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Sample records for active site metal

  1. Development of METAL-ACTIVE SITE and ZINCCLUSTER tool to predict active site pockets.

    Science.gov (United States)

    Ajitha, M; Sundar, K; Arul Mugilan, S; Arumugam, S

    2018-03-01

    The advent of whole genome sequencing leads to increasing number of proteins with known amino acid sequences. Despite many efforts, the number of proteins with resolved three dimensional structures is still low. One of the challenging tasks the structural biologists face is the prediction of the interaction of metal ion with any protein for which the structure is unknown. Based on the information available in Protein Data Bank, a site (METALACTIVE INTERACTION) has been generated which displays information for significant high preferential and low-preferential combination of endogenous ligands for 49 metal ions. User can also gain information about the residues present in the first and second coordination sphere as it plays a major role in maintaining the structure and function of metalloproteins in biological system. In this paper, a novel computational tool (ZINCCLUSTER) is developed, which can predict the zinc metal binding sites of proteins even if only the primary sequence is known. The purpose of this tool is to predict the active site cluster of an uncharacterized protein based on its primary sequence or a 3D structure. The tool can predict amino acids interacting with a metal or vice versa. This tool is based on the occurrence of significant triplets and it is tested to have higher prediction accuracy when compared to that of other available techniques. © 2017 Wiley Periodicals, Inc.

  2. The nature of the active site in heterogeneous metal catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Bligaard, Thomas; Larsen, Britt Hvolbæk

    2008-01-01

    This tutorial review, of relevance for the surface science and heterogeneous catalysis communities, provides a molecular-level discussion of the nature of the active sites in metal catalysis. Fundamental concepts such as "Bronsted-Evans-Polanyi relations'' and "volcano curves'' are introduced...

  3. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei

    2015-01-01

    -ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation......Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X...

  4. Conversion of agonist site to metal-ion chelator site in the beta(2)-adrenergic receptor

    DEFF Research Database (Denmark)

    Elling, C E; Thirstrup, K; Holst, Birgitte

    1999-01-01

    Previously metal-ion sites have been used as structural and functional probes in seven transmembrane receptors (7TM), but as yet all the engineered sites have been inactivating. Based on presumed agonist interaction points in transmembrane III (TM-III) and -VII of the beta(2)-adrenergic receptor,...... as generic, pharmacologic tools to switch 7TM receptors with engineered metal-ion sites on or off at will.......Previously metal-ion sites have been used as structural and functional probes in seven transmembrane receptors (7TM), but as yet all the engineered sites have been inactivating. Based on presumed agonist interaction points in transmembrane III (TM-III) and -VII of the beta(2)-adrenergic receptor......, in this paper we construct an activating metal-ion site between the amine-binding Asp-113 in TM-III-or a His residue introduced at this position-and a Cys residue substituted for Asn-312 in TM-VII. No increase in constitutive activity was observed in the mutant receptors. Signal transduction was activated...

  5. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    KAUST Repository

    Wang, Liang

    2018-04-04

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  6. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

    KAUST Repository

    Wang, Liang; Guan, Erjia; Zhang, Jian; Yang, Junhao; Zhu, Yihan; Han, Yu; Yang, Ming; Cen, Cheng; Fu, Gang; Gates, Bruce C.; Xiao, Feng-Shou

    2018-01-01

    Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles.

  7. Crystal structures reveal metal-binding plasticity at the metallo-β-lactamase active site of PqqB from Pseudomonas putida

    Energy Technology Data Exchange (ETDEWEB)

    Tu, Xiongying; Latham, John A.; Klema, Valerie J.; Evans III, Robert L.; Li, Chao; Klinman, Judith P.; Wilmot, Carrie M. (UMM); (UCB)

    2017-08-19

    PqqB is an enzyme involved in the biosynthesis of pyrroloquinoline quinone and a distal member of the metallo-β-lactamase (MBL) superfamily. PqqB lacks two residues in the conserved signature motif HxHxDH that makes up the key metal-chelating elements that can bind up to two metal ions at the active site of MBLs and other members of its superfamily. Here, we report crystal structures of PqqB bound to Mn2+, Mg2+, Cu2+, and Zn2+. These structures demonstrate that PqqB can still bind metal ions at the canonical MBL active site. The fact that PqqB can adapt its side chains to chelate a wide spectrum of metal ions with different coordination features on a uniform main chain scaffold demonstrates its metal-binding plasticity. This plasticity may provide insights into the structural basis of promiscuous activities found in ensembles of metal complexes within this superfamily. Furthermore, PqqB belongs to a small subclass of MBLs that contain an additional CxCxxC motif that binds a structural Zn2+. Our data support a key role for this motif in dimerization.

  8. Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

    Energy Technology Data Exchange (ETDEWEB)

    Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L., E-mail: tait@indiana.edu [Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, Indiana 47405 (United States)

    2015-03-14

    Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

  9. Metal ion site engineering indicates a global toggle switch model for seven-transmembrane receptor activation

    DEFF Research Database (Denmark)

    Elling, Christian E; Frimurer, Thomas M; Gerlach, Lars-Ole

    2006-01-01

    for monoamine binding in TM-III, was used as the starting point to engineer activating metal ion sites between the extracellular segments of the beta2-adrenergic receptor. Cu(II) and Zn(II) alone and in complex with aromatic chelators acted as potent (EC50 decreased to 0.5 microm) and efficacious agonists...

  10. Mutational analysis of divalent metal ion binding in the active site of class II α-mannosidase from sulfolobus solfataricus

    DEFF Research Database (Denmark)

    Hansen, Dennis K.; Webb, Helen; Nielsen, Jonas Willum

    2015-01-01

    Mutational analysis of Sulfolobus solfataricus class II α-mannosidase was focused on side chains that interact with the hydroxyls of the-1 mannosyl of the substrate (Asp-534) or form ligands to the active site divalent metal ion (His-228 and His-533) judged from crystal structures of homologous e......, although less dramatically with some activating metal ions. No major differences in the pH dependence between wild-type and mutant enzymes were found in the presence of different metal ions. The pH optimum was 5, but enzyme instability was observed at pH...

  11. MetalS(3), a database-mining tool for the identification of structurally similar metal sites.

    Science.gov (United States)

    Valasatava, Yana; Rosato, Antonio; Cavallaro, Gabriele; Andreini, Claudia

    2014-08-01

    We have developed a database search tool to identify metal sites having structural similarity to a query metal site structure within the MetalPDB database of minimal functional sites (MFSs) contained in metal-binding biological macromolecules. MFSs describe the local environment around the metal(s) independently of the larger context of the macromolecular structure. Such a local environment has a determinant role in tuning the chemical reactivity of the metal, ultimately contributing to the functional properties of the whole system. The database search tool, which we called MetalS(3) (Metal Sites Similarity Search), can be accessed through a Web interface at http://metalweb.cerm.unifi.it/tools/metals3/ . MetalS(3) uses a suitably adapted version of an algorithm that we previously developed to systematically compare the structure of the query metal site with each MFS in MetalPDB. For each MFS, the best superposition is kept. All these superpositions are then ranked according to the MetalS(3) scoring function and are presented to the user in tabular form. The user can interact with the output Web page to visualize the structural alignment or the sequence alignment derived from it. Options to filter the results are available. Test calculations show that the MetalS(3) output correlates well with expectations from protein homology considerations. Furthermore, we describe some usage scenarios that highlight the usefulness of MetalS(3) to obtain mechanistic and functional hints regardless of homology.

  12. Metal ion effects on enolase activity

    International Nuclear Information System (INIS)

    Lee, M.E.; Nowak, T.

    1986-01-01

    Most metal binding studies with yeast enolase suggest that two metals per monomer are required for catalytic activity. The functions of metal I and metal II have not been unequivocally defined. In a series of kinetic experiments where the concentration of MgII is kept constant at subsaturating levels (1mM), the addition of MnII or of ZnII gives a hyperbolic decrease in activity. The final velocity of these mixed metal systems is the same velocity obtained with either only MnII or ZnII respectively. The concentration of MnII (40 μM) or of Zn (2μM) which gives half maximal effect in the presence of (1mM) MgII is approximately the same as the Km' value for MnII (9μM) or ZnII (3μM) respectively. Direct binding of MnII to enolase in the absence and presence of MgII shows that MnII and MgII compete for the same metal site on enolase. In the presence of 2-phosphoglycerate (2-PGA) and MgII, only a single site is occupied by MnII. Results suggest MnII at site I and MgII at site II. PRR and high resolution 1 H and 31 P NMR studies of enzyme-ligand complexes containing MnII and MgII and MnII are consistent with this model. 31 P measurements allow a measure of the equilibrium constant (0.36) for enolase. Saturation transfer measurements yield net rate constants (k/sub f/ = 0.49s -1 ; k/sub r/ = 1.3s -1 ) for the overall reaction. These values are smaller than k/sub cat/ (38s -1 ) measured under analogous conditions. The cation at site I appears to determine catalytic activity

  13. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin (UC)

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  14. Assessment of Water Quality Index and Heavy Metal Contamination in Active and Abandoned Iron Ore Mining Sites in Pahang, Malaysia

    Directory of Open Access Journals (Sweden)

    Madzin Zafira

    2017-01-01

    Full Text Available The composition of heavy metals in water and surface soils of iron ore mining sites were investigated to evaluate on the potential occurrence of heavy metal contamination. Physico-chemical characteristics of the waters were also investigated to determine the current status of water quality index (WQI of the sites. Samples of water and surface soils of active mine (Kuala Lipis and abandoned mine (Bukit Ibam in Pahang were collected at four locations, respectively. The physico-chemical parameters measured for WQI were pH, dissolved oxygen, biological oxygen demand (BOD, chemical oxygen demand (COD, suspended solids (SS, and ammoniacal nitrogen (AN. The water quality parameters were classified according to the Department of Environment (DOE water quality classification. The study revealed that most of the sites in Bukit Ibam and Kuala Lipis were categorized as clean to slightly polluted. On the other hand, heavy metal analysis in water showed that aluminium and manganese level in both sites have exceeded the allowable limits for raw and treated water standards by the Ministry of Health. For heavy metal compositions in soils showed most of the heavy metal concentrations were below the recommended guideline values except for lead, arsenic, zinc and copper.

  15. Metal active site elasticity linked to activation of homocysteine in methionine synthases

    Energy Technology Data Exchange (ETDEWEB)

    Koutmos, Markos; Pejchal, Robert; Bomer, Theresa M.; Matthews, Rowena G.; Smith, Janet L.; Ludwig, Martha L. (Michigan)

    2008-04-02

    Enzymes possessing catalytic zinc centers perform a variety of fundamental processes in nature, including methyl transfer to thiols. Cobalamin-independent (MetE) and cobalamin-dependent (MetH) methionine synthases are two such enzyme families. Although they perform the same net reaction, transfer of a methyl group from methyltetrahydrofolate to homocysteine (Hcy) to form methionine, they display markedly different catalytic strategies, modular organization, and active site zinc centers. Here we report crystal structures of zinc-replete MetE and MetH, both in the presence and absence of Hcy. Structural investigation of the catalytic zinc sites of these two methyltransferases reveals an unexpected inversion of zinc geometry upon binding of Hcy and displacement of an endogenous ligand in both enzymes. In both cases a significant movement of the zinc relative to the protein scaffold accompanies inversion. These structures provide new information on the activation of thiols by zinc-containing enzymes and have led us to propose a paradigm for the mechanism of action of the catalytic zinc sites in these and related methyltransferases. Specifically, zinc is mobile in the active sites of MetE and MetH, and its dynamic nature helps facilitate the active site conformational changes necessary for thiol activation and methyl transfer.

  16. Mechanism of Metal Ion Activation of the Diphtheria Toxin Repressor DtxR

    Energy Technology Data Exchange (ETDEWEB)

    D' Aquino,J.; Tetenbaum-Novatt, J.; White, A.; Berkovitch, F.; Ringe, D.

    2005-01-01

    The diphtheria toxin repressor (DtxR) is a metal ion-activated transcriptional regulator that has been linked to the virulence of Corynebacterium diphtheriae. Structure determination has shown that there are two metal ion binding sites per repressor monomer, and site-directed mutagenesis has demonstrated that binding site 2 (primary) is essential for recognition of the target DNA repressor, leaving the role of binding site 1 (ancillary) unclear. Calorimetric techniques have demonstrated that although binding site 1 (ancillary) has high affinity for metal ion with a binding constant of 2 x 10{sup -7}, binding site 2 (primary) is a low-affinity binding site with a binding constant of 6.3 x 10{sup -4}. These two binding sites act in an independent fashion, and their contribution can be easily dissected by traditional mutational analysis. Our results clearly demonstrate that binding site 1 (ancillary) is the first one to be occupied during metal ion activation, playing a critical role in stabilization of the repressor. In addition, structural data obtained for the mutants Ni-DtxR(H79A, C102D), reported here, and the previously reported DtxR(H79A) have allowed us to propose a mechanism of metal activation for DtxR.

  17. Heavy metal contamination of soil and water in the vicinity of an abandoned e-waste recycling site: implications for dissemination of heavy metals.

    Science.gov (United States)

    Wu, Qihang; Leung, Jonathan Y S; Geng, Xinhua; Chen, Shejun; Huang, Xuexia; Li, Haiyan; Huang, Zhuying; Zhu, Libin; Chen, Jiahao; Lu, Yayin

    2015-02-15

    Illegal e-waste recycling activity has caused heavy metal pollution in many developing countries, including China. In recent years, the Chinese government has strengthened enforcement to impede such activity; however, the heavy metals remaining in the abandoned e-waste recycling site can still pose ecological risk. The present study aimed to investigate the concentrations of heavy metals in soil and water in the vicinity of an abandoned e-waste recycling site in Longtang, South China. Results showed that the surface soil of the former burning and acid-leaching sites was still heavily contaminated with Cd (>0.39 mg kg(-1)) and Cu (>1981 mg kg(-1)), which exceeded their respective guideline levels. The concentration of heavy metals generally decreased with depth in both burning site and paddy field, which is related to the elevated pH and reduced TOM along the depth gradient. The pond water was seriously acidified and contaminated with heavy metals, while the well water was slightly contaminated since heavy metals were mostly retained in the surface soil. The use of pond water for irrigation resulted in considerable heavy metal contamination in the paddy soil. Compared with previous studies, the reduced heavy metal concentrations in the surface soil imply that heavy metals were transported to the other areas, such as pond. Therefore, immediate remediation of the contaminated soil and water is necessary to prevent dissemination of heavy metals and potential ecological disaster. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Chao; Feng, Zhenxing; Scherer, Günther G.; Barber, James; Shao-Horn, Yang; Xu, Zhichuan J. (Nanyang); (ICL); (Oregon State U.); (TUM-CREATE); (MIT)

    2017-04-10

    Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7, 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.

  19. Evolution of Metal(Loid) Binding Sites in Transcriptional Regulators

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez, E.; Thiyagarajan, S.; Cook, J.D.; Stemmler, T.L.; Gil, J.A.; Mateos, L.M.; Rosen, B.P.

    2009-05-22

    Expression of the genes for resistance to heavy metals and metalloids is transcriptionally regulated by the toxic ions themselves. Members of the ArsR/SmtB family of small metalloregulatory proteins respond to transition metals, heavy metals, and metalloids, including As(III), Sb(III), Cd(II), Pb(II), Zn(II), Co(II), and Ni(II). These homodimeric repressors bind to DNA in the absence of inducing metal(loid) ion and dissociate from the DNA when inducer is bound. The regulatory sites are often three- or four-coordinate metal binding sites composed of cysteine thiolates. Surprisingly, in two different As(III)-responsive regulators, the metalloid binding sites were in different locations in the repressor, and the Cd(II) binding sites were in two different locations in two Cd(II)-responsive regulators. We hypothesize that ArsR/SmtB repressors have a common backbone structure, that of a winged helix DNA-binding protein, but have considerable plasticity in the location of inducer binding sites. Here we show that an As(III)-responsive member of the family, CgArsR1 from Corynebacterium glutamicum, binds As(III) to a cysteine triad composed of Cys{sup 15}, Cys{sup 16}, and Cys{sup 55}. This binding site is clearly unrelated to the binding sites of other characterized ArsR/SmtB family members. This is consistent with our hypothesis that metal(loid) binding sites in DNA binding proteins evolve convergently in response to persistent environmental pressures.

  20. Screening of active metals for reactive adsorption desulfurization adsorbent using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lei; Zhao, Liang, E-mail: liangzhao@cup.edu.cn; Xu, Chunming; Wang, Yuxian; Gao, Jinsen

    2017-03-31

    Highlights: • Electronic characteristics determined adsorption characteristics of transition metals. • Cobalt has the similar adsorption ability of thiophene as nickel. • Adsorption capacity of Cr and Mo was extremely fierce, while Cu has the potential ability for adsorbing thiophene. • The preference adsorption site for thiophene was hollow site on all the seven surface. - Abstract: To explore characteristics of active metals for reactive adsorption desulfurization (RADS) technology, the adsorption of thiophene on M (100) (M = Cr, Mo, Co, Ni, Cu, Au, and Ag) surfaces was systematically studied by density functional theory with vdW correction (DFT + D3). We found that, in all case, the most stable molecular adsorption site was the hollow site and adsorptive capabilities of thiophene followed the order: Cr > Mo > Co ≈ Ni > Cu > Au ≈ Ag. By analyzing the nature of binding between thiophene and corresponding metals and the electronic structure of metals, the excessive activities of Cr and Mo were found to have a negative regeneration, the passive activities of Au and Ag were found to have an inactive adsorption for RADS adsorbent alone, while Ni and Co have appropriate characteristics as the active metals for RADS, followed by Cu.

  1. Distinct roles of beta1 metal ion-dependent adhesion site (MIDAS), adjacent to MIDAS (ADMIDAS), and ligand-associated metal-binding site (LIMBS) cation-binding sites in ligand recognition by integrin alpha2beta1.

    Science.gov (United States)

    Valdramidou, Dimitra; Humphries, Martin J; Mould, A Paul

    2008-11-21

    Integrin-ligand interactions are regulated in a complex manner by divalent cations, and previous studies have identified ligand-competent, stimulatory, and inhibitory cation-binding sites. In collagen-binding integrins, such as alpha2beta1, ligand recognition takes place exclusively at the alpha subunit I domain. However, activation of the alphaI domain depends on its interaction with a structurally similar domain in the beta subunit known as the I-like or betaI domain. The top face of the betaI domain contains three cation-binding sites: the metal-ion dependent adhesion site (MIDAS), the ADMIDAS (adjacent to MIDAS), and LIMBS (ligand-associated metal-binding site). The role of these sites in controlling ligand binding to the alphaI domain has yet to be elucidated. Mutation of the MIDAS or LIMBS completely blocked collagen binding to alpha2beta1; in contrast mutation of the ADMIDAS reduced ligand recognition but this effect could be overcome by the activating monoclonal antibody TS2/16. Hence, the MIDAS and LIMBS appear to be essential for the interaction between alphaI and betaI, whereas occupancy of the ADMIDAS has an allosteric effect on the conformation of betaI. An activating mutation in the alpha2 I domain partially restored ligand binding to the MIDAS and LIMBS mutants. Analysis of the effects of Ca(2+), Mg(2+), and Mn(2+) on ligand binding to these mutants showed that the MIDAS is a ligand-competent site through which Mn(2+) stimulates ligand binding, whereas the LIMBS is a stimulatory Ca(2+)-binding site, occupancy of which increases the affinity of Mg(2+) for the MIDAS.

  2. Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts

    Science.gov (United States)

    Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

    2017-01-01

    Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (~5 nm) Pd-Ni-P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni-P heterodimers into Pd-Ni-P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites.

  3. Microbial characterization of a radionuclide- and metal-contaminated waste site

    International Nuclear Information System (INIS)

    Bolton, H. Jr.; Lumppio, H.L.; Ainsworth, C.C.; Plymale, A.E.

    1993-04-01

    The operation of nuclear processing facilities and defense-related nuclear activities has resulted in contamination of near-surface and deep-subsurface sediments with both radionuclides and metals. The presence of mixed inorganic contaminants may result in undetectable microbial populations or microbial populations that are different from those present in uncontaminated sediments. To determine the impact of mixed radionuclide and metal contaminants on sediment microbial communities, we sampled a processing pond that was used from 1948 to 1975 for the disposal of radioactive and metal-contaminated wastewaters from laboratories and nuclear fuel fabrication facilities on the Hanford Site in Washington State. Because the Hanford Site is located in a semiarid environment with average rainfall of 159 mm/year, the pond dried and a settling basin remained after wastewater input into the pond ceased in 1975. This processing pond basin offered a unique opportunity to obtain near-surface sediments that had been contaminated with both radionuclides and metals for several decades. Our objectives were to determine the viable populations of microorganisms in the sediments and to test several hypotheses about how the addition of both radionuclides and metals influenced the microbial ecology of the sediments. Our first hypothesis was that viable populations of microorganisms would be lower in the more contaminated sediments. Second, we expected that long-term metal exposure would result in enhanced metal resistance. Finally, we hypothesized that microorganisms from the most radioactive sediments should have had enhanced radiation resistance

  4. Mapping the active site of vaccinia virus RNA triphosphatase

    International Nuclear Information System (INIS)

    Gong Chunling; Shuman, Stewart

    2003-01-01

    The RNA triphosphatase component of vaccinia virus mRNA capping enzyme (the product of the viral D1 gene) belongs to a family of metal-dependent phosphohydrolases that includes the RNA triphosphatases of fungi, protozoa, Chlorella virus, and baculoviruses. The family is defined by two glutamate-containing motifs (A and C) that form the metal-binding site. Most of the family members resemble the fungal and Chlorella virus enzymes, which have a complex active site located within the hydrophilic interior of a topologically closed eight-stranded β barrel (the so-called ''triphosphate tunnel''). Here we queried whether vaccinia virus capping enzyme is a member of the tunnel subfamily, via mutational mapping of amino acids required for vaccinia triphosphatase activity. We identified four new essential side chains in vaccinia D1 via alanine scanning and illuminated structure-activity relationships by conservative substitutions. Our results, together with previous mutational data, highlight a constellation of six acidic and three basic amino acids that likely compose the vaccinia triphosphatase active site (Glu37, Glu39, Arg77, Lys107, Glu126, Asp159, Lys161, Glu192, and Glu194). These nine essential residues are conserved in all vertebrate and invertebrate poxvirus RNA capping enzymes. We discerned no pattern of clustering of the catalytic residues of the poxvirus triphosphatase that would suggest structural similarity to the tunnel proteins (exclusive of motifs A and C). We infer that the poxvirus triphosphatases are a distinct lineage within the metal-dependent RNA triphosphatase family. Their unique active site, which is completely different from that of the host cell's capping enzyme, recommends the poxvirus RNA triphosphatase as a molecular target for antipoxviral drug discovery

  5. Remediating sites contaminated with heavy metals

    International Nuclear Information System (INIS)

    Swartzbaugh, J.; Sturgill, J.; Cormier, B.; Williams, H.D.

    1992-01-01

    This article is intended to serve as a reference for decision makers who must choose an approach to remediate sites contaminated with heavy metals. Its purpose is to explain pertinent chemical and physical characteristics of heavy metals, how to use these characteristics to select remedial technologies, and how to interpret and use data from field investigations. Different metal species are typically associated with different industrial processes. The contaminant species behave differently in various media (i.e., groundwater, soils, air), and require different technologies for containment and treatment. We focus on the metals that are used in industries that generate regulated waste. These include steelmaking, paint and pigment manufacturing, metal finishing, leather tanning, papermaking, aluminum anodizing, and battery manufacturing. Heavy metals are also present in refinery wastes as well as in smelting wastes and drilling muds

  6. Improved ethanol electrooxidation performance by shortening Pd–Ni active site distance in Pd–Ni–P nanocatalysts

    Science.gov (United States)

    Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

    2017-01-01

    Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (∼5 nm) Pd–Ni–P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni–P heterodimers into Pd–Ni–P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites. PMID:28071650

  7. High-frequency EPR on high-spin transition-metal sites

    NARCIS (Netherlands)

    Mathies, Guinevere

    2012-01-01

    The electronic structure of transition-metal sites can be probed by electron-paramagnetic-resonance (EPR) spectroscopy. The study of high-spin transition-metal sites benefits from EPR spectroscopy at frequencies higher than the standard 9.5 GHz. However, high-frequency EPR is a developing field. In

  8. A Chemical Route to Activation of Open Metal Sites in the Copper-Based Metal-Organic Framework Materials HKUST-1 and Cu-MOF-2.

    Science.gov (United States)

    Kim, Hong Ki; Yun, Won Seok; Kim, Min-Bum; Kim, Jeung Yoon; Bae, Youn-Sang; Lee, JaeDong; Jeong, Nak Cheon

    2015-08-12

    Open coordination sites (OCSs) in metal-organic frameworks (MOFs) often function as key factors in the potential applications of MOFs, such as gas separation, gas sorption, and catalysis. For these applications, the activation process to remove the solvent molecules coordinated at the OCSs is an essential step that must be performed prior to use of the MOFs. To date, the thermal method performed by applying heat and vacuum has been the only method for such activation. In this report, we demonstrate that methylene chloride (MC) itself can perform the activation role: this process can serve as an alternative "chemical route" for the activation that does not require applying heat. To the best of our knowledge, no previous study has demonstrated this function of MC, although MC has been popularly used in the pretreatment step prior to the thermal activation process. On the basis of a Raman study, we propose a plausible mechanism for the chemical activation, in which the function of MC is possibly due to its coordination with the Cu(2+) center and subsequent spontaneous decoordination. Using HKUST-1 film, we further demonstrate that this chemical activation route is highly suitable for activating large-area MOF films.

  9. Structural Basis for the Inhibition of RNase H Activity of HIV-1 Reverse Transcriptase by RNase H Active Site-Directed Inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Su, Hua-Poo; Yan, Youwei; Prasad, G. Sridhar; Smith, Robert F.; Daniels, Christopher L.; Abeywickrema, Pravien D.; Reid, John C.; Loughran, H. Marie; Kornienko, Maria; Sharma, Sujata; Grobler, Jay A.; Xu, Bei; Sardana, Vinod; Allison, Timothy J.; Williams, Peter D.; Darke, Paul L.; Hazuda, Daria J.; Munshi, Sanjeev (Merck)

    2010-09-02

    HIV/AIDS continues to be a menace to public health. Several drugs currently on the market have successfully improved the ability to manage the viral burden in infected patients. However, new drugs are needed to combat the rapid emergence of mutated forms of the virus that are resistant to existing therapies. Currently, approved drugs target three of the four major enzyme activities encoded by the virus that are critical to the HIV life cycle. Although a number of inhibitors of HIV RNase H activity have been reported, few inhibit by directly engaging the RNase H active site. Here, we describe structures of naphthyridinone-containing inhibitors bound to the RNase H active site. This class of compounds binds to the active site via two metal ions that are coordinated by catalytic site residues, D443, E478, D498, and D549. The directionality of the naphthyridinone pharmacophore is restricted by the ordering of D549 and H539 in the RNase H domain. In addition, one of the naphthyridinone-based compounds was found to bind at a second site close to the polymerase active site and non-nucleoside/nucleotide inhibitor sites in a metal-independent manner. Further characterization, using fluorescence-based thermal denaturation and a crystal structure of the isolated RNase H domain reveals that this compound can also bind the RNase H site and retains the metal-dependent binding mode of this class of molecules. These structures provide a means for structurally guided design of novel RNase H inhibitors.

  10. Heavy metal biosorption sites in Penicillium cyclopium | Tsekova ...

    African Journals Online (AJOL)

    The biomass of Penicillium cyclopium was subjected to chemical treatment to study the role of the functional groups in the biosorption of heavy metal ions. The modifications of the functional groups were examined with infrared spectroscopy. Hydroxyl groups were identified as providing the major sites of heavy metal ...

  11. Individual and cumulative effects of agriculture, forestry and metal mining activities on the metal and phosphorus content of fluvial fine-grained sediment; Quesnel River Basin, British Columbia, Canada.

    Science.gov (United States)

    Smith, Tyler B; Owens, Philip N

    2014-10-15

    The impact of agriculture, forestry and metal mining on the quality of fine-grained sediment (sediment were collected monthly during the snow-free season in 2008 using time-integrated samplers at replicate sites representative of agriculture, forestry and mining activities in the basin (i.e. "impacted" sites). Samples were also collected from replicate reference sites and also from the main stem of the Quesnel River at the downstream confluence with the Fraser River. Generally, metal(loid) and phosphorus (P) concentrations for "impacted" sites were greater than for reference sites. Furthermore, concentrations of copper (forestry and mining sites), manganese (agriculture and forestry sites) and selenium (agriculture, forestry and mining sites) exceeded upper sediment quality guideline (SQG) thresholds. These results suggest that agriculture, forestry and metal mining activities are having an influence on the concentrations of sediment-associated metal(loid)s and P in the Quesnel basin. Metal(loid) and P concentrations of sediment collected from the downstream site were not significantly greater than values for the reference sites, and were typically lower than the values for the impacted sites. This suggests that the cumulative effects of agriculture, forestry and mining activities in the QRB are presently not having a measureable effect at the river basin-scale. The lack of a cumulative effect at the basin-scale is thought to reflect: (i) the relatively recent occurrence of land use disturbances in this basin; (ii) the dominance of sediment contributions from natural forest and agriculture; and (iii) the potential for storage of contaminants on floodplains and other storage elements between the locations of disturbance activities and the downstream sampling site, which may be attenuating the disturbance signal. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Final Report for Project ''Role of Metal Bioavailability in In Situ Bioremediation of Metal and Organic Co-Contaminated Sites''; FINAL

    International Nuclear Information System (INIS)

    Raina M. Maier

    2002-01-01

    A large proportion of hazardous waste sites are co-contaminated with organics and various metals. Such co-contaminated sites are difficult to bioremediate due to the nature of the mixed contaminants. Specifically, the presence of a co-contaminating metal imposes increased stress on indigenous populations already impacted by organic contaminant stress. The overall objective of this research is to investigate the effect of varying metal bioavailability on microbial populations and biodegradation of organics to allow a better understanding of how optimize remediation of co-contaminated sites. The hypothesis for this project is that metal bioavailability is not directly correlated with metal stress imposed on microbial populations that are degrading organics in soil and that further understanding of the relationship between metal bioavailability and metal stress is required for successful treatment of sites contaminated with mixtures of organics and metals. The specific objectives to be addressed to accomplish this goal are: (1) To determine the influence of metal bioavailability in soil microcosms co-contaminated with organics and metals on degradation of the organic contaminants and on mechanisms of metal resistance and (2) To determine the efficacy of different bioremediation strategies for co-contaminated soils based on metal bioavailability

  13. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    KAUST Repository

    Osadchii, Dmitrii; Olivos Suarez, Alma Itzel; Szé csé nyi, Á gnes; Li, Guanna; Nasalevich, Maxim A.; Dugulan, A Iulian; Serra-Crespo, Pablo; Hensen, Emiel J. M.; Veber, Sergey L.; Fedin, Matvey V.; Sankar, Gopinathan; Pidko, Evgeny A; Gascon, Jorge

    2018-01-01

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  14. Isolated Fe sites in Metal Organic Framework catalyze the direct conversion of methane to methanol

    KAUST Repository

    Osadchii, Dmitrii

    2018-05-10

    Hybrid materials bearing organic and inorganic motives have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal Metal Organic Framework that mimics the reactivity of soluble methane monooxygenase enzyme reactivity and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterisation of an Fe-containing MOF that comprises the desired antiferromagnetically cou-pled high spin species in a coordination environment closely resembling that of the enzyme. An electrochemi-cal synthesis method is used to build the microporous MOF matrix while integrating, with an exquisite con-trol, the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behaviour of the enzyme to produce methanol, and shows that the key to this reactivity is the for-mation of isolated oxo-bridged Fe units.

  15. Considering bioavailability in the remediation of heavy metal contaminated sites

    Directory of Open Access Journals (Sweden)

    Leita L.

    2013-04-01

    Full Text Available Many years of research have demonstrated that instead of the total concentration of metals in soil, bioavailability is the key to understand the environmental risk derived by metals, since adverse effects are related only to the biologically available forms of these elements. The knowledge of bioavailability can decrease the uncertainties in evaluating exposure in human and ecological risk assessment. At the same time, the efficiency of remediation treatments could be greatly influenced by availability of the contaminants. Consideration of the bioavailability processes at contaminated sites could be useful in site-specific risk assessment: the fraction of mobile metals, instead of total content should be provided as estimates of metal exposure. Moreover, knowledge of the chemical forms of heavy metals in soils is a critical component in the evaluation of applicability of different remediation technologies such as phytoremdiation or soil washing.

  16. Dehydroisomerization of n-butane over Pt-ZSMMMm5(I): effect of the metal loading and acid site concentration

    NARCIS (Netherlands)

    Pirngruber, G.D.; Seshan, Kulathuiyer; Lercher, J.A.

