportional to the concentrations of NaCl and Na2SO4, the use of concentrations above 20 mM of NaCl and Na2SO4 inhibited arsenate treatment due to competition effects between anions and arsenate in adsorption onto the iron hydroxide. The dominant iron hydroxide produced at the iron anode was found to be lepidocrocite by means of Raman spectroscopy. A liter-scale four-stack iron-air fuel cell with 10 mM NaCl electrolyte was found to be able to treat about 300 L of 1 ppm arsenate solution to below 10 ppb during 1 day, based on its 60-min treatment capacity, as well as produce the maximum power density of 250 mW/m(2).

  16. New clues to the local atomic structure of short-range ordered ferric arsenate from extended X-ray absorption fine structure spectroscopy.

    PubMed

    Mikutta, Christian; Mandaliev, Petar N; Kretzschmar, Ruben

    2013-04-02

    Short-range ordered ferric arsenate (FeAsO4 · xH2O) is a secondary As precipitate frequently encountered in acid mine waste environments. Two distinct structural models have recently been proposed for this phase. The first model is based on the structure of scorodite (FeAsO4 · 2H2O) where isolated FeO6 octahedra share corners with four adjacent arsenate (AsO4) tetrahedra in a three-dimensional framework (framework model). The second model consists of single chains of corner-sharing FeO6 octahedra being bridged by AsO4 bound in a monodentate binuclear (2)C complex (chain model). In order to rigorously test the accuracy of both structural models, we synthesized ferric arsenates and analyzed their local (<6 Å) structure by As and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. We found that both As and Fe K-edge EXAFS spectra were most compatible with isolated FeO6 octahedra being bridged by AsO4 tetrahedra (RFe-As = 3.33 ± 0.01 Å). Our shell-fit results further indicated a lack of evidence for single corner-sharing FeO6 linkages in ferric arsenate. Wavelet-transform analyses of the Fe K-edge EXAFS spectra of ferric arsenates complemented by shell fitting confirmed Fe atoms at an average distance of ∼5.3 Å, consistent with crystallographic data of scorodite and in disagreement with the chain model. A scorodite-type local structure of short-range ordered ferric arsenates provides a plausible explanation for their rapid transformation into scorodite in acid mining environments.

  17. Raman spectroscopy of selected tsumcorite Pb(Zn,Fe3+)2(AsO4)2(OH,H2O) minerals--implications for arsenate accumulation.

    PubMed

    Frost, Ray L; Xi, Yunfei

    2012-02-01

    The presence of arsenic in the environment is a hazard. The accumulation of arsenate by a range of cations in the formation of minerals provides a mechanism for the accumulation of arsenate. The formation of the tsumcorite minerals is an example of a series of minerals which accumulate arsenate. There are about twelve examples in this mineral group. Raman spectroscopy offers a method for the analysis of these minerals. The structure of selected tsumcorite minerals with arsenate and sulphate anions were analysed by Raman spectroscopy. Isomorphic substitution of sulphate for arsenate is observed for gartrellite and thometzekite. A comparison is made with the sulphate bearing mineral natrochalcite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO(4)(3-) anion. Characteristic Raman spectra of the minerals enable the assignment of the bands to specific vibrational modes.

  18. Structure-activity relationship of pyrrole based S-nitrosoglutathione reductase inhibitors: carboxamide modification.

    PubMed

    Sun, Xicheng; Qiu, Jian; Strong, Sarah A; Green, Louis S; Wasley, Jan W F; Blonder, Joan P; Colagiovanni, Dorothy B; Stout, Adam M; Mutka, Sarah C; Richards, Jane P; Rosenthal, Gary J

    2012-03-15

    The enzyme S-nitrosoglutathione reductase (GSNOR) is a member of the alcohol dehydrogenase family (ADH) that regulates the levels of S-nitrosothiols (SNOs) through catabolism of S-nitrosoglutathione (GSNO). GSNO and SNOs are implicated in the pathogenesis of many diseases including those in respiratory, gastrointestinal, and cardiovascular systems. The pyrrole based N6022 was recently identified as a potent, selective, reversible, and efficacious GSNOR inhibitor which is currently in clinical development for acute asthma. We describe here the synthesis and structure-activity relationships (SAR) of novel pyrrole based analogs of N6022 focusing on carboxamide modifications on the pendant N-phenyl moiety. We have identified potent and novel GSNOR inhibitors that demonstrate efficacy in an ovalbumin (OVA) induced asthma model in mice.

  19. Discovery of potent and novel S-nitrosoglutathione reductase inhibitors devoid of cytochrome P450 activities.

    PubMed

    Sun, Xicheng; Qiu, Jian; Strong, Sarah A; Green, Louis S; Wasley, Jan W F; Blonder, Joan P; Colagiovanni, Dorothy B; Mutka, Sarah C; Stout, Adam M; Richards, Jane P; Rosenthal, Gary J

    2011-10-01

    The pyrrole based N6022 was recently identified as a potent, selective, reversible, and efficacious S-nitrosoglutathione reductase (GSNOR) inhibitor and is currently undergoing clinical development for the treatment of acute asthma. GSNOR is a member of the alcohol dehydrogenase family (ADH) and regulates the levels of S-nitrosothiols (SNOs) through catabolism of S-nitrosoglutathione (GSNO). Reduced levels of GSNO, as well as other nitrosothiols (SNOs), have been implicated in the pathogenesis of many diseases including those of the respiratory, cardiovascular, and gastrointestinal systems. Preservation of endogenous SNOs through GSNOR inhibition presents a novel therapeutic approach with broad applicability. We describe here the synthesis and structure-activity relationships (SAR) of novel pyrrole based analogues of N6022 focusing on removal of cytochrome P450 inhibition activities. We identified potent and novel GSNOR inhibitors having reduced CYP inhibition activities and demonstrated efficacy in a mouse ovalbumin (OVA) model of asthma.

  20. Kinetic mechanism of pulmonary carbonyl reductase.

    PubMed

    Matsuura, K; Nakayama, T; Nakagawa, M; Hara, A; Sawada, H

    1988-05-15

    The kinetic mechanism of guinea-pig lung carbonyl reductase was studied at pH 7 in the forward reaction with five carbonyl substrates and NAD(P)H and in the reverse reaction with propan-2-ol and NAD(P)+. In each case the enzyme mechanism was sequential, and product-inhibition studies were consistent with a di-iso ordered bi bi mechanism, in which NAD(P)H binds to the enzyme first and NAD(P)+ leaves last and the binding of cofactor induces isomerization. The kinetic and binding studies of the cofactors and several inhibitors such as pyrazole, benzoic acid, Cibacron Blue and benzamide indicate that the cofactor and Cibacron Blue bind to the free enzyme whereas the other inhibitors bind to the binary and/or ternary complexes.