    1999-01-01

    The dehydroisomerization of n-butane to isobutene over Pt–ZSM5 catalysts with a high Si/Al ratio was studied. The catalytic activity increases with increasing metal loading. Butenes formed via dehydrogenation over the metallic particles are converted to isobutene over the Brønsted acid sites. The

  17. Glomeromycota communities survive extreme levels of metal toxicity in an orphan mining site.

    Science.gov (United States)

    Sánchez-Castro, I; Gianinazzi-Pearson, V; Cleyet-Marel, J C; Baudoin, E; van Tuinen, D

    2017-11-15

    Abandoned tailing basins and waste heaps of orphan mining sites are of great concern since extreme metal contamination makes soil improper for any human activity and is a permanent threat for nearby surroundings. Although spontaneous revegetation can occur, the process is slow or unsuccessful and rhizostabilisation strategies to reduce dispersal of contaminated dust represent an option to rehabilitate such sites. This requires selection of plants tolerant to such conditions, and optimization of their fitness and growth. Arbuscular mycorrhizal fungi (AMF) can enhance metal tolerance in moderately polluted soils, but their ability to survive extreme levels of metal contamination has not been reported. This question was addressed in the tailing basin and nearby waste heaps of an orphan mining site in southern France, reaching in the tailing basin exceptionally high contents of zinc (ppm: 97,333 total) and lead (ppm: 31,333 total). In order to contribute to a better understanding of AMF ecology under severe abiotic stress and to identify AMF associated with plants growing under such conditions, that may be considered in future revegetation and rhizostabilisation of highly polluted areas, nine plant species were sampled at different growing seasons and AMF root colonization was determined. Glomeromycota diversity was monitored in mycorrhizal roots by sequencing of the ribosomal LSU. This first survey of AMF in such highly contaminated soils revealed the presence of several AMF ribotypes, belonging mainly to the Glomerales, with some examples from the Paraglomerales and Diversisporales. AMF diversity and root colonization in the tailing basin were lower than in the less-contaminated waste heaps. A Paraglomus species previously identified in a polish mining site was common in roots of different plants. Presence of active AMF in such an environment is an outstanding finding, which should be clearly considered for the design of efficient rhizostabilisation processes

  18. Uptake of heavy metals by Typha capensis from wetland sites polluted by effluent from mineral processing plants: implications of metal-metal interactions.

    Science.gov (United States)

    Zaranyika, M F; Nyati, W

    2017-10-01

    The aim of the present work was to demonstrate the existence of metal-metal interactions in plants and their implications for the absorption of toxic elements like Cr. Typha capensis , a good accumulator of heavy metals, was chosen for the study. Levels of Fe, Cr, Ni, Cd, Pb, Cu and Zn were determined in the soil and roots, rhizomes, stems and leaves of T. capensis from three Sites A, B and C polluted by effluent from a chrome ore processing plant, a gold ore processing plant, and a nickel ore processing plant, respectively. The levels of Cr were extremely high at Site A at 5415 and 786-16,047 μg g -1 dry weight in the soil and the plant, respectively, while the levels of Ni were high at Site C at 176 and 24-891 μg g -1 in the soil and the plant, respectively. The levels of Fe were high at all three sites at 2502-7500 and 906-13,833 μg g -1 in the soil and plant, respectively. For the rest of the metals, levels were modest at 8.5-148 and 2-264 μg g -1 in the soil and plant, respectively. Pearson's correlation analysis confirmed mutual synergistic metal-metal interactions in the uptake of Zn, Cu, Co, Ni, Fe, and Cr, which are attributed to the similarity in the radii and coordination geometry of the cations of these elements. The implications of such metal-metal interactions (or effects of one metal on the behaviour of another) on the uptake of Cr, a toxic element, and possible Cr detoxification mechanism within the plant, are discussed.

  19. The influence of soil organic carbon on interactions between microbial parameters and metal concentrations at a long-term contaminated site

    Energy Technology Data Exchange (ETDEWEB)

    Muhlbachova, G. [Crop Research Institute, Drnovska 507, 161 06 Prague 6, Ruzyne (Czech Republic); Sagova-Mareckova, M., E-mail: sagova@vurv.cz [Crop Research Institute, Drnovska 507, 161 06 Prague 6, Ruzyne (Czech Republic); Omelka, M. [Charles University, Faculty of Mathematics and Physics, Dept. of Probability and Mathematical Statistics, Prague 8, Karlin (Czech Republic); Szakova, J.; Tlustos, P. [Czech University of Life Sciences, Department of Agroenvironmental Chemistry and Plant Nutrition, Prague 6, Suchdol (Czech Republic)

    2015-01-01

    The effects of lead, zinc, cadmium, arsenic and copper deposits on soil microbial parameters were investigated at a site exposed to contamination for over 200 years. Soil samples were collected in triplicates at 121 sites differing in contamination and soil organic carbon (SOC). Microbial biomass, respiration, dehydrogenase activity and metabolic quotient were determined and correlated with total and extractable metal concentrations in soil. The goal was to analyze complex interactions between toxic metals and microbial parameters by assessing the effect of soil organic carbon in the relationships. The effect of SOC was significant in all interactions and changed the correlations between microbial parameters and metal fractions from negative to positive. In some cases, the effect of SOC was combined with that of clay and soil pH. In the final analysis, dehydrogenase activity was negatively correlated to total metal concentrations and acetic acid extractable metals, respiration and metabolic quotient were to ammonium nitrate extractable metals. Dehydrogenase activity was the most sensitive microbial parameter correlating most frequently with contamination. Total and extractable zinc was most often correlated with microbial parameters. The large data set enabled robust explanation of discrepancies in organic matter functioning occurring frequently in analyzing of contaminated soil processes. - Highlights: • Soil organic carbon affected all interactions between metals and microorganisms. • Soil organic carbon adjustment changed correlations from positive to negative. • Ammonium nitrate extractable metals were the most influencing fraction. • Dehydrogenase activity was the most affected soil parameter. • Zinc was the most toxic metal among studied metals.

  20. The influence of soil organic carbon on interactions between microbial parameters and metal concentrations at a long-term contaminated site

    International Nuclear Information System (INIS)

    Muhlbachova, G.; Sagova-Mareckova, M.; Omelka, M.; Szakova, J.; Tlustos, P.

    2015-01-01

    The effects of lead, zinc, cadmium, arsenic and copper deposits on soil microbial parameters were investigated at a site exposed to contamination for over 200 years. Soil samples were collected in triplicates at 121 sites differing in contamination and soil organic carbon (SOC). Microbial biomass, respiration, dehydrogenase activity and metabolic quotient were determined and correlated with total and extractable metal concentrations in soil. The goal was to analyze complex interactions between toxic metals and microbial parameters by assessing the effect of soil organic carbon in the relationships. The effect of SOC was significant in all interactions and changed the correlations between microbial parameters and metal fractions from negative to positive. In some cases, the effect of SOC was combined with that of clay and soil pH. In the final analysis, dehydrogenase activity was negatively correlated to total metal concentrations and acetic acid extractable metals, respiration and metabolic quotient were to ammonium nitrate extractable metals. Dehydrogenase activity was the most sensitive microbial parameter correlating most frequently with contamination. Total and extractable zinc was most often correlated with microbial parameters. The large data set enabled robust explanation of discrepancies in organic matter functioning occurring frequently in analyzing of contaminated soil processes. - Highlights: • Soil organic carbon affected all interactions between metals and microorganisms. • Soil organic carbon adjustment changed correlations from positive to negative. • Ammonium nitrate extractable metals were the most influencing fraction. • Dehydrogenase activity was the most affected soil parameter. • Zinc was the most toxic metal among studied metals

  1. Radioactive metal scrap recycling by melting process at the Chernobyl site

    International Nuclear Information System (INIS)

    Steinwarz, W.

    1995-01-01

    Within its TACIS programme the European Union ordered a feasibility study on the cleaning-up of the Chernobyl area from radioactively contaminated metallic material. The study was performed by a Ukrainian German Working Group under the leadership of Siempelkamp and finalized at the end of March 1994. The on-site evaluation for the 30 km exclusion zone showed an overall mass of metal scrap of min. 100,000 Mg with a maximum specific activity of 400 Bq/g based on 48 open depositories within the restricted area. Dominant radionuclides were Cs-137 and Sr-90 accompanied by a very low proportion of α-activity. The study report showed the technical feasibility of a melting plant designed with a throughput of 10'000 Mg per year and its suitability for the overall concept to handle the Chernobyl waste. The main task for the near future can be identified as the establishing of a sound financial concept. (author) 5 figs., 3 tabs., 2 refs

  2. Heavy metals distribution and risk assessment in soil from an informal E-waste recycling site in Lagos State, Nigeria.

    Science.gov (United States)

    Isimekhai, Khadijah A; Garelick, Hemda; Watt, John; Purchase, Diane

    2017-07-01

    Informal E-waste recycling can pose a risk to human health and the environment which this study endeavours to evaluate. The distribution of a number of heavy metals in soil from an informal recycling site in the largest market for used and new electronics and electrical equipment in West Africa was investigated. The potential bioavailability of heavy metals, extent of contamination, potential risk due to the recycling activities and impact of external factors such as rainfall were also assessed. The concentrations of all the heavy metals tested were higher in the area where burning of the waste occurred than at the control site, suggesting an impact of the recycling activities on the soil. The order of total metal concentrations was Cu > Pb > Zn > Mn > Ni > Sb > Cr > Cd for both the dry and wet seasons. The total concentrations of Cd, Cu, Mn, Ni and Zn were all significantly higher (p  Sb > Zn > Cu > Ni > Pb > Cr. When the risk was assessed using the Potential Ecological Risk Index (PERI), Cu was found to contribute the most to the potential ecological risk and Cd gave rise to the greatest concern due to its high toxic-response factor within the study site. Similarly, utilising the Risk Assessment Code (RAC) suggested that Cd posed the most risk in this site. This research establishes a high level of contamination in the study site and underscores the importance of applying the appropriate chemical speciation in risk assessment.

  3. Sequence of ligand binding and structure change in the diphtheria toxin repressor upon activation by divalent transition metals.

    Science.gov (United States)

    Rangachari, Vijayaraghavan; Marin, Vedrana; Bienkiewicz, Ewa A; Semavina, Maria; Guerrero, Luis; Love, John F; Murphy, John R; Logan, Timothy M

    2005-04-19

    The diphtheria toxin repressor (DtxR) is an Fe(II)-activated transcriptional regulator of iron homeostatic and virulence genes in Corynebacterium diphtheriae. DtxR is a two-domain protein that contains two structurally and functionally distinct metal binding sites. Here, we investigate the molecular steps associated with activation by Ni(II)Cl(2) and Cd(II)Cl(2). Equilibrium binding energetics for Ni(II) were obtained from isothermal titration calorimetry, indicating apparent metal dissociation constants of 0.2 and 1.7 microM for two independent sites. The binding isotherms for Ni(II) and Cd(II) exhibited a characteristic exothermic-endothermic pattern that was used to infer the metal binding sequence by comparing the wild-type isotherm with those of several binding site mutants. These data were complemented by measuring the distance between specific backbone amide nitrogens and the first equivalent of metal through heteronuclear NMR relaxation measurements. Previous studies indicated that metal binding affects a disordered to ordered transition in the metal binding domain. The coupling between metal binding and structure change was investigated using near-UV circular dichroism spectroscopy. Together, the data show that the first equivalent of metal is bound by the primary metal binding site. This binding orients the DNA binding helices and begins to fold the N-terminal domain. Subsequent binding at the ancillary site completes the folding of this domain and formation of the dimer interface. This model is used to explain the behavior of several mutants.

  4. Underground Corrosion of Activated Metals in an Arid Vadose Zone Environment

    International Nuclear Information System (INIS)

    Adler Flitton, M.K; Mizia, R.E.; Bishop, C.W.

    2001-01-01

    The subsurface radioactive disposal site located at the Idaho National Engineering and Environmental Laboratory contains neutron-activated metals from nonfuel nuclear-reactor- core components. A long-term corrosion test is being conducted to obtain site-specific corrosion rates to support efforts to more accurately estimate the transfer of activated elements in an arid vadose zone environment. The tests use nonradioactive metal coupons representing the prominent neutron-activated material buried at the disposal location, namely, Type 304L stainless steel, Type 315L stainless steel, nickel-chromium alloy (UNS NO7718), beryllium, aluminum 6061-T6, and a zirconium alloy, (UNS R60804). In addition, carbon steel (the material presently used in the cask disposal liners and other disposal containers) and a duplex stainless steel (UNS S32550) (the proposed material for the high- integrity disposal containers) are also included in the test program. This paper briefly describes the test program and presents the early corrosion rate results after 1 year and 3 years of underground exposure

  5. MetalS2: a tool for the structural alignment of minimal functional sites in metal-binding proteins and nucleic acids.

    Science.gov (United States)

    Andreini, Claudia; Cavallaro, Gabriele; Rosato, Antonio; Valasatava, Yana

    2013-11-25

    We developed a new software tool, MetalS(2), for the structural alignment of Minimal Functional Sites (MFSs) in metal-binding biological macromolecules. MFSs are 3D templates that describe the local environment around the metal(s) independently of the larger context of the macromolecular structure. Such local environment has a determinant role in tuning the chemical reactivity of the metal, ultimately contributing to the functional properties of the whole system. On our example data sets, MetalS(2) unveiled structural similarities that other programs for protein structure comparison do not consistently point out and overall identified a larger number of structurally similar MFSs. MetalS(2) supports the comparison of MFSs harboring different metals and/or with different nuclearity and is available both as a stand-alone program and a Web tool ( http://metalweb.cerm.unifi.it/tools/metals2/).

  6. Novel bis-(−)-nor-meptazinol derivatives act as dual binding site AChE inhibitors with metal-complexing property

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Wei [Department of Medicinal Chemistry, School of Pharmacy, Fudan University, 826 Zhangheng Road, Shanghai 200032 (China); NPFPC Key Laboratory of Contraceptives and Devices, Shanghai Institute of Planned Parenthood Research, 2140 Xietu Road, Shanghai 200032 (China); Li, Juan [Department of Pharmacology, Institute of Medical Sciences, Shanghai Jiaotong University School of Medicine, 280 South Chongqing Road, Shanghai 200025 (China); Qiu, Zhuibai [Department of Medicinal Chemistry, School of Pharmacy, Fudan University, 826 Zhangheng Road, Shanghai 200032 (China); Xia, Zheng [Department of Pharmacology, Institute of Medical Sciences, Shanghai Jiaotong University School of Medicine, 280 South Chongqing Road, Shanghai 200025 (China); Li, Wei [Department of Medicinal Chemistry, School of Pharmacy, Fudan University, 826 Zhangheng Road, Shanghai 200032 (China); Yu, Lining; Chen, Hailin; Chen, Jianxing [NPFPC Key Laboratory of Contraceptives and Devices, Shanghai Institute of Planned Parenthood Research, 2140 Xietu Road, Shanghai 200032 (China); Chen, Yan; Hu, Zhuqin; Zhou, Wei; Shao, Biyun; Cui, Yongyao [Department of Pharmacology, Institute of Medical Sciences, Shanghai Jiaotong University School of Medicine, 280 South Chongqing Road, Shanghai 200025 (China); Xie, Qiong, E-mail: xiejoanxq@gmail.com [Department of Medicinal Chemistry, School of Pharmacy, Fudan University, 826 Zhangheng Road, Shanghai 200032 (China); Chen, Hongzhuan, E-mail: yaoli@shsmu.edu.cn [Department of Pharmacology, Institute of Medical Sciences, Shanghai Jiaotong University School of Medicine, 280 South Chongqing Road, Shanghai 200025 (China)

    2012-10-01

    The strategy of dual binding site acetylcholinesterase (AChE) inhibition along with metal chelation may represent a promising direction for multi-targeted interventions in the pathophysiological processes of Alzheimer's disease (AD). In the present study, two derivatives (ZLA and ZLB) of a potent dual binding site AChE inhibitor bis-(−)-nor-meptazinol (bis-MEP) were designed and synthesized by introducing metal chelating pharmacophores into the middle chain of bis-MEP. They could inhibit human AChE activity with IC{sub 50} values of 9.63 μM (for ZLA) and 8.64 μM (for ZLB), and prevent AChE-induced amyloid-β (Aβ) aggregation with IC{sub 50} values of 49.1 μM (for ZLA) and 55.3 μM (for ZLB). In parallel, molecular docking analysis showed that they are capable of interacting with both the catalytic and peripheral anionic sites of AChE. Furthermore, they exhibited abilities to complex metal ions such as Cu(II) and Zn(II), and inhibit Aβ aggregation triggered by these metals. Collectively, these results suggest that ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency, and may be potential leads of value for further study on disease-modifying treatment of AD. -- Highlights: ► Two novel bis-(−)-nor-meptazinol derivatives are designed and synthesized. ► ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency. ► They are potential leads for disease-modifying treatment of Alzheimer's disease.

  7. Novel bis-(−)-nor-meptazinol derivatives act as dual binding site AChE inhibitors with metal-complexing property

    International Nuclear Information System (INIS)

    Zheng, Wei; Li, Juan; Qiu, Zhuibai; Xia, Zheng; Li, Wei; Yu, Lining; Chen, Hailin; Chen, Jianxing; Chen, Yan; Hu, Zhuqin; Zhou, Wei; Shao, Biyun; Cui, Yongyao; Xie, Qiong; Chen, Hongzhuan

    2012-01-01

    The strategy of dual binding site acetylcholinesterase (AChE) inhibition along with metal chelation may represent a promising direction for multi-targeted interventions in the pathophysiological processes of Alzheimer's disease (AD). In the present study, two derivatives (ZLA and ZLB) of a potent dual binding site AChE inhibitor bis-(−)-nor-meptazinol (bis-MEP) were designed and synthesized by introducing metal chelating pharmacophores into the middle chain of bis-MEP. They could inhibit human AChE activity with IC 50 values of 9.63 μM (for ZLA) and 8.64 μM (for ZLB), and prevent AChE-induced amyloid-β (Aβ) aggregation with IC 50 values of 49.1 μM (for ZLA) and 55.3 μM (for ZLB). In parallel, molecular docking analysis showed that they are capable of interacting with both the catalytic and peripheral anionic sites of AChE. Furthermore, they exhibited abilities to complex metal ions such as Cu(II) and Zn(II), and inhibit Aβ aggregation triggered by these metals. Collectively, these results suggest that ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency, and may be potential leads of value for further study on disease-modifying treatment of AD. -- Highlights: ► Two novel bis-(−)-nor-meptazinol derivatives are designed and synthesized. ► ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency. ► They are potential leads for disease-modifying treatment of Alzheimer's disease.

  8. Heavy metal contamination of surface soil in electronic waste dismantling area: site investigation and source-apportionment analysis.

    Science.gov (United States)

    Jinhui Li; Huabo Duan; Pixing Shi

    2011-07-01

    The dismantling and disposal of electronic waste (e-waste) in developing countries is causing increasing concern because of its impacts on the environment and risks to human health. Heavy-metal concentrations in the surface soils of Guiyu (Guangdong Province, China) were monitored to determine the status of heavy-metal contamination on e-waste dismantling area with a more than 20 years history. Two metalloids and nine metals were selected for investigation. This paper also attempts to compare the data among a variety of e-waste dismantling areas, after reviewing a number of heavy-metal contamination-related studies in such areas in China over the past decade. In addition, source apportionment of heavy metal in the surface soil of these areas has been analysed. Both the MSW open-burning sites probably contained invaluable e-waste and abandoned sites formerly involved in informal recycling activities are the new sources of soil-based environmental pollution in Guiyu. Although printed circuit board waste is thought to be the main source of heavy-metal emissions during e-waste processing, requirement is necessary to soundly manage the plastic separated from e-waste, which mostly contains heavy metals and other toxic substances.

  9. Impact of heavy metal on activity of some microbial enzymes in the riverbed sediments: Ecotoxicological implications in the Ganga River (India).

    Science.gov (United States)

    Jaiswal, Deepa; Pandey, Jitendra

    2018-04-15

    We studied the extracellular enzyme activity (EEA) in the riverbed sediment along a 518km gradient of the Ganga River receiving carbon and nutrient load from varied human sources. Also, we tested, together with substrate-driven stimulation, if the heavy metal accumulated in the sediment inhibits enzyme activities. Because pristine values are not available, we considered Dev Prayag, a least polluted site located 624km upstream to main study stretch, as a reference site. There were distinct increases in enzyme activities in the sediment along the study gradient from Dev Prayag, however, between-site differences were in concordance with sediment carbon(C), nitrogen (N) and phosphorus (P). Fluorescein diacetate hydrolysis (FDAase), β-glucosidase (Glu) and protease activities showed positive correlation with C, N and P while alkaline phosphatase was found negatively correlated with P. Enzyme activities were found negatively correlated with heavy metal, although ecological risk index (E R i ) varied with site and metal species. Dynamic fit curves showed significant positive correlation between heavy metal and microbial metabolic quotient (qCO 2 ) indicating a decrease in microbial activity in response to increasing heavy metal concentrations. This study forms the first report linking microbial enzyme activities to regional scale sediment heavy metal accumulation in the Ganga River, suggests that the microbial enzyme activities in the riverbed sediment were well associated with the proportion of C, N and P and appeared to be a sensitive indicator of C, N and P accumulation in the river. Heavy metal accumulated in the sediment inhibits enzyme activities, although C rich sediment showed relatively low toxicity due probably to reduced bioavailability of the metal. The study has relevance from ecotoxicological as well as from biomonitoring perspectives. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction

    DEFF Research Database (Denmark)

    Bagger, Alexander; Ju, Wen; Varela, Ana Sofia

    2017-01-01

    Currently, no catalysts are completely selective for the electrochemical CO2 Reduction Reaction (CO2RR). Based on trends in density functional theory calculations of reaction intermediates we find that the single metal site in a porphyrine-like structure has a simple advantage of limiting...... the competing Hydrogen Evolution Reaction (HER). The single metal site in a porphyrine-like structure requires an ontop site binding of hydrogen, compared to the hollow site binding of hydrogen on a metal catalyst surface. The difference in binding site structure gives a fundamental energy-shift in the scaling...... relation of ∼0.3eV between the COOH* vs. H* intermediate (CO2RR vs. HER). As a result, porphyrine-like catalysts have the advantage over metal catalyst of suppressing HER and enhancing CO2RR selectivity....

  11. Real-Time Visualization of Active Species in a Single-Site Metal–Organic Framework Photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Sizhuo [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States; Pattengale, Brian [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States; Lee, Sungsik [X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60349, United States; Huang, Jier [Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States

    2018-02-06

    In this work, we report a new single-site photocatalyst (Co-Ru-UIO- 67(bpy)) based on a metal-organic framework platform with incorporated molecular photosensitizer and catalyst. We show that this catalyst not only demonstrates exceptional activity for light-driven H2 production but also can be recycled without loss of activity. Using the combination of optical transient absorption spectroscopy and in situ X-ray absorption spectroscopy, we not only captured the key CoI intermediate species formed after ultrafast charge transfer from the incorporated photosensitizer but also identified the rate-limiting step in the catalytic cycle, providing insight into the catalysis mechanism of these single-site metal-organic framework photocatalysts.

  12. Effect of metal ion on the structure and function of LiPDF: The study of the fine structure around the metal site using XANES

    International Nuclear Information System (INIS)

    Wang Yu; Chu Wangsheng; Yang Feifei; Yu Meijuan; Zhao Haifeng; Gong Weimin; Dong Yuhui; Xie Yaning; Wu, Ziyu

    2010-01-01

    We used X-ray absorption near edge structure (XANES) spectroscopy to investigate the metal-dependent enzymatic activity of the peptide deformylase from Leptospira interrogans (LiPDF). Ab initio full multiple scattering calculations performed by MXAN are applied to obtain the local structure of the cobalt-containing LiPDF (Co-LiPDF) and zinc-containing LiPDF (Zn-LiPDF) around the metal sites in pH9.0 buffer solution. The result shows the cobalt-wat1 (the bond water molecule) distance of Co-LiPDF is 1.89 A, much shorter than that of Zn-LiPDF, 2.50 A. That is an essential factor for its low catalytic activity.

  13. Effect of metal ion on the structure and function of LiPDF: The study of the fine structure around the metal site using XANES

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yu [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Chu Wangsheng, E-mail: cws@ihep.ac.c [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Yang Feifei; Yu Meijuan; Zhao Haifeng [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Gong Weimin [National Laboratory of Biomacromolecules, Institute of Biophysics, Chinese Academy of Sciences, Beijing 100101 (China); Dong Yuhui; Xie Yaning [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wu, Ziyu, E-mail: wuzy@ustc.edu.c [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

    2010-07-21

    We used X-ray absorption near edge structure (XANES) spectroscopy to investigate the metal-dependent enzymatic activity of the peptide deformylase from Leptospira interrogans (LiPDF). Ab initio full multiple scattering calculations performed by MXAN are applied to obtain the local structure of the cobalt-containing LiPDF (Co-LiPDF) and zinc-containing LiPDF (Zn-LiPDF) around the metal sites in pH9.0 buffer solution. The result shows the cobalt-wat1 (the bond water molecule) distance of Co-LiPDF is 1.89 A, much shorter than that of Zn-LiPDF, 2.50 A. That is an essential factor for its low catalytic activity.

  14. Biomonitoring for metal contamination near two Superfund sites in Woburn, Massachusetts, using phytochelatins

    International Nuclear Information System (INIS)

    Gawel, James E.; Hemond, Harold F.

    2004-01-01

    Characterizing the spatial extent of groundwater metal contamination traditionally requires installing sampling wells, an expensive and time-consuming process in urban areas. Moreover, extrapolating biotic effects from metal concentrations alone is problematic, making ecological risk assessment difficult. Our study is the first to examine the use of phytochelatin measurements in tree leaves for delimiting biological metal stress in shallow, metal-contaminated groundwater systems. Three tree species (Rhamnus frangula, Acer platanoides, and Betula populifolia) growing above the shallow groundwater aquifer of the Aberjona River watershed in Woburn, Massachusetts, display a pattern of phytochelatin production consistent with known sources of metal contamination and groundwater flow direction near the Industri-Plex Superfund site. Results also suggest the existence of a second area of contaminated groundwater and elevated metal stress near the Wells G and H Superfund site downstream, in agreement with a recent EPA ecological risk assessment. Possible contamination pathways at this site are discussed

  15. Determination of heavy metals in soils from dump site of tanneries ...

    African Journals Online (AJOL)

    Heavy metals were determined in soil samples at the dump site, Challawa town, Karfi Irrigation site and farmlands near the dump site by flame Atomic Absorption Spectrophotometer (AAS). The results showed that soil at the dump site contains significant amount of toxic elements. Hence remediation processes were ...

  16. Binding of Mn-deoxyribonucleoside Triphosphates to the Active Site of the DNA Polymerase of Bacteriophage T7

    Energy Technology Data Exchange (ETDEWEB)

    B Akabayov; C Richardson

    2011-12-31

    Divalent metal ions are crucial as cofactors for a variety of intracellular enzymatic activities. Mg{sup 2+}, as an example, mediates binding of deoxyribonucleoside 5'-triphosphates followed by their hydrolysis in the active site of DNA polymerase. It is difficult to study the binding of Mg{sup 2+} to an active site because Mg{sup 2+} is spectroscopically silent and Mg{sup 2+} binds with low affinity to the active site of an enzyme. Therefore, we substituted Mg{sup 2+} with Mn{sup 2+}:Mn{sup 2+} that is not only visible spectroscopically but also provides full activity of the DNA polymerase of bacteriophage T7. In order to demonstrate that the majority of Mn{sup 2+} is bound to the enzyme, we have applied site-directed titration analysis of T7 DNA polymerase using X-ray near edge spectroscopy. Here we show how X-ray near edge spectroscopy can be used to distinguish between signal originating from Mn{sup 2+} that is free in solution and Mn{sup 2+} bound to the active site of T7 DNA polymerase. This method can be applied to other enzymes that use divalent metal ions as a cofactor.

  17. Identification of metal ion binding sites based on amino acid sequences.

    Science.gov (United States)

    Cao, Xiaoyong; Hu, Xiuzhen; Zhang, Xiaojin; Gao, Sujuan; Ding, Changjiang; Feng, Yonge; Bao, Weihua

    2017-01-01

    The identification of metal ion binding sites is important for protein function annotation and the design of new drug molecules. This study presents an effective method of analyzing and identifying the binding residues of metal ions based solely on sequence information. Ten metal ions were extracted from the BioLip database: Zn2+, Cu2+, Fe2+, Fe3+, Ca2+, Mg2+, Mn2+, Na+, K+ and Co2+. The analysis showed that Zn2+, Cu2+, Fe2+, Fe3+, and Co2+ were sensitive to the conservation of amino acids at binding sites, and promising results can be achieved using the Position Weight Scoring Matrix algorithm, with an accuracy of over 79.9% and a Matthews correlation coefficient of over 0.6. The binding sites of other metals can also be accurately identified using the Support Vector Machine algorithm with multifeature parameters as input. In addition, we found that Ca2+ was insensitive to hydrophobicity and hydrophilicity information and Mn2+ was insensitive to polarization charge information. An online server was constructed based on the framework of the proposed method and is freely available at http://60.31.198.140:8081/metal/HomePage/HomePage.html.

  18. Roles of the active site residues and metal cofactors in noncanonical base-pairing during catalysis by human DNA polymerase iota.

    Science.gov (United States)

    Makarova, Alena V; Ignatov, Artem; Miropolskaya, Nataliya; Kulbachinskiy, Andrey

    2014-10-01

    Human DNA polymerase iota (Pol ι) is a Y-family polymerase that can bypass various DNA lesions but possesses very low fidelity of DNA synthesis in vitro. Structural analysis of Pol ι revealed a narrow active site that promotes noncanonical base-pairing during catalysis. To better understand the structure-function relationships in the active site of Pol ι we investigated substitutions of individual amino acid residues in its fingers domain that contact either the templating or the incoming nucleotide. Two of the substitutions, Y39A and Q59A, significantly decreased the catalytic activity but improved the fidelity of Pol ι. Surprisingly, in the presence of Mn(2+) ions, the wild-type and mutant Pol ι variants efficiently incorporated nucleotides opposite template purines containing modifications that disrupted either Hoogsteen or Watson-Crick base-pairing, suggesting that Pol ι may use various types of interactions during nucleotide addition. In contrast, in Mg(2+) reactions, wild-type Pol ι was dependent on Hoogsteen base-pairing, the Y39A mutant was essentially inactive, and the Q59A mutant promoted Watson-Crick interactions with template purines. The results suggest that Pol ι utilizes distinct mechanisms of nucleotide incorporation depending on the metal cofactor and reveal important roles of specific residues from the fingers domain in base-pairing and catalysis. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Trace Metal Content of Sediments Close to Mine Sites in the Andean Region

    Directory of Open Access Journals (Sweden)

    Cristina Yacoub

    2012-01-01

    Full Text Available This study is a preliminary examination of heavy metal pollution in sediments close to two mine sites in the upper part of the Jequetepeque River Basin, Peru. Sediment concentrations of Al, As, Cd, Cu, Cr, Fe, Hg, Ni, Pb, Sb, Sn, and Zn were analyzed. A comparative study of the trace metal content of sediments shows that the highest concentrations are found at the closest points to the mine sites in both cases. The sediment quality analysis was performed using the threshold effect level of the Canadian guidelines (TEL. The sediment samples analyzed show that potential ecological risk is caused frequently at both sites by As, Cd, Cu, Hg, Pb, and Zn. The long-term influence of sediment metals in the environment is also assessed by sequential extraction scheme analysis (SES. The availability of metals in sediments is assessed, and it is considered a significant threat to the environment for As, Cd, and Sb close to one mine site and Cr and Hg close to the other mine site. Statistical analysis of sediment samples provides a characterization of both subbasins, showing low concentrations of a specific set of metals and identifies the main characteristics of the different pollution sources. A tentative relationship between pollution sources and possible ecological risk is established.

  20. Bioavailability of particulate metal to zebra mussels: Biodynamic modelling shows that assimilation efficiencies are site-specific

    Energy Technology Data Exchange (ETDEWEB)

    Bourgeault, Adeline, E-mail: bourgeault@ensil.unilim.fr [Cemagref, Unite de Recherche Hydrosystemes et Bioprocedes, 1 rue Pierre-Gilles de Gennes, 92761 Antony (France); FIRE, FR-3020, 4 place Jussieu, 75005 Paris (France); Gourlay-France, Catherine, E-mail: catherine.gourlay@cemagref.fr [Cemagref, Unite de Recherche Hydrosystemes et Bioprocedes, 1 rue Pierre-Gilles de Gennes, 92761 Antony (France); FIRE, FR-3020, 4 place Jussieu, 75005 Paris (France); Priadi, Cindy, E-mail: cindy.priadi@eng.ui.ac.id [LSCE/IPSL CEA-CNRS-UVSQ, Avenue de la Terrasse, 91198 Gif-sur-Yvette (France); Ayrault, Sophie, E-mail: Sophie.Ayrault@lsce.ipsl.fr [LSCE/IPSL CEA-CNRS-UVSQ, Avenue de la Terrasse, 91198 Gif-sur-Yvette (France); Tusseau-Vuillemin, Marie-Helene, E-mail: Marie-helene.tusseau@ifremer.fr [IFREMER Technopolis 40, 155 rue Jean-Jacques Rousseau, 92138 Issy-Les-Moulineaux (France)

    2011-12-15

    This study investigates the ability of the biodynamic model to predict the trophic bioaccumulation of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) in a freshwater bivalve. Zebra mussels were transplanted to three sites along the Seine River (France) and collected monthly for 11 months. Measurements of the metal body burdens in mussels were compared with the predictions from the biodynamic model. The exchangeable fraction of metal particles did not account for the bioavailability of particulate metals, since it did not capture the differences between sites. The assimilation efficiency (AE) parameter is necessary to take into account biotic factors influencing particulate metal bioavailability. The biodynamic model, applied with AEs from the literature, overestimated the measured concentrations in zebra mussels, the extent of overestimation being site-specific. Therefore, an original methodology was proposed for in situ AE measurements for each site and metal. - Highlights: > Exchangeable fraction of metal particles did not account for the bioavailability of particulate metals. > Need for site-specific biodynamic parameters. > Field-determined AE provide a good fit between the biodynamic model predictions and bioaccumulation measurements. - The interpretation of metal bioaccumulation in transplanted zebra mussels with biodynamic modelling highlights the need for site-specific assimilation efficiencies of particulate metals.

  1. High-resolution insight into the competitive adsorption of heavy metals on natural sediment by site energy distribution.

    Science.gov (United States)

    Huang, Limin; Jin, Qiang; Tandon, Puja; Li, Aimin; Shan, Aidang; Du, Jiajie

    2018-04-01

    Investigating competitive adsorption on river/lake sediments is valuable for understanding the fate and transport of heavy metals. Most studies have studied the adsorption isotherms of competitive heavy metals, which mainly comparing the adsorption information on the same concentration. However, intrinsically, the concentration of each heavy metal on competitive adsorption sites is different, while the adsorption energy is identical. Thus, this paper introduced the site energy distribution theory to increase insight into the competitive adsorption of heavy metals (Cu, Cd and Zn). The site energy distributions of each metal with and without other coexisting heavy metals were obtained. It illustrated that site energy distributions provide much more information than adsorption isotherms through screening of the full energy range. The results showed the superior heavy metal in each site energy area and the influence of competitive metals on the site energy distribution of target heavy metal. Site energy distributions can further help in determining the competitive sites and ratios of coexisting metals. In particular, in the high-energy area, which has great environmental significance, the ratios of heavy metals in the competitive adsorption sites obtained for various competitive systems were as follows: slightly more than 3:1 (Cu-Cd), slightly less than 3:1 (Cu-Zn), slightly more than 1:1 (Cd-Zn), and nearly 7:2:2 (Cu-Cd-Zn). The results from this study are helpful to deeply understand competitive adsorption of heavy metals (Cu, Cd, Zn) on sediment. Therefore, this study was effective in presenting a general pattern for future reference in competitive adsorption studies on sediments. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. Entrapment of metal clusters in metal-organic framework channels by extended hooks anchored at open metal sites.

    Science.gov (United States)

    Zheng, Shou-Tian; Zhao, Xiang; Lau, Samuel; Fuhr, Addis; Feng, Pingyun; Bu, Xianhui

    2013-07-17

    Reported here are the new concept of utilizing open metal sites (OMSs) for architectural pore design and its practical implementation. Specifically, it is shown here that OMSs can be used to run extended hooks (isonicotinates in this work) from the framework walls to the channel centers to effect the capture of single metal ions or clusters, with the concurrent partitioning of the large channel spaces into multiple domains, alteration of the host-guest charge relationship and associated guest-exchange properties, and transfer of OMSs from the walls to the channel centers. The concept of the extended hook, demonstrated here in the multicomponent dual-metal and dual-ligand system, should be generally applicable to a range of framework types.

  3. Yeast enolase: mechanism of activation by metal ions.

    Science.gov (United States)

    Brewer, J M

    1981-01-01

    Yeast enolase as prepared by current procedures is inherently chemically homogeneous, though deamidation and partial denaturation can produce electrophoretically distinct forms. A true isozyme of the enzyme exists but does not survive the purification procedure. The chemical sequence for both has been established. The enzyme behaves in solution like a compact, nearly spherical molecule of moderate hydration. Strong intramolecular forces maintain the structure of the individual subunits. The enzyme as isolated is dimeric. If dissociated in the presence of magnesium ions and substrate, then the subunits are active, but if the dissociation occurs in the absence of metal ions, they are inactive until they have reassociated and undergone a first order "annealing" process. Magnesium (II) enhances association. The interaction between the subunits is hydrophobic in character. The enzyme can bind up to 2 mol of most metal ions in "conformational" sites which then allows up to 2 mol of substrate or some substrate analogue to bind. This is not sufficient for catalysis, but conformational metal ions do more than just allow substrate binding. A change in the environment of the metal ions occurs on substrate or substrate analogue binding. There is an absolute correlation between the occurrence of a structural change undergone by the 3-amino analogue of phosphoenolpyruvate and whether the metal ions produce any level of enzymatic activity. For catalysis, two more moles of metal ions, called "catalytic", must bind. There is evidence that the enzymatic reaction involves a carbanion mechanism. It is likely that two more moles of metal ion can bind which inhibit the reaction. The requirement for 2 mol of metal ion per subunit which contribute in different ways to catalysis is exhibited by a number of other enzymes.

  4. Heavy metals uptake by sonicated activated sludge: Relation with floc surface properties

    International Nuclear Information System (INIS)

    Laurent, Julien; Casellas, Magali; Dagot, Christophe

    2009-01-01

    The effects of sonication of activated sludge on heavy metal uptake were in a first time investigated in respect with potential modifications of floc surface properties. The treatment led to the simultaneous increase of specific surface area and of the availability of negative and/or hydrophilic sites. In parallel, organic matter was released in the soluble fraction. Sorption isotherms of cadmium and copper showed that uptake characteristics and mechanisms were highly dependent on both heavy metal species and specific energy supplied. The increase of both specific surface area and fixation sites availability led to the increase of Cd(II) uptake. For Cu(II), organic matter released in soluble phase during the treatment seemed to act as a ligand and to limit adsorption on flocs surface. Three different heavy metals uptake mechanisms have been identified: proton exchange, ion exchange and (co)precipitation

  5. Risks to humans and wildlife from metal contamination in soils/sediments at CERCLA sites

    International Nuclear Information System (INIS)

    Hitch, J.P.; Hovatter, P.S.; Opresko, D.M.; Sample, B.; Young, R.A.

    1994-01-01

    A common problem that occurs at DOD and DOE CERCLA sites is metal contamination in soils and aquatic sediments and the protection of humans and wildlife from potential exposure to this contamination. Consequently, the authors have developed a site-specific reference dose for mercury in sediments at the Oak Ridge Reservation and site-specific cleanup levels for certain metals, including arsenic and nickel, in soils at an Army ammunition plant. Another concern during remediation of these sites is that limited data are available to determine the direct risks to indigenous wildlife. Therefore, the authors have developed toxicological benchmarks for certain metals and metal compounds to be used as screening tools to determine the potential hazard of a contaminant to representative mammalian and avian wildlife species. These values should enable the Army and DOE to more accurately determine the risks to humans and wildlife associated with exposure to these contaminated media at their sites in order to achieve a more effective remediation. This effort is ongoing at ORNL with toxicological benchmarks also being developed for metal compounds and other chemicals of concern to DOD and DOE in order to address the potential hazard to

  6. Pollution assessment and source apportionment of heavy metals in contaminated site soils

    Science.gov (United States)

    Zheng, Hongbo; Ma, Yan

    2018-03-01

    Pollution characteristics of heavy metals in soil were analyzed with a typical contaminated site as the case area. The pollution degree of the element was evaluated by indexes of geoaccumulation (Igeo). The potential ecological risk of heavy metals was assessed with potential ecological risk index model. Principal component analysis (PCA) model was simultaneously carried out to identify the main sources of heavy metals in topsoils. The results indicated that: 1. Mean values of 11 kinds of metals in topsoils were greater than respective soil background values, following the order: Zn>Pb>V>Cr>Cu>Ni>Co>As>Sb>Cd>Hg. Heavy metals with a certain accumulation in the research area were significantly affected by external factors. 2. Igeo results showed that Cd and Zn reached strongly polluted degree, while Pb with moderately to strongly polluted, Sb and Hg with moderately polluted, Cu, Co, Ni and Cr with unpolluted to moderately polluted, V and As with un-polluted. 3. Potential ecological risk assessment showed the degree of ecological risk with Cd at very high risk, Hg at high risk, Pb at moderate risk and others at low risk. The comprehensive risk of all the metals was very high. 4. PCA got three main sources with contributions, including industrial activities (44.18%), traffic and burning dust (26.68%) and soil parent materials (12.20%).

  7. Impaired microbial activity caused by metal pollution: A field study in a deactivated uranium mining area

    International Nuclear Information System (INIS)

    Antunes, Sara Cristina; Pereira, Ruth; Marques, Sérgio Miguel; Castro, Bruno Branco; Gonçalves, Fernando

    2011-01-01

    European frameworks for the ecological risk assessment (ERA) of contaminated sites integrate information from three lines of evidence: chemical, ecotoxicological, and ecological. Regarding the last one, field observations at the contaminated sites are compared to reference site(s) and the differences recorded are analysed at the light of a cause-effect relationship, taking into account the site-specific contamination. Thus, included in the tier 2 of a site-specific risk assessment that is being carried out in an deactivated uranium mining area, a battery of soil enzyme activities (dehydrogenases, urease, arysulphatase, cellulase, acid phosphate) and potential nitrification were assessed in seven sampling sites (A–D–E–F–G–H–I) at different distances from the mine pit. These parameters have been considered good indicators of impacts on soil microbial communities and, subsequently, on soil functions. Soil enzyme activities were impaired in the most contaminated site (A, near the mine pit), for which a higher degree of risk was determined in the tier 1 of ERA. Three other sites within the mining area (F, G, and D) were discriminated on the basis of their low microbial activity, using uni- and multivariate approaches, and validating what had been previously found with chemical and ecotoxicological lines of evidence. We observed considerable among-site heterogeneity in terms of soil physical and chemical properties, combined with seasonal differences in enzyme activities. Still, the correlation between microbial parameters and soil general physical and chemical parameters was weak. In opposition, significant and negative correlations were found between soil enzyme activities and several metallic elements (Al, Be, Cu, U). These findings suggest a clear correlation between compromised soil function (nutrient recycling) and metal contamination. Such information reinforces the evidence of risks for some sites within the mining area and is an important

  8. Sizing and melting development activities using noncontaminated metal at the Waste Experimental Reduction Facility

    International Nuclear Information System (INIS)

    Larsen, M.M.; Logan, J.A.

    1984-05-01

    EG and G Idaho, Inc., has established the Waste Experimental Reduction Facility (WERF) at the Idaho National Engineering Laboratory (INEL) to develop the capability to reduce the volume that low-level beta/gamma wastes occupy at the disposal site. The work effort at WERF includes a waste sizing development activity (WSDA), a waste melting development activity (WMDA), and a waste incineration development activity (WIDA). This report describes work and developments to date in the WSDA and WMDA with noncontaminated metallic waste in preparation for operations at WERF involving beta/gamma-contaminated metal

  9. Seasonal changes in antioxidant enzyme activities of freshwater biofilms in a metal polluted Mediterranean stream.

    Science.gov (United States)

    Bonet, Berta; Corcoll, Natàlia; Acuňa, Vicenç; Sigg, Laura; Behra, Renata; Guasch, Helena

    2013-02-01

    While seasonal variations in fluvial communities have been extensively investigated, effects of seasonality on community responses to environmental and/or chemical stress are poorly documented. The aim of this study was to describe antioxidant enzyme activity (AEA) variability in fluvial biofilms over an annual cycle, under multi-stress scenarios due to environmental variability (e.g., light intensity, water flow, and temperature) and metal pollution (Zn, Mn and Fe). The annual monitoring study was performed at three sites according to their water and biofilm metal concentrations. Metal concentration was affected by water flow due to dilution. Low flow led to higher dissolved Zn concentrations, and thus to higher Zn accumulation in the biofilm. Water temperature, light intensity and phosphate concentration were the environmental factors which determined the seasonality of biofilm responses, whereas dissolved Zn and Zn accumulation in biofilms were the parameters linked to sites and periods of highest metal pollution. Community algal succession, from diatoms in cold conditions to green algae in warm conditions, was clearer in the non metal-polluted site than in those metal-polluted, presumably due to the selection pressure exerted by metals. Most AEA were related with seasonal environmental variability at the sites with low or no-metal pollution, except glutathione-S-transferase (GST) which was related with Zn (dissolved and accumulated in biofilm) pollution occurring at the most polluted site. We can conclude that seasonal variations of community composition and function are masked by metal pollution. From this study we suggest the use of a multi-biomarker approach, including AEA and a set of biological and physicochemical parameters as an effect-based field tool to assess metal pollution. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Basis of the detection, assessment and cleaning up of sites contaminated with heavy metals

    International Nuclear Information System (INIS)

    Calmano, W.; Foerstner, U.

    1993-01-01

    The cleaning up of sites contaminated with heavy metals is still in its infancy. Depending on the type and extent of the contamination, new methods of treatment must be developed and matched to each situation. A survey is given of the groundwater contamination of soil heavy metals; the binding, availability and mobilisation of heavy metals; geo-chemical concepts for sites contaminated by heavy metals; judging the potential danger; safety measures; cleaning up processes and the reinstatement and renaturing of the soil. (orig.) [de

  11. Glyceraldehyde-3-phosphate dehydrogenase from Chironomidae showed differential activity towards metals.

    Science.gov (United States)

    Chong, Isaac K W; Ho, Wing S

    2013-09-01

    Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) is known to interact with different biomolecules and was implicated in many novel cellular activities including programmed cell death, nuclear RNA transport unrelated to the commonly known carbohydrate metabolism. We reported here the purification of GAPDH from Chironomidae larvae (Insecta, Diptera) that showed different biologic activity towards heavy metals. It was inhibited by copper, cobalt nickel, iron and lead but was activated by zinc. The GAPDH was purified by ammonium sulphate fractionation and Chelating Sepharose CL-6B chromatography followed by Blue Sepharose CL-6B chromatography. The 150-kDa tetrameric GAPDH showed optimal activity at pH 8.5 and 37°C. The multiple alignment of sequence of the Chironomidae GAPDH with other known species showed 78 - 88% identity to the conserved regions of the GADPH. Bioinformatic analysis unveils substantial N-terminal sequence similarity of GAPDH of Chironomidae larvae to mammalian GADPHs. However, the GADPH of Chironomidae larvae showed different biologic activities and cytotoxicity towards heavy metals. The GAPDH enzyme would undergo adaptive molecular changes through binding at the active site leading to higher tolerance to heavy metals.

  12. Earliest evidence of pollution by heavy metals in archaeological sites.

    Science.gov (United States)

    Monge, Guadalupe; Jimenez-Espejo, Francisco J; García-Alix, Antonio; Martínez-Ruiz, Francisca; Mattielli, Nadine; Finlayson, Clive; Ohkouchi, Naohiko; Sánchez, Miguel Cortés; de Castro, Jose María Bermúdez; Blasco, Ruth; Rosell, Jordi; Carrión, José; Rodríguez-Vidal, Joaquín; Finlayson, Geraldine

    2015-09-21

    Homo species were exposed to a new biogeochemical environment when they began to occupy caves. Here we report the first evidence of palaeopollution through geochemical analyses of heavy metals in four renowned archaeological caves of the Iberian Peninsula spanning the last million years of human evolution. Heavy metal contents reached high values due to natural (guano deposition) and anthropogenic factors (e.g. combustion) in restricted cave environments. The earliest anthropogenic pollution evidence is related to Neanderthal hearths from Gorham's Cave (Gibraltar), being one of the first milestones in the so-called "Anthropocene". According to its heavy metal concentration, these sediments meet the present-day standards of "contaminated soil". Together with the former, the Gibraltar Vanguard Cave, shows Zn and Cu pollution ubiquitous across highly anthropic levels pointing to these elements as potential proxies for human activities. Pb concentrations in Magdalenian and Bronze age levels at El Pirulejo site can be similarly interpreted. Despite these high pollution levels, the contaminated soils might not have posed a major threat to Homo populations. Altogether, the data presented here indicate a long-term exposure of Homo to these elements, via fires, fumes and their ashes, which could have played certain role in environmental-pollution tolerance, a hitherto neglected influence.

  13. SEQUESTERING AGENTS FOR ACTIVE CAPS - REMEDIATION OF METALS AND ORGANICS

    Energy Technology Data Exchange (ETDEWEB)

    Knox, A; Michael Paller, M; Danny D. Reible, D; Xingmao Ma, X; Ioana G. Petrisor, I

    2007-05-10

    This research evaluated organoclays, zeolites, phosphates, and a biopolymer as sequestering agents for inorganic and organic contaminants. Batch experiments were conducted to identify amendments and mixtures of amendments for metal and organic contaminants removal and retention. Contaminant removal was evaluated by calculating partitioning coefficients. Metal retention was evaluated by desorption studies in which residue from the removal studies was extracted with 1 M MgCl{sub 2} solution. The results indicated that phosphate amendments, some organoclays, and the biopolymer, chitosan, were very effective sequestering agents for metals in fresh and salt water. Organoclays were very effective sorbents for phenanthrene, pyrene, and benzo(a)pyrene. Partitioning coefficients for the organoclays were 3000-3500 ml g{sup -1} for benzo(a)pyrene, 400-450 ml g{sup -1} for pyrene, and 50-70 ml g{sup -1} for phenanthrene. Remediation of sites with a mixture of contaminants is more difficult than sites with a single contaminant because metals and organic contaminants have different fate and transport mechanisms in sediment and water. Mixtures of amendments (e.g., organoclay and rock phosphate) have high potential for remediating both organic and inorganic contaminants under a broad range of environmental conditions, and have promise as components in active caps for sediment remediation.

  14. Determination of heavy metal pollution in soils from selected potentially contaminated sites in Tema

    International Nuclear Information System (INIS)

    Nyaaba, A.K.L.

    2011-01-01

    The objective of the study was to assess the concentration and determine the level of pollution by harmful heavy metals in soils from selected potentially contaminated sites in Tema. The metals of interest include; mercury, lead, cadmium, cobalt zinc, arsenic, nickel, copper and chromium. A total of forty seven (47) samples comprising thirty eight sub-samples (38) and nine (9) composite samples were collected from nine (9) different locations. These included playgrounds, steel processing factories, used Lead Acid Battery (ULAB) recycling plant, mechanic workshops and the municipal waste disposal site. The samples were prepared after which the elemental concentrations were determined using energy dispersive X-ray fluorescence (EDXRF) with a secondary target excitation arrangement (5.9 keV). The analysis of the samples yielded the following mean heavy metal concentrations in mg/kg: 424.38 (Cr); 408.68 (Ni); 14427 (Cu); 4129.87 (Zn); 1580.68 (As); 647.48 (Hg); 73361.51 (Pb) and 1176.16 (Co). The mean concentrations of heavy metals in the soils were in the following order Pb>Zn>As>Co>Cu>Hg>Cr>Ni. Mercury was detected at only two of the sites. The average heavy metals in the soils from the sites were generally high since most of them exceeded the optimum and action values of the New Dutch List. The Enrichment Factor (EF) ratios show that the enrichment of the elements in the soils ranged from deficiently to extremely highly enriched. The contamination factor show that the contamination by the heavy metals were low at some of the sites and very high at others. The geoaccumulation indices indicated that the playground (PG) has not been contaminated by any of the metals, C8 is contaminated strongly by mercury only and the contamination at the remaining sites varied from moderately contaminated to extremely contaminated by the metals. The Igeo also indicated that the elements accounting for extreme contamination are lead, arsenic, copper, zinc mercury and chromium. Lead

  15. Metal based biologically active compounds: Design, synthesis, DNA binding and antidiabetic activity of 6-methyl-3-formyl chromone derived hydrazones and their metal (II) complexes.

    Science.gov (United States)

    Philip, Jessica Elizabeth; Shahid, Muhammad; Prathapachandra Kurup, M R; Velayudhan, Mohanan Puzhavoorparambil

    2017-10-01

    Two chromone hydrazone ligands HL 1 and HL 2 were synthesized and characterized by elemental analyses, IR, 1 H NMR & 13 C NMR, electronic absorption and mass spectra. The reactions of the chromone hydrazones with transition metals such as Ni, Cu, and Zn (II) salts of acetate afforded mononuclear metal complexes. Characterization and structure elucidation of the prepared chromone hydrazone metal (II) complexes were done by elemental, IR, electronic, EPR spectra and thermo gravimetric analyses as well as conductivity and magnetic susceptibility measurements. The spectroscopic data showed that the ligand acts as a mono basic bidentate with coordination sites are azomethine nitrogen and hydrazonic oxygen, and they exhibited distorted geometry. The biological studies involved antidiabetic activity i.e. enzyme inhibition of α-amylase and α-glucosidase, Calf Thymus - DNA (CT-DNA) interaction and molecular docking. Potential capacity of synthesized compounds to inhibit the α-amylase and α-glucosidase activity was assayed whereas DNA interaction studies were carried out with the help UV-Vis absorption titration and viscosity method. The docking studies of chromone hydrazones show that they are minor groove binders. Complexes were found to be good DNA - intercalates. Chromone hydrazones and its transition metal complexes have shown comparable antidiabetic activity with a standard drug acarbose. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. 113Cd NMR as a Probe of the Active Sites of Metalloenzymes

    NARCIS (Netherlands)

    Armitage, Ian M.; Schoot Uiterkamp, Antonius J.M.; Chlebowski, Jan F.; Coleman, Joseph E.

    1978-01-01

    113Cd NMR has been used to study the active site metal ion(s) of the 113Cd(II) derivatives of four Zn(II) metalloenzymes, carboxypeptidase A, carbonic anhydrases, alkaline phosphatase, and superoxide dismutase. The resonances of the enzyme-bound 113Cd(II) ions are extremely sensitive to ligand

  17. Abundance, composition and activity of ammonia oxidizer and denitrifier communities in metal polluted rice paddies from South China.

    Directory of Open Access Journals (Sweden)

    Yuan Liu

    Full Text Available While microbial nitrogen transformations in soils had been known to be affected by heavy metal pollution, changes in abundance and community structure of the mediating microbial populations had been not yet well characterized in polluted rice soils. Here, by using the prevailing molecular fingerprinting and enzyme activity assays and comparisons to adjacent non-polluted soils, we examined changes in the abundance and activity of ammonia oxidizing and denitrifying communities of rice paddies in two sites with different metal accumulation situation under long-term pollution from metal mining and smelter activities. Potential nitrifying activity was significantly reduced in polluted paddies in both sites while potential denitrifying activity reduced only in the soils with high Cu accumulation up to 1300 mg kg-1. Copy numbers of amoA (AOA and AOB genes were lower in both polluted paddies, following the trend with the enzyme assays, whereas that of nirK was not significantly affected. Analysis of the DGGE profiles revealed a shift in the community structure of AOA, and to a lesser extent, differences in the community structure of AOB and denitrifier between soils from the two sites with different pollution intensity and metal composition. All of the retrieved AOB sequences belonged to the genus Nitrosospira, among which species Cluster 4 appeared more sensitive to metal pollution. In contrast, nirK genes were widely distributed among different bacterial genera that were represented differentially between the polluted and unpolluted paddies. This could suggest either a possible non-specific target of the primers conventionally used in soil study or complex interactions between soil properties and metal contents on the observed community and activity changes, and thus on the N transformation in the polluted rice soils.

  18. Speciation dynamics of metals in dispersion of nanoparticles with discrete distribution of charged binding sites.

    Science.gov (United States)

    Polyakov, Pavel D; Duval, Jérôme F L

    2014-02-07

    We report a comprehensive theory to evaluate the kinetics of complex formation between metal ions and charged spherical nanoparticles. The latter consist of an ion-impermeable core surrounded by a soft shell layer characterized by a discrete axisymmetric 2D distribution of charged sites that bind metal ions. The theory explicitly integrates the conductive diffusion of metal ions from bulk solution toward the respective locations of the reactive sites within the particle shell volume. The kinetic constant k for outer-sphere nanoparticle-metal association is obtained from the sum of the contributions stemming from all reactive sites, each evaluated from the corresponding incoming flux of metal ions derived from steady-state Poisson-Nernst-Planck equations. Illustrations are provided to capture the basic intertwined impacts of particle size, overall particle charge, spatial heterogeneity in site distribution, type of particle (hard, core-shell or porous) and concentration of the background electrolyte on k. As a limit, k converges with predictions from previously reported analytical expressions derived for porous particles with low and high charge density, cases that correspond to coulombic and mean-field (smeared-out) electrostatic treatments, respectively. The conditions underlying the applicability of these latter approaches are rigorously identified in terms of (i) the extent of overlap between electric double layers around charged neighbouring sites, and (ii) the magnitude of the intraparticulate metal concentration gradient. For the first time, the proposed theory integrates the differentiated impact of the local potential around the charged binding sites amidst the overall particle field, together with that of the so-far discarded intraparticulate flux of metal ions.

  19. Metal accumulation and performance of nestlings of passerine bird species at an urban brownfield site

    Energy Technology Data Exchange (ETDEWEB)

    Hofer, Charles; Gallagher, Frank J. [Department of Ecology, Evolution and Natural Resources, Rutgers, the State University of New Jersey, 14 College Farm Rd., New Brunswick, NJ 08901-8551 (United States); Holzapfel, Claus, E-mail: holzapfe@andromeda.rutgers.ed [Department of Biological Sciences, Rutgers, the State University of New Jersey, Newark, 195 University Ave., Newark, NJ 07102-1811 (United States)

    2010-05-15

    The use of passerine species as bioindicators of metal bioaccumulation is often underutilized when examining the wildlife habitat value of polluted sites. In this study we tested feathers of nestlings of two common bird species (house wren and American robin) for accumulation of Pb, Zn, As, Cr, Cu, Fe in comparison of a polluted, urban brownfield with a rural, unpolluted site. House wren nestlings at the study site accumulated significantly greater concentrations of all target metals except Zn. At the polluted site we found significant species differences of metal concentrations in feathers, with house wrens accumulating greater concentrations of Pb, Fe, and Zn but slightly lesser accumulations of Cr and Cu than American robins. Although house wren nestlings demonstrated significant accumulation of metals, these concentrations showed little effect on size metrics or fledge rates during the breeding season compared to nestlings from the control site. - Nestlings of birds in an urban brownfield accumulated soil contaminants but did not show signs of reduced breeding success or growth.

  20. Metal accumulation and performance of nestlings of passerine bird species at an urban brownfield site

    International Nuclear Information System (INIS)

    Hofer, Charles; Gallagher, Frank J.; Holzapfel, Claus

    2010-01-01

    The use of passerine species as bioindicators of metal bioaccumulation is often underutilized when examining the wildlife habitat value of polluted sites. In this study we tested feathers of nestlings of two common bird species (house wren and American robin) for accumulation of Pb, Zn, As, Cr, Cu, Fe in comparison of a polluted, urban brownfield with a rural, unpolluted site. House wren nestlings at the study site accumulated significantly greater concentrations of all target metals except Zn. At the polluted site we found significant species differences of metal concentrations in feathers, with house wrens accumulating greater concentrations of Pb, Fe, and Zn but slightly lesser accumulations of Cr and Cu than American robins. Although house wren nestlings demonstrated significant accumulation of metals, these concentrations showed little effect on size metrics or fledge rates during the breeding season compared to nestlings from the control site. - Nestlings of birds in an urban brownfield accumulated soil contaminants but did not show signs of reduced breeding success or growth.

  1. Structural and Biochemical Characterization of a Copper-Binding Mutant of the Organomercurial Lyase MerB: Insight into the Key Role of the Active Site Aspartic Acid in Hg-Carbon Bond Cleavage and Metal Binding Specificity.

    Science.gov (United States)

    Wahba, Haytham M; Lecoq, Lauriane; Stevenson, Michael; Mansour, Ahmed; Cappadocia, Laurent; Lafrance-Vanasse, Julien; Wilkinson, Kevin J; Sygusch, Jurgen; Wilcox, Dean E; Omichinski, James G

    2016-02-23

    In bacterial resistance to mercury, the organomercurial lyase (MerB) plays a key role in the detoxification pathway through its ability to cleave Hg-carbon bonds. Two cysteines (C96 and C159; Escherichia coli MerB numbering) and an aspartic acid (D99) have been identified as the key catalytic residues, and these three residues are conserved in all but four known MerB variants, where the aspartic acid is replaced with a serine. To understand the role of the active site serine, we characterized the structure and metal binding properties of an E. coli MerB mutant with a serine substituted for D99 (MerB D99S) as well as one of the native MerB variants containing a serine residue in the active site (Bacillus megaterium MerB2). Surprisingly, the MerB D99S protein copurified with a bound metal that was determined to be Cu(II) from UV-vis absorption, inductively coupled plasma mass spectrometry, nuclear magnetic resonance, and electron paramagnetic resonance studies. X-ray structural studies revealed that the Cu(II) is bound to the active site cysteine residues of MerB D99S, but that it is displaced following the addition of either an organomercurial substrate or an ionic mercury product. In contrast, the B. megaterium MerB2 protein does not copurify with copper, but the structure of the B. megaterium MerB2-Hg complex is highly similar to the structure of the MerB D99S-Hg complexes. These results demonstrate that the active site aspartic acid is crucial for both the enzymatic activity and metal binding specificity of MerB proteins and suggest a possible functional relationship between MerB and its only known structural homologue, the copper-binding protein NosL.

  2. Anisotropic Covalency Contributions to Superexchange Pathways in Type One Copper Active Sites

    Science.gov (United States)

    2015-01-01

    Type one (T1) Cu sites deliver electrons to catalytic Cu active sites: the mononuclear type two (T2) Cu site in nitrite reductases (NiRs) and the trinuclear Cu cluster in the multicopper oxidases (MCOs). The T1 Cu and the remote catalytic sites are connected via a Cys-His intramolecular electron-transfer (ET) bridge, which contains two potential ET pathways: P1 through the protein backbone and P2 through the H-bond between the Cys and the His. The high covalency of the T1 Cu–S(Cys) bond is shown here to activate the T1 Cu site for hole superexchange via occupied valence orbitals of the bridge. This covalency-activated electronic coupling (HDA) facilitates long-range ET through both pathways. These pathways can be selectively activated depending on the geometric and electronic structure of the T1 Cu site and thus the anisotropic covalency of the T1 Cu–S(Cys) bond. In NiRs, blue (π-type) T1 sites utilize P1 and green (σ-type) T1 sites utilize P2, with P2 being more efficient. Comparing the MCOs to NiRs, the second-sphere environment changes the conformation of the Cys-His pathway, which selectively activates HDA for superexchange by blue π sites for efficient turnover in catalysis. These studies show that a given protein bridge, here Cys-His, provides different superexchange pathways and electronic couplings depending on the anisotropic covalencies of the donor and acceptor metal sites. PMID:25310460

  3. Effects of metal-ion replacement on pyrazinamidase activity: A quantum mechanical study.

    Science.gov (United States)

    Khadem-Maaref, Mahmoud; Mehrnejad, Faramarz; Phirouznia, Arash

    2017-05-01

    Pyrazinamidase (PZase), a metalloenzyme, is responsible for acidic modification of pyrazinamide (PZA), a drug used in tuberculosis treatment. The metal coordination site of the enzyme is able to coordinate various divalent metal cofactors. Previous experimental studies have demonstrated that metal ions, such as Co 2+ , Mn 2+ , and Zn 2+ , are able to reactivate metal-depleted PZase, while others including Cu 2+ , Fe 2+ , and Mg 2+ , cannot restore activity. In this study, we investigated binding of various metal ions to the metal coordination site (MCS) of the enzyme using quantum mechanical calculations. We calculated the metal-ligand (residue) binding energy and the atomic partial charges in the presence of various ions. The results indicated that the tendency of alkaline earth metals to bind to PZase MCS is very low and not suitable for enzyme structural and catalytic function. In contrast, Co 2+ and Ni 2+ ions have very high binding affinity and are favorable to the structural and functional properties of the enzyme. Furthermore, we observed that the rate at which Ni 2+ , Co 2+ and Fe 2+ ions in PZase MCS polarize the OH bond of coordinated water molecules is much higher than the polarization rate created by other ions. This finding suggests that the coordination of Ni 2+ , Co 2+ , or Fe 2+ to PZase facilitates the deprotonation of coordinated water molecules to generate a nucleophile that catalyzes the enzymatic reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. ENHANCEMENT OF ACIDITY AND CATALYTIC ACTIVITY OF ALUMINA BASED METAL ORGANIC FRAMEWORK (MIL-53 Al)

    OpenAIRE

    Yilmaz, Esra; Sert, Emine; Atalay, Ferhan Sami

    2017-01-01

    Metal organic frameworks are highly porous materials which are formed bycombination of metal precursor and salts as inorganic part and ligand asorganic part. They have many advantages such as low density, high surface area,tunable pore size and high porosity. Due to peculiar features, such asunsaturated metal active sites, high surface area and easily functionalization,its usage as catalyst are promising.  The MIL-53(Al) structure contains chains of transcorner-sharing [AlO4(OH)2] oc...