  1. Kinetic mechanism of pulmonary carbonyl reductase.

    PubMed Central

    Matsuura, K; Nakayama, T; Nakagawa, M; Hara, A; Sawada, H

    1988-01-01

    The kinetic mechanism of guinea-pig lung carbonyl reductase was studied at pH 7 in the forward reaction with five carbonyl substrates and NAD(P)H and in the reverse reaction with propan-2-ol and NAD(P)+. In each case the enzyme mechanism was sequential, and product-inhibition studies were consistent with a di-iso ordered bi bi mechanism, in which NAD(P)H binds to the enzyme first and NAD(P)+ leaves last and the binding of cofactor induces isomerization. The kinetic and binding studies of the cofactors and several inhibitors such as pyrazole, benzoic acid, Cibacron Blue and benzamide indicate that the cofactor and Cibacron Blue bind to the free enzyme whereas the other inhibitors bind to the binary and/or ternary complexes. PMID:3048244

  2. Methylenetetrahydrofolate reductase: biochemical characterization and medical significance.

    PubMed

    Trimmer, Elizabeth E

    2013-01-01

    Methylenetetrahydrofolate reductase (MTHFR) catalyzes the reduction of 5,10-methylenetetrahydofolate (CH2-H4folate) to 5-methyltetrahydrofolate (CH3-H4folate). The enzyme employs a noncovalently-bound flavin adenine dinucleotide (FAD), which accepts reducing equivalents from NAD(P)H and transfers them to CH2-H4folate. The reaction provides the sole source of CH3-H4folate, which is utilized by methionine synthase in the synthesis of methionine from homocysteine. MTHFR plays a key role in folate metabolism and in the homeostasis of homocysteine; mutations in the enzyme lead to hyperhomocyst(e)inemia. A common C677T polymorphism in MTHFR has been associated with an increased risk for the development of cardiovascular disease, Alzheimer's disease, and depression in adults, and of neural tube defects in the fetus. The mutation also confers protection for certain types of cancers. This review presents the current knowledge of the enzyme, its biochemical characterization, and medical significance.

  3. Enhanced silver nanoparticle synthesis by optimization of nitrate reductase activity.

    PubMed

    Vaidyanathan, Ramanathan; Gopalram, Shubaash; Kalishwaralal, Kalimuthu; Deepak, Venkataraman; Pandian, Sureshbabu Ram Kumar; Gurunathan, Sangiliyandi

    2010-01-01

    Nanostructure materials are attracting a great deal of attention because of their potential for achieving specific processes and selectivity, especially in biological and pharmaceutical applications. The generation of silver nanoparticles using optimized nitrate reductase for the reduction of Ag(+) with the retention of enzymatic activity in the complex is being reported. This report involves the optimization of enzyme activity to bring about enhanced nanoparticle synthesis. Response surface methodology and central composite rotary design (CCRD) were employed to optimize a fermentation medium for the production of nitrate reductase by Bacillus licheniformis at pH 8. The four variables involved in the study of nitrate reductase were Glucose, Peptone, Yeast extract and KNO(3). Glucose had a significant effect on nitrate reductase production. The optimized medium containing (%) Glucose: 1.5, Peptone: 1, Yeast extract: 0.35 and KNO(3): 0.35 resulted in a nitrate reductase activity of 452.206 U/ml which is same as that of the central level. The medium A (showing least nitrate reductase activity) and the medium B (showing maximum nitrate reductase activity) were compared for the synthesis. Spectrophotometric analysis revealed that the particles exhibited a peak at 431 nm and the A(431) for the medium B was 2-fold greater than that of the medium A. The particles were also characterized using TEM. The particles synthesized using the optimized enzyme activity ranged from 10 to 80 nm and therefore can be extended to various medicinal applications.

  4. Chapter 10 Purification of the cytochrome C reductase/cytochrome C oxidase super complex of yeast mitochondria.

    PubMed

    Braun, Hans-Peter; Sunderhaus, Stephanie; Boekema, Egbert J; Kouril, Roman

    2009-01-01

    The protein complexes of the respiratory chain interact by forming large protein particles called respiratory supercomplexes or "respirasomes". Biochemical characterization of these particles proved to be difficult because of their instability. Here we describe a strategy to isolate and characterize the cytochrome c reductase/cytochrome c oxidase supercomplex of yeast, also termed the III + IV supercomplex, which is based on lactate cultivation of yeast, gentle isolation of mitochondria, membrane solubilization by digitonin, sucrose gradient ultracentrifugation, and native gel electrophoresis. The procedure yields pure forms of two varieties of the III + IV supercomplex composed of dimeric complex III and one or two copies of monomeric complex IV. Supercomplex preparations can be used for physiological or structural investigations.

  5. Newborn Respiratory Distress.

    PubMed

    Hermansen, Christian L; Mahajan, Anand

    2015-12-01

    Newborn respiratory distress presents a diagnostic and management challenge. Newborns with respiratory distress commonly exhibit tachypnea with a respiratory rate of more than 60 respirations per minute. They may present with grunting, retractions, nasal flaring, and cyanosis. Common causes include transient tachypnea of the newborn, respiratory distress syndrome, meconium aspiration syndrome, pneumonia, sepsis, pneumothorax, persistent pulmonary hypertension of the newborn, and delayed transition. Congenital heart defects, airway malformations, and inborn errors of metabolism are less common etiologies. Clinicians should be familiar with updated neonatal resuscitation guidelines. Initial evaluation includes a detailed history and physical examination. The clinician should monitor vital signs and measure oxygen saturation with pulse oximetry, and blood gas measurement may be considered. Chest radiography is helpful in the diagnosis. Blood cultures, serial complete blood counts, and C-reactive protein measurement are useful for the evaluation of sepsis. Most neonates with respiratory distress can be treated with respiratory support and noninvasive methods. Oxygen can be provided via bag/mask, nasal cannula, oxygen hood, and nasal continuous positive airway pressure. Ventilator support may be used in more severe cases. Surfactant is increasingly used for respiratory distress syndrome. Using the INSURE technique, the newborn is intubated, given surfactant, and quickly extubated to nasal continuous positive airway pressure. Newborns should be screened for critical congenital heart defects via pulse oximetry after 24 hours but before hospital discharge. Neonatology consultation is recommended if the illness exceeds the clinician's expertise and comfort level or when the diagnosis is unclear in a critically ill newborn.

  6. Inhibition of reductase systems by 2-AAPA modulates peroxiredoxin oxidation and mitochondrial function in A172 glioblastoma cells.

    PubMed

    de Souza, Luiz Felipe; Schmitz, Ariana Ern; da Silva, Luana Caroline Schüler; de Oliveira, Karen Andrinéia; Nedel, Cláudia Beatriz; Tasca, Carla Inês; de Bem, Andreza Fabro; Farina, Marcelo; Dafre, Alcir Luiz

    2017-08-01

    Thiol homeostasis has a critical role in the maintenance of proper cellular functions and survival, being coordinated by the action of several reductive enzymes, including glutathione (GSH)/glutathione reductase (GR) and thioredoxin (Trx)/thioredoxin reductase (TrxR) systems. Here, we investigated the effects of the GR inhibitor 2-acetylamino-3-[4-(2-acetylamino-2-carboxyethylsulfanylthiocarbonylamino)phenylthiocarbamoylsulfanyl]propionic acid (2-AAPA) on the activity of thiol reductases (GR and TrxR), redox balance and mitochondrial function of A172 glioblastoma cells. 2-AAPA inhibited cell GR (IC50=6.7μM) and TrxR (IC50=8.7μM). A significant decrease in the cellular ability to decompose cumene hydroperoxide was observed and associated to a greater susceptibility to this peroxide. The redox state of peroxiredoxins (Prx1, Prx2 and Prx3) was markedly shifted to dimer 30min after treatment with 100μM 2-AAPA, an event preceding 2-AAPA-induced decrease in cell viability. Furthermore, mitochondrial function was also severely impaired, leading to a decrease in the respiratory control ratio, reserve capacity, and ATP synthesis-coupled respiration, as well as an increase in mitochondrial membrane potential. Our results indicate that inhibition of GR and TrxR activities, disruption of the ability to detoxify peroxides, increased oxidation of Prxs, as well as compromised mitochondrial function represent early events mediating 2-AAPA toxicity to A172 glioblastoma cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. 2,4-Dienoyl-coenzyme A reductase deficiency: a possible new disorder of fatty acid oxidation.

    PubMed Central

    Roe, C R; Millington, D S; Norwood, D L; Kodo, N; Sprecher, H; Mohammed, B S; Nada, M; Schulz, H; McVie, R

    1990-01-01

    Several inherited disorders of fatty acid beta-oxidation have been described that relate mainly to saturated precursors. This study is the first report of an enzyme defect related only to unsaturated fatty acid oxidation and provides the first in vivo evidence that fat oxidation in humans proceeds by the reductase-dependent pathway. The patient was a black female, presenting in the neonatal period with persistent hypotonia. Biochemical studies revealed hyperlysinemia, hypocarnitinemia, normal organic acid profile, and an unusual acylcarnitine species in both urine and blood. The new metabolite was positively identified by mass spectrometry as 2-trans,4-cis-decadienoylcarnitine, derived from incomplete oxidation of linoleic acid. In spite of dietary therapy, the patient died of respiratory acidosis at four months of age. Samples of liver and muscle from the autopsy were assayed for 2,4-dienoyl-coenzyme A reductase activity. Using the substrate 2-trans,4-cis-decadienoylcoenzyme A, the reductase activity was 40% of the control value in liver and only 17% of that found in normal muscle. It is suggested that unsaturated substrates should be used for in vitro testing to cover the full range of potential beta-oxidation defects and that acylcarnitine species identification be used for in vivo detection of this disorder. PMID:2332510

  8. Respiratory medicine of reptiles.

    PubMed

    Schumacher, Juergen

    2011-05-01

    Noninfectious and infectious causes have been implicated in the development of respiratory tract disease in reptiles. Treatment modalities in reptiles have to account for species differences in response to therapeutic agents as well as interpretation of diagnostic findings. Data on effective drugs and dosages for the treatment of respiratory diseases are often lacking in reptiles. Recently, advances have been made on the application of advanced imaging modalities, especially computed tomography for the diagnosis and treatment monitoring of reptiles. This article describes common infectious and noninfectious causes of respiratory disease in reptiles, including diagnostic and therapeutic regimen.

  9. Other Community Respiratory Viruses.

    PubMed

    Wunderink, Richard G

    2017-03-01

    Polymerase chain reaction-based diagnosis has become the standard for viral pneumonia and other respiratory tract infections. Expansion of respiratory viral panels (RVPs) outside of influenza and, possibly, respiratory syncytial virus has led to the ability to diagnose viral infections for which no approved specific antiviral treatment exists. Careful clinical evaluation of the patient with a positive RVP is, therefore, critical given the limited repertoire of treatments. Generic treatments with intravenous immunoglobulin, ribavirin, and interferons may benefit select severe viral pneumonia patients, whereas cidofovir has activity for severe adenoviral pneumonia.

  10. Influences of size-fractionated humic acids on arsenite and arsenate complexation and toxicity to Daphnia magna.

    PubMed

    Ren, Jinqian; Fan, Wenhong; Wang, Xiangrui; Ma, Qingquan; Li, Xiaomin; Xu, Zhizhen; Wei, Chaoyang

    2017-01-01

    The intrinsic physicochemical properties of dissolved organic matter (DOM) may affect the mobility and toxicity of arsenic in aquatic environments. In the present study, the humic acid (HA) was ultra-filtered into five fractions according to molecular weight, and their physicochemical properties were characterized. Complexation of HA fractions with arsenite and arsenate was first determined by differential pulse polarography (DPP). The influences of HA fractions on arsenic toxicity were then examined using Daphnia magna as a model organism. As(V) had a higher affinity with HA than As(III), and their complexation was dependent on the total acidity and fluorescence characteristics of DOM. We demonstrated that the acidity and fluorescence also better explained the As toxicity to daphnids than UV absorbance and hydraulic diameter. Arsenic speciation determined by DPP significantly affected the toxicity of arsenite and arsenate. The results extended the free-ion activity model application to the case of arsenic. The present study clearly indicated that DOM with different molecular weights has distinct physicochemical properties, and could influence the speciation and toxicity of As to different extent. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

    PubMed

    Troyer, Lyndsay D; Tang, Yuanzhi; Borch, Thomas

    2014-12-16

    Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 μM U(VI) at concentrations ranging from 0 to 640 μM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 μM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions.

  12. Na3Co2(AsO4)(As2O7): a new sodium cobalt arsenate

    PubMed Central

    Guesmi, Abderrahmen; Driss, Ahmed

    2012-01-01

    In the title compound, tris­odium dicobalt arsenate diarsenate, Na3Co2AsO4As2O7, the two Co atoms, one of the two As and three of the seven O atoms lie on special positions, with site symmetries 2 and m for the Co, m for the As, and 2 and twice m for the O atoms. The two Na atoms are disordered over two general and special positions [occupancies 0.72 (3):0.28 (3) and 0.940 (6):0.060 (6), respectively]. The main structural feature is the association of the CoO6 octa­hedra in the ab plane, forming Co4O20 units, which are corner- and edge-connected via AsO4 and As2O7 arsenate groups, giving rise to a complex polyhedral connectivity with small tunnels, such as those running along the b- and c-axis directions, in which the Na+ ions reside. The structural model is validated by both bond-valence-sum and charge-distribution methods, and the distortion of the coordination polyhedra is analyzed by means of the effective coordination number. PMID:22807699

  13. Rhizosphere colonization and arsenic translocation in sunflower (Helianthus annuus L.) by arsenate reducing Alcaligenes sp. strain Dhal-L.