  5. Release of Radioactive Scrap Metal/Scrap Metal (RSM/SM) at Nevada Test Site (NTS)

    International Nuclear Information System (INIS)

    1993-01-01

    Reynolds Electrical and Engineering Company, Inc. (REECo) is the prime contractor to the US Department of Energy (DOE) in providing service and support for NTS operations. Mercury Base Camp is the main control point for the many forward areas at NTS, which covers 1,350 square miles. The forward areas are where above-ground and underground nuclear tests have been performed over the last 41 years. No metal (or other material) is returned to Mercury without first being tested for radioactivity. No radioactive metals are allowed to reenter Mercury from the forward areas, other than testing equipment. RAMATROL is the monitor check point. They check material in various ways, including swipe tests, and have a large assortment of equipment for testing. Scrap metal is also checked to address Resource Conservation and Recovery Act concerns. After addressing these issues, the scrap metals are categorized. Federal Property Management Regulations (FPMR) are followed by REECo. The nonradioactive scrap material is sold through the GSA on a scheduled basis. Radioactive scrap metal are presently held in forward areas where they were used. REECo has gained approval of their Nevada Test Site Defense Waste Acceptance Criteria, Certification, and Transfer Requirements, NVO-325 application, which will allow disposal on site, when RSM is declared a waste. The guideline that REECo uses for release limits is DOE Order 5480.11, Radiation Protection for Occupational Works, Attachment 2, Surface Radioactivity Guides, of this order, give release limits for radioactive materials. However, the removal of radioactive materials from NTS require approval by DOE Nevada Operations Office (DOE/NV) on a case-by-case basis. Requirements to consider before removal are found in DOE Order 5820.2A, Radioactive Waste Management

  6. Effects of site substitution and metal ion addition on doped manganites

    CERN Document Server

    Pradhan, A K; Roul, B K; Sahu, D R; Muralidhar, M

    2002-01-01

    We report transport, magnetization and transmission electron microscopy studies of the effects of A-and B-site substitution, and the addition of metal ions such as Pt, Ag and Sr, on doped ABO sub 3 perovskites, where A = La, Pr etc and B = Mn. Disorder induced by such substitution changes the behaviour of the charge-ordered (CO) state significantly. A-and B-site substitution suppresses the CO phase due to size mismatch and disorder produced by inhomogeneity. On the other hand, addition of metal ions such as Pt and Ag improves several colossal-magnetoresistance properties significantly due to microstructural effects and enhanced current percolation through grain boundaries.

  7. On-site and off-site activities

    International Nuclear Information System (INIS)

    Martin, H.D.

    1986-01-01

    Design principles for NPP training programs. Effects of NPP contracts. Effects of domestic industrial activities. The role of international bodies. Requirements for on-site training. Training abroad, technical, financial and social aspects. Training center on-site, an evaluation. (orig.)

  8. Concentration and transportation of heavy metals in vegetables and risk assessment of human exposure to bioaccessible heavy metals in soil near a waste-incinerator site, South China.

    Science.gov (United States)

    Li, Ning; Kang, Yuan; Pan, Weijian; Zeng, Lixuan; Zhang, Qiuyun; Luo, Jiwen

    2015-07-15

    There is limited study focusing on the bioaccumulation of heavy metals in vegetables and human exposure to bioaccessible heavy metals in soil. In the present study, heavy metal concentrations (Cr, Ni, Cu, Pb and Cd) were measured in five types of vegetables, soil, root, and settled air particle samples from two sites (at a domestic waste incinerator and at 20km away from the incinerator) in Guangzhou, South China. Heavy metal concentrations in soil were greater than those in aerial parts of vegetables and roots, which indicated that vegetables bioaccumulated low amount of heavy metals from soil. The similar pattern of heavy metal (Cr, Cd) was found in the settled air particle samples and aerial parts of vegetables from two sites, which may suggest that foliar uptake may be an important pathway of heavy metal from the environment to vegetables. The highest levels of heavy metals were found in leaf lettuce (125.52μg/g, dry weight) and bitter lettuce (71.2μg/g) for sites A and B, respectively, followed by bitter lettuce and leaf lettuce for sites A and B, respectively. Swamp morning glory accumulated the lowest amount of heavy metals (81.02μg/g for site A and 53.2μg/g for site B) at both sites. The bioaccessibility of heavy metals in soil ranged from Cr (2%) to Cu (71.78%). Risk assessment showed that Cd and Pb in soil samples resulted in the highest non-cancer risk and Cd would result in unacceptable cancer risk for children and risk. The non-dietary intake of soil was the most important exposure pathway, when the bioaccessibility of heavy metals was taken into account. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Bioavailability of particulate metal to zebra mussels: biodynamic modelling shows that assimilation efficiencies are site-specific.

    Science.gov (United States)

    Bourgeault, Adeline; Gourlay-Francé, Catherine; Priadi, Cindy; Ayrault, Sophie; Tusseau-Vuillemin, Marie-Hélène

    2011-12-01

    This study investigates the ability of the biodynamic model to predict the trophic bioaccumulation of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) in a freshwater bivalve. Zebra mussels were transplanted to three sites along the Seine River (France) and collected monthly for 11 months. Measurements of the metal body burdens in mussels were compared with the predictions from the biodynamic model. The exchangeable fraction of metal particles did not account for the bioavailability of particulate metals, since it did not capture the differences between sites. The assimilation efficiency (AE) parameter is necessary to take into account biotic factors influencing particulate metal bioavailability. The biodynamic model, applied with AEs from the literature, overestimated the measured concentrations in zebra mussels, the extent of overestimation being site-specific. Therefore, an original methodology was proposed for in situ AE measurements for each site and metal. Copyright © 2011 Elsevier Ltd. All rights reserved.

  10. Impaired microbial activity caused by metal pollution: A field study in a deactivated uranium mining area.

    Science.gov (United States)

    Antunes, Sara Cristina; Pereira, Ruth; Marques, Sérgio Miguel; Castro, Bruno Branco; Gonçalves, Fernando

    2011-12-01

    European frameworks for the ecological risk assessment (ERA) of contaminated sites integrate information from three lines of evidence: chemical, ecotoxicological, and ecological. Regarding the last one, field observations at the contaminated sites are compared to reference site(s) and the differences recorded are analysed at the light of a cause-effect relationship, taking into account the site-specific contamination. Thus, included in the tier 2 of a site-specific risk assessment that is being carried out in an deactivated uranium mining area, a battery of soil enzyme activities (dehydrogenases, urease, arysulphatase, cellulase, acid phosphate) and potential nitrification were assessed in seven sampling sites (A-D-E-F-G-H-I) at different distances from the mine pit. These parameters have been considered good indicators of impacts on soil microbial communities and, subsequently, on soil functions. Soil enzyme activities were impaired in the most contaminated site (A, near the mine pit), for which a higher degree of risk was determined in the tier 1 of ERA. Three other sites within the mining area (F, G, and D) were discriminated on the basis of their low microbial activity, using uni- and multivariate approaches, and validating what had been previously found with chemical and ecotoxicological lines of evidence. We observed considerable among-site heterogeneity in terms of soil physical and chemical properties, combined with seasonal differences in enzyme activities. Still, the correlation between microbial parameters and soil general physical and chemical parameters was weak. In opposition, significant and negative correlations were found between soil enzyme activities and several metallic elements (Al, Be, Cu, U). These findings suggest a clear correlation between compromised soil function (nutrient recycling) and metal contamination. Such information reinforces the evidence of risks for some sites within the mining area and is an important contribution for the

  11. Heavy metals in vegetables sampled from farm and market sites in Accra metropolis, Ghana

    International Nuclear Information System (INIS)

    Fordjour, Linda Addae

    2015-07-01

    This study reports for the first time in Ghana long-term monitoring of heavy metal contamination of vegetables. As reliable residue data analysis resulting from monitoring programs in foods is of great value to the general populace; this could address the possible risk of heavy metal exposure to human health. In this study, monitoring of heavy metals (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in consumable vegetables was assessed for a period of 2 years, 2013-2014. In all, a total of 479 vegetables (cabbage (Brassica oleracea), carrot (Daucus carota), cucumber (Cucumis sativus), green pepper (Capsicum annuum) and lettuce (Lactuca sativa)) were purchased from farm (production) and market sites within Accra Metropolis, Ghana. Samples were subjected to acid digestion and analyzed with atomic absorption spectrometer (AAS). All the vegetables studied contained at least two (2) or more metals; 18.99% of the samples had metal detections below the European Union (EU) guideline values, whereas 81% were above limits. Vegetables from Mallam Attah market and the Ghana Broadcasting Corporation (GBC) sites registered the highest percentage exceedances (100%) with the largest violation occurring in lettuce (97.41%). Elevated concentrations of these metals were also observed in vegetables from markets compared to the farms except As, Cd, Co and Fe. Ni and Cr were undetected in vegetables from farms, however their maximum concentrations (1.236 and 2.459 mg/kg) were recorded in lettuce at market sites. Additionally, the significant metal increases in vegetables from the markets could be due to atmospheric depositions and mode of handling by both farmers and buyers. On the other hand, studies of the soils from the various farm sites had varying mean concentrations of heavy metals, Fe (189.703), Mn (142.246) and As (9.145 mg/kg). However, all the metal levels in the soil were below EU limits, except As (24.2 mg/kg) found at Dzorwulu site, which exceeded the 20.0 mg/kg limit for As in

  12. Ion activity and distribution of heavy metals in acid mine drainage polluted subtropical soils

    International Nuclear Information System (INIS)

    Li Yongtao; Becquer, Thierry; Dai Jun; Quantin, Cecile; Benedetti, Marc F.

    2009-01-01

    The oxidative dissolution of mine wastes gives rise to acidic, metal-enriched mine drainage (AMD) and has typically posed an additional risk to the environment. The poly-metallic mine Dabaoshan in South China is an excellent test site to understand the processes affecting the surrounding polluted agricultural fields. Our objectives were firstly to investigate metal ion activity in soil solution, distribution in solid constituents, and spatial distribution in samples, secondly to determine dominant environment factors controlling metal activity in the long-term AMD-polluted subtropical soils. Soil Column Donnan Membrane Technology (SC-DMT) combined with sequential extraction shows that unusually large proportion of the metal ions are present as free ion in the soil solutions. The narrow range of low pH values prevents any pH effects during the binding onto oxides or organic matter. The differences in speciation of the soil solutions may explain the different soil degradation observed between paddy and non-paddy soils. - First evidence of the real free metal ion concentrations in acid mine drainage context in tropical systems

  13. Comparison of soil heavy metal pollution caused by e-waste recycling activities and traditional industrial operations.

    Science.gov (United States)

    He, Kailing; Sun, Zehang; Hu, Yuanan; Zeng, Xiangying; Yu, Zhiqiang; Cheng, Hefa

    2017-04-01

    The traditional industrial operations are well recognized as an important source of heavy metal pollution, while that caused by the e-waste recycling activities, which have sprouted in some developing countries, is often overlooked. This study was carried out to compare the status of soil heavy metal pollution caused by the traditional industrial operations and the e-waste recycling activities in the Pearl River Delta, and assess whether greater attention should be paid to control the pollution arising from e-waste recycling activities. Both the total contents and the chemical fractionation of major heavy metals (As, Cr, Cd, Ni, Pb, Cu, and Zn) in 50 surface soil samples collected from the e-waste recycling areas and 20 soil samples from the traditional industrial zones were determined. The results show that the soils in the e-waste recycling areas were mainly polluted by Cu, Zn, As, and Cd, while Cu, Zn, As, Cd, and Pb were the major heavy metals in the soils from the traditional industrial zones. Statistical analyses consistently show that Cu, Cd, Pb, and Zn in the surface soils from both types of sites were contributed mostly by human activities, while As, Cr, and Ni in the soils were dominated by natural background. No clear distinction was found on the pollution characteristic of heavy metals in the surface soils between the e-waste recycling areas and traditional industrial zones. The potential ecological risk posed by heavy metals in the surface soils from both types of sites, which was dominated by that from Cd, ranged from low to moderate. Given the much shorter development history of e-waste recycling and its largely unregulated nature, significant efforts should be made to crack down on illegal e-waste recycling and strengthen pollution control for related activities.

  14. Investigation of the metal binding site in methionine aminopeptidase by density functional theory

    DEFF Research Database (Denmark)

    Jørgensen, Anne Techau; Norrby, Per-Ola; Liljefors, Tommy

    2002-01-01

    All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co2+ ions or Zn2+ ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions....... This was the case for both of the systems studied; one based on the X-ray structure of the human methionine aminopeptidase type 2 (hMetAP-2) and the other based on the X-ray structure of the E. coli methionine aminopeptidase type 1 (eMetAP-1). Another important structural issue is the identity of the bridging...

  15. Metal compounds in zeolites as active components of chemisorption and catalysis. Quantum chemical approach

    International Nuclear Information System (INIS)

    Zhidomirov, G.M.

    1996-01-01

    A short review of possible catalitic active sites associated with various types of metal species in zoolite is presented. The structural and electronic peculiarity of aluminum ions in zeolite lattice and their distribution in the lattice are discussed on the basis of quantum chemical calculations in connection with the formation of Broensted activity of zeolites. Various molecular models of Lewis Acid Sites associated the extra-lattice oxide-hydroxide aluminum species have been investigated by means of density functional model cluster calculations using CO molecule as a probe. Probable ways of formation of the selective oxidation center in FeZSM-5 by decomposition of dinitrogen monoxide have been studied by ab-initio quantum chemical calculations. The immediate oxidizing site is reasonably represented by the binuclear iron-hydroxide cluster with peroxo-like fragment located between iron atoms. Various probable intermediates of the selective oxidation center formation resulted from interaction of a hydroperoxide molecule with a lattice titanium ion in titanium silicalite have been investigated by quantum chemical calculations. It was concluded that this reaction requires essential structural reconstruction in the vicinity of the titanium ion. Probability of this structural reconstruction is discussed. Possible reasons of an electron-deficient and electron-enriched state of metal particles entrapped in zoolite cavities are discussed. Also, various probable molecular models of such modified metal particles in zeolite are considered

  16. Actively convected liquid metal divertor

    International Nuclear Information System (INIS)

    Shimada, Michiya; Hirooka, Yoshi

    2014-01-01

    The use of actively convected liquid metals with j × B force is proposed to facilitate heat handling by the divertor, a challenging issue associated with magnetic fusion experiments such as ITER. This issue will be aggravated even more for DEMO and power reactors because the divertor heat load will be significantly higher and yet the use of copper would not be allowed as the heat sink material. Instead, reduced activation ferritic/martensitic steel alloys with heat conductivities substantially lower than that of copper, will be used as the structural materials. The present proposal is to fill the lower part of the vacuum vessel with liquid metals with relatively low melting points and low chemical activities including Ga and Sn. The divertor modules, equipped with electrodes and cooling tubes, are immersed in the liquid metal. The electrode, placed in the middle of the liquid metal, can be biased positively or negatively with respect to the module. The j × B force due to the current between the electrode and the module provides a rotating motion for the liquid metal around the electrodes. The rise in liquid temperature at the separatrix hit point can be maintained at acceptable levels from the operation point of view. As the rotation speed increases, the current in the liquid metal is expected to decrease due to the v × B electromotive force. This rotating motion in the poloidal plane will reduce the divertor heat load significantly. Another important benefit of the convected liquid metal divertor is the fast recovery from unmitigated disruptions. Also, the liquid metal divertor concept eliminates the erosion problem. (letter)

  17. Understanding hydrogen sorption in a metal-organic framework with open-metal sites and amide functional groups

    KAUST Repository

    Pham, Tony T.

    2013-05-09

    /catalytic sites and characteristics through the active interplay of theory and experiment. The ability of accurate, carefully parametrized and transferable force fields to model and predict small molecule sorption in MOFs, even including open-metal sites, is demonstrated. © 2013 American Chemical Society.

  18. Synthesis, spectroscopic, biological activity and thermal characterization of ceftazidime with transition metals

    Science.gov (United States)

    Masoud, Mamdouh S.; Ali, Alaa E.; Elasala, Gehan S.; Kolkaila, Sherif A.

    2018-03-01

    Synthesis, physicochemical characterization and thermal analysis of ceftazidime complexes with transition metals (Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)) were discussed. It's obtained that ceftazidime act as bidentate ligand. From magnetic measurement and spectral data, octahedral structures were proposed for all complexes except for cobalt, nickel and mercury had tetrahedral structural. Hyper chemistry program confirmed binding sites of ceftazidime. Ceftazidime complexes show higher activity than ceftazidime for some strains. From TG and DTA curves the thermal decomposition mechanisms of ceftazidime and their metal complexes were suggested. The thermal decomposition of the complexes ended with the formation of metal oxides as a final product except in case of Hg complex.

  19. Assisted phytoremediation of heavy metal contaminated soil from a mined site with Typha latifolia and Chrysopogon zizanioides.

    Science.gov (United States)

    Anning, Alexander Kofi; Akoto, Ruth

    2018-02-01

    Chemically assisted phytoremediation is fast gaining attention as a biotechnology to accelerate heavy metal removal from contaminated substrates, but how different chemical amendments affect the process remains an important research question. Here, bioaccumulation factor (BAF), translocation factor (TF), removal efficiency (RE) and uptake of Hg, As, Pb, Cu and Zn by cattail (Typha latifolia) and vetiver (Chrysopogon zizanioides) were quantified in a potted experiment to determine the effects of amendments on the phytoremediation success. Baseline concentrations of heavy metals within the studied mined site were determined. The experiment involved three soil treatments (each comprising 16 samples amended with 0.05mol/L ethylene di-aminetetraacetic acid (EDTA), 3g of aluminum sulfate [Al 2 (SO 4 ) 3 ], and unamended control) transplanted with equal numbers of vetiver and cattail. Growth performance (height) of plant species was monitored every two weeks. Sixteen weeks after transplanting, heavy metal levels in plant and soil samples were quantified following standard protocols, and the biomass and root length measured for each plant species. Results indicated strong negative impact of mining activities on heavy metal levels of soil in the study area. Soil amendment considerably enhanced the BAF, TF, RE and uptake but the effect varied with plant species and heavy metal in question. The amendment also stimulated strong positive correlation between RE and BAF, TF and metal uptake, and generally did not show any negative effects on plant growth performance. In general, soil amendment aided the accumulation and translocation of heavy metals in the plant species studied, and could be explored for cleaning up contaminated sites. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Electrochemical probing into the active sites of graphitic-layer encapsulated iron oxygen reduction reaction electrocatalysts

    DEFF Research Database (Denmark)

    Zhong, Lijie; Jensen, Jens Oluf; Cleemann, Lars Nilausen

    2018-01-01

    is still unclear compared with the well-recognized surface coordinated FeNx/C structure. Using the strong complexing effect of the iron component with anions, cyanide (CN−) in alkaline and thiocyanate (SCN−) in acidic media, the metal containing active sites are electrochemically probed. Three...

  1. Abundance, composition and activity of denitrifier communities in metal polluted paddy soils

    Science.gov (United States)

    Liu, Yuan; Liu, Yongzhuo; Zhou, Huimin; Li, Lianqing; Zheng, Jinwei; Zhang, Xuhui; Zheng, Jufeng; Pan, Genxing

    2016-01-01

    Denitrification is one of the most important soil microbial processes leading to the production of nitrous oxide (N2O). The potential changes with metal pollution in soil microbial community for N2O production and reduction are not well addressed. In this study, topsoil samples were collected both from polluted and non-polluted rice paddy fields and denitrifier communities were characterized with molecular fingerprinting procedures. All the retrieved nirK sequences could be grouped into neither α- nor β- proteobacteria, while most of the nosZ sequences were affiliated with α-proteobacteria. The abundances of the nirK and nosZ genes were reduced significantly in the two polluted soils. Thus, metal pollution markedly affected composition of both nirK and nosZ denitrifiers. While the total denitrifying activity and N2O production rate were both reduced under heavy metal pollution of the two sites, the N2O reduction rate showed no significant change. These findings suggest that N2O production activity could be sensitive to heavy metal pollution, which could potentially lead to a decrease in N2O emission in polluted paddies. Therefore, metal pollution could have potential impacts on soil N transformation and thus on N2O emission from paddy soils. PMID:26739424

  2. Monitoring the solid-state electrochemistry of Cu(2,7-AQDC) (AQDC = anthraquinone dicarboxylate) in a lithium battery: coexistence of metal and ligand redox activities in a metal-organic framework.

    Science.gov (United States)

    Zhang, Zhongyue; Yoshikawa, Hirofumi; Awaga, Kunio

    2014-11-19

    By adopting a facile synthetic strategy, we obtained a microporous redox-active metal-organic framework (MOF), namely, Cu(2,7-AQDC) (2,7-H2AQDC = 2,7-anthraquinonedicarboxylic acid) (1), and utilized it as a cathode active material in lithium batteries. With a voltage window of 4.0-1.7 V, both metal clusters and anthraquinone groups in the ligands exhibited reversible redox activity. The valence change of copper cations was clearly evidenced by in situ XANES analysis. By controlling the voltage window of operation, extremely high recyclability of batteries was achieved, suggesting the framework was robust. This MOF is the first example of a porous material showing independent redox activity on both metal cluster nodes and ligand sites.

  3. Pollution distribution of heavy metals in surface soil at an informal electronic-waste recycling site.

    Science.gov (United States)

    Fujimori, Takashi; Takigami, Hidetaka

    2014-02-01

    We studied distribution of heavy metals [lead (Pb), copper (Cu) and zinc (Zn)] in surface soil at an electronic-waste (e-waste) recycling workshop near Metro Manila in the Philippines to evaluate the pollution size (spot size, small area or the entire workshop), as well as to assess heavy metal transport into the surrounding soil environment. On-site length-of-stride-scale (~70 cm) measurements were performed at each surface soil point using field-portable X-ray fluorescence (FP-XRF). The surface soil at the e-waste recycling workshop was polluted with Cu, Zn and Pb, which were distributed discretely in surface soil. The site was divided into five areas based on the distance from an entrance gate (y-axis) of the e-waste recycling workshop. The three heavy metals showed similar concentration gradients in the y-axis direction. Zn, Pb and Cu concentrations were estimated to decrease to half of their maximum concentrations at ~3, 7 and 7 m from the pollution spot, respectively, inside the informal e-waste recycling workshop. Distance from an entrance may play an important role in heavy metal transport at the soil surface. Using on-site FP-XRF, we evaluated the metal ratio to characterise pollution features of the solid surface. Variability analysis of heavy metals revealed vanishing surficial autocorrelation over metre ranges. Also, the possibility of concentration prediction at unmeasured points using geostatistical kriging was evaluated, and heavy metals had a relative "small" pollution scales and remained inside the original workshop compared with toxic organohalogen compounds. Thus, exposure to heavy metals may directly influence the health of e-waste workers at the original site rather than the surrounding habitat and environmental media.

  4. DOE site performance assessment activities

    International Nuclear Information System (INIS)

    1990-07-01

    Information on performance assessment capabilities and activities was collected from eight DOE sites. All eight sites either currently dispose of low-level radioactive waste (LLW) or plan to dispose of LLW in the near future. A survey questionnaire was developed and sent to key individuals involved in DOE Order 5820.2A performance assessment activities at each site. The sites surveyed included: Hanford Site (Hanford), Idaho National Engineering Laboratory (INEL), Los Alamos National Laboratory (LANL), Nevada Test Site (NTS), Oak Ridge National Laboratory (ORNL), Paducah Gaseous Diffusion Plant (Paducah), Portsmouth Gaseous Diffusion Plant (Portsmouth), and Savannah River Site (SRS). The questionnaire addressed all aspects of the performance assessment process; from waste source term to dose conversion factors. This report presents the information developed from the site questionnaire and provides a comparison of site-specific performance assessment approaches, data needs, and ongoing and planned activities. All sites are engaged in completing the radioactive waste disposal facility performance assessment required by DOE Order 5820.2A. Each site has achieved various degrees of progress and have identified a set of critical needs. Within several areas, however, the sites identified common needs and questions

  5. The application of passive sampler (DGT technology for improved understanding of metal behaviour at a marine disposal site

    Directory of Open Access Journals (Sweden)

    Parker R.

    2013-04-01

    Full Text Available Metal behaviour and availability at a contaminated dredge material disposal site within UK waters has been investigated using Diffusive Gradient in Thin films (DGT passive sampling technology. Three stations representing contrasting history and presence of maintenance dredge disposal, including a control station outside the disposal site, have been studied and depth profiles of fluxes of different metals (Fe, Mn, Pb, Cu, Cd, Cr, Ni, Zn to the binding gel (Chelex 100 have been derived. Higher flux rates and shallower mobilisation of metals (Mn and Fe to the binding gel were observed at the disposal stations compared to the control station. Here we describe metal mobilization at different depths, linking the remobilization of Fe2+ and Mn2+ to the sediment (resupply of other heavy metals of interest with a focus on Cd, Ni and Pb and as they are on the Water Framework Directive (WFD list of priority substances and OSPAR list of priority pollutants. Results showed that Cd, Pb and Ni exhibited signs of resupply at the sediment-water interface (SWI. There was a potential increased mobilisation and source to the water column of Pb and Ni at the disposal site stations, but there was no Cd source, despite higher total loadings. This information has the potential to improve our current understanding of metal cycles at disposal sites. This work can be used as an indication of likely metal bioavailability and also assist in determining whether the sites act as sources or sinks of heavy metals. This information could assist disposal site monitoring and dredge material licensing.

  6. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst

    Science.gov (United States)

    Chung, Hoon T.; Cullen, David A.; Higgins, Drew; Sneed, Brian T.; Holby, Edward F.; More, Karren L.; Zelenay, Piotr

    2017-08-01

    Platinum group metal-free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)-based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H2)-air fuel cell. Herein, we demonstrate H2-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. Current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The proposed catalytic active site, carbon-embedded nitrogen-coordinated iron (FeN4), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.

  7. Insights into Substrate Specificity and Metal Activation of Mammalian Tetrahedral Aspartyl Aminopeptidase

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yuanyuan; Farquhar, Erik R.; Chance, Mark R.; Palczewski, Krzysztof; Kiser, Philip D. (Case Western)

    2012-07-11

    Aminopeptidases are key enzymes involved in the regulation of signaling peptide activity. Here, we present a detailed biochemical and structural analysis of an evolutionary highly conserved aspartyl aminopeptidase called DNPEP. We show that this peptidase can cleave multiple physiologically relevant substrates, including angiotensins, and thus may play a key role in regulating neuron function. Using a combination of x-ray crystallography, x-ray absorption spectroscopy, and single particle electron microscopy analysis, we provide the first detailed structural analysis of DNPEP. We show that this enzyme possesses a binuclear zinc-active site in which one of the zinc ions is readily exchangeable with other divalent cations such as manganese, which strongly stimulates the enzymatic activity of the protein. The plasticity of this metal-binding site suggests a mechanism for regulation of DNPEP activity. We also demonstrate that DNPEP assembles into a functionally relevant tetrahedral complex that restricts access of peptide substrates to the active site. These structural data allow rationalization of the enzyme's preference for short peptide substrates with N-terminal acidic residues. This study provides a structural basis for understanding the physiology and bioinorganic chemistry of DNPEP and other M18 family aminopeptidases.

  8. Can standard sequential extraction determinations effectively define heavy metal species in superfund site soils?

    Energy Technology Data Exchange (ETDEWEB)

    Dahlin, Cheryl L.; Williamson, Connie A.; Collins, Wesley K.; Dahlin, David C.

    2001-01-01

    Speciation and distribution of heavy metals in soils controls the degree to which metals and their compounds are mobile, extractable, and plant-available. Consequently, speciation impacts the success of remediation efforts both by defining the relationship of the contaminants with their environment and by guiding development and evaluation of workable remediation strategies. The U.S. Department of Energy, Albany Research Center (Albany, OR), under a two-year interagency project with the U.S. Environmental Protection Agency (EPA), examined the suitability of sequential extraction as a definitive means to determine species of heavy metals in soil samples. Representative soil samples, contaminated with lead, arsenic, and/or chromium, were collected by EPA personnel from two Superfund sites, the National Lead Company site in Pedricktown, NJ, and the Roebling Steel, Inc., site in Florence, NJ. Data derived from Tessier=s standard three-stage sequential-extraction procedure were compared to data from a comprehensive characterization study that combined optical- and scanning-electron microscopy (with energy-dispersive x-ray and wavelength-dispersive x-ray analyses), x-ray diffraction, and chemical analyses. The results show that standard sequential-extraction procedures that were developed for characterizing species of contaminants in river sediments may be unsuitable for sole evaluation of contaminant species in industrial-site materials (particularly those that contain larger particles of the contaminants, encapsulated contaminants, and/or man-made materials such as slags, metals, and plastics). However, each sequential extraction or comprehensive characterization procedure has it=s own strengths and weaknesses. Findings of this study indicate that the use of both approaches, during the early stages of site studies, would be a best practice. The investigation also highlights the fact that an effective speciation study does not simply identify metal contaminants as

  9. Activation volume and interaction of metal particulate media

    Energy Technology Data Exchange (ETDEWEB)

    Tetsukawa, Hiroki [Sony Corporation, 6-7-35 Kitashinagawa, Shinagawa-ku, Tokyo 141-0001 (Japan)]. E-mail: tetsukaw@arc.sony.co.jp; Kondo, Hirofumi [Sony Corporation, 6-7-35 Kitashinagawa, Shinagawa-ku, Tokyo 141-0001 (Japan)

    2005-09-15

    We have investigated the activation volume (V{sub ac}) and magnetostatic interaction of metal particulate (MP) media. The activation volume of MP media decreases with the decrease of physical volume (V{sub phy}) of metal particles. The activation volume and the ratio of V{sub phy}/V{sub ac} of advanced metal particles are 6x10{sup -24}m{sup 3} and 1.5, respectively. It can be predicted that the physical volume of metal particle is about 3x10{sup -24}m{sup 3} when the physical volume is equal to the activation volume. This value is agreement with the practical lower limit of physical volume of metal particle predicted by Sharrock. The negative interaction (demagnetization effect) in MP media decreases with low saturation magnetization of the metal particles, a thin magnetic layer, a high orientation of MP media, and a low packing fraction of metal particles in the MP media. The activation volume of the MP media decreased as the negative interactions decreased. In advanced MP media with low M{sub r}.t (M{sub r}=remanent magnetization and t=thickness), the influence of interaction on the activation volume is reduced.

  10. Activation volume and interaction of metal particulate media

    International Nuclear Information System (INIS)

    Tetsukawa, Hiroki; Kondo, Hirofumi

    2005-01-01

    We have investigated the activation volume (V ac ) and magnetostatic interaction of metal particulate (MP) media. The activation volume of MP media decreases with the decrease of physical volume (V phy ) of metal particles. The activation volume and the ratio of V phy /V ac of advanced metal particles are 6x10 -24 m 3 and 1.5, respectively. It can be predicted that the physical volume of metal particle is about 3x10 -24 m 3 when the physical volume is equal to the activation volume. This value is agreement with the practical lower limit of physical volume of metal particle predicted by Sharrock. The negative interaction (demagnetization effect) in MP media decreases with low saturation magnetization of the metal particles, a thin magnetic layer, a high orientation of MP media, and a low packing fraction of metal particles in the MP media. The activation volume of the MP media decreased as the negative interactions decreased. In advanced MP media with low M r .t (M r =remanent magnetization and t=thickness), the influence of interaction on the activation volume is reduced

  11. Engineering the metal sensitive sites in Macrolampis sp2 firefly luciferase and use as a novel bioluminescent ratiometric biosensor for heavy metals.

    Science.gov (United States)

    Gabriel, Gabriele V M; Viviani, Vadim R

    2016-12-01

    Most luminescent biosensors for heavy metals are fluorescent and rely on intensity measurements, whereas a few are ratiometric and rely on spectral changes. Bioluminescent biosensors for heavy metals are less common. Firefly luciferases have been coupled to responsive promoters for mercury and arsenium, and used as light on biosensors. Firefly luciferase bioluminescence spectrum is naturally sensitive to heavy metal cations such as zinc and mercury and to pH. Although pH sensitivity of firefly luciferases was shown to be useful for ratiometric estimation of intracellular pH, its potential use for ratiometric estimation of heavy metals was never considered. Using the yellow-emitting Macrolampis sp2 firefly luciferase and site-directed mutagenesis, we show that the residues H310 and E354 constitute two critical sites for metal sensitivity that can be engineered to increase sensitivity to zinc, nickel, and mercury. A linear relationship between cation concentration and the ratio of bioluminescence intensities at 550 and 610 nm allowed, for the first time, the ratiometric estimation of heavy metals concentrations down to 0.10 mM, demonstrating the potential applicability of firefly luciferases as enzymatic and intracellular ratiometric metal biosensors.

  12. Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations.