    PubMed

    Cavalca, Lucia; Corsini, Anna; Bachate, Sachin Prabhakar; Andreoni, Vincenza

    2013-10-01

    In the present study, six arsenic-resistant strains previously isolated were tested for their plant growth promoting characteristics and heavy metal resistance, in order to choose one model strain as an inoculum for sunflower plants in pot experiments. The aim was to investigate the effect of arsenic-resistant strain on sunflower growth and on arsenic uptake from arsenic contaminated soil. Based on plant growth promoting characteristics and heavy metal resistance, Alcaligenes sp. strain Dhal-L was chosen as an inoculum. Beside the ability to reduce arsenate to arsenite via an Ars operon, the strain exhibited 1-amino-cyclopropane-1-carboxylic acid deaminase activity and it was also able to produce siderophore and indole acetic acid. Pot experiments were conducted with an agricultural soil contaminated with arsenic (214 mg kg⁻¹). A real time PCR method was set up based on the quantification of ACR3(2) type of arsenite efflux pump carried by Alcaligenes sp. strain Dhal-L, in order to monitor presence and colonisation of the strain in the bulk and rhizospheric soil. As a result of strain inoculation, arsenic uptake by plants was increased by 53 %, whereas ACR3(2) gene copy number in rhizospheric soil was 100 times higher in inoculated than in control pots, indicating the colonisation of strain. The results indicated that the presence of arsenate reducing strains in the rhizosphere of sunflower influences arsenic mobilization and promotes arsenic uptake by plant.

  14. Facile synthesis of mesoporous Ce-Fe bimetal oxide and its enhanced adsorption of arsenate from aqueous solutions.

    PubMed

    Chen, Bo; Zhu, Zhiliang; Guo, Yanwei; Qiu, Yanling; Zhao, Jianfu

    2013-05-15

    The mesoporous Ce-Fe bimetal oxide (MCFO) was synthesized through a soft-template method and first applied in the adsorption of arsenate in aqueous solutions. The synthesized MCFO was characterized with BET surface area, X-ray diffraction (XRD), zeta potential, scanning electron microscope (SEM), and Fourier transform infrared (FTIR) analysis. The mesoporous structure of the MCFO was determined according to the characterization result. The adsorption efficiency of arsenate ions on the MCFO was studied as a function of initial As(V) concentration, contact time, pH, and coexistent anions. It was found that the adsorption isotherms could be well described by Langmuir model, and the calculated maximum adsorption capacity of MCFO-1 for As(V) was 91.74 mg g(-1), which was significantly greater than that of ordinary Ce-Fe bimetal oxide (CFO). The results showed that the adsorption kinetic data obeyed the pseudo-second order model. Lower pH was favorable for As(V) adsorption on the MCFO. Coexistent phosphate ions exhibited an obvious interference on As(V) adsorption, followed by silicate and fluoride ions. The analysis of BET and FTIR indicated that the high efficiency of As(V) adsorption on this Ce-Fe bimetal oxide (MCFO) was closely related to its uniform mesoporous structure and abundant surface hydroxyl groups. Copyright © 2013 Elsevier Inc. All rights reserved.

  15. Carboxylation mechanism and stereochemistry of crotonyl-CoA carboxylase/reductase, a carboxylating enoyl-thioester reductase

    PubMed Central

    Erb, Tobias J.; Brecht, Volker; Fuchs, Georg; Müller, Michael; Alber, Birgit E.

    2009-01-01

    Chemo- and stereoselective reductions are important reactions in chemistry and biology, and reductases from biological sources are increasingly applied in organic synthesis. In contrast, carboxylases are used only sporadically. We recently described crotonyl-CoA carboxylase/reductase, which catalyzes the reduction of (E)-crotonyl-CoA to butyryl-CoA but also the reductive carboxylation of (E)-crotonyl-CoA to ethylmalonyl-CoA. In this study, the complete stereochemical course of both reactions was investigated in detail. The pro-(4R) hydrogen of NADPH is transferred in both reactions to the re face of the C3 position of crotonyl-CoA. In the course of the carboxylation reaction, carbon dioxide is incorporated in anti fashion at the C2 atom of crotonyl-CoA. For the reduction reaction that yields butyryl-CoA, a solvent proton is added in anti fashion instead of the CO2. Amino acid sequence analysis showed that crotonyl-CoA carboxylase/reductase is a member of the medium-chain dehydrogenase/reductase superfamily and shares the same phylogenetic origin. The stereospecificity of the hydride transfer from NAD(P)H within this superfamily is highly conserved, although the substrates and reduction reactions catalyzed by its individual representatives differ quite considerably. Our findings led to a reassessment of the stereospecificity of enoyl(-thioester) reductases and related enzymes with respect to their amino acid sequence, revealing a general pattern of stereospecificity that allows the prediction of the stereochemistry of the hydride transfer for enoyl reductases of unknown specificity. Further considerations on the reaction mechanism indicated that crotonyl-CoA carboxylase/reductase may have evolved from enoyl-CoA reductases. This may be useful for protein engineering of enoyl reductases and their application in biocatalysis. PMID:19458256

  16. The structure of apo and holo forms of xylose reductase, a dimeric aldo-keto reductase from Candida tenuis.

    PubMed

    Kavanagh, Kathryn L; Klimacek, Mario; Nidetzky, Bernd; Wilson, David K

    2002-07-16

    Xylose reductase is a homodimeric oxidoreductase dependent on NADPH or NADH and belongs to the largely monomeric aldo-keto reductase superfamily of proteins. It catalyzes the first step in the assimilation of xylose, an aldose found to be a major constituent monosaccharide of renewable plant hemicellulosic material, into yeast metabolic pathways. It does this by reducing open chain xylose to xylitol, which is reoxidized to xylulose by xylitol dehydrogenase and metabolically integrated via the pentose phosphate pathway. No structure has yet been determined for a xylose reductase, a dimeric aldo-keto reductase or a family 2 aldo-keto reductase. The structures of the Candida tenuis xylose reductase apo- and holoenzyme, which crystallize in spacegroup C2 with different unit cells, have been determined to 2.2 A resolution and an R-factor of 17.9 and 20.8%, respectively. Residues responsible for mediating the novel dimeric interface include Asp-178, Arg-181, Lys-202, Phe-206, Trp-313, and Pro-319. Alignments with other superfamily members indicate that these interactions are conserved in other dimeric xylose reductases but not throughout the remainder of the oligomeric aldo-keto reductases, predicting alternate modes of oligomerization for other families. An arrangement of side chains in a catalytic triad shows that Tyr-52 has a conserved function as a general acid. The loop that folds over the NAD(P)H cosubstrate is disordered in the apo form but becomes ordered upon cosubstrate binding. A slow conformational isomerization of this loop probably accounts for the observed rate-limiting step involving release of cosubstrate. Xylose binding (K(m) = 87 mM) is mediated by interactions with a binding pocket that is more polar than a typical aldo-keto reductase. Modeling of xylose into the active site of the holoenzyme using ordered waters as a guide for sugar hydroxyls suggests a convincing mode of substrate binding.