    Science.gov (United States)

    Ratheal, Ian M; Virgin, Gail K; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

    2010-10-26

    The Na/K pump is a P-type ATPase that exchanges three intracellular Na(+) ions for two extracellular K(+) ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na(+) or K(+); site III binds only Na(+)) are poorly understood. We studied cation selectivity by outward-facing sites (high K(+) affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium(+), methylguanidinium(+), and aminoguanidinium(+) produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K(+), and (ii) induction of pump-mediated, guanidinium-derivative-carried inward current at negative potentials without Na(+) and K(+). In contrast, formamidinium(+) and acetamidinium(+) induced K(+)-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K(+) congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li(+) induced Na(+)-like VDI, whereas all metals tested except Na(+) induced K(+)-like outward currents. Pump-mediated K(+)-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium(+) derivatives suggest that Na(+) binds to site III in a hydrated form and that the inward current observed without external Na(+) and K(+) represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites.

  13. Mathematical modeling of heavy metals contamination from MSW landfill site in Khon Kaen, Thailand.

    Science.gov (United States)

    Tantemsapya, N; Naksakul, Y; Wirojanagud, W

    2011-01-01

    Kham Bon landfill site is one of many municipality waste disposal sites in Thailand which are in an unsanitary condition. The site has been receiving municipality wastes without separating hazardous waste since 1968. Heavy metals including, Pb, Cr and Cd are found in soil and groundwater around the site, posing a health risk to people living nearby. In this research, contamination transport modelling of Pb, Cr and Cd was simulated using MODFLOW for two periods, at the present (2010) and 20 years prediction (2030). Model results showed that heavy metals, especially Pb and Cr migrated toward the north-eastern and south-eastern direction. The 20 years prediction showed that, heavy metals tend to move from the top soil to the deeper aquifer. The migration would not exceed 500 m radius from the landfill centre in the next 20 years, which is considered to be a slow process. From the simulation model, it is recommended that a mitigation measure should be performed to reduce the risk from landfill contamination. Hazardous waste should be separated for proper management. Groundwater contamination in the aquifer should be closely monitored. Consumption of groundwater in a 500 m radius must be avoided. In addition, rehabilitation of the landfill site should be undertaken to prevent further mobilization of pollutants.

  14. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-01

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  15. Research of mercury removal from sintering flue gas of iron and steel by the open metal site of Mil-101(Cr).

    Science.gov (United States)

    Zhao, Songjian; Mei, Jian; Xu, Haomiao; Liu, Wei; Qu, Zan; Cui, Yong; Yan, Naiqiang

    2018-06-05

    Metal-organic frameworks (MOFs) adsorbent Mil-101(Cr) was introduced for the removal of elemental mercury from sintering flue gas. Physical and chemical characterization of the adsorbents showed that MIL-101(Cr) had the largest BET surface area, high thermal stability and oxidation capacity. Hg 0 removal performance analysis indicated that the Hg 0 removal efficiency of MIL-101(Cr) increased with the increasing temperature and oxygen content. Besides, MIL-101(Cr) had the highest Hg 0 removal performance compared with Cu-BTC, UiO-66 and activated carbon, which can reach about 88% at 250 °C. The XPS and Hg-TPD methods were used to analyze the Hg 0 removal mechanism; the results show that Hg 0 was first adsorbed on the surface of Mil-101(Cr), and then oxidized by the open metal site Cr 3+ . The generated Hg 2+ was then combined surface adsorbed oxygen of adsorbent to form HgO, and the open metal site Cr 2+ was oxidized to Cr 3+ by surface active oxygen again. Furthermore, MIL-101(Cr) had good chemical and thermal stability. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. The use of tetragnathid spiders as bioindicators of metal exposure at a coal ash spill site.

    Science.gov (United States)

    Otter, Ryan R; Hayden, Mary; Mathews, Teresa; Fortner, Allison; Bailey, Frank C

    2013-09-01

    On 22 December 2008, a dike containing coal fly ash from the Tennessee Valley Authority Kingston Fossil Fuel Plant (TN, USA) failed, resulting in the largest coal ash spill in US history. The present study was designed to determine sediment metal concentrations at multiple site locations and to determine whether site-specific bioaccumulation of metals existed in tetragnathid spiders. Selenium and nickel were the only 2 metals to exceed the US Environmental Protection Agency sediment screening levels. Selenium concentrations in spiders were significantly higher at ash-affected sites than in those from reference sites. The ratio of methylmercury to total mercury in spiders was found to be similar to that in other organisms (65-75%), which highlights the potential use of tetragnathid spiders as an indicator species for tracing contaminant transfer between the aquatic and terrestrial ecosystems. Copyright © 2013 SETAC.

  17. Distribution of trace metals at Hopewell Furnace National Historic Site, Berks and Chester Counties, Pennsylvania

    Science.gov (United States)

    Sloto, Ronald A.; Reif, Andrew G.

    2011-01-01

    Hopewell Furnace, located approximately 50 miles northwest of Philadelphia, was a cold-blast, charcoal iron furnace that operated for 113 years (1771 to 1883). The purpose of this study by the U.S. Geological Survey, in cooperation with the National Park Service, was to determine the distribution of trace metals released to the environment from an historical iron smelter at Hopewell Furnace National Historic Site (NHS). Hopewell Furnace used iron ore from local mines that contained abundant magnetite and accessory sulfide minerals enriched in arsenic, cobalt, copper, and other metals. Ore, slag, cast iron furnace products, soil, groundwater, stream base flow, streambed sediment, and benthic macroinvertebrates were sampled for this study. Soil samples analyzed in the laboratory had concentrations of trace metals low enough to meet Pennsylvania Department of Environmental Protection standards for non-residential use. Groundwater samples from the supply well met U.S. Environmental Protection Agency drinking-water regulations. Concentrations of metals in surface-water base flow at the five stream sampling sites were below continuous concentration criteria for protection of aquatic organisms. Concentrations of metals in sediment at the five stream sites were below probable effects level guidelines for protection of aquatic organisms except for copper at site HF-3. Arsenic, copper, lead, zinc, and possibly cobalt were incorporated into the cast iron produced by Hopewell Furnace. Manganese was concentrated in slag along with iron, nickel, and zinc. The soil near the furnace has elevated concentrations of chromium, copper, iron, lead, and zinc compared to background soil concentrations. Concentrations of toxic elements were not present at concentrations of concern in water, soil, or stream sediments, despite being elevated in ore, slag, and cast iron furnace products. The base-flow surface-water samples indicated good overall quality. The five sampled sites generally had

  18. Assessment of potentially toxic metal contamination in the soils of a legacy mine site in Central Victoria, Australia.

    Science.gov (United States)

    Abraham, Joji; Dowling, Kim; Florentine, Singarayer

    2018-02-01

    The environmental impact of toxic metal contamination from legacy mining activities, many of which had operated and were closed prior to the enforcement of robust environmental legislation, is of growing concern to modern society. We have carried out analysis of As and potentially toxic metals (Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, and Zn) in the surface soil of a legacy gold mining site in Maldon, Victoria, Australia, to reveal the status of the current metal concentration. The results revealed the median concentrations of metals from highest to lowest, in the order: Mn > Zn > As > Cr > Cu > Pb > Ni > Co > Hg > Cd. The status of site was assessed directly by comparing the metal concentrations in the study area with known Australian and Victorian average top soil levels and the health investigation levels set by the National Environmental Protection Measures (NEPM) and the Department of Environment and Conservation (DEC) of the State of Western Australia. Although, median concentrations of As, Hg, Pb, Cu and Zn exceeded the average Australian and Victorian top soil concentrations, only As and Hg exceeded the ecological investigation levels (EIL) set by DEC and thus these metals are considered as risk to the human and aquatic ecosystems health due to their increase in concentration and toxicity. In an environment of climate fluctuation with increased storm events and forest fires may mobilize these toxic metals contaminants, pose a real threat to the environment and the community. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Remediation of heavy metal contaminated sites in the Venice lagoon and conterminous areas (Northern Italy)

    Science.gov (United States)

    Bini, Claudio; Wahsha, Mohammad; Fontana, Silvia; Maleci, Laura

    2013-04-01

    The lagoon of Venice and the conterminous land are affected by heavy contamination of anthropogenic origin, and for this reason the whole area has been classified as site of national interest, and must be restored. Heavy metals (As, Cd, Cr, Cu, Hg, Mn, Pb, Sb, Se, Zn) and organic compounds (IPA, PCB, Dioxine) have been identified as the main contaminants at various sites, owing to agriculture and industrial wastes discharged on soils and convoyed to the lagoon. Five case studies of soil remediation are here reported. S. Giuliano is a former palustrine area reclaimed since the 60's with various human transported materials (HTM). In this area, hot spots overpassing the reference limits for residential and green areas have been recorded for Cd, Cu, Pb, Zn and IPA. Campalto is a site bordering the Venice lagoon and subjected to oscillating water level, that enhances metal mobility; diffuse contamination by heavy metals, particularly Pb, has been recorded at this site, utilized since 30 years for military and sport (skate) activities. Marghera is dramatically famous for its numerous factories and for oil refineries that affected the lagoon sediments since the 50's. Sediments proved heavily contaminated by As (up to 137 mgkg-1), Cd (57 mgkg-1), Hg (30mgkg-1), Ni, Pb (700 mgkg-1), Zn (5818 mgkg-1). Murano is a small island where many glass factories (the most famous all over the world) are running since XIII century. Glass is stained with several metals and, moreover, some substances are used to regulate fusion temperature, purity, etc., and therefore the surrounding environment is heavily contaminated by these substances. Mean concentrations of As (429 mgkg-1), Cd (1452 mgkg-1), Pb (749 mgkg-1), Zn (1624 mgkg-1), Se (341 mgkg-1), Sb (74 mgkg-1) widely overpass the reference values for both residential and industrial areas in national guidelines. Molo Serbatoi is a former oil container currently under restoration in the port of Venice. Soil contamination by As, Hg, Zn and

  20. Cupryphans, metal-binding, redox-active, redesigned conopeptides.

    Science.gov (United States)

    Barba, Marco; Sobolev, Anatoli P; Romeo, Cristina; Schininà, M Eugenia; Pietraforte, Donatella; Mannina, Luisa; Musci, Giovanni; Polticelli, Fabio

    2009-03-01

    Contryphans are bioactive peptides, isolated from the venom of marine snails of the genus Conus, which are characterized by the short length of the polypeptide chain and the high degree of unusual post-translational modifications. The cyclization of the polypeptide chain through a single disulphide bond, the presence of two conserved Pro residues, and the epimerization of a Trp/Leu residue confer to Contryphans a stable and well-defined structure in solution, conserved in all members of the family, and tolerant to multiple substitutions. The potential of Contryphans as scaffolds for the design of redox-active (macro)molecules was tested by engineering a copper-binding site on two different variants of the natural peptide Contryphan-Vn. The binding site was designed by computational modeling, and the redesigned peptides were synthesized and characterized by optical, fluorescence, electron spin resonance, and nuclear magnetic resonance spectroscopy. The novel peptides, named Cupryphan and Arg-Cupryphan, bind Cu(2+) ions with a 1:1 stoichiometry and a K(d) in the 100 nM range. Other divalent metals (e.g., Zn(2+) and Mg(2+)) are bound with much lower affinity. In addition, Cupryphans catalyze the dismutation of superoxide anions with an activity comparable to other nonpeptidic superoxide dismutase mimics. We conclude that the Contryphan motif represents a natural robust scaffold which can be engineered to perform different functions, providing additional means for the design of catalytically active mini metalloproteins.

  1. Plant growth promotion, metabolite production and metal tolerance of dark septate endophytes isolated from metal-polluted poplar phytomanagement sites.

    Science.gov (United States)

    Berthelot, Charlotte; Leyval, Corinne; Foulon, Julie; Chalot, Michel; Blaudez, Damien

    2016-10-01

    Numerous studies address the distribution and the diversity of dark septate endophytes (DSEs) in the literature, but little is known about their ecological role and their effect on host plants, especially in metal-polluted soils. Seven DSE strains belonging to Cadophora, Leptodontidium, Phialophora and Phialocephala were isolated from roots of poplar trees from metal-polluted sites. All strains developed on a wide range of carbohydrates, including cell-wall-related compounds. The strains evenly colonized birch, eucalyptus and ryegrass roots in re-synthesis experiments. Root and shoot growth promotion was observed and was both plant and strain dependent. Two Phialophora and Leptodontidium strains particularly improved plant growth. However, there was no correlation between the level of root colonization by DSEs and the intensity of growth promotion. All strains produced auxin and six also stimulated plant growth through the release of volatile organic compounds (VOCs). SPME-GC/MS analyses revealed four major VOCs emitted by Cadophora and Leptodontidium The strains exhibited growth at high concentrations of several metals. The ability of metal-resistant DSE strains to produce both soluble and volatile compounds for plant growth promotion indicates interesting microbial resources with high potential to support sustainable production of bioenergy crops within the context of the phytomanagement of metal-contaminated sites. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  2. The effect of the metal-on-metal hip controversy on internet search activity.

    LENUS (Irish Health Repository)

    Phelan, Nigel

    2014-01-04

    The recall of the articular surface replacement (ASR) hip prosthesis in 2010 represents one of the most controversial areas in orthopaedic surgery in recent years. The aim of this study was to compare the impact of the metal-on-metal hip controversy on Internet search activity in four different regions and determine whether the number of related news reports affected Internet search activity. The Google Trends, Keywords and News applications were used to record the number of news articles and Internet search activity for the terms "hip recall", "metal-on-metal hip" and "ASR hip" from October 2009 to October 2012 in the USA, the UK, Australia and Ireland. There was a large increase in search activity following the official recall in August 2010 in all countries. There was significantly greater search activity after the recall in Ireland compared with the UK for the search term "hip recall" (P = 0.004). For the term "metal-on-metal hip", the UK had significantly more search activity (P = 0.0009). There was a positive correlation between the number of news stories in UK and Ireland with Internet search activity but not in the USA or Australia. Differences between countries affected by the same recall highlight the complex effects of the media on public awareness. The data demonstrates a window of opportunity prior to the official recall for the development of an awareness campaign to provide patients with accurate information.

  3. Breast milk metal ion levels in a young and active patient with a metal-on-metal hip prosthesis.

    Science.gov (United States)

    Nelis, Raymond; de Waal Malefijt, Jan; Gosens, Taco

    2013-01-01

    Metal-on-metal resurfacing arthroplasty of the hip has been used increasingly over the last 10 years in younger active patients. The dissolution of the metal wear particles results in measurable increases in cobalt and chromium ions in the serum and urine of patients with a metal-on-metal bearing. We measured the cobalt, chromium, and molybdenum ion levels in urine; serum; and breast milk in a young and active patient with a metal-on-metal hip prosthesis after a pathologic fracture of the femoral neck. Metal-on-metal hip prosthesis leads to increasing levels of molybdenum in breast milk in the short-term follow-up. There are no increasing levels of chromium and cobalt ions in breast milk. Besides the already known elevated concentrations in serum of chromium and cobalt after implantation of a metal-on-metal hip prosthesis, we found no increasing levels of chromium and cobalt in urine. Copyright © 2013 Elsevier Inc. All rights reserved.

  4. Pollution in the urban soils of Lianyungang, China, evaluated using a pollution index, mobility of heavy metals, and enzymatic activities.

    Science.gov (United States)

    Li, Yu; Li, Hong-Guan; Liu, Fu-Cheng

    2017-01-01

    Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had

  5. Characterization of natural adsorbent material for heavy metal removal in a petrochemical site contamination

    Directory of Open Access Journals (Sweden)

    Bianchi F.

    2013-04-01

    Full Text Available Despite of over 25 years of intensive technological efforts, sub-surface environment cleanup still remains a challenge, especially in case of highly contaminated sites. In this context, ion exchanger technologies could provide simple and effective solutions for heavy metal removal in water treatment. The challenge is finding exchanger able to operate in extreme natural environments or in situations involving natural interfering species such as inorganic ions. In this paper we exam the use of natural zeolites as versatile exchanger for environmental protection of coastal refinery's groundwater against pollution of Ni, Cd, Pb. The influence of particle diameter on clinoptilolite performances toward heavy metal removal is studied. Also, we evaluate the exchanger activities in condition of high ionic strength, commonly present in groundwater located under coastal petrol industries. The obtained results confirmed that ion exchangers could provide an effective solutions for remediation in complex environmental conditions.

  6. X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

    International Nuclear Information System (INIS)

    Tan, G.O.

    1993-06-01

    X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it, from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here

  7. Site preference of metal atoms in Gd_5_-_xM_xTt_4 (M = Zr, Hf; Tt = Si, Ge)

    International Nuclear Information System (INIS)

    Yao, Jinlei; Mozharivskyj, Yurij

    2011-01-01

    Zirconium and hafnium were incorporated into the Gd_5Ge_4 and Gd_5Si_4 parent compounds in order to study the metal-site occupation in the M_5X_4 magnetocaloric phases (M = metals; X = p elements) family. The Gd_5_-_xZr_xGe_4 phases adopt the orthorhombic Sm_5Ge_4-type (space group Pnma) structure for x ≤ 1.49 and the tetragonal Zr_5Si_4-type (P4_12_12) structure for x ≥ 1.77. The Gd_5_-_xHf_xSi_4 compounds crystallize in the orthorhombic Gd_5Si_4-type (Pnma) structure for x ≤ 0.41 and the Zr_5Si_4-type structure for x ≥ 0.7. In both systems, single-crystal X-ray diffraction reveals that the Zr/Hf atoms preferentially occupy the slab-surface M2 and slab-center M3 sites, both of which have a significantly larger Zr/Hf population than the slab-surface M1 site. The metal-site preference, i.e. the coloring problem on the three metal sites, is discussed considering geometric and electronic effects of the local coordination environments. The analysis of the metal-site occupation in Gd_5_-_xZr_xGe_4 and Gd_5_-_xHf_xSi_4 as well as other metal-substituted M_5X_4 systems suggests that both geometric and electronic effects can be used to explain the metal-site occupation. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Haematology, genotoxicity, enzymatic activity and histopathology as biomarkers of metal pollution in the shrew Crocidura russula

    International Nuclear Information System (INIS)

    Sanchez-Chardi, A.; Marques, C.C.; Gabriel, S.I.; Capela-Silva, F.; Cabrita, A.S.; Lopez-Fuster, M.J.; Nadal, J.; Mathias, M.L.

    2008-01-01

    Haematological (WBC, RBC, Hgb and Hct) and genotoxicity (MNT) parameters, hepatic enzymatic activities (GST, GPx and GR), and a histopathological evaluation of liver, kidneys and gonads were assessed as general biomarkers of metal pollution in the shrew Crocidura russula inhabiting a pyrite mining area. Specimens exposed to metals presented a few significant alterations when compared with reference animals: GST activity decreased; micronuclei increased; and evident liver alterations related to metal exposure were observed. On the basis of all the parameters studied, age was an important factor that partly explained the observed variation, whereas sex was the least important factor. Significant correlations were also found between heavy metal concentrations and biomarkers evaluated, demonstrating the great influence of these metals in the metabolic alterations. To the best of our knowledge, these data constitute the first measurements of a battery of biomarkers in shrews from a mine site and are among the few available for insectivorous mammals. - Metals from an abandoned pyrite mine produce alterations in haematological parameters, GST, MNT, and histopathology in shrews

  9. Associative diazotrophic bacteria in grass roots and soils from heavy metal contaminated sites.

    Science.gov (United States)

    Moreira, Fátima M S; Lange, Anderson; Klauberg-Filho, Osmar; Siqueira, José O; Nóbrega, Rafaela S A; Lima, Adriana S

    2008-12-01

    This work aimed to evaluate density of associative diazotrophic bacteria populations in soil and grass root samples from heavy metal contaminated sites, and to characterize isolates from these populations, both, phenotypically (Zinc, Cadmium and NaCl tolerance in vitro, and protein profiles) and genotypically (16S rDNA sequencing), as compared to type strains of known diazotrophic species. Densities were evaluated by using NFb, Fam and JNFb media, commonly used for enrichment cultures of diazotrophic bacteria. Bacterial densities found in soil and grass root samples from contaminated sites were similar to those reported for agricultural soils. Azospirillum spp. isolates from contaminated sites and type strains from non-contaminated sites varied substantially in their in vitro tolerance to Zn+2 and Cd+2, being Cd+2 more toxic than Zn+2. Among the most tolerant isolates (UFLA 1S, 1R, S181, S34 and S22), some (1R, S34 and S22) were more tolerant to heavy metals than rhizobia from tropical and temperate soils. The majority of the isolates tolerant to heavy metals were also tolerant to salt stress as indicated by their ability to grow in solid medium supplemented with 30 g L(-1) NaCl. Five isolates exhibited high dissimilarity in protein profiles, and the 16S rDNA sequence analysis of two of them revealed new sequences for Azospirillum.

  10. An unsaturated metal site-promoted approach to construct strongly coupled noble metal/HNb3O8 nanosheets for efficient thermo/photo-catalytic reduction.

    Science.gov (United States)

    Shen, Lijuan; Xia, Yuzhou; Lin, Sen; Liang, Shijing; Wu, Ling

    2017-10-05

    Creating two-dimensional (2D) crystal-metal heterostructures with an ultrathin thickness has spurred increasing research endeavors in catalysis because of its fascinating opportunities in tuning the electronic state at the surface and enhancing the chemical reactivity. Here we report a novel and facile Nb 4+ -assisted strategy for the in situ growth of highly dispersed Pd nanoparticles (NPs) on monolayer HNb 3 O 8 nanosheets (HNb 3 O 8 NS) constituting a 2D Pd/HNb 3 O 8 NS heterostructure composite without using extra reducing agents and stabilizing agents. The Pd NP formation is directed via a redox reaction between an oxidative Pd salt precursor (H 2 PdCl 4 ) and reductive unsaturated surface metal (Nb 4+ ) sites induced by light irradiation on monolayer HNb 3 O 8 NS. The periodic arrangement of metal Nb nodes on HNb 3 O 8 NS leads to a homogeneous distribution of Pd NPs. Density functional theory (DFT) calculations reveal that the direct redox reaction between the Nb 4+ and Pd 2+ ions leads to a strong chemical interaction between the formed Pd metal NPs and the monolayer HNb 3 O 8 support. Consequently, the as-obtained Pd/HNb 3 O 8 composite serves as a highly efficient bifunctional catalyst in both heterogeneous thermocatalytic and photocatalytic selective reduction of aromatic nitro compounds in water under ambient conditions. The achieved high activity originates from the unique 2D nanosheet configuration and in situ Pd incorporation, which leads to a large active surface area, strong metal-support interaction and enhanced charge transport capability. Moreover, this facile Nb 4+ -assisted synthetic route has demonstrated to be general, which can be applied to load other metals such as Au and Pt on monolayer HNb 3 O 8 NS. It is anticipated that this work can extend the facile preparation of noble metal/nanosheet 2D heterostructures, as well as promote the simultaneous capture of duple renewable thermal and photon energy sources to drive an energy efficient

  11. Heat of solution and site energies of hydrogen in disordered transition-metal alloys

    International Nuclear Information System (INIS)

    Brouwer, R.C.; Griessen, R.

    1989-01-01

    Site energies, long-range effective hydrogen-hydrogen interactions, and the enthalpy of solution in transition-metal alloys are calculated by means of an embedded-cluster model. The energy of a hydrogen atom is assumed to be predominantly determined by the first shell of neighboring metal atoms. The semiempirical local band-structure model is used to calculate the energy of the hydrogen atoms in the cluster, taking into account local deviations from the average lattice constant. The increase in the solubility limit and the weak dependence of the enthalpy of solution on hydrogen concentration in disordered alloys are discussed. Calculated site energies and enthalpies of solution in the alloys are compared with experimental data, and good agreement is found. Due to the strong interactions with the nearest-neighbor metal atoms, hydrogen atoms can be used to determine local lattice separations and the extent of short-range order in ''disordered'' alloys

  12. Soil criteria to protect terrestrial wildlife and open-range livestock from metal toxicity at mining sites.

    Science.gov (United States)

    Ford, Karl L; Beyer, W Nelson

    2014-03-01

    Thousands of hard rock mines exist in the western USA and in other parts of the world as a result of historic and current gold, silver, lead, and mercury mining. Many of these sites in the USA are on public lands. Typical mine waste associated with these sites are tailings and waste rock dumps that may be used by wildlife and open-range livestock. This report provides wildlife screening criteria levels for metals in soil and mine waste to evaluate risk and to determine the need for site-specific risk assessment, remediation, or a change in management practices. The screening levels are calculated from toxicity reference values based on maximum tolerable levels of metals in feed, on soil and plant ingestion rates, and on soil to plant uptake factors for a variety of receptors. The metals chosen for this report are common toxic metals found at mining sites: arsenic, cadmium, copper, lead, mercury, and zinc. The resulting soil screening values are well above those developed by the US Environmental Protection Agency. The difference in values was mainly a result of using toxicity reference values that were more specific to the receptors addressed rather than the most sensitive receptor.

  13. Methods for evaluating potential impacts to aquatic receptors at a metal-contaminated superfund site

    International Nuclear Information System (INIS)

    Hattemer-Frey, H.A.; Quinlan, R.E.; Krieger, G.R.

    1994-01-01

    An ecological risk assessment (ERA) was conducted for a metals mining site in the midwestern United States. Chemicals of potential concern were shown to be heavy metals associated with mine wastes and with base metal ore deposits that are characteristic of this area. Environmental receptors were identified by considering the relevant exposure pathways and the potential or known occurrence of species exposed via those pathways. Selection of key receptor species was designed to minimize the possibility that other species would be more exposed than the key species themselves and to include representation of sensitive organisms present at the subsites. In addition, an EPA-approved method was use to developed site-specific ambient water quality criteria. Ecological impacts were assessed using two complimentary approaches. First, potential chronic impacts were assessed by applying the toxicity quotient approach (i.e., a comparison of the measured concentration of site-related metals in surface water with available health-based criteria). Secondly, semi-quantitative comparative ecology data were used to obtain to provide a direct measure of impacts to key species. Results from these two approaches were used to provide a direct measure of impacts to key species. Results from these two approaches were used to obtain a realistic picture of actual and potential risks associated with exposure by key species to mining-related metals. This paper discusses the uncertainties associated with both methods and presents a method for interpreting disparate and sometimes confusing ecological data using the results from a case study

  14. Nucleation of recrystallization at selected sites in deformed fcc metals

    DEFF Research Database (Denmark)

    Xu, Chaoling

    The objective of this thesis is to explore nucleation of recrystallization at selected sites in selected face-centered-cubic (FCC) metals, namely cold rolled columnar-grained nickel and high purity aluminum further deformed by indenting. Various techniques, including, optical microscopy, electron...... backscattered diffraction (EBSD), electron channeling contrast (ECC) and synchrotron X-ray technique, differential-aperture X-ray microscopy (DAXM), were used to characterize the microstructures, to explore nucleation sites, orientation relationships between nuclei and deformed microstructures, and nucleation...... mechanisms. In the cold rolled nickel samples, the preference of triple junctions (TJs) and grain boundaries (GBs) as nucleation sites is observed. The majorities of the nuclei have the same orientations as the surrounding matrix or are twin-related to a surrounding deformed grain. Only a few nuclei...

  15. Evaluation of site-specific factors influencing heavy metal contents in the topsoil of vegetated infiltration swales

    International Nuclear Information System (INIS)

    Horstmeyer, Nils; Huber, Maximilian; Drewes, Jörg E.; Helmreich, Brigitte

    2016-01-01

    Stormwater runoff of traffic areas is usually polluted by organic and inorganic substances and must be treated prior to discharge into groundwater. One widely used treatment method is infiltrating the runoff over the topsoil of vegetated swales. The aim of this study was to evaluate the factors influencing the heavy metal contents in such topsoil layers of vegetated infiltration swales near highways, roads, and parking lots. In total, 262 topsoil samples were taken from 35 sampling sites, which varied in age, traffic volume, road design, driving style, and site-specific conditions. In the evaluation of all soil samples, the median heavy metal values of cadmium, chromium, copper, lead, and zinc were yielding 0.36 (mean: 1.21) mg/kg DM, 37.0 (mean: 44.5) mg/kg DM, 28.0 (mean: 61.5) mg/kg DM, 27.0 (mean: 71.9) mg/kg DM, and 120 (mean: 257) mg/kg DM, respectively. The main purpose was to evaluate the site-specific data (i.e., surrounding land use characteristics, traffic area site data, and operational characteristics). In general, heavy metal contents increased with increasing traffic volumes. However, other factors also had a notable impact. Factors such as road design (e.g., curves, crossings, and roundabouts) and grade of congestion significantly influenced the heavy metal contents. High heavy metal contents were detected for stop-and-go areas, roundabouts, crossings, and sites with traffic lights, signs, and guardrails. Findings of this study can be used to identify highly polluted traffic areas and to verify or improve standards regarding the treatment of runoff from traffic areas. - Highlights: • Correlation of contents with traffic volume, road design, and stop-and-go traffic • Increased heavy metal contents at stop-and-go sites, roundabouts, and crossings • Different soil contents and behavior of cadmium, chromium, copper, lead, and zinc • Identification of factors influencing the variability of zinc in topsoil samples

  16. Evaluation of site-specific factors influencing heavy metal contents in the topsoil of vegetated infiltration swales

    Energy Technology Data Exchange (ETDEWEB)

    Horstmeyer, Nils; Huber, Maximilian; Drewes, Jörg E.; Helmreich, Brigitte, E-mail: b.helmreich@tum.de

    2016-08-01

    Stormwater runoff of traffic areas is usually polluted by organic and inorganic substances and must be treated prior to discharge into groundwater. One widely used treatment method is infiltrating the runoff over the topsoil of vegetated swales. The aim of this study was to evaluate the factors influencing the heavy metal contents in such topsoil layers of vegetated infiltration swales near highways, roads, and parking lots. In total, 262 topsoil samples were taken from 35 sampling sites, which varied in age, traffic volume, road design, driving style, and site-specific conditions. In the evaluation of all soil samples, the median heavy metal values of cadmium, chromium, copper, lead, and zinc were yielding 0.36 (mean: 1.21) mg/kg DM, 37.0 (mean: 44.5) mg/kg DM, 28.0 (mean: 61.5) mg/kg DM, 27.0 (mean: 71.9) mg/kg DM, and 120 (mean: 257) mg/kg DM, respectively. The main purpose was to evaluate the site-specific data (i.e., surrounding land use characteristics, traffic area site data, and operational characteristics). In general, heavy metal contents increased with increasing traffic volumes. However, other factors also had a notable impact. Factors such as road design (e.g., curves, crossings, and roundabouts) and grade of congestion significantly influenced the heavy metal contents. High heavy metal contents were detected for stop-and-go areas, roundabouts, crossings, and sites with traffic lights, signs, and guardrails. Findings of this study can be used to identify highly polluted traffic areas and to verify or improve standards regarding the treatment of runoff from traffic areas. - Highlights: • Correlation of contents with traffic volume, road design, and stop-and-go traffic • Increased heavy metal contents at stop-and-go sites, roundabouts, and crossings • Different soil contents and behavior of cadmium, chromium, copper, lead, and zinc • Identification of factors influencing the variability of zinc in topsoil samples.

  17. The dapE-encoded N-succinyl-L,L-Diaminopimelic Acid Desuccinylase from Haemophilus influenzae Contains two Active Site Histidine Residues

    Science.gov (United States)

    Gillner, Danuta M.; Bienvenue, David L.; Nocek, Boguslaw P.; Joachimiak, Andrzej; Zachary, Vincentos; Bennett, Brian; Holz, Richard C.

    2009-01-01

    The catalytic and structural properties of the H67A and H349A altered dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase (DapE) from H. influenzae were investigated. Based on sequence alignment with CPG2 both H67 and H349 were predicted to be Zn(II) ligands. Catalytic activity was observed for the H67A altered DapE enzyme which exhibited kcat = 1.5 ± 0.5 sec−1 and Km = 1.4 ± 0.3 mM. No catalytic activity was observed for H349A under the experimental conditions used. The EPR and electronic absorption data indicate that the Co(II) ion bound to H349A-DapE is analogous to WT DapE after the addition of a single Co(II) ion. The addition of one equivalent of Co(II) to H67A altered DapE provides spectra that are very different from the first Co(II) binding site of the WT enzyme, but similar to the second binding site. The EPR and electronic absorption data, in conjunction with the kinetic data, are consistent with the assignment of H67 and H349 as active site metal ligands for the DapE from H. influenzae. Furthermore, the data suggest that H67 is a ligand in the first metal binding site while H349 resides in the second metal binding site. A three-dimensional homology structure of the DapE from H. influenzae was generated using the X-ray crystal structure of the DapE from N. meningitidis as a template and superimposed on the structure of AAP. This homology structure confirms the assignment of H67 and H349 as active site ligands. The superimposition of the homology model of DapE with the dizinc(II) structure of AAP indicates that within 4.0 Å of the Zn(II) binding sites of AAP, all of the amino acid residues of DapE are nearly identical. PMID:18712420

  18. Removal and recovery of toxic metal ions from aqueous waste sites using polymer pendant ligands

    International Nuclear Information System (INIS)

    Fish, D.

    1996-01-01

    The purpose of this project is to investigate the use of polymer pendant ligand technology to remove and recover toxic metal ions from DOE aqueous waste sites. Polymer pendant lgiands are organic ligands, anchored to crosslinked, modified divinylbenzene-polystyrene beads, that can selectively complex metal ions. The metal ion removal step usually occurs through a complexation or ion exchange phenomena, thus recovery of the metal ions and reuse of the beads is readily accomplished

  19. The relative influence of metal ion binding sites in the I-like domain and the interface with the hybrid domain on rolling and firm adhesion by integrin alpha4beta7.

    Science.gov (United States)

    Chen, JianFeng; Takagi, Junichi; Xie, Can; Xiao, Tsan; Luo, Bing-Hao; Springer, Timothy A

    2004-12-31

    We examined the effect of conformational change at the beta(7) I-like/hybrid domain interface on regulating the transition between rolling and firm adhesion by integrin alpha(4)beta(7). An N-glycosylation site was introduced into the I-like/hybrid domain interface to act as a wedge and to stabilize the open conformation of this interface and hence the open conformation of the alpha(4) beta(7) headpiece. Wild-type alpha(4)beta(7) mediates rolling adhesion in Ca(2+) and Ca(2+)/Mg(2+) but firm adhesion in Mg(2+) and Mn(2+). Stabilizing the open headpiece resulted in firm adhesion in all divalent cations. The interaction between metal binding sites in the I-like domain and the interface with the hybrid domain was examined in double mutants. Changes at these two sites can either counterbalance one another or be additive, emphasizing mutuality and the importance of multiple interfaces in integrin regulation. A double mutant with counterbalancing deactivating ligand-induced metal ion binding site (LIMBS) and activating wedge mutations could still be activated by Mn(2+), confirming the importance of the adjacent to metal ion-dependent adhesion site (ADMIDAS) in integrin activation by Mn(2+). Overall, the results demonstrate the importance of headpiece allostery in the conversion of rolling to firm adhesion.

  20. Heavy metal accumulation and ecosystem engineering by two common mine site-nesting ant species: implications for pollution-level assessment and bioremediation of coal mine soil.

    Science.gov (United States)

    Khan, Shbbir R; Singh, Satish K; Rastogi, Neelkamal

    2017-04-01

    The present study focuses on the abundance, heavy metal content, and the impact of ecosystem engineering activities of two coal mine site-inhabiting ant species, Cataglyphis longipedem and Camponotus compressus. The abundance of Ct. longipedem increased while that of C. compressus decreased, with increasing soil pollution. Correspondence analysis reveals a close association between soil heavy metal concentrations and Ct. longipedem abundance, but this association is lacking in the case of C. compressus. Cataglyphis ants which occupy stress-characterized niches appear to be pre-adapted to tolerate heavy metal pollution. Higher concentrations of Zn and Mn in Ct. longipedem may contribute to the strengthening of the cuticular structures, necessary for nest excavation in the hard, arid soil and for single load carrying. C. compressus ants appear to be pollution sensitive. Their higher Fe content may be related to metal uptake via plant-derived liquids and species-specific regulatory mechanisms. The metal pollution index and biota-to-soil accumulation factors, calculated by using the ant body metal content of the two species, indicate an overall decrease of soil heavy metal concentrations with increase of the site age, which reflects the degree of pollution related to the mine site age. The concentrations of total and available heavy metals (Fe, Zn, Mn, Pb, and Cu) were significantly lower in the ant nest debris soil as compared to the reference soil. The results of the present study highlight the role of ants as bioindicators and in bioremediation of contaminated soil.

  1. Heavy metal contamination in soils and vegetables near an e-waste processing site, South China.

    Science.gov (United States)

    Luo, Chunling; Liu, Chuanping; Wang, Yan; Liu, Xiang; Li, Fangbai; Zhang, Gan; Li, Xiangdong

    2011-02-15

    Environmental pollution due to uncontrolled e-waste recycling activities has been reported in a number of locations of China. In the present study, metal pollution to the surrounding environment from a primitive e-waste processing facility was investigated. Soils at sites where e-waste is burned in the open air, those of surrounding paddy fields and vegetable gardens, as well as common vegetable samples were collected and analyzed for heavy metals. The results showed that the soils of former incineration sites had the highest concentrations of Cd, Cu, Pb, and Zn with mean values of 17.1, 11,140, 4500, and 3690 mg kg(-1), respectively. The soils of nearby paddy fields and vegetable gardens also had relatively high concentrations of Cd and Cu. In the edible tissues of vegetables, the concentrations of Cd and Pb in most samples exceeded the maximum level permitted for food in China. Sequential leaching tests revealed that the Cu, Pb, and Zn were predominantly associated with the residual fraction, followed by the carbonate/specifically adsorbed phases with the exception of Cd, which was mainly in the extractable form in paddy fields and vegetable soils. The data showed that uncontrolled e-waste processing operations caused serious pollution to local soils and vegetables. The cleaning up of former incineration sites should be a priority in any future remediation program. Copyright © 2010 Elsevier B.V. All rights reserved.

  2. Distribution and mobility of metals in contaminated sites. chemometric investigation of pollutant profiles.

    Science.gov (United States)

    Abollino, Ornella; Aceto, Maurizio; Malandrino, Mery; Mentasti, Edoardo; Sarzanini, Corrado; Barberis, Renzo

    2002-01-01

    The distribution and mobility of heavy metals in the soils of two contaminated sites in Piedmont (Italy) was investigated, evaluating the horizontal and vertical profiles of 15 metals, namely Al, Cd, Cu, Cr, Fe. La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr. The concentrations in the most polluted areas of the sites were higher than the acceptable limits reported in Italian and Dutch legislations for soil reclamation. Chemometric elaboration of the results by pattern recognition techniques allowed us to identify groups of samples with similar characteristics and to find correlations among the variables. The pollutant mobility was studied by extraction with water, dilute acetic acid and EDTA and by applying Tessier's procedure. The fraction of mobile species, which potentially is the most harmful for the environment, was found to be higher than the one normally present in unpolluted soils, where heavy metals are, to a higher extent, strongly bound to the matrix.

  3. Study of the levels of air pollution by heavy metals on an urban site of Algiers using neutron activation analysis (NAA)

    International Nuclear Information System (INIS)

    Khodja, Z.; Nedjar, A.; Azli, T.; Zergoug, Z.; Mouhouche, F.; Belamri, M.; Omari, L.; Lakhdar, C.C.

    2010-01-01

    Today, the high threshold reached by air pollution makes us become aware of the importance of the problem and the dangers which it represents for the health of the living beings and man in particular. The list of the atmospheric pollutants is long. To traditional usual but always real pollutants such as dust, SO 2 , Nox, CO, heavy metals, etc came to be added gradually to other substances such as gases for greenhouse effect: C0 2 , the CH 4 , the N 2 0, CFC, HFC, PFC and SF 6 and other substances such as ozone, the organochlorinated ones (dioxanes and furans), the HAP (Polycyclic Aromatic Hydrocarbons), etc. In Algeria, the lack of relative data to air quality makes that the impact of this form of pollution on the environment very badly known. The sources of pollution are numerous and the harmful effects are already perceived, but their direct relationship or indirect with the environmental pollution is not established. It is in this context and in continuity with work under development at the Nuclear Research Center of Algiers that we propose by this study the levels of air pollution by the fine particles and more particularly by heavy metals on the level of an urban site of Algiers with force directly exposed population density with the transmitting sources of pollution. We have used a nuclear method: neutron activation analysis technique (NAA), for the detection of traces of heavy metals in our samples of filters collected throughout one year at a rate of approximately a sample per week. One will note that this pollution varies considerably according to the components, in particular for Chromium (Cr), Iron (Fe), Mercury (Hg) and Cobalt (Co). The results were compared with other results obtained with other techniques and show a better sensitivity.

  4. Vapor-Phase Hydrodeoxygenation of Guaiacol to Aromatics over Pt/HBeta: Identification of the Role of Acid Sites and Metal Sites on the Reaction Pathway

    Energy Technology Data Exchange (ETDEWEB)

    Nie, Lei [Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 P.R. China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Peng, Bo [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999 Richland WA 99352 USA; Zhu, Xinli [Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 P.R. China

    2018-02-05

    Hydrodeoxygenation of guaiacol, a phenolic compound derived from lignin fraction of biomass, over a Pt/HBeta catalyst at 350 °C and atmospheric pressure produces benzene, toluene, xylenes, and C9+ aromatics with yield of 42%, 29%, 12%, and 5%, respectively. Reaction pathways for conversion of two functional groups (hydroxyl and methoxyl) over the bifunctional catalyst were studied. Both guaiacol and intermediate products (catechol and cyclopentanone) were fed onto zeolite HBeta and Pt/SiO2 to identify the individual role of acid site and metal site. Acid sites (mainly Brønsted acid site, BAS) catalyze transalkylation and dehydroxylation reactions in sequence, producing phenol, cresols and xylenols as the major products at high conversion. Pt sites catalyze demethylation reaction resulting in catechol as the primary product, which can either be deoxygenated to phenol followed by phenol to benzene, or decarbonylated to cyclopentanone and further to butane. The close proximity of Pt and BAS in bifunctional Pt/HBeta enables both transalkylation and deoxygenation reactions with inhibited demethylation and decarbonylation reactions, producing aromatics as major final products with a total yield > 85%. Both activity and stability of bifunctional Pt/HBeta during hydrodeoxygenation of guaiacol is improved compared to HBeta and Pt/SiO2. The addition of water to the feed further improves the activity and stability via hydrolysis of O-CH3 bond of guaiacol on BAS and removing coke around Pt.

  5. Iron Is the Active Site in Nickel/Iron Water Oxidation Electrocatalysts

    Directory of Open Access Journals (Sweden)

    Bryan M. Hunter

    2018-04-01

    Full Text Available Efficient catalysis of the oxygen-evolution half-reaction (OER is a pivotal requirement for the development of practical solar-driven water splitting devices. Heterogeneous OER electrocatalysts containing first-row transition metal oxides and hydroxides have attracted considerable recent interest, owing in part to the high abundance and low cost of starting materials. Among the best performing OER electrocatalysts are mixed Fe/Ni layered double hydroxides (LDH. A review of the available experimental data leads to the conclusion that iron is the active site for [NiFe]-LDH-catalyzed alkaline water oxidation.

  6. Strategy utilized for assessing baseline risks to human health from K-65 and metal oxide residues stored at the Fernald Site

    International Nuclear Information System (INIS)

    Harmon, J.E.; Janke, R.C.

    1995-01-01

    The U.S. Department of Energy (DOE) is responsible for cleanup activities at the Fernald Environmental Management Project (FEMP) site in southwestern Ohio. The 425-hectare site consists of a former 55-hectare Production Area, an adjacent Waste Storage Area and various support facilities. From 1952 until 1989, the FEMP processed uranium into metallic open-quotes feedclose quotes materials for other DOE facilities in the nation's defense program. In accordance with the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA), the FEMP site is currently listed on the National Priorities List (NPL). To facilitate an expeditious cleanup effort, environmental issues associated with site cleanup are being managed under five operable units. This paper summarizes the risk assessment strategy employed to determine baseline human health risks associated with K-65 and metal oxide residues currently stored in Operable Unit 4. The K-65 and metal oxide residues were generated during the 1950s as a result of the extraction of uranium from uranium-bearing ores and concentrates. These residues are currently stored within Operable Unit 4 in concrete silos. Silos I and 2 contain approximately 6,120 cubic meters [m 3 ] (8,005 cubic yards [yd 3 ]) of K-65 residues, while silos 3 contains approximately 3890 m 3 (5,080 yd 3 ) of cold metal oxides. These concrete silos are beyond their design life and require remedial action. The risk assessment conducted for Operable Unit 4 constitutes the first detailed human health risk assessment to be approved by the Environmental Protection Agency (EPA) for the CERCLA clean-up effort at the FEMP Site. This paper discusses the FEMP's use of a Risk Information Quality Objective process in concert with the traditional risk assessment approach to determine baseline risk to human health and the environment posed by Operable Unit 4. A summary of the baseline risks to human health is also presented

  7. Scoping evaluation of the technical capabilities of DOE sites for disposal of hazardous metals in mixed low-level waste

    International Nuclear Information System (INIS)

    Gruebel, M.M.; Waters, R.D.; Langkopf, B.S.

    1997-05-01

    A team of analysts designed and conducted a scoping evaluation to estimate the technical capabilities of fifteen Department of Energy sites for disposal of the hazardous metals in mixed low-level waste (i.e., waste that contains both low-level radioactive materials and hazardous constituents). Eight hazardous metals were evaluated: arsenic, barium, cadmium, chromium, lead, mercury, selenium, and silver. The analysis considered transport only through the groundwater pathway. The results are reported as site-specific estimates of maximum concentrations of each hazardous metal in treated mixed low-level waste that do not exceed the performance measures established for the analysis. Also reported are site-specific estimates of travel times of each hazardous metal to the point of compliance

  8. Active sites of ligand-protected Au25 nanoparticle catalysts for CO2 electroreduction to CO

    Science.gov (United States)

    Alfonso, Dominic R.; Kauffman, Douglas; Matranga, Christopher

    2016-05-01

    Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO2) into CO at atomically precise negatively charged Au25- nanoclusters. The studies showed CO2 conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO2 reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO2 reduction catalyst because formation of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO2 reduction at gold nanocluster catalysts.

  9. Correlation between heavy metal contents and antioxidant activities in medicinal plants grown in copper mining areas

    International Nuclear Information System (INIS)

    Maharia, R.S.; Dutta, R.K.; Acharya, R.; Reddy, A.V.R.

    2012-01-01

    Three commonly used medicinal plants, e.g., Adhatoda vasica, Cassia fistula, and Withania somnifera grown in two contrasting environmental conditions, namely from copper mining site and from control site corresponding to soil not contaminated with Cu, to understand correlations between high Cu bioaccumulation in medicinal plants on their antioxidant activities. Concentrations of some essential metals, e.g., Cr, Mn, Fe, Cu, Zn, and Se in the leaves of these plants were measured by instrumental neutron activation analysis. The Cu levels in the samples from mining site were in the range of 32.6 to 57.2 mg/kg, which were 5-7 folds higher than the control samples, while Cr levels were about 2-folds higher in the mining site. Speciation studies of Cr revealed negligible content of toxic hexavalent Cr. Antioxidant assay of these plants from both the sampling sites, measured as total phenolic content, total flavonoid content, 2,2'-diphenyl-1-picrylhydrazyl, free radical scavenging ability, and chelating ability with ferrous ions exhibited maximum activity for A. vasica, while that of W. somnifera was minimum. However, the variations in the antioxidant activities for each medicinal plant species from mining site and control site did not reveal significant differences. (author)

  10. Selective metal binding to Cys-78 within endonuclease V causes an inhibition of catalytic activities without altering nontarget and target DNA binding

    International Nuclear Information System (INIS)

    Prince, M.A.; Friedman, B.; Gruskin, E.A.; Schrock, R.D. III; Lloyd, R.S.

    1991-01-01

    T4 endonuclease V is a pyrimidine dimer-specific DNA repair enzyme which has been previously shown not to require metal ions for either of its two catalytic activities or its DNA binding function. However, we have investigated whether the single cysteine within the enzyme was able to bind metal salts and influence the various activities of this repair enzyme. A series of metals (Hg2+, Ag+, Cu+) were shown to inactivate both endonuclease Vs pyrimidine dimer-specific DNA glycosylase activity and the subsequent apurinic nicking activity. The binding of metal to endonuclease V did not interfere with nontarget DNA scanning or pyrimidine dimer-specific binding. The Cys-78 codon within the endonuclease V gene was changed by oligonucleotide site-directed mutagenesis to Thr-78 and Ser-78 in order to determine whether the native cysteine was directly involved in the enzyme's DNA catalytic activities and whether the cysteine was primarily responsible for the metal binding. The mutant enzymes were able to confer enhanced ultraviolet light (UV) resistance to DNA repair-deficient Escherichia coli at levels equal to that conferred by the wild type enzyme. The C78T mutant enzyme was purified to homogeneity and shown to be catalytically active on pyrimidine dimer-containing DNA. The catalytic activities of the C78T mutant enzyme were demonstrated to be unaffected by the addition of Hg2+ or Ag+ at concentrations 1000-fold greater than that required to inhibit the wild type enzyme. These data suggest that the cysteine is not required for enzyme activity but that the binding of certain metals to that amino acid block DNA incision by either preventing a conformational change in the enzyme after it has bound to a pyrimidine dimer or sterically interfering with the active site residue's accessibility to the pyrimidine dimer

  11. Site-selective electroless nickel plating on patterned thin films of macromolecular metal complexes.

    Science.gov (United States)

    Kimura, Mutsumi; Yamagiwa, Hiroki; Asakawa, Daisuke; Noguchi, Makoto; Kurashina, Tadashi; Fukawa, Tadashi; Shirai, Hirofusa

    2010-12-01

    We demonstrate a simple route to depositing nickel layer patterns using photocross-linked polymer thin films containing palladium catalysts, which can be used as adhesive interlayers for fabrication of nickel patterns on glass and plastic substrates. Electroless nickel patterns can be obtained in three steps: (i) the pattern formation of partially quaterized poly(vinyl pyridine) by UV irradiation, (ii) the formation of macromolecular metal complex with palladium, and (iii) the nickel metallization using electroless plating bath. Metallization is site-selective and allows for a high resolution. And the resulting nickel layered structure shows good adhesion with glass and plastic substrates. The direct patterning of metallic layers onto insulating substrates indicates a great potential for fabricating micro/nano devices.

  12. A New Neutron Multiplicity Counter for the Measurement of Impure Plutonium Metal at Westinghouse Savannah River Site

    International Nuclear Information System (INIS)

    Baker, L.B.; Faison, D.M.; Langner, D.G.; Sweet, M.R.; Salazar, S.D.; Kroncke, K.E.

    1998-07-01

    A new neutron multiplicity counter has been designed, fabricated, characterized, and installed for use in the assay of impure plutonium metal buttons from the FB-Line at the Westinghouse Savannah River Site (WSRS). This instrument incorporates the performance characteristics of the Pyrochemical or In-plant Multiplicity Counter with the package size of the Plutonium Scrap Multiplicity Counter. In addition, state-of-the art features such as the de-randomizer circuit and separate ring outputs have been added. The counter consists of 113, 71 cm active length 3He tubes in a polyethylene moderator. Its efficiency for 252Cf is 57.8 percent, the highest of any multiplicity counter to date. Its die-away time is 50.4 ms and its deadtime is 50 ns. In this paper we will present the characterization data for the counter and the results of preliminary metal measurements at WSRS. We will also discuss the new challenges the impure metal buttons from FB-Line are presenting to the multiplicity counting technique

  13. Heavy Metal Contamination in Urban Soils II Comparison of Urban Park Soils Between Two Cities with Different City and Industrial Activities

    OpenAIRE

    KOMAI, Yutaka

    1981-01-01

    A comparative investigation on the state of heavy metal contamination in park soils of two cities with different city and industrial activities was carried out. Sakai and Kishiwada, both situated in southern Osaka Prefecture, were chosen as the investigated cities which had similar natural conditions but different human activities. Park soils were regarded as suitable sites for the investigation of heavy metal problem in urban environments. Samples were taken at 34 parks distributed widely in...

  14. Classifying the metal dependence of uncharacterized nitrogenases

    Directory of Open Access Journals (Sweden)

    Shawn E Mcglynn

    2013-01-01

    Full Text Available Nitrogenase enzymes have evolved complex iron-sulfur (Fe-S containing cofactors that most commonly contain molybdenum (MoFe, Nif as a heterometal but also exist as vanadium (VFe, Vnf and heterometal independent (Fe-only, Anf forms. All three varieties are capable of the reduction of dinitrogen (N2 to ammonia (NH3 but exhibit differences in catalytic rates and substrate specificity unique to metal type. Recently, N2 reduction activity was observed in archaeal methanotrophs and methanogens that encode for nitrogenase homologs which do not cluster phylogenetically with previously characterized nitrogenases. To gain insight into the metal cofactors of these uncharacterized nitrogenase homologs, predicted three-dimensional structures of the nitrogenase active site metal-cofactor binding subunits NifD, VnfD, and AnfD were generated and compared. Dendograms based on structural similarity indicate nitrogenase homologs cluster based on heterometal content and that uncharacterized nitrogenase D homologs cluster with NifD, providing evidence that the structure of the enzyme has evolved in response to metal utilization. Characterization of the structural environment of the nitrogenase active site revealed amino acid variations that are unique to each class of nitrogenase as defined by heterometal cofactor content; uncharacterized nitrogenases contain amino acids near the active site most similar to NifD. Together, these results suggest that uncharacterized nitrogenase homologs present in numerous anaerobic methanogens, archaeal methanotrophs, and firmicutes bind FeMo-co in their active site, and add to growing evidence that diversification of metal utilization likely occurred in an anaerobic habitat.

  15. Health risk assessments of heavy metal exposure via consumption of marine mussels collected from anthropogenic sites

    International Nuclear Information System (INIS)

    Yap, Chee Kong; Cheng, Wan Hee; Karami, Ali; Ismail, Ahmad

    2016-01-01

    A total of 40 marine mussel Perna viridis populations collected (2002–2009) from 20 geographical sites located in two busy shipping lanes namely the Straits of Malacca (10 sites; 16 populations) and the Straits of Johore (8 sites; 21 populations) and three populations (2 sites) on the east coast of Peninsular Malaysia, was determined for Cd, Cu, Fe, Ni, Pb and Zn concentrations. In comparison with the maximum permissible limits (MPLs) set by existing food safety guidelines, all metal concentrations found in all the mussel populations were lower than the prescribed MPLs. In terms of the provisional tolerable weekly intake prescribed by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) and oral reference doses (ORDs) by the USEPA, all the studied metals (except for Pb) were unlikely to become the limiting factors or unlikely to pose a risk for the consumption of the mussel populations. The estimated daily intake (EDI) for average level mussel (ALM) and high level mussel (HLM) consumers of mussels was found to be lower than the ORD guidelines for Cd, Cu, Fe, Ni and Zn. Furthermore, the target hazard quotient (THQ) was found to be less than 1 for ALM consumers but higher than 1 for HLM consumers in some sites. Therefore, there were no potential human health risks to the ALM consumers of the mussels. However, for Pb THQ values, the Pb levels in some mussel populations could create a health risk problem. Present results indicate that the consumption amounts of mussels should be limited for minimizing potential health risks of heavy metals to the HLM consumers. - Highlights: • Human health risk assessments of heavy metals in Perna viridis were investigated. • All metals in the mussels were below the established seafood safety guidelines. • Pb in mussels could easily reach the percentage of prescribed PTWI value of Pb. • Potential health risk with Pb exposure was found for the mussel consumers. • Consumption rate of mussels should be limited to

  16. Health risk assessments of heavy metal exposure via consumption of marine mussels collected from anthropogenic sites

    Energy Technology Data Exchange (ETDEWEB)

    Yap, Chee Kong, E-mail: yapckong@hotmail.com [Department of Biology, Faculty of Science, Universiti Putra Malaysia (UPM), 43400 Serdang, Selangor (Malaysia); Cheng, Wan Hee [Inti International University, Persiaran Perdana BBN, 71800 Nilai, Negeri Sembilan (Malaysia); Karami, Ali [Laboratory of Aquatic Toxicology, Faculty of Medicine and Health Sciences, Universiti Putra Malaysia (UPM), 43400 Serdang, Selangor (Malaysia); Ismail, Ahmad [Department of Biology, Faculty of Science, Universiti Putra Malaysia (UPM), 43400 Serdang, Selangor (Malaysia)

    2016-05-15

    A total of 40 marine mussel Perna viridis populations collected (2002–2009) from 20 geographical sites located in two busy shipping lanes namely the Straits of Malacca (10 sites; 16 populations) and the Straits of Johore (8 sites; 21 populations) and three populations (2 sites) on the east coast of Peninsular Malaysia, was determined for Cd, Cu, Fe, Ni, Pb and Zn concentrations. In comparison with the maximum permissible limits (MPLs) set by existing food safety guidelines, all metal concentrations found in all the mussel populations were lower than the prescribed MPLs. In terms of the provisional tolerable weekly intake prescribed by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) and oral reference doses (ORDs) by the USEPA, all the studied metals (except for Pb) were unlikely to become the limiting factors or unlikely to pose a risk for the consumption of the mussel populations. The estimated daily intake (EDI) for average level mussel (ALM) and high level mussel (HLM) consumers of mussels was found to be lower than the ORD guidelines for Cd, Cu, Fe, Ni and Zn. Furthermore, the target hazard quotient (THQ) was found to be less than 1 for ALM consumers but higher than 1 for HLM consumers in some sites. Therefore, there were no potential human health risks to the ALM consumers of the mussels. However, for Pb THQ values, the Pb levels in some mussel populations could create a health risk problem. Present results indicate that the consumption amounts of mussels should be limited for minimizing potential health risks of heavy metals to the HLM consumers. - Highlights: • Human health risk assessments of heavy metals in Perna viridis were investigated. • All metals in the mussels were below the established seafood safety guidelines. • Pb in mussels could easily reach the percentage of prescribed PTWI value of Pb. • Potential health risk with Pb exposure was found for the mussel consumers. • Consumption rate of mussels should be limited to

  17. Soil heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    Sherameti, Irena [Jena Univ. (Germany). Inst. fuer Allgemeine Botanik und Pflanzenphysiologie; Varma, Ajit (eds.) [Amity Univ., Uttar Pradesh (India). Amity Inst. of Microbial Technology; Amity Science, Technology and Innovation Foundation, Noida, UP (India)

    2010-07-01

    Human activities have dramatically changed the composition and organisation of soils. Industrial and urban wastes, agricultural application and also mining activities resulted in an increased concentration of heavy metals in soils. How plants and soil microorganisms cope with this situation and the sophisticated techniques developed for survival in contaminated soils is discussed in this volume. The topics presented include: the general role of heavy metals in biological soil systems; the relation of inorganic and organic pollutions; heavy metal, salt tolerance and combined effects with salinity; effects on abuscular mycorrhizal and on saprophytic soil fungi; heavy metal resistance by streptomycetes; trace element determination of environmental samples; the use of microbiological communities as indicators; phytostabilization of lead polluted sites by native plants; effects of soil earthworms on removal of heavy metals and the remediation of heavy metal contaminated tropical land. (orig.)

  18. Geochemical and mineralogical study of a site severely polluted with heavy metals (Maatheide, Lommel, Belgium)

    Science.gov (United States)

    Horckmans, L.; Swennen, R.; Deckers, J.

    2006-07-01

    The former zinc smelter site ‘de Maatheide’ in Lommel (Belgium) was severely polluted with heavy metals and the pollution spread into the surroundings by rain water leaching and wind transportation. This study focuses on the processes of immobilization and natural attenuation that took place on the site. Three important factors were found. Firstly, the high pH values (pH 7-8) in the topsoil influence the mobility of heavy metals. Secondly, the spodic horizons below the polluted top layer seem to accumulate heavy metals, thereby slowing down their release into the environment. Finally, the glassy phases and iron oxi/hydroxides that are present can encapsulate heavy metals during their formation/recrystallization, thereby immobilizing them. An additional shielding effect results from the reaction rims of goethite around the contaminant phases, which partially inhibit the weathering process and release of contaminants. This shielding effect is an important factor to take into account when modelling contaminant release.

  19. Effect of heavy metals on soil enzyme activity at different field conditions in Middle Spis mining area (Slovakia).

    Science.gov (United States)

    Angelovičová, Lenka; Lodenius, Martin; Tulisalo, Esa; Fazekašová, Danica

    2014-12-01

    Heavy metals concentrations were measured in the former mining area located in Hornad river valley (Slovakia). Soil samples were taken in 2012 from 20 sites at two field types (grasslands, heaps of waste material) and two different areas. Total content of heavy metals (Cu, Pb, Zn, Hg), urease (URE), acid phosphatase (ACP), alkaline phosphatase (ALP), soil reaction (pH) were changing depending on the field/area type. The tailing pond and processing plants have been found as the biggest sources of pollution. URE, ACP and ALP activities significantly decreased while the heavy metal contents increased. Significant differences were found among area types in the heavy metal contents and activity of URE. No statistical differences in the content of heavy metals but significant statistical differences for soil pH were found for field types (grassland and heaps). Significant negative correlation was found for URE-Pb, URE-Zn and also between soil reaction and ACP and ALP.

  20. The Relative Influence of Metal Ion Binding Sites in the I-like Domain and the Interface with the Hybrid Domain on Rolling and Firm Adhesion by Integrin α4β7*

    Science.gov (United States)

    Chen, JianFeng; Takagi, Junichi; Xie, Can; Xiao, Tsan; Luo, Bing-Hao; Springer, Timothy A.

    2015-01-01

    We examined the effect of conformational change at the β7 I-like/hybrid domain interface on regulating the transition between rolling and firm adhesion by integrin α4β7. An N-glycosylation site was introduced into the I-like/hybrid domain interface to act as a wedge and to stabilize the open conformation of this interface and hence the open conformation of the α4β7 headpiece. Wild-type α4β7 mediates rolling adhesion in Ca2+ and Ca2+/Mg2+ but firm adhesion in Mg2+ and Mn2+. Stabilizing the open headpiece resulted in firm adhesion in all divalent cations. The interaction between metal binding sites in the I-like domain and the interface with the hybrid domain was examined in double mutants. Changes at these two sites can either counterbalance one another or be additive, emphasizing mutuality and the importance of multiple interfaces in integrin regulation. A double mutant with counterbalancing deactivating ligand-induced metal ion binding site (LIMBS) and activating wedge mutations could still be activated by Mn2+, confirming the importance of the adjacent to metal ion-dependent adhesion site (ADMIDAS) in integrin activation by Mn2+. Overall, the results demonstrate the importance of headpiece allostery in the conversion of rolling to firm adhesion. PMID:15448154

  1. Relationships between waste physicochemical properties, microbial activity and vegetation at coal ash and sludge disposal sites.

    Science.gov (United States)

    Woch, Marcin W; Radwańska, Magdalena; Stanek, Małgorzata; Łopata, Barbara; Stefanowicz, Anna M

    2018-06-11

    The aim of the study was to assess the relationships between vegetation, physicochemical and microbial properties of substrate at coal ash and sludge disposal sites. The study was performed on 32 plots classified into 7 categories: dried ash sedimentation ponds, dominated by a grass Calamagrostis epigejos (AH-Ce), with the admixture of Pinus sylvestris (AH-CePs) or Robinia pseudoacacia (AH-CeRp), dry ash landfill dominated by Betula pendula and Pinus sylvestris (AD-BpPs) or Salix viminalis (AD-Sv) and coal sludge pond with drier parts dominated by Tussilago farfara (CS-Tf) and the wetter ones by Cyperus flavescens (CS-Cf). Ash sites were covered with soil layer imported as a part of technical reclamation. Ash had relatively high concentrations of some alkali and alkaline earth metals, Mn and pH, while coal sludge had high water and C, S, P and K contents. Concentrations of heavy metals were lower than allowable limits in all substrate types. Microbial biomass and, particularly, enzymatic activity in ash and sludge were generally low. The only exception were CS-Tf plots characterized by the highest microbial biomass, presumably due to large deposits of organic matter that became available for aerobic microbial biomass when water level fell. The properties of ash and sludge adversely affected microbial biomass and enzymatic activity as indicated by significant negative correlations between the content of alkali/alkaline earth metals, heavy metals, and macronutrients with enzymatic activity and/or microbial biomass, as well as positive correlations of these parameters with metabolic quotient (qCO 2 ). Plant species richness and cover were relatively high, which may be partly associated with alleviating influence of soil covering the ash. The effect of the admixture of R. pseudoacacia or P. sylvestris to stands dominated by C. epigejos was smaller than expected. The former species increased NNH 4 , NNO 3 and arylsulfatase activity, while the latter reduced activity of

  2. Ultralow contact resistance at an epitaxial metal/oxide heterojunction through interstitial site doping.

    Science.gov (United States)

    Chambers, Scott A; Gu, Meng; Sushko, Peter V; Yang, Hao; Wang, Chongmin; Browning, Nigel D

    2013-08-07

    Heteroepitaxial growth of Cr metal on Nb-doped SrTiO₃(001) is accompanied by Cr diffusion to interstitial sites within the first few atomic planes, an anchoring of the Cr film to the substrate, charge transfer from Cr to Ti, and metallization of the near-surface region, as depicted in the figure. The contact resistance of the resulting interface is exceedingly low. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The Distribution and Health Risk Assessment of Metals in Soils in the Vicinity of Industrial Sites in Dongguan, China

    Directory of Open Access Journals (Sweden)

    Chao Liu

    2016-08-01

    Full Text Available Exponential industrialization and rapid urbanization have resulted in contamination of soil by metals from anthropogenic sources in Dongguan, China. The aims of this research were to determine the concentration and distribution of various metals (arsenic (As, cadmium (Cd, chromium (Cr, copper (Cu, mercury (Hg, nickel (Ni, lead (Pb and zinc (Zn in soils and identify their potential health risks for local residents. A total of 106 soil samples were collected from the vicinity of industrial sites in Dongguan. Two types of samples were collected from each site: topsoil (0–20 cm, TS and shallow soil (20–50 cm, SS. Results showed that the soils were contaminated by metals and pollution was mainly focused on TS. The geoaccumulation index (Igeo and pollution indexes (PI implied that there was a slight increase in the concentrations of Cd, Cu, Hg, Ni, and Pb, but the metal pollution caused by industrial activities was less severe, and elements of As and Cr exhibited non-pollution level. The risk assessment results suggested that there was a potential health risk associated with As and Cr exposure for residents because the carcinogenic risks of As and Cr via corresponding exposure pathways exceeded the safety limit of 10−6 (the acceptable level of carcinogenic risk for humans. Furthermore, oral ingestion and inhalation of soil particles are the main exposure pathways for As and Cr to enter the human body. This study may provide basic information of metal pollution control and human health protection in the vicinity of industrial regions.