  17. Arsenate toxicity and metabolism in the halotolerant microalga Dunaliella salina under various phosphate regimes.

    PubMed

    Wang, Ya; Zheng, Yanheng; Liu, Cong; Xu, Pingping; Li, Hao; Lin, Qiaoyun; Zhang, Chunhua; Ge, Ying

    2016-06-15

    Microalgae play an important role in arsenic (As) biogeochemical cycles as they are capable of accumulating and metabolizing this metalloid efficiently. This study aimed to investigate the toxicity, accumulation and transformation of arsenate (As(v)) in Dunaliella salina, an exceptionally halotolerant microalga, under various phosphate (PO4(3-)) regimes. The results of the 72-h toxicity test showed that D. salina was tolerant to As(v). In addition, the toxicity of As(v) was mitigated by an increased PO4(3-) supply. D. salina resisted the adverse effects of As(v) through the suppression of As uptake, enhancement of As reduction, methylation in the cell and excretion from the cell. Our study revealed that D. salina reduced As(v) toxicity using different strategies, i.e., reduction of As uptake upon acute As stress (24 h) and increase of As efflux following chronic As exposure (9 day). Moreover, PO4(3-) strongly affected the adsorption, uptake and transformation of As(v) in D. salina. As(v) reduction, DMA production and As excretion were enhanced under P-limited conditions (0.112 mg L(-1)) or upon higher As(v) exposure (1120 μg L(-1)). Furthermore, PO4(3-) had a significant influence on the As removal ability of D. salina. A high As removal efficiency (>95.6%) was observed in the 5-day cultures at an initial As concentration of 11.2 μg L(-1) and PO4(3-) of 0.112 and 1.12 mg L(-1). However, only 10.9% of total As was removed under 11.2 mg L(-1) PO4(3-) after 9 days of incubation. The findings of this study illustrate the pivotal roles of extracellular PO4(3-) in As(v) toxicity and metabolism, and the results may be relevant for future research on the minimization of As contamination in algal products as well as on the enhancement of As removal from the environment.

  18. Exogenous proline application ameliorates toxic effects of arsenate in Solanum melongena L. seedlings.

    PubMed

    Singh, Madhulika; Pratap Singh, Vijay; Dubey, Gunjan; Mohan Prasad, Sheo

    2015-07-01

    Hydroponic experiments were conducted to investigate an effect of exogenous application of proline (Pro; 25 µM) in alleviating arsenate (As(V); 5 and 25 µM) toxicity in Solanum melongena L. (eggplant) seedlings. Exposure of As(V) declined growth of eggplant, which was coincided with an enhanced accumulation of As. However, exogenous Pro application alleviated As(V) toxicity in eggplant seedlings by reducing the accumulation of As. The fluorescence characteristics (JIP-test): φP0, Ψ0, φE0, PIABS, ABS/RC, TR0/RC, ET0/RC, DI0/RC, NPQ and qP were also affected by As(V). However, the effects of As(V) were more prominent on PIABS DI0/RC and NPQ. In Pro treated seedlings, following parameters viz. φP0, Ψ0, φE0 and PIABS were stimulated, while, energy flux parameters (ABS/RC, TR0/RC, ET0/RC and DI0/RC) were inhibited. Toxic effects of As(V) on photochemistry of photosystem II (PS II) were ameliorated by an exogenous application of Pro. Oxidative stress markers: superoxide radical, hydrogen peroxide and malondialdehyde (lipid peroxidation) were enhanced by As(V) exposure, however, their levels were significantly diminished by an exogenous application of Pro. Treatment of As(V) stimulated the activities of superoxide dismutase, peroxidase and catalase except that of glutathione-S-transferase. Exogenous Pro application improved the activities of enzymatic antioxidants. The level of endogenous Pro was higher in As(V) treated as well as in Pro fed seedlings. The activity of a key enzyme of Pro biosynthesis: Δ(1)-pyrroline-5-carboxylate synthetase was higher in Pro fed seedlings. The activity of Pro dehydrogenase was inhibited under As(V) stress, and its activity was minimum in case of Pro+As(V) combination. These results indicate that Pro metabolism could play a key role in regulating the accumulation of As and levels of antioxidants, which concomitantly result into a better growth of eggplant seedlings when compared to the As(V) treatments alone. Copyright © 2015

  19. Anaerobic microbial mobilization and biotransformation of arsenate adsorbed onto activated alumina.

    PubMed

    Sierra-Alvarez, Reyes; Field, Jim A; Cortinas, Irail; Feijoo, Gumersindo; Teresa Moreira, Maria; Kopplin, Mike; Jay Gandolfi, A

    2005-01-01

    Due to the enactment of a stricter drinking water standard for arsenic in the United States, larger quantities of arsenic will be treated resulting in larger volumes of treatment residuals. The current United States Environmental Protection Agency recommendation is to dispose spent adsorbent residuals from arsenic treatment into non-hazardous municipal solid waste (MSW) landfills. The potential of microorganisms to alter the speciation affecting the mobility of arsenic in the disposal environment is therefore a concern. The purpose of this paper was to evaluate the potential of an anaerobic microbial consortium to biologically mobilize arsenate (As(V)) adsorbed onto activated alumina (AA), a common adsorbent used for treating arsenic in drinking water. Three anaerobic columns (0.27 l) packed with 100 g dry weight of AA containing 0.657 mg adsorbed As(V) (expressed as arsenic) per gram dry weight were continuously flushed with synthetic landfill leachate for 257 days. The fully biologically active column was inoculated with methanogenic anaerobic sludge (10 g volatile suspended solids l(-1) column) and was operated with a mixture of volatile fatty acids (VFA) in the feed (2.5 g chemical oxygen demand l(-1) feed). At the end of the experiment, 37% of the arsenic was removed from the column, of which 48% was accounted for by arsenical species identified in the column effluent. The most important form of arsenic eluted was arsenite (As(III)), accounting for nearly all of the identified arsenic in periods of high mobilization. Additionally, two methylated metabolites, methylarsonic acid and dimethylarsinic acid were observed. Mobilization of arsenic is attributed to the biological reduction of As(V) to As(III) since literature data indicates that As(III) is more weakly adsorbed to AA compared to As(V). Batch and continuous assays confirmed that VFA, present in landfill leachates, served as an electron donating substrate supporting enhanced rates of As(V) reduction to As

  20. Arsenate and fluoride enhanced each other's uptake in As-sensitive plant Pteris ensiformis.

    PubMed

    Das, Suchismita; de Oliveira, Letuzia M; da Silva, Evandro; Ma, Lena Q

    2017-08-01

    We investigated the effects of arsenate (AsV) and fluoride (F) on each other's uptake in an As-sensitive plant Pteris ensiformis. Plants were exposed to 1) 0.1 × Hoagland solution control, 2) 3.75 mg L(-1) As and 1.9, 3.8, or 7.6 mg L(-1) F, or 3) 1 mg L(-1) F and 3.75 mg L(-1) or 7.5 mg L(-1) As for 7 d in hydroponics. P. ensiformis accumulated 14.7-32.6 mg kg(-1) As at 3.75 mg L(-1) AsV, and 99-145 mg kg(-1) F at 1 mg L(-1) F. Our study revealed that AsV and F increased each other's uptake when co-present. At 1.9 mg L(-1), F increased frond As uptake from 14.7 to 40.3 mg kg(-1), while 7.5 mg L(-1) As increased frond F uptake from 99 to 371 mg kg(-1). Although, AsV was the predominant As species in all tissues, F enhanced AsIII levels in the rhizomes and fronds, while the reverse was observed in the roots. Increasing As concentrations also enhanced TBARS and H2O2 in tissues, indicating oxidative stress. However, F alleviated As stress by lowering their levels in the fronds. Frond and root membrane leakage were also evident due to As or F exposure. The results may facilitate better understanding of the mechanisms underlying the co-uptake of As and F in plants. However, the mechanisms of how they enhance each other's uptake in P. ensiformis need further investigation. Published by Elsevier Ltd.

  1. Aerobic Reduction of Arsenate by a Bacterium Isolated From Activated Sludge

    NASA Astrophysics Data System (ADS)

    Kozai, N.; Ohnuki, T.; Hanada, S.; Nakamura, K.; Francis, A. J.

    2006-12-01

    Microlunatus phosphovorus strain NM-1 is a polyphosphate-accumulating bacterium isolated from activated sludge. This bacterium takes up a large amount of polyphosphate under aerobic conditions and release phosphate ions by hydrolysis of polyphosphate to orthophosphate under anaerobic conditions to derive energy for taking up substrates. To understand the nature of this strain, especially, influence of potential contaminants in sewage and wastewater on growth, we have been investigating behavior of this bacterium in media containing arsenic. The present paper mainly reports reduction of arsenate by this bacterium under aerobic conditions. The strain NM-1 (JCM 9379) was aerobically cultured at 30 °C in a nutrient medium containing 2.5 g/l peptone, 0.5 g/l glucose, 1.5 g/l yeast extract, and arsenic [Na2HAsO4 (As(V)) or Na3AsO3 (As(III))] at concentrations between 0 and 50 mM. The cells collected from arsenic-free media were dispersed in buffer solutions containing 2mM HEPES, 10mM NaCl, prescribed concentrations of As(V), and 0-0.2 percent glucose. Then, this cell suspension was kept at 20 °C under aerobic or anaerobic conditions. The speciation of arsenic was carried out by ion chromatography and ICP-MS. The growth of the strain under aerobic conditions was enhanced by the addition of As(V) at the concentration between 1 and 10 mM. The maximum optical density of the culture in the medium containing 5mM As(V) was 1.4 times greater than that of the control culture. Below the As(V) concentration of 10mM, most of the As(V) was reduced to As(III). The growth of the strain under anaerobic conditions has not been observed so far. The cells in the buffer solutions reduced As(V) under aerobic condition. The reduction was enhanced by the addition of glucose. However, the cell did not reduce As(V) under anaerobic conditions. The strain NM-1 showed high resistance to As(V) and As(III). The maximum optical density of the culture grown in a medium containing 50 mM As(V) was only

  2. Arsenate Reduction of Sediment is a Critical Step for Arsenic Release in Bangladesh Aquifers

    NASA Astrophysics Data System (ADS)

    Mailloux, B. J.; Silvern, R. F.; Kim, C.; Sun, J.; Ahmed, K.; van Geen, A.; Choudhury, I.; Bostick, B. C.

    2013-12-01

    Long-term exposure to trace levels of arsenic (As) in shallow groundwater puts millions of people at risk for chronic diseases in Bangladesh. Though the arsenic is naturally occurring in the shallow aquifers, the mobilization of arsenic from the sediment to the groundwater is predominantly driven by the coupling of microbial metabolism to the reduction of iron (Fe) oxides. However, it is unknown whether the reduction of arsenate, As(V), to arsenite, As(III), is a critical part of the mobilization process. The goal of this work was to determine the mineral phase speciation of arsenic in sediment across two arsenic gradients in shallow aquifers. Sediment cores were collected from two well-characterized sites in Araihazar, Bangladesh located about 25km east of the capital, Dhaka. Site B, a high arsenic, slow recharge, shallow aquifer, was located in the village of Baylakandi, and site F, a low arsenic, fast recharge, shallow aquifer, was located in the village of Lashkardi. Samples were collected from drill cuttings and cores taken every five feet from the surface to 60 feet at site B and 88 feet at site F and preserved in glycerol for analysis. The sediment was characterized for arsenic speciation using x-ray absorption near edge structure (XANES) on beamline 11-2 at the Stanford Synchrotron Radiation Lightsource which in bulk mode can determine As speciation on samples with less than 1 mg/kg As in the solid phase. Arsenic XANES linear combination fits were described by As(V), As(III) and As2S3 standards for each depth. At both sites, at depths with low concentrations of aqueous As the sediment was dominated by As(V). In contrast, at depths with elevated concentrations of aqueous As the sediment was dominated by As(III). These changes in solid phase As speciation cannot be accounted for by changes in aqueous As concentrations and indicate a bulk change occurs in the As speciation of the sediment in zones of elevated aqueous As concentrations. Therefore, reduction of