  4. The dapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase from Haemophilus influenzae contains two active-site histidine residues.

    Science.gov (United States)

    Gillner, Danuta M; Bienvenue, David L; Nocek, Boguslaw P; Joachimiak, Andrzej; Zachary, Vincentos; Bennett, Brian; Holz, Richard C

    2009-01-01

    The catalytic and structural properties of the H67A and H349A dapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase (DapE) from Haemophilus influenzae were investigated. On the basis of sequence alignment with the carboxypeptidase from Pseudomonas sp. strain RS-16, both H67 and H349 were predicted to be Zn(II) ligands. The H67A DapE enzyme exhibited a decreased catalytic efficiency (180-fold) compared with wild-type (WT) DapE towards N-succinyldiaminopimelic acid. No catalytic activity was observed for H349A under the experimental conditions used. The electronic paramagnetic resonance (EPR) and electronic absorption data indicate that the Co(II) ion bound to H349A-DapE is analogous to that of WT DapE after the addition of a single Co(II) ion. The addition of 1 equiv of Co(II) to H67A DapE provides spectra that are very different from those of the first Co(II) binding site of the WT enzyme, but that are similar to those of the second binding site. The EPR and electronic absorption data, in conjunction with the kinetic data, are consistent with the assignment of H67 and H349 as active-site metal ligands for the DapE from H. influenzae. Furthermore, the data suggest that H67 is a ligand in the first metal binding site, while H349 resides in the second metal binding site. A three-dimensional homology structure of the DapE from H. influenzae was generated using the X-ray crystal structure of the DapE from Neisseria meningitidis as a template and superimposed on the structure of the aminopeptidase from Aeromonas proteolytica (AAP). This homology structure confirms the assignment of H67 and H349 as active-site ligands. The superimposition of the homology model of DapE with the dizinc(II) structure of AAP indicates that within 4.0 A of the Zn(II) binding sites of AAP all of the amino acid residues of DapE are nearly identical.

  5. Metal-organic frameworks: structure, properties, methods of synthesis and characterization

    International Nuclear Information System (INIS)

    Butova, V V; Soldatov, M A; Guda, A A; Lomachenko, K A; Lamberti, C

    2016-01-01

    This review deals with key methods of synthesis and characterization of metal-organic frameworks (MOFs). The modular structure affords a wide variety of MOFs with different active metal sites and organic linkers. These compounds represent a new stage of development of porous materials in which the pore size and the active site structure can be modified within wide limits. The set of experimental methods considered in this review is sufficient for studying the short-range and long-range order of the MOF crystal structure, determining the morphology of samples and elucidating the processes that occur at the active metal site in the course of chemical reactions. The interest in metal-organic frameworks results, first of all, from their numerous possible applications, ranging from gas separation and storage to chemical reactions within the pores. The bibliography includes 362 references

  6. SITE demonstration of the Dynaphore/Forager Sponge technology to remove dissolved metals from contaminated groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Esposito, C.R. [Environmental Protection Agency, Edison, NJ (United States); Vaccaro, G. [Science Applications International Corp., Hackensack, NJ (United States)

    1995-10-01

    A Superfund Innovative Technology Evaluation (SITE) demonstration was conducted of the Dynaphore/Forager Sponge technology during the week of April 3, 1994 at the N.L. Industries Superfund Site in Pedricktown, New Jersey. The Forager Sponge is an open-celled cellulose sponge incorporating an amine-containing chelating polymer that selectively absorbs dissolved heavy metals in both cationic and anionic states. This technology is a volume reduction technology in which heavy metal contaminants from an aqueous medium are concentrated into a smaller volume for facilitated disposal. The developer states that the technology can be used to remove heavy metals from a wide variety of aqueous media, such as groundwater, surface waters and process waters. The sponge matrix can be directly disposed, or regenerated with chemical solutions. For this demonstration the sponge was set up as a mobile pump-and-treat system which treated groundwater contaminated with heavy metals. The demonstration focused on the system`s ability to remove lead, cadmium, chromium and copper from the contaminated groundwater over a continuous 72-hour test. The removal of heavy metals proceeded in the presence of significantly higher concentrations of innocuous cations such as calcium, magnesium, sodium, potassium and aluminum.

  7. Heavy Metal Contamination of Soils around a Hospital Waste Incinerator Bottom Ash Dumps Site.

    Science.gov (United States)

    Adama, M; Esena, R; Fosu-Mensah, B; Yirenya-Tawiah, D

    2016-01-01

    Waste incineration is the main waste management strategy used in treating hospital waste in many developing countries. However, the release of dioxins, POPs, and heavy metals in fly and bottom ash poses environmental and public health concerns. To determine heavy metal (Hg, Pb, Cd, Cr, and Ag) in levels in incinerator bottom ash and soils 100 m around the incinerator bottom ash dump site, ash samples and surrounding soil samples were collected at 20 m, 40 m, 60 m, 80 m, 100 m, and 1,200 m from incinerator. These were analyzed using the absorption spectrophotometer method. The geoaccumulation (I geo) and pollution load indices (PLI) were used to assess the level of heavy metal contamination of surrounding soils. The study revealed high concentrations in mg/kg for, Zn (16417.69), Pb (143.80), Cr (99.30), and Cd (7.54) in bottom ash and these were above allowable limits for disposal in landfill. The study also found soils within 60 m radius of the incinerator to be polluted with the metals. It is recommended that health care waste managers be educated on the implication of improper management of incinerator bottom ash and regulators monitor hospital waste incinerator sites.

  8. Activation and discharge kinetics of metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, Stein Egil

    2003-07-01

    Potential step chronoamperometry and Electrochemical Impedance Spectroscopy (eis) measurements were performed on single metal hydride particles. For the {alpha}-phase, the bulk diffusion coefficient and the absorption/adsorption rate parameters were determined. Materials produced by atomisation, melt spinning and conventional casting were investigated. The melt spun and conventional cast materials were identical and the atomised material similar in composition. The particles from the cast and the melt spun material were shaped like parallelepipeds. A corresponding equation, for this geometry, for diffusion coupled to an absorption/adsorption reaction was developed. It was found that materials produced by melt spinning exhibited lower bulk diffusion (1.7E-14 m2/s) and absorption/adsorption reaction rate (1.0E-8 m/s), compared to materials produced by conventionally casting (1.1E-13 m2/s and 5.5E-8 m/s respectively). In addition, the influence of particle active surface and relative diffusion length were discussed. It was concluded that there are uncertainties connected to these properties, which may explain the large distribution in the kinetic parameters measured on metal hydride particles. Activation of metal hydride forming materials has been studied and an activation procedure, for porous electrodes, was investigated. Cathodic polarisation of the electrode during a hot alkaline surface treatment gave the maximum discharge capacity on the first discharge of the electrode. The studied materials were produced by gas atomisation and the spherical shape was retained during the activation. Both an AB{sub 5} and an AB{sub 2} alloy was successfully activated and discharge rate properties determined. The AB{sub 2} material showed a higher maximum discharge capacity, but poor rate properties, compared to the AB{sub 5} material. Reduction of surface oxides, and at the same time protection against corrosion of active metallic nickel, can explain the satisfying results of

  9. Fungitoxicity of metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Somers, E

    1961-01-01

    The in vitro fungistatic activity of some twenty-four metal cations has been determine against Alternaria tenuis and Botrytis fabae. The metal salts, mainly nitrates, were tested in aqueous solution without added spore germination stimulant. The logarithm of the metal ion concentration at the ED 50 value has been found to conform to the exponenttial relationship with electronegativity proposed by Danielli and Davies (1951). These results are discussed in relation to the site of action of metal cations on the fungal cell.

  10. Spatial distribution of heavy metal contamination in soils near a primitive e-waste recycling site.

    Science.gov (United States)

    Quan, Sheng-Xiang; Yan, Bo; Yang, Fan; Li, Ning; Xiao, Xian-Ming; Fu, Jia-Mo

    2015-01-01

    The total concentrations of 12 heavy metals in surface soils (SS, 0-20 cm), middle soils (MS, 30-50 cm) and deep soils (DS, 60-80 cm) from an acid-leaching area, a deserted paddy field and a deserted area of Guiyu were measured. The results showed that the acid-leaching area was heavily contaminated with heavy metals, especially in SS. The mean concentrations of Ni, Cu, Zn, Cd, Sn, Sb and Pb in SS from the acid-leaching area were 278.4, 684.1, 572.8, 1.36, 3,472, 1,706 and 222.8 mg/kg, respectively. Heavy metal pollution in the deserted paddy field was mainly concentrated in SS and MS. The average values of Sb in SS and MS from the deserted paddy field were 16.3 and 20.2 mg/kg, respectively. However, heavy metal contamination of the deserted area was principally found in the DS. Extremely high concentrations of heavy metals were also observed at some special research sites, further confirming that the level of heavy metal pollution was very serious. The geoaccumulation index (Igeo) values revealed that the acid-leaching area was severely polluted with heavy metals in the order of Sb > Sn > Cu > Cd > Ni > Zn > Pb, while deserted paddy field was contaminated predominately by metals in the order of Sb > Sn > Cu. It was obvious that the concentrations of some uncommon contaminants, such as Sb and Sn, were higher than principal contaminants, such as Ni, Cu, Zn and Pb, suggesting that particular attention should be directed to Sn and Sb contamination in the future research of heavy metals in soils from e-waste-processing areas. Correlation analysis suggested that Li and Be in soils from the acid-leaching area and its surrounding environment might have originated from other industrial activities and from batteries, whereas Ni, Cu, Zn, Cd, Pb, Sn and Sb contamination was most likely caused by uncontrolled electronic waste (e-waste) processing. These results indicate the significant need for optimisation of e-waste-dismantling technologies and remediation of polluted soil

  11. INTEGRAL FIELD SPECTROSCOPY OF SUPERNOVA EXPLOSION SITES: CONSTRAINING THE MASS AND METALLICITY OF THE PROGENITORS. I. TYPE Ib AND Ic SUPERNOVAE

    Energy Technology Data Exchange (ETDEWEB)

    Kuncarayakti, Hanindyo; Maeda, Keiichi [Kavli Institute for the Physics and Mathematics of the Universe (WPI), Todai Institutes for Advanced Study, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8583 (Japan); Doi, Mamoru; Morokuma, Tomoki; Hashiba, Yasuhito [Institute of Astronomy, Graduate School of Science, The University of Tokyo, 2-21-1 Osawa, Mitaka, Tokyo 181-0015 (Japan); Aldering, Greg [Physics Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States); Arimoto, Nobuo [National Astronomical Observatory of Japan, 2-21-1 Osawa, Mitaka, Tokyo 181-0015 (Japan); Pereira, Rui [CNRS/IN2P3, Institut de Physique Nucleaire de Lyon, 4 Rue Enrico Fermi, F-69622 Villeurbanne Cedex (France); Usuda, Tomonori, E-mail: hanindyo.kuncarayakti@ipmu.jp [Subaru Telescope, National Astronomical Observatory of Japan, 650 North A' ohoku Place, Hilo, HI 96720 (United States)

    2013-08-01

    Integral field spectroscopy of 11 Type Ib/Ic supernova (SN Ib/Ic) explosion sites in nearby galaxies has been obtained using UH88/SNIFS and Gemini-N/GMOS. The use of integral field spectroscopy enables us to obtain both spatial and spectral information about the explosion site, enabling the identification of the parent stellar population of the SN progenitor star. The spectrum of the parent population provides metallicity determination via strong-line method and age estimation obtained via comparison with simple stellar population models. We adopt this information as the metallicity and age of the SN progenitor, under the assumption that it was coeval with the parent stellar population. The age of the star corresponds to its lifetime, which in turn gives the estimate of its initial mass. With this method we were able to determine both the metallicity and initial (zero-age main sequence) mass of the progenitor stars of SNe Ib and Ic. We found that on average SN Ic explosion sites are more metal-rich and younger than SN Ib sites. The initial mass of the progenitors derived from parent stellar population age suggests that SN Ic has more massive progenitors than SN Ib. In addition, we also found indication that some of our SN progenitors are less massive than {approx}25 M{sub Sun }, indicating that they may have been stars in a close binary system that have lost their outer envelope via binary interactions to produce SNe Ib/Ic, instead of single Wolf-Rayet stars. These findings support the current suggestions that both binary and single progenitor channels are in effect in producing SNe Ib/Ic. This work also demonstrates the power of integral field spectroscopy in investigating SN environments and active star-forming regions.

  12. Metal ion interaction of an oligopeptide fragment representing the regulatory metal binding site of a CueR protein

    DEFF Research Database (Denmark)

    Jancsó, Attila; Szokolai, Hajnalka; Roszahegyi, Livia

    2013-01-01

    Metalloregulatory proteins of the MerR family are transcriptional activators that sense/control the concentration of various metal ions inside bacteria.1 The Cu+ efflux regulator CueR, similarly to other MerR proteins, possesses a short multiple Cys-containing metal binding loop close to the C...... of cognate metal ions.2 Nevertheless, it is an interesting question whether the same sequence, when removed from the protein, shows a flexibility to adopt different coordination environments and may efficiently bind metal ions having preferences for larger coordination numbers....

  13. Spectroscopic characterization of metal complexes of novel Schiff base. Synthesis, thermal and biological activity studies

    Science.gov (United States)

    Omar, M. M.; Mohamed, Gehad G.; Ibrahim, Amr A.

    2009-07-01

    Novel Schiff base (HL) ligand is prepared via condensation of 4-aminoantipyrine and 2-aminobenzoic acid. The ligand is characterized based on elemental analysis, mass, IR and 1H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA, DrTGA and DTA). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a uninegatively tridentate manner with NNO donor sites of the azomethine N, amino N and deprotonated caroxylic-O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia Coli, Pseudomonas aeruginosa, Staphylococcus Pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Shciff base ligand against one or more bacterial species.

  14. Phytoremediation of heavy metal polluted sites

    International Nuclear Information System (INIS)

    Aery, N.C.; Panchal, Jayesh

    2007-01-01

    The nature of soil, the contaminant's chemical and physical characteristics and environmental factors such as climate and hydrology interact to determine the accumulation, mobility, toxicity, and overall significance of the contaminant in any specific instance. Although many metals are essential, all metals are toxic at higher concentrations, because they cause oxidative stress by formation of free radicals. Another reason why metals may be toxic is that they can replace essential metals in enzymes disrupting their function. Thus, metals render the land unsuitable for plant growth and destroy the biodiversity. Metal contaminated soil can be remediated by chemical, physical and biological techniques

  15. Step sites in syngas catalysis

    DEFF Research Database (Denmark)

    Rostrup-Nielsen, J.; Nørskov, Jens Kehlet

    2006-01-01

    Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative explanat......Step sites play an important role in many catalytic reactions. This paper reviews recent results on metal catalysts for syngas reactions with emphasis on steam reforming. Modern characterization techniques (STEM, HREM...) and theoretical calculations (DFT) has allowed a more quantitative...... explanation of the impact of step sites on catalyst activity and side reactions such as carbon formation. This leads to a discussion of principles for catalyst promotion....

  16. Progress report on decommissioning activities at the Fernald Environmental Management Project (FEMP) site

    International Nuclear Information System (INIS)

    1998-01-01

    The Fernald Environmental Management Project (FEMP), is located about 18 miles northwest of Cincinnati, Ohio. Between 1953 and 1989, the facility, then called the Feed Material Production Center or FMPC, produced uranium metal products used in the eventual production of weapons grade material for use by other US Department of Energy (DOE) sites. In 1989, FMPC's production was suspended by the federal government in order to focus resources on environmental restoration versus defense production. In 1992, Fluor Daniel Fernald assumed responsibility for managing all cleanup activities at the FEMP under contract to the DOE. In 1990, as part of the remediation effort, the site was divided into five operable units based on physical proximity of contaminated areas, similar amounts of types of contamination, or the potential for a similar technology to be used in cleanup activities. This report continues the outline of the decontamination and decommissioning (D and D) activities at the FEMP site Operable Unit 3 (OU3) and provides an update on the status of the decommissioning activities. OU3, the Facilities Closure and Demolition Project, involves the remediation of more than 200 uranium processing facilities. The mission of the project is to remove nuclear materials stored in these buildings, then perform the clean out of the buildings and equipment, and decontaminate and dismantle the facilities

  17. Strategy utilized for assessing baseline risks to human health from K-65 and metal oxide residues stored at the Fernald Site

    Energy Technology Data Exchange (ETDEWEB)

    Harmon, J.E. [FERMCO, Cincinnati, OH (United States). Fernald Environmental Management Project; Janke, R.C.

    1995-04-01

    The U.S. Department of Energy (DOE) is responsible for cleanup activities at the Fernald Environmental Management Project (FEMP) site in southwestern Ohio. The 425-hectare site consists of a former 55-hectare Production Area, an adjacent Waste Storage Area and various support facilities. From 1952 until 1989, the FEMP processed uranium into metallic {open_quotes}feed{close_quotes} materials for other DOE facilities in the nation`s defense program. In accordance with the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA), the FEMP site is currently listed on the National Priorities List (NPL). To facilitate an expeditious cleanup effort, environmental issues associated with site cleanup are being managed under five operable units. This paper summarizes the risk assessment strategy employed to determine baseline human health risks associated with K-65 and metal oxide residues currently stored in Operable Unit 4. The K-65 and metal oxide residues were generated during the 1950s as a result of the extraction of uranium from uranium-bearing ores and concentrates. These residues are currently stored within Operable Unit 4 in concrete silos. Silos I and 2 contain approximately 6,120 cubic meters [m{sup 3}] (8,005 cubic yards [yd{sup 3}]) of K-65 residues, while silos 3 contains approximately 3890 m{sup 3} (5,080 yd{sup 3}) of cold metal oxides. These concrete silos are beyond their design life and require remedial action. The risk assessment conducted for Operable Unit 4 constitutes the first detailed human health risk assessment to be approved by the Environmental Protection Agency (EPA) for the CERCLA clean-up effort at the FEMP Site. This paper discusses the FEMP`s use of a Risk Information Quality Objective process in concert with the traditional risk assessment approach to determine baseline risk to human health and the environment posed by Operable Unit 4. A summary of the baseline risks to human health is also presented.

  18. Model synthetic complexes of the hydrogenase with different protonation sites; Complexes synthetiques modeles de l'hydrogenase avec differents sites de protonation

    Energy Technology Data Exchange (ETDEWEB)

    Capon, J.F.; Gloaguen, F.; Morvan, D.; Schollhammer, Ph.; Talarmin, J.; Yaouanc, J.J. [Universite de Bretagne Occidentale, UMR CNRS 6521, Chimie, Electrochimie Moleculaires et Chimie Analytique, Faculte des Sciences, 29 - Brest (France)

    2005-07-01

    The data obtained until now seem to indicate that the hydrogen production by hydrogenases induces a proton-hydride coupling. In taking the structures of theses enzymes active sites (determined by X-ray diffraction) as a basis, it can be thought that this proton-hydride coupling is facilitated by the juxtaposition of two protonation sites, the metallic center M and the basic group of an E ligand of the coordination sphere. Contrarily to the supposed running of the hydrogenases enzymes, the homogeneous catalysts of the protons reduction, described in the literature, present a reactivity which is either on an alone metallic site or on a metal-metal bond. This work deals then with the preparation of complexes having two juxtaposed protonation sites. Some iron dinuclear compounds have been synthesized and their properties studied. (O.M.)

  19. Heavy metals contamination of air and soil in Karak solid waste disposal site, Jordan

    International Nuclear Information System (INIS)

    Jiries, A. G.; Jaradat, Q. M.; Momani, K. A.

    1996-01-01

    The level of air and soil pollution in the municipal solid waste disposal site of Karak(Jordan) were investigated during spring of 1995 by monitoring the amounts of heavy metals. The concentration (mg/kg)of Cu, Pb, and Zn in the upper soil were found to have a range of 15.3-39.3, 21.2-38.0 and 60.0-127.0 respectively. However, for the lower soil, the ranges are 13.4-18.9, 18.5-23.7, and 50.6-90.4, respectively. The soil contamination with heavy metals was almost confined to the upper soil in the locations closely surrounding the burning site, which could be accounted to the arid climate conditions of the area. (authors). 20 refs., 3 tabs., 5 figs

  20. Experiments with activated metal foils

    Energy Technology Data Exchange (ETDEWEB)

    Malati, M A [Medway and Maidstone Coll. of Tech., Chatham (UK)

    1978-09-01

    Experiments based on the activation of metal foils by slow neutron bombardment which can be used to demonstrate various aspects of artificial radioactivity are described and discussed. Suitable neutron sources and foils are considered.

  1. Assessment of a mussel as a metal bioindicator of coastal contamination: Relationships between metal bioaccumulation and multiple biomarker responses

    International Nuclear Information System (INIS)

    Chandurvelan, Rathishri; Marsden, Islay D.; Glover, Chris N.; Gaw, Sally

    2015-01-01

    This is the first study to use a multiple biomarker approach on the green-lipped mussel, Perna canaliculus to test its feasibility as a bioindicator of coastal metal contamination in New Zealand (NZ). Mussels were collected from six low intertidal sites varying in terms of anthropogenic impacts, within two regions (West Coast and Nelson) of the South Island of NZ. Trace elements, including arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn), were measured in the gills, digestive gland, foot and mantle, and in the surface sediments from where mussels were collected. Metal levels in the sediment were relatively low and there was only one site (Mapua, Nelson) where a metal (Ni) exceeded the Australian and New Zealand Interim Sediment Quality Guideline values. Metal levels in the digestive gland were generally higher than those from the other tissues. A variety of biomarkers were assessed to ascertain mussel health. Clearance rate, a physiological endpoint, correlated with metal level in the tissues, and along with scope for growth, was reduced in the most contaminated site. Metallothionein-like protein content and catalase activity in the digestive gland, and catalase activity and lipid peroxidation in the gill, were also correlated to metal accumulation. Although there were few regional differences, the sampling sites were clearly distinguishable based on the metal contamination profiles and biomarker responses. P. canaliculus appears to be a useful bioindicator species for coastal habitats subject to metal contamination. In this study tissue and whole organism responses provided insight into the biological stress responses of mussels to metal contaminants, indicating that such measurements could be a useful addition to biomonitoring programmes in NZ. - Highlights: • Multiple biomarker responses were measured in mussels from 6 sites. • Metal content of mussel tissues correlated with specific biomarker responses. • Clearance rate

  2. Assessment of a mussel as a metal bioindicator of coastal contamination: Relationships between metal bioaccumulation and multiple biomarker responses

    Energy Technology Data Exchange (ETDEWEB)

    Chandurvelan, Rathishri, E-mail: rch118@uclive.ac.nz [School of Biological Sciences, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); Marsden, Islay D., E-mail: islay.marsden@canterbury.ac.nz [School of Biological Sciences, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); Glover, Chris N., E-mail: chris.glover@canterbury.ac.nz [School of Biological Sciences, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand); Gaw, Sally, E-mail: sally.gaw@canterbury.ac.nz [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand)

    2015-04-01

    This is the first study to use a multiple biomarker approach on the green-lipped mussel, Perna canaliculus to test its feasibility as a bioindicator of coastal metal contamination in New Zealand (NZ). Mussels were collected from six low intertidal sites varying in terms of anthropogenic impacts, within two regions (West Coast and Nelson) of the South Island of NZ. Trace elements, including arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn), were measured in the gills, digestive gland, foot and mantle, and in the surface sediments from where mussels were collected. Metal levels in the sediment were relatively low and there was only one site (Mapua, Nelson) where a metal (Ni) exceeded the Australian and New Zealand Interim Sediment Quality Guideline values. Metal levels in the digestive gland were generally higher than those from the other tissues. A variety of biomarkers were assessed to ascertain mussel health. Clearance rate, a physiological endpoint, correlated with metal level in the tissues, and along with scope for growth, was reduced in the most contaminated site. Metallothionein-like protein content and catalase activity in the digestive gland, and catalase activity and lipid peroxidation in the gill, were also correlated to metal accumulation. Although there were few regional differences, the sampling sites were clearly distinguishable based on the metal contamination profiles and biomarker responses. P. canaliculus appears to be a useful bioindicator species for coastal habitats subject to metal contamination. In this study tissue and whole organism responses provided insight into the biological stress responses of mussels to metal contaminants, indicating that such measurements could be a useful addition to biomonitoring programmes in NZ. - Highlights: • Multiple biomarker responses were measured in mussels from 6 sites. • Metal content of mussel tissues correlated with specific biomarker responses. • Clearance rate

  3. A catalytic metal ion interacts with the cleavage site G•U wobble in the HDV ribozyme†

    Science.gov (United States)

    Chen, Jui-Hui; Gong, Bo; Bevilacqua, Philip C.; Carey, Paul R.; Golden, Barbara L.

    2009-01-01

    The HDV ribozyme self-cleaves by a chemical mechanism involving general acid-base catalysis to generate a 2′,3′-cyclic phosphate and a 5′-hydroxyl termini. Biochemical studies from several laboratories have implicated C75 as the general acid and hydrated magnesium as the general base. We have previously shown that C75 has a pKa shifted > 2 pH units toward neutrality [Gong, B., Chen, J. H., Chase, E., Chadalavada, D. M., Yajima, R., Golden, B. L., Bevilacqua, P. C., and Carey, P. R. (2007) J. Am. Chem. Soc. 129, 13335–13342.], while in crystal structures, it is well-positioned for proton transfer. However no crystallographic evidence for a hydrated magnesium poised to serve as a general base in the reaction has been observed in high-resolution crystal structures of various reaction states and mutants. Herein, we use solution kinetic experiments and parallel Raman crystallographic studies to examine the effects of pH on rate and Mg2+-binding properties of wild-type and 7-deazaguanosine mutants of the HDV ribozyme. These data suggest that a previously-unobserved hydrated magnesium ion interacts with the N7 of the cleavage site G•U wobble base pair. Integrating this metal ion binding site with the available crystal structures provides a new three-dimensional model for the active site of the ribozyme that accommodates all available biochemical data and appears competent for catalysis. The position of this metal is consistent with a role of a magnesium-bound hydroxide as a general base as dictated by biochemical data. PMID:19178151

  4. Determining site-specific background level with geostatistics for remediation of heavy metals in neighborhood soils

    OpenAIRE

    Tammy M. Milillo; Gaurav Sinha; Joseph A. Gardella Jr.

    2017-01-01

    The choice of a relevant, uncontaminated site for the determination of site-specific background concentrations for pollutants is critical for planning remediation of a contaminated site. The guidelines used to arrive at concentration levels vary from state to state, complicating this process. The residential neighborhood of Hickory Woods in Buffalo, NY is an area where heavy metal concentrations and spatial distributions were measured to plan remediation. A novel geostatistics based decision ...

  5. Heavy Metal Contamination of Soils around a Hospital Waste Incinerator Bottom Ash Dumps Site

    Directory of Open Access Journals (Sweden)

    M. Adama

    2016-01-01

    Full Text Available Waste incineration is the main waste management strategy used in treating hospital waste in many developing countries. However, the release of dioxins, POPs, and heavy metals in fly and bottom ash poses environmental and public health concerns. To determine heavy metal (Hg, Pb, Cd, Cr, and Ag in levels in incinerator bottom ash and soils 100 m around the incinerator bottom ash dump site, ash samples and surrounding soil samples were collected at 20 m, 40 m, 60 m, 80 m, 100 m, and 1,200 m from incinerator. These were analyzed using the absorption spectrophotometer method. The geoaccumulation (Igeo and pollution load indices (PLI were used to assess the level of heavy metal contamination of surrounding soils. The study revealed high concentrations in mg/kg for, Zn (16417.69, Pb (143.80, Cr (99.30, and Cd (7.54 in bottom ash and these were above allowable limits for disposal in landfill. The study also found soils within 60 m radius of the incinerator to be polluted with the metals. It is recommended that health care waste managers be educated on the implication of improper management of incinerator bottom ash and regulators monitor hospital waste incinerator sites.

  6. Heavy Metal Contamination of Soils around a Hospital Waste Incinerator Bottom Ash Dumps Site

    Science.gov (United States)

    Adama, M.; Esena, R.; Fosu-Mensah, B.; Yirenya-Tawiah, D.

    2016-01-01

    Waste incineration is the main waste management strategy used in treating hospital waste in many developing countries. However, the release of dioxins, POPs, and heavy metals in fly and bottom ash poses environmental and public health concerns. To determine heavy metal (Hg, Pb, Cd, Cr, and Ag) in levels in incinerator bottom ash and soils 100 m around the incinerator bottom ash dump site, ash samples and surrounding soil samples were collected at 20 m, 40 m, 60 m, 80 m, 100 m, and 1,200 m from incinerator. These were analyzed using the absorption spectrophotometer method. The geoaccumulation (I geo) and pollution load indices (PLI) were used to assess the level of heavy metal contamination of surrounding soils. The study revealed high concentrations in mg/kg for, Zn (16417.69), Pb (143.80), Cr (99.30), and Cd (7.54) in bottom ash and these were above allowable limits for disposal in landfill. The study also found soils within 60 m radius of the incinerator to be polluted with the metals. It is recommended that health care waste managers be educated on the implication of improper management of incinerator bottom ash and regulators monitor hospital waste incinerator sites. PMID:27034685

  7. Anaerobic bioleaching of metals from waste activated sludge

    International Nuclear Information System (INIS)

    Meulepas, Roel J.W.; Gonzalez-Gil, Graciela; Teshager, Fitfety Melese; Witharana, Ayoma; Saikaly, Pascal E.; Lens, Piet N.L.

    2015-01-01

    Heavy metal contamination of anaerobically digested waste activated sludge hampers its reuse as fertilizer or soil conditioner. Conventional methods to leach metals require aeration or the addition of leaching agents. This paper investigates whether metals can be leached from waste activated sludge during the first, acidifying stage of two-stage anaerobic digestion without the supply of leaching agents. These leaching experiments were done with waste activated sludge from the Hoek van Holland municipal wastewater treatment plant (The Netherlands), which contained 342 μg g −1 of copper, 487 μg g −1 of lead, 793 μg g −1 of zinc, 27 μg g −1 of nickel and 2.3 μg g −1 of cadmium. During the anaerobic acidification of 3 g dry weight L −1 waste activated sludge, 80–85% of the copper, 66–69% of the lead, 87% of the zinc, 94–99% of the nickel and 73–83% of the cadmium were leached. The first stage of two-stage anaerobic digestion can thus be optimized as an anaerobic bioleaching process and produce a treated sludge (i.e., digestate) that meets the land-use standards in The Netherlands for copper, zinc, nickel and cadmium, but not for lead. - Highlights: • Heavy metals were leached during anaerobic acidification of waste activated sludge. • The process does not require the addition of chelating or oxidizing agents. • The metal leaching efficiencies (66 to 99%) were comparable to chemical leaching. • The produced leachate may be used for metal recovery and biogas production. • The produced digested sludge may be used as soil conditioner

  8. In Situ Evaluation of Crop Productivity and Bioaccumulation of Heavy Metals in Paddy Soils after Remediation of Metal-Contaminated Soils.

    Science.gov (United States)

    Kim, Shin Woong; Chae, Yooeun; Moon, Jongmin; Kim, Dokyung; Cui, Rongxue; An, Gyeonghyeon; Jeong, Seung-Woo; An, Youn-Joo

    2017-02-15

    Soils contaminated with heavy metals have been reused for agricultural, building, and industrial uses following remediation. This study assesses plant growth and bioaccumulation of heavy metals following remediation of industrially contaminated soil. The soil was collected from a field site near a nonferrous smelter and was subjected to laboratory- and field-scale studies. Soil from the contaminated site was remediated by washing with acid or mixed with soil taken from a distant uncontaminated site. The activities of various soil exoenzymes, the rate of plant growth, and the bioaccumulations of six heavy metals were measured to assess the efficacy of these bioremediation techniques. Growth of rice (Oryza sativa) was unaffected in acid-washed soil or the amended soil compared to untreated soil from the contaminated site. The levels of heavy metals in the rice kernels remained within safe limits in treated and untreated soils. Rice, sorghum (Sorghum bicolor), and wheat (Triticum aestivum) cultivated in the same soils in the laboratory showed similar growth rates. Soil exoenzyme activities and crop productivity were not affected by soil treatment in field experiments. In conclusion, treatment of industrially contaminated soil by acid washing or amendment did not adversely affect plant productivity or lead to increased bioaccumulation of heavy metals in rice.