  3. No laughing matter: the unmaking of the greenhouse gas dinitrogen monoxide by nitrous oxide reductase.

    PubMed

    Schneider, Lisa K; Wüst, Anja; Pomowski, Anja; Zhang, Lin; Einsle, Oliver

    2014-01-01

    The gas nitrous oxide (N₂O) is generated in a variety of abiotic, biotic, and anthropogenic processes and it has recently been under scrutiny for its role as a greenhouse gas. A single enzyme, nitrous oxide reductase, is known to reduce N₂O to uncritical N₂, in a two-electron reduction process that is catalyzed at two unusual metal centers containing copper. Nitrous oxide reductase is a bacterial metalloprotein from the metabolic pathway of denitrification, and it forms a 130 kDa homodimer in which the two metal sites CuA and CuZ from opposing monomers are brought into close contact to form the active site of the enzyme. CuA is a binuclear, valence-delocalized cluster that accepts and transfers a single electron. The CuA site of nitrous oxide reductase is highly similar to that of respiratory heme-copper oxidases, but in the denitrification enzyme the site additionally undergoes a conformational change on a ligand that is suggested to function as a gate for electron transfer from an external donor protein. CuZ, the tetranuclear active center of nitrous oxide reductase, is isolated under mild and anoxic conditions as a unique [4Cu:2S] cluster. It is easily desulfurylated to yield a [4Cu:S] state termed CuZ (*) that is functionally distinct. The CuZ form of the cluster is catalytically active, while CuZ (*) is inactive as isolated in the [3Cu(1+):1Cu(2+)] state. However, only CuZ (*) can be reduced to an all-cuprous state by sodium dithionite, yielding a form that shows higher activities than CuZ. As the possibility of a similar reductive activation in the periplasm is unconfirmed, the mechanism and the actual functional state of the enzyme remain under debate. Using enzyme from anoxic preparations with CuZ in the [4Cu:2S] state, N2O was shown to bind between the CuA and CuZ sites, suggesting direct electron transfer from CuA to the substrate after its activation by CuZ.

  4. Noninvasive respiratory monitoring

    SciTech Connect

    Nochomovitz, M.L.; Cherniack, N.S.

    1986-01-01

    This book contains 10 selections. Some of the titles are: Transcutaneous Monitoring of Respiratory Gases; Computed Tomography of the Chest; Measurement and Monitoring of Exhaled Carbon Dioxide; Oximetry; and Ultrasonic Evaluation of the Chest Wall and Pleura.

  5. Respiratory syncytial virus (RSV)

    MedlinePlus

    Respiratory syncytial virus (RSV) is a very common virus that leads to mild, cold-like symptoms in adults and older healthy children. It can be more serious in young babies, especially those in certain high-risk groups.

  6. Respiratory Syncytial Virus (RSV)

    MedlinePlus

    ... and premature birth: Are you at risk? Zika virus and pregnancy Folic acid Medicine safety and pregnancy ... It's been added to your dashboard . Respiratory syncytial virus (RSV) is a common virus that infects the ...

  7. Respiratory Syncytial Virus Infections

    MedlinePlus

    Respiratory syncytial virus (RSV) causes mild, cold-like symptoms in adults and older healthy children. It can cause serious problems in ... tests can tell if your child has the virus. There is no specific treatment. You should give ...

  8. Respiratory effects of sevoflurane.

    PubMed

    Doi, M; Ikeda, K

    1987-03-01

    The respiratory effects of sevoflurane were studied in seven patients and compared with values obtained in another seven patients anesthetized with halothane. Resting ventilation, resting PaCO2, and ventilatory response to CO2 were measured awake and at 1.1 and 1.4 MAC levels of both anesthetic agents. We found that with sevoflurane, tidal volume and the slopes of the CO2 response curves decreased and PaCO2 increased with increasing depth of anesthesia, as with other inhaled anesthetics. A compensatory increase in respiratory frequency was not enough to prevent a decrease in minute volume with increasing depth of anesthesia. At 1.1 MAC, sevoflurane produced almost the same degree of respiratory depression as halothane. At 1.4 MAC, sevoflurane produced more profound respiratory depression than halothane.

  9. Respiratory muscle plasticity.

    PubMed

    Rowley, Katharine L; Mantilla, Carlos B; Sieck, Gary C

    2005-07-28

    Plasticity of respiratory muscles must be considered in the context of their unique physiological demands. The continuous rhythmic activation of respiratory muscles makes them among the most active in the body. Respiratory muscles, especially the diaphragm, are non-weight-bearing, and thus, in contrast to limb muscles, are not exposed to gravitational effects. Perturbations in normal activation and load known to induce plasticity in limb muscles may not cause similar adaptations in respiratory muscles. In this review, we explore the structural and functional properties of the diaphragm muscle and their response to alterations in load and activity. Overall, relatively modest changes in diaphragm structural and functional properties occur in response to perturbations in load or activity. However, disruptions in the normal influence of phrenic innervation by frank denervation, tetrodotoxin nerve block and spinal hemisection, induce profound changes in the diaphragm, indicating the substantial trophic influence of phrenic motoneurons on diaphragm muscle.

  10. Respiratory Syncytial Virus

    MedlinePlus

    ... respiratory syncytial virus (RSV) using indirect immunofluorescence technique. Biology & Genetics For more than 50 years, NIAID’s commitment ... Nucleotide Polymorphism Phylogenetics & Ontology Proteomics & Protein Analysis Systems Biology Data Portals Software Applications BCBB Mobyle Interface Designer ( ...

  11. What Causes Respiratory Failure?

    MedlinePlus

    ... Conditions Causing Respiratory Failure Figure A shows the location of the lungs, airways, diaphragm, rib cage, pulmonary arteries, brain, and spinal cord ... STATEMENT FOIA NO FEAR ACT OIG CONTACT US ...

  12. The microbiota of the respiratory tract: gatekeeper to respiratory health.

    PubMed

    Man, Wing Ho; de Steenhuijsen Piters, Wouter A A; Bogaert, Debby

    2017-03-20

    The respiratory tract is a complex organ system that is responsible for the exchange of oxygen and carbon dioxide. The human respiratory tract spans from the nostrils to the lung alveoli and is inhabited by niche-specific communities of bacteria. The microbiota of the respiratory tract probably acts as a gatekeeper that provides resistance to colonization by respiratory pathogens. The respiratory microbiota might also be involved in the maturation and maintenance of homeostasis of respiratory physiology and immunity. The ecological and environmental factors that direct the development of microbial communities in the respiratory tract and how these communities affect respiratory health are the focus of current research. Concurrently, the functions of the microbiome of the upper and lower respiratory tract in the physiology of the human host are being studied in detail. In this Review, we will discuss the epidemiological, biological and functional evidence that support the physiological role of the respiratory microbiota in the maintenance of human health.

  13. Solubilization and Resolution of the Membrane-Bound Nitrite Reductase from Paracoccus Halodenitrificans into Nitrite and Nitric Oxide Reductases

    NASA Technical Reports Server (NTRS)

    Grant, Michael A.; Cronin, Sonja E.; Hochstein, Lawrence I.

    1984-01-01

    Membranes prepared from Paracoccus halodenitrificans reduced nitrite or nitric oxide to nitrous oxide. Extraction of these membranes with the detergent CHAPSO [3-(3-Chlolamidoporopyldimethylammonio)-1-(2- hydroxy-1-propanesulfonate)], followed by ammonium sulfate fractionation of the solubilized proteins, resulted in the separation of nitrite and nitric oxide reductase activities. The fraction containing nitrite reductase activity spectrally resembled a cd-type cytochrome. Several cytochromes were detected in the nitric oxide reductase fraction. Which, if any, of these cytochromes is associated with the reduction of nitric oxide is not clear at this time.