  9. Characterization of soil and plant-associated bacteria on a metal contaminated site

    International Nuclear Information System (INIS)

    Boulet, J.; Weyens, N.; Barac, T.; Dupae, J.; Lelie, D. van der; Taghavi, S.; Vaqngronsveld, J.

    2009-01-01

    Conventional methods for the remediation of heavy metal contaminated soils and ground water are very expensive and often damaging to the environment. Complementary to these traditional methods, especially for sites with a diffuse contamination in relatively low concentrations, phyto extraction is proposed as a promising technology for effective and inexpensive radiation. (Author)

  10. Mycorrhizal fungi modulate phytochemical production and antioxidant activity of Cichorium intybus L. (Asteraceae) under metal toxicity.

    Science.gov (United States)

    Rozpądek, P; Wężowicz, K; Stojakowska, A; Malarz, J; Surówka, E; Sobczyk, Ł; Anielska, T; Ważny, R; Miszalski, Z; Turnau, K

    2014-10-01

    Cichorium intybus (common chicory), a perennial plant, common in anthropogenic sites, has been the object of a multitude of studies in recent years due to its high content of antioxidants utilized in pharmacy and food industry. Here, the role of arbuscular mycorrhizal fungi (AMF) in the biosynthesis of plant secondary metabolites and the activity of enzymatic antioxidants under toxic metal stress was studied. Plants inoculated with Rhizophagus irregularis and non-inoculated were grown on non-polluted and toxic metal enriched substrata. The results presented here indicate that AMF improves chicory fitness. Fresh and dry weight was found to be severely affected by the fungi and heavy metals. The concentration of hydroxycinnamates was increased in the shoots of mycorrhizal plants cultivated on non-polluted substrata, but no differences were found in plants cultivated on metal enriched substrata. The activity of SOD and H2O2 removing enzymes CAT and POX was elevated in the shoots of mycorrhizal plants regardless of the cultivation environment. Photochemical efficiency of inoculated chicory was significantly improved. Our results indicate that R. irregularis inoculation had a beneficial role in sustaining the plants ability to cope with the deleterious effects of metal toxicity. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Heavy metals modulate the activity of the purinergic P2X4 receptor

    International Nuclear Information System (INIS)

    Coddou, Claudio; Lorca, Ramon A.; Acuna-Castillo, Claudio; Grauso, Marta; Rassendren, Francois; Huidobro-Toro, J.Pablo

    2005-01-01

    To further characterize the nature of the regulatory metal-binding sites of the rat P2X 4 receptor, several transition heavy metals were tested to examine their ability to mimic the facilitator action of zinc or the inhibitory action of copper. cDNA coding for the rat P2X 4 receptor was injected into Xenopus laevis oocytes; the two-electrode voltage-clamp technique was used to measure and quantify the ATP-evoked currents in the absence or presence of the metals. Cadmium facilitated the ATP-gated currents in a reversible and voltage-independent manner; maximal potentiation occurred within less than 1 min. Cadmium displaced leftward, in a concentration-dependent manner, the ATP concentration-response curve. In contrast, mercury reduced the ATP-gated currents in a reversible, time, and concentration manner. Maximal inhibition occurred after about 5 min of metal application. Cobalt also augmented the ATP-evoked currents, but its action was long lasting and did not reverse even after 45 min of metal washout. Other metals such as lead, nickel, manganese, silver, or gallium did not significantly alter the ATP-gated currents. The co-application of cadmium plus zinc or mercury plus copper caused additive effects. Mutation of H140 by alanine (H140A) augmented both the cadmium-induced facilitation and the mercury-induced inhibition. In contrast, the H241A mutant showed characteristics indistinguishable from the wild type. The H286A mutant showed a normal cadmium-induced potentiation, but an increased mercury inhibition. Out of the metals examined, only cadmium mimicked closely the action of zinc, evidencing commonalities. While mercury mimicked the action of copper, both metals apparently interact at distinct metal-binding sites. The present findings allow us to infer that heavy metals modulate the P2X 4 receptor by acting in at least three separate metal-binding sites

  12. Site Restoration

    Energy Technology Data Exchange (ETDEWEB)

    Noynaert, L.; Bruggeman, A.; Cornelissen, R.; Massaut, V.; Rahier, A

    2002-04-01

    The objectives, the programme, and the achievements of SCK-CEN's Site Restoration Department for 2001 are described. Main activities include the decommissioning of the BR3 PWR-reactor as well as other clean-up activities, projects on waste minimisation and the management of spent fuel and the flow of dismantled materials and the recycling of materials from decommissioning activities based on the smelting of metallic materials in specialised foundries. The department provides consultancy and services to external organisations and performs R and D on new techniques including processes for the treatment of various waste components including the reprocessing of spent fuel, the treatment of tritium, the treatment of liquid alkali metals into cabonates through oxidation, the treatment of radioactive organic waste and the reconditioning of bituminised waste products.

  13. Electrometallurgical treatment of metallic spent nuclear fuel stored at the Hanford Site

    International Nuclear Information System (INIS)

    Laidler, J.J.; Gay, E.C.

    1996-01-01

    The major component of the DOE spent nuclear fuel inventory is the metallic fuel stored at the Hanford site in the southeastern part of the state of Washington. Most of this fuel was discharged from the N-Reactor; a small part of the inventory is fuel from the early Hanford production reactors. The U.S. Department of Energy (DOE) plans to remove these fuels from the spent fuel storage pools in which they are presently stored, dry them, and place them in interim storage at a location at the Hanford site that is far removed from the Columbia River. It is not yet certain that these fuels will be acceptable for disposal in a mined geologic repository without further treatment, due to their potential pyrophoric character. A practical method for treatment of the Hanford metallic spent fuel, based on an electrorefining process, has been developed and has been demonstrated with unirradiated N-Reactor fuel and with simulated single-pass reactor (SPR) spent fuel. The process can be operated with any desired throughput rates; being a batch process, it is simply a matter of setting the size of the electrorefiner modules and the number of such modules. A single module, prototypic of a production-scale module, has been fabricated and testing is in progress at a throughput rate of 150 kg (heavy metal) per day. The envisioned production version would incorporate additional anode baskets and cathode tubes and provide a throughput rate of 333 kgHM/day. A system with four of these modules would permit treatment of Hanford metallic fuels at a rate of at least 250 metric tons per year

  14. Processing capabilties for the elimination of contaminated metal scrapyards at DOE/ORO-managed sites

    International Nuclear Information System (INIS)

    Mack, J.E.; Williams, L.C.

    1982-01-01

    Capabilities exist for reducing all the contaminated nickel, aluminum, and copper scrap to ingot form by smelting. Processing these metals at existing facilities could be completed in about 5 or 6 years. However, these metals represent only about 20% of the total metal inventories currently on hand at the DOE/ORO-managed sites. No provisions have been made for the ferrous scrap. Most of the ferrous scrap is unclassified and does not require secured storage. Also, the potential resale value of the ferrous scrap at about $100 per ton is very low in comparison. Consequently, this scrap has been allowed to accumulate. With several modifications and equipment additions, the induction melter at PGDP could begin processing ferrous scrap after its commitment to nickel and aluminum. The PGDP smelter is a retrofit installation, and annual throughput capabilities are limited. Processing of the existing ferrous scrap inventories would not be completed until the FY 1995-2000 time frame. An alternative proposal has been the installation of induction melters at the other two enrichment facilities. Conceptual design of a generic metal smelting facility is under way. The design study includes capital and operating costs for scrap preparation through ingot storage at an annual throughput of 10,000 tons per year. Facility design includes an induction melter with the capability of melting both ferrous and nonferrous metals. After three years of operation with scrapyard feed, the smelter would have excess capacity to support on-site decontamination and decomissioning projects or upgrading programs. The metal smelting facility has been proposed for FY 1984 line item funding with start-up operations in FY 1986

  15. Metals other than uranium affected microbial community composition in a historical uranium-mining site.

    Science.gov (United States)

    Sitte, Jana; Löffler, Sylvia; Burkhardt, Eva-Maria; Goldfarb, Katherine C; Büchel, Georg; Hazen, Terry C; Küsel, Kirsten

    2015-12-01

    To understand the links between the long-term impact of uranium and other metals on microbial community composition, ground- and surface water-influenced soils varying greatly in uranium and metal concentrations were investigated at the former uranium-mining district in Ronneburg, Germany. A soil-based 16S PhyloChip approach revealed 2358 bacterial and 35 archaeal operational taxonomic units (OTU) within diverse phylogenetic groups with higher OTU numbers than at other uranium-contaminated sites, e.g., at Oak Ridge. Iron- and sulfate-reducing bacteria (FeRB and SRB), which have the potential to attenuate uranium and other metals by the enzymatic and/or abiotic reduction of metal ions, were found at all sites. Although soil concentrations of solid-phase uranium were high, ranging from 5 to 1569 μg·g (dry weight) soil(-1), redundancy analysis (RDA) and forward selection indicated that neither total nor bio-available uranium concentrations contributed significantly to the observed OTU distribution. Instead, microbial community composition appeared to be influenced more by redox potential. Bacterial communities were also influenced by bio-available manganese and total cobalt and cadmium concentrations. Bio-available cadmium impacted FeRB distribution while bio-available manganese and copper as well as solid-phase zinc concentrations in the soil affected SRB composition. Archaeal communities were influenced by the bio-available lead as well as total zinc and cobalt concentrations. These results suggest that (i) microbial richness was not impacted by heavy metals and radionuclides and that (ii) redox potential and secondary metal contaminants had the strongest effect on microbial community composition, as opposed to uranium, the primary source of contamination.

  16. Soil microbial activity, mycelial lengths and physiological groups of bacteria in a heavy metal polluted area

    Energy Technology Data Exchange (ETDEWEB)

    Nordgren, A; Kauri, T; Baeaeth, E; Soederstroem, B

    1986-01-01

    The biological effects of heavy metal contamination of coniferous forest soils were studied in the A/sub 01//A/sub 02/ layer around a primary smelter in Northern Sweden. Soil concentrations of 17 elements were determined. Smelter-emitted heavy metals were 5 to 75 times higher in the plot closest to the smelter compared with background levels. Despite emission of sulfur no decrease in pH was found. Bacteria producing acid from maltose, cellobiose, arabinose or xylose and bacteria hydrolyzing starch, pectin, xyland or cellulose decreased 8- to 11-fold due to the soil contamination. Chitin hydrolyzers were 5 times less abundant at the most polluted site compared with background levels. Soil respiration rate and urease activity decreased by about a factor of 4, but phosphatase activity and mycelial lengths were unaffected by the soil contamination. Soil bacteria showed a sigmoidal response to the log of metal concentration in the soil and were affected at a lower pollution level than the other biological variables in the study. A multivariate analysis (partial least squares) showed that soil metal contamination and soil pH were the two environmental factors influencing the soil microorganisms.

  17. Anaerobic bioleaching of metals from waste activated sludge

    Energy Technology Data Exchange (ETDEWEB)

    Meulepas, Roel J.W., E-mail: roel.meulepas@wetsus.nl [UNESCO-IHE, Westvest 7, 2611 AX Delft (Netherlands); Gonzalez-Gil, Graciela [UNESCO-IHE, Westvest 7, 2611 AX Delft (Netherlands); King Abdullah University of Science and Technology, Water Desalination and Reuse Center, Thuwal 13955-69000 (Saudi Arabia); Teshager, Fitfety Melese; Witharana, Ayoma [UNESCO-IHE, Westvest 7, 2611 AX Delft (Netherlands); Saikaly, Pascal E. [King Abdullah University of Science and Technology, Water Desalination and Reuse Center, Thuwal 13955-69000 (Saudi Arabia); Lens, Piet N.L. [UNESCO-IHE, Westvest 7, 2611 AX Delft (Netherlands)

    2015-05-01

    Heavy metal contamination of anaerobically digested waste activated sludge hampers its reuse as fertilizer or soil conditioner. Conventional methods to leach metals require aeration or the addition of leaching agents. This paper investigates whether metals can be leached from waste activated sludge during the first, acidifying stage of two-stage anaerobic digestion without the supply of leaching agents. These leaching experiments were done with waste activated sludge from the Hoek van Holland municipal wastewater treatment plant (The Netherlands), which contained 342 μg g{sup −1} of copper, 487 μg g{sup −1} of lead, 793 μg g{sup −1} of zinc, 27 μg g{sup −1} of nickel and 2.3 μg g{sup −1} of cadmium. During the anaerobic acidification of 3 g{sub dry} {sub weight} L{sup −1} waste activated sludge, 80–85% of the copper, 66–69% of the lead, 87% of the zinc, 94–99% of the nickel and 73–83% of the cadmium were leached. The first stage of two-stage anaerobic digestion can thus be optimized as an anaerobic bioleaching process and produce a treated sludge (i.e., digestate) that meets the land-use standards in The Netherlands for copper, zinc, nickel and cadmium, but not for lead. - Highlights: • Heavy metals were leached during anaerobic acidification of waste activated sludge. • The process does not require the addition of chelating or oxidizing agents. • The metal leaching efficiencies (66 to 99%) were comparable to chemical leaching. • The produced leachate may be used for metal recovery and biogas production. • The produced digested sludge may be used as soil conditioner.

  18. Relations between metals (Zn, Pb, Cd and Cu) and glutathione-dependent detoxifying enzymes in spiders from a heavy metal pollution gradient

    Energy Technology Data Exchange (ETDEWEB)

    Wilczek, Grazyna [Department of Animal Physiology and Ecotoxicology, University of Silesia, Bankowa 9, 40-007 Katowice (Poland); Babczynska, Agnieszka [Department of Animal Physiology and Ecotoxicology, University of Silesia, Bankowa 9, 40-007 Katowice (Poland); Augustyniak, Maria [Department of Animal Physiology and Ecotoxicology, University of Silesia, Bankowa 9, 40-007 Katowice (Poland); Migula, Pawel [Department of Animal Physiology and Ecotoxicology, University of Silesia, Bankowa 9, 40-007 Katowice (Poland)]. E-mail: migula@us.edu.pl

    2004-12-01

    We studied the relations between glutathione-dependent detoxifying enzymes and heavy metal burdens in the web-building spider Agelena labyrinthica (Agelenidae) and the wolf spider Pardosa lugubris (Lycosidae) from five meadow sites along a heavy metal pollution gradient. We assayed the activity of glutathione-S-transferase (GST) and glutathione peroxidases (GPOX, GSTPx), and glutathione (GSH) levels in both sexes. Except for GSH vs Pb content, we found significant correlations between GPOX and GSTPx activity and metal concentrations in females of A. labyrinthica. The highest activity of these enzymes measured in the web-building spiders was found in the individuals from the most polluted sites. In P. lugubris males significant correlations were found between GST and Pb and Zn concentrations, and between GPOX and GSTPx and the concentration of Cu. GST activity was higher in males collected from less polluted areas. Thus, detoxifying strategies against pollutants seemed to be sex-dependent. Actively hunting spiders had higher metal concentrations, maintaining lower activity of detoxifying enzymes and a lower glutathione level. - Capsule: Glutathione-linked enzyme activity in spiders from polluted areas depends on hunting strategy and sex.

  19. Relations between metals (Zn, Pb, Cd and Cu) and glutathione-dependent detoxifying enzymes in spiders from a heavy metal pollution gradient

    International Nuclear Information System (INIS)

    Wilczek, Grazyna; Babczynska, Agnieszka; Augustyniak, Maria; Migula, Pawel

    2004-01-01

    We studied the relations between glutathione-dependent detoxifying enzymes and heavy metal burdens in the web-building spider Agelena labyrinthica (Agelenidae) and the wolf spider Pardosa lugubris (Lycosidae) from five meadow sites along a heavy metal pollution gradient. We assayed the activity of glutathione-S-transferase (GST) and glutathione peroxidases (GPOX, GSTPx), and glutathione (GSH) levels in both sexes. Except for GSH vs Pb content, we found significant correlations between GPOX and GSTPx activity and metal concentrations in females of A. labyrinthica. The highest activity of these enzymes measured in the web-building spiders was found in the individuals from the most polluted sites. In P. lugubris males significant correlations were found between GST and Pb and Zn concentrations, and between GPOX and GSTPx and the concentration of Cu. GST activity was higher in males collected from less polluted areas. Thus, detoxifying strategies against pollutants seemed to be sex-dependent. Actively hunting spiders had higher metal concentrations, maintaining lower activity of detoxifying enzymes and a lower glutathione level. - Capsule: Glutathione-linked enzyme activity in spiders from polluted areas depends on hunting strategy and sex

  20. Anaerobic bioleaching of metals from waste activated sludge

    KAUST Repository

    Meulepas, Roel J W; Gonzalez-Gil, Graciela; Teshager, Fitfety Melese; Witharana, Ayoma; Saikaly, Pascal; Lens, Piet Nl L

    2015-01-01

    Heavy metal contamination of anaerobically digested waste activated sludge hampers its reuse as fertilizer or soil conditioner. Conventional methods to leach metals require aeration or the addition of leaching agents. This paper investigates whether

  1. Distribution and Identification of Sources of Heavy Metals in the Voghji River Basin Impacted by Mining Activities (Armenia

    Directory of Open Access Journals (Sweden)

    A. V. Gabrielyan

    2018-01-01

    Full Text Available The objective of this research is to assess the distribution of heavy metals in the waters and sediments of the Voghji River and its tributaries impacted by mining activity and to reveal the real source of each of the heavy metals in the environment for assessing the pollution level of heavy metals. Voghji River with two main tributaries (Geghi and Norashenik drain two mining regions. To identify distribution and pollution sources of heavy metals, the water and sediment samples were collected from eight sampling sites. The results of statistical analysis based on data sets of the period 2014–2016 showed that, after the influence of drainage water and wastewater of mining regions, heavy metal contents in the Voghji River basin dramatically increased. The waters of the Voghji River were highly polluted by Mn, Co, Cu, Zn, Mo, Cd, and Pb. The relation of metals content was highly changed due to anthropogenic impact disturbing the geochemical balance of the Voghji River. The water quality based on only heavy metal contents in the source of the Voghji River belongs to “good” chemical status, and in the sources of Geghi and Norashenik Rivers it is “moderate.” The water quality of Voghji and Norashenik Rivers is sharply worsening after the influence of mining activity, becoming “bad” chemical status. The research revealed the pollution sources of each metal.

  2. Effects of metals on blood oxidative stress biomarkers and acetylcholinesterase activity in dice snakes (Natrix tessellata from Serbia

    Directory of Open Access Journals (Sweden)

    Gavrić Jelena P.

    2015-01-01

    Full Text Available The effects of waterborne metals in water on the activities of blood copper-zinc superoxide dismutase (CuZnSOD, catalase (CAT, glutathione peroxidase (GSH-Px, glutathione reductase (GR, glutathione-S-transferase (GST, and acetylcholinesterase (AChE, and on the concentrations of total glutathione (GSH and lipid peroxides (TBARS in the blood of dice snakes (Natrix tessellata caught in Obedska Bara, Sebia (control area, with snakes caught in Pančevački Rit, a contaminated area in Serbia were examined. The activities of CAT, GSH-Px, GR and AChE, and the concentration of TBARS were significantly decreased, while GST activity and GSH concentration were significantly increased in snakes from the contaminated area compared to specimens from the control area. Significantly increased concentrations of Al, As, B, Ba, Ca, Cu, Fe, K, Li, Mn, Na, Ni and Zn in the water at the contaminated area as compared to control area were detected. The metals Ag, Bi, Cd, Co, Hg, In and Tl were not observed in any of the localities. Cr, Mo and Pb were not detected at the control area but were observed at the contaminated area. The concentrations of Sr were similar at both sites. The concentration of Mg was 2-fold higher at the control site than at the contaminated area. The obtained results show that most of the investigated blood biomarkers correlate with concentrations of metals present in the environment. These findings suggest that dice snakes are sensitive bioindicator species for monitoring the effects of increased metal concentrations in the environment. [Projekat Ministarstva nauke Republike Srbije, br. 173041 i br. 173043

  3. Identification of a divalent metal cation binding site in herpes simplex virus 1 (HSV-1) ICP8 required for HSV replication.

    Science.gov (United States)

    Bryant, Kevin F; Yan, Zhipeng; Dreyfus, David H; Knipe, David M

    2012-06-01

    Herpes simplex virus 1 (HSV-1) ICP8 is a single-stranded DNA-binding protein that is necessary for viral DNA replication and exhibits recombinase activity in vitro. Alignment of the HSV-1 ICP8 amino acid sequence with ICP8 homologs from other herpesviruses revealed conserved aspartic acid (D) and glutamic acid (E) residues. Amino acid residue D1087 was conserved in every ICP8 homolog analyzed, indicating that it is likely critical for ICP8 function. We took a genetic approach to investigate the functions of the conserved ICP8 D and E residues in HSV-1 replication. The E1086A D1087A mutant form of ICP8 failed to support the replication of an ICP8 mutant virus in a complementation assay. E1086A D1087A mutant ICP8 bound DNA, albeit with reduced affinity, demonstrating that the protein is not globally misfolded. This mutant form of ICP8 was also recognized by a conformation-specific antibody, further indicating that its overall structure was intact. A recombinant virus expressing E1086A D1087A mutant ICP8 was defective in viral replication, viral DNA synthesis, and late gene expression in Vero cells. A class of enzymes called DDE recombinases utilize conserved D and E residues to coordinate divalent metal cations in their active sites. We investigated whether the conserved D and E residues in ICP8 were also required for binding metal cations and found that the E1086A D1087A mutant form of ICP8 exhibited altered divalent metal binding in an in vitro iron-induced cleavage assay. These results identify a novel divalent metal cation-binding site in ICP8 that is required for ICP8 functions during viral replication.

  4. Indicators of Lake Temsah Potential by some heavy metals Heavy Metals in Sediment

    International Nuclear Information System (INIS)

    Abdel Sabour, M.F.; Aly, R.O.; Khalil, M.T.; Attwa, A.H.A.

    1999-01-01

    The Environmental impact of industrial, agricultural and domestic waster on heavy metals sediment content in lake Temsah has been investigated. Seven sites were chosen, differ in nature of activity and quantity of wastes, namely from south to north-west; Arab contractors shipyard workshop(A), The junction between the western logon and the lake(B), El-Temsah workshop (C), El-Temsah shipyard (private workshop) (D), El-Karakat workshop for SCA (E), El-Forsan drain out fall to the lake (F) and SCA Press outlet (G). Eight of heavy metal concentrations of concern (Fe, Mn, Zn, Cu, Co, Ni, Cd and Pb) were estimated in sediment samples collected from different chosen sites during the seasons; summer , autumn 1995 and winter , spring 1996. Results of this study reveal that pollution is directly related to the type of the activity in each site. Sediment samples results showed that the most suffering sites were found to be in the order of B> D> C> G> F, and the least polluted ones were E> A. And the highest polluted season was summer, whereas the least one was winter. It is obvious that the general mean values of Cu, Ni and Cd are exceeding the allowed concentrations documented for diverse trace components in coastal sediments. Strict regulations that must be followed in order to minimize this pollution specially, by heavy metals from marine workshop

  5. Elucidating the Origin of Hydrogen Evolution Reaction Activity in Mono- and Bimetallic Metal- and Nitrogen-Doped Carbon Catalysts (Me-N-C).

    Science.gov (United States)

    Shahraei, Ali; Moradabadi, Ashkan; Martinaiou, Ioanna; Lauterbach, Stefan; Klemenz, Sebastian; Dolique, Stephanie; Kleebe, Hans-Joachim; Kaghazchi, Payam; Kramm, Ulrike I

    2017-08-02

    In this work, we present a comprehensive study on the role of metal species in MOF-based Me-N-C (mono- and bimetallic) catalysts for the hydrogen evolution reaction (HER). The catalysts are investigated with respect to HER activity and stability in alkaline electrolyte. On the basis of the structural analysis by X-ray diffraction, X-ray-induced photoelectron spectroscopy, and transmission electron microscopy, it is concluded that MeN 4 sites seem to dominate the HER activity of these catalysts. There is a strong relation between the amount of MeN 4 sites that are formed and the energy of formation related to these sites integrated at the edge of a graphene layer, as obtained from density functional theory (DFT) calculations. Our results show, for the first time, that the combination of two metals (Co and Mo) in a bimetallic (Co,Mo)-N-C catalyst allows hydrogen production with a significantly improved overpotential in comparison to its monometallic counterparts and other Me-N-C catalysts. By the combination of experimental results with DFT calculations, we show that the origin of the enhanced performance of our (Co,Mo)-N-C catalyst seems to be provided by an improved hydrogen binding energy on one MeN 4 site because of the presence of a second MeN 4 site in its close vicinity, as investigated in detail for our most active (Co,Mo)-N-C catalyst. The outstanding stability and good activity make especially the bimetallic Me-N-C catalysts interesting candidates for solar fuel applications.

  6. [Adsorption of heavy metals on the surface of birnessite relationship with its Mn average oxidation state and adsorption sites].

    Science.gov (United States)

    Wang, Yan; Tan, Wen-Feng; Feng, Xiong-Han; Qiu, Guo-Hong; Liu, Fan

    2011-10-01

    Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.

  7. Achieving high-powered Zn/air fuel cell through N and S co-doped hierarchically porous carbons with tunable active-sites as oxygen electrocatalysts

    Science.gov (United States)

    Tang, Qiaowei; Wang, Luming; Wu, Mingjie; Xu, Nengneng; Jiang, Lei; Qiao, Jinli

    2017-10-01

    Electrochemical reduction of oxygen is the heart of the next-generation energy technologies to fuel cells and metal-air batteries, of which the reference catalysts suffer from two critical bottlenecks lying in their insufficient electroactivities and unclear active site structures. Herein, we introduce the effectively hierarchically porous carbons (HPCs) as the active-sites enriched platform for oxygen electroreduction. Three quaternized copolymers (PUB, PAADDA and PICP) with different chemical structures are used to pursue Fe/N/S-tailored ORR electrocatalysts. The most efficient one prepared by PAADDA gives the onset potential of 0.94 V and a half-wave potential of 0.85 V in basic solution, as well as superb electroactivities of low H2O2% and high electron transfer number in both alkaline and acidic medium. Surprisingly, they all display high discharge power density as applied to Zn-air fuel cells, and the HPCs-PAADDA catalyst thrillingly reaches 516.3 mW cm-2 when catalyst loading is optimized to 5.0 mg cm-2. The results elucidate that the polymer with long aliphatic chain is propitious to trap metals to create active sites and enwrap silica template to construct uniform pore structure. Only two kinds of nitrogen configuration (pyridinic-N and graphitic-N) are found with distinct structure in these HPCs, which happens to be active sites.

  8. Oxidation of ethane to ethanol by N2O in a metal-organic framework with coordinatively unsaturated iron(II) sites.

    Science.gov (United States)

    Xiao, Dianne J; Bloch, Eric D; Mason, Jarad A; Queen, Wendy L; Hudson, Matthew R; Planas, Nora; Borycz, Joshua; Dzubak, Allison L; Verma, Pragya; Lee, Kyuho; Bonino, Francesca; Crocellà, Valentina; Yano, Junko; Bordiga, Silvia; Truhlar, Donald G; Gagliardi, Laura; Brown, Craig M; Long, Jeffrey R

    2014-07-01

    Enzymatic haem and non-haem high-valent iron-oxo species are known to activate strong C-H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, although nature's non-haem iron(IV)-oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc), are able to activate the C-H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)-oxo species.

  9. Efficient oxygen electrocatalysis on special active sites

    DEFF Research Database (Denmark)

    Halck, Niels Bendtsen

    throughout this thesis to understand these local structure effects and their influence on surface reactions. The concept of these special active sites is used to explain how oxygen evolution reaction (OER) catalysts can have activities beyond the limits of what was previously thought possible. The concept...... stored in these bonds in an eco-friendly fashion in fuel cells. This thesis explores catalysts for oxygen electrocatalysis and how carefully designed local structures on catalysts surfaces termed special active sites can influence the activity. Density functional theory has been used as a method...... is used to explain the increase in activity observed for the OER catalyst ruthenium dioxide when it is mixed with nickel or cobalt. Manganese and cobalt oxides when in the vicinity of gold also display an increase in OER activity which can be explained by locally created special active sites. Density...

  10. Four-electron deoxygenative reductive coupling of carbon monoxide at a single metal site

    Science.gov (United States)

    Buss, Joshua A.; Agapie, Theodor

    2016-01-01

    Carbon dioxide is the ultimate source of the fossil fuels that are both central to modern life and problematic: their use increases atmospheric levels of greenhouse gases, and their availability is geopolitically constrained. Using carbon dioxide as a feedstock to produce synthetic fuels might, in principle, alleviate these concerns. Although many homogeneous and heterogeneous catalysts convert carbon dioxide to carbon monoxide, further deoxygenative coupling of carbon monoxide to generate useful multicarbon products is challenging. Molybdenum and vanadium nitrogenases are capable of converting carbon monoxide into hydrocarbons under mild conditions, using discrete electron and proton sources. Electrocatalytic reduction of carbon monoxide on copper catalysts also uses a combination of electrons and protons, while the industrial Fischer-Tropsch process uses dihydrogen as a combined source of electrons and electrophiles for carbon monoxide coupling at high temperatures and pressures. However, these enzymatic and heterogeneous systems are difficult to probe mechanistically. Molecular catalysts have been studied extensively to investigate the elementary steps by which carbon monoxide is deoxygenated and coupled, but a single metal site that can efficiently induce the required scission of carbon-oxygen bonds and generate carbon-carbon bonds has not yet been documented. Here we describe a molybdenum compound, supported by a terphenyl-diphosphine ligand, that activates and cleaves the strong carbon-oxygen bond of carbon monoxide, enacts carbon-carbon coupling, and spontaneously dissociates the resulting fragment. This complex four-electron transformation is enabled by the terphenyl-diphosphine ligand, which acts as an electron reservoir and exhibits the coordinative flexibility needed to stabilize the different intermediates involved in the overall reaction sequence. We anticipate that these design elements might help in the development of efficient catalysts for

  11. UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation

    KAUST Repository

    Luo, Feng

    2016-04-26

    A new metal-organic framework Zn2(H2O)-(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the wellestablished MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn2+ sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm3/cm3) to Zn-MOF-74. Interestingly, the accessible Zn2+ sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm3/cm3) than Zn-MOF-74 (146 cm3/cm3) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result. © 2016 American Chemical Society.

  12. Potential use of Pseudomonas koreensis AGB-1 in association with Miscanthus sinensis to remediate heavy metal(loid)-contaminated mining site soil.

    Science.gov (United States)

    Babu, A Giridhar; Shea, Patrick J; Sudhakar, D; Jung, Ik-Boo; Oh, Byung-Taek

    2015-03-15

    Endophytic bacteria have the potential to promote plant growth and heavy metal(loid) (HM) removal from contaminated soil. Pseudomonas koreensis AGB-1, isolated from roots of Miscanthus sinensis growing in mine-tailing soil, exhibited high tolerance to HMs and plant growth promoting traits. Transmission electron microscope (TEM) analysis revealed that AGB-1 sequestered HMs extracellularly and their accumulation was visible as dark metal complexes on bacterial surfaces and outside of the cells. DNA sequencing of HM resistance marker genes indicated high homology to the appropriate regions of the arsB, ACR3(1), aoxB, and bmtA determinants. Inoculating mining site soil with AGB-1 increased M. sinensis biomass by 54%, chlorophyll by 27%, and protein content by 28%. High superoxide dismutase and catalase activities, and the lower malondialdehyde content of plants growing in AGB-1-inoculated soil indicate reduced oxidative stress. Metal(loid) concentrations in roots and shoots of plants grown in inoculated soil were higher than those of the controls in pot trials with mine tailing soil. Results suggest that AGB-1 can be used in association with M. sinensis to promote phytostabilization and remediation of HM-contaminated sites. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. NANOSTRUCTURED METAL OXIDE CATALYSTS VIA BUILDING BLOCK SYNTHESES

    Energy Technology Data Exchange (ETDEWEB)

    Craig E. Barnes

    2013-03-05

    A broadly applicable methodology has been developed to prepare new single site catalysts on silica supports. This methodology requires of three critical components: a rigid building block that will be the main structural and compositional component of the support matrix; a family of linking reagents that will be used to insert active metals into the matrix as well as cross link building blocks into a three dimensional matrix; and a clean coupling reaction that will connect building blocks and linking agents together in a controlled fashion. The final piece of conceptual strategy at the center of this methodology involves dosing the building block with known amounts of linking agents so that the targeted connectivity of a linking center to surrounding building blocks is obtained. Achieving targeted connectivities around catalytically active metals in these building block matrices is a critical element of the strategy by which single site catalysts are obtained. This methodology has been demonstrated with a model system involving only silicon and then with two metal-containing systems (titanium and vanadium). The effect that connectivity has on the reactivity of atomically dispersed titanium sites in silica building block matrices has been investigated in the selective oxidation of phenols to benezoquinones. 2-connected titanium sites are found to be five times as active (i.e. initial turnover frequencies) than 4-connected titanium sites (i.e. framework titanium sites).

  14. Assessment of Selected Heavy Metals and Enzymes