  14. Solubilization and Resolution of the Membrane-Bound Nitrite Reductase from Paracoccus Halodenitrificans into Nitrite and Nitric Oxide Reductases

    NASA Technical Reports Server (NTRS)

    Grant, Michael A.; Cronin, Sonja E.; Hochstein, Lawrence I.

    1984-01-01

    Membranes prepared from Paracoccus halodenitrificans reduced nitrite or nitric oxide to nitrous oxide. Extraction of these membranes with the detergent CHAPSO [3-(3-Chlolamidoporopyldimethylammonio)-1-(2- hydroxy-1-propanesulfonate)], followed by ammonium sulfate fractionation of the solubilized proteins, resulted in the separation of nitrite and nitric oxide reductase activities. The fraction containing nitrite reductase activity spectrally resembled a cd-type cytochrome. Several cytochromes were detected in the nitric oxide reductase fraction. Which, if any, of these cytochromes is associated with the reduction of nitric oxide is not clear at this time.

  15. Feline respiratory disease complex.

    PubMed

    Cohn, Leah A

    2011-11-01

    Feline respiratory disease complex (FRDC) refers to the characteristic acute presentation of a contagious respiratory or ocular disease caused by one or multiple pathogens. Environmental and host factors impact the transmission, clinical presentation, preventive strategy, and treatment of affected cats. The FRDC is especially problematic in settings where large numbers of cats cohabit, including animal shelters, catteries, and semi-feral colonies. Although elimination of FRDC is an unrealistic goal, improved understanding can lead to strategies to minimize disease impact.

  16. Respiratory RNA Viruses.

    PubMed

    Hodinka, Richard L

    2016-08-01

    Acute upper and lower respiratory infections are a major public health problem and a leading cause of morbidity and mortality worldwide. At greatest risk are young children, the elderly, the chronically ill, and those with suppressed or compromised immune systems. Viruses are the predominant cause of respiratory tract illnesses and include RNA viruses such as respiratory syncytial virus, influenza virus, parainfluenza virus, metapneumovirus, rhinovirus, and coronavirus. Laboratory testing is required for a reliable diagnosis of viral respiratory infections, as a clinical diagnosis can be difficult since signs and symptoms are often overlapping and not specific for any one virus. Recent advances in technology have resulted in the development of newer diagnostic assays that offer great promise for rapid and accurate detection of respiratory viral infections. This chapter emphasizes the fundamental characteristics and clinical importance of the various RNA viruses that cause upper and lower respiratory tract diseases in the immunocompromised host. It highlights the laboratory methods that can be used to make a rapid and definitive diagnosis for the greatest impact on the care and management of ill patients, and the prevention and control of hospital-acquired infections and community outbreaks.

  17. Exploration of Nitrate Reductase Metabolic Pathway in Corynebacterium pseudotuberculosis

    PubMed Central

    Abreu, Vinícius; Diniz, Carlos; Dorneles, Elaine M. S.; Barh, Debmalya

    2017-01-01

    Based on the ability of nitrate reductase synthesis, Corynebacterium pseudotuberculosis is classified into two biovars: Ovis and Equi. Due to the presence of nitrate reductase, the Equi biovar can survive in absence of oxygen. On the other hand, Ovis biovar that does not have nitrate reductase is able to adapt to various ecological niches and can grow on certain carbon sources. Apart from these two biovars, some other strains are also able to carry out the reduction of nitrate. The enzymes that are involved in electron transport chain are also identified by in silico methods. Findings about pathogen metabolism can contribute to the identification of relationship between nitrate reductase and the C. pseudotuberculosis pathogenicity, virulence factors, and discovery of drug targets. PMID:28316974

  18. Exploration of Nitrate Reductase Metabolic Pathway in Corynebacterium pseudotuberculosis.

    PubMed

    Almeida, Sintia; Sousa, Cassiana; Abreu, Vinícius; Diniz, Carlos; Dorneles, Elaine M S; Lage, Andrey P; Barh, Debmalya; Azevedo, Vasco

    2017-01-01

    Based on the ability of nitrate reductase synthesis, Corynebacterium pseudotuberculosis is classified into two biovars: Ovis and Equi. Due to the presence of nitrate reductase, the Equi biovar can survive in absence of oxygen. On the other hand, Ovis biovar that does not have nitrate reductase is able to adapt to various ecological niches and can grow on certain carbon sources. Apart from these two biovars, some other strains are also able to carry out the reduction of nitrate. The enzymes that are involved in electron transport chain are also identified by in silico methods. Findings about pathogen metabolism can contribute to the identification of relationship between nitrate reductase and the C. pseudotuberculosis pathogenicity, virulence factors, and discovery of drug targets.

  19. Enantioselective imine reduction catalyzed by imine reductases and artificial metalloenzymes.

    PubMed

    Gamenara, Daniela; Domínguez de María, Pablo

    2014-05-21

    Adding value to organic synthesis. Novel imine reductases enable the enantioselective reduction of imines to afford optically active amines. Likewise, novel bioinspired artificial metalloenzymes can perform the same reaction as well. Emerging proof-of-concepts are herein discussed.

  20. Analysis of the Actinobacillus pleuropneumoniae ArcA Regulon Identifies Fumarate Reductase as a Determinant of Virulence▿ †

    PubMed Central

    Buettner, Falk F. R.; Bendallah, Ibrahim M.; Bosse, Janine T.; Dreckmann, Karla; Nash, John H. E.; Langford, Paul R.; Gerlach, Gerald-F.

    2008-01-01

    The ability of the bacterial pathogen Actinobacillus pleuropneumoniae to grow anaerobically allows the bacterium to persist in the lung. The ArcAB two-component system is crucial for metabolic adaptation in response to anaerobic conditions, and we recently showed that an A. pleuropneumoniae arcA mutant had reduced virulence compared to the wild type (F. F. Buettner, A. Maas, and G.-F. Gerlach, Vet. Microbiol. 127:106-115, 2008). In order to understand the attenuated phenotype, we investigated the ArcA regulon of A. pleuropneumoniae by using a combination of transcriptome (microarray) and proteome (two-dimensional difference gel electrophoresis and subsequent mass spectrometry) analyses. We show that ArcA negatively regulates the expression of many genes, including those encoding enzymes which consume intermediates during fumarate synthesis. Simultaneously, the expression of glycerol-3-phosphate dehydrogenase, a component of the respiratory chain serving as a direct reduction equivalent for fumarate reductase, was upregulated. This result, together with the in silico analysis finding that A. pleuropneumoniae has no oxidative branch of the citric acid cycle, led to the hypothesis that fumarate reductase might be crucial for virulence by providing (i) energy via fumarate respiration and (ii) succinate and other essential metabolic intermediates via the reductive branch of the citric acid cycle. To test this hypothesis, an isogenic A. pleuropneumoniae fumarate reductase deletion mutant was constructed and studied by using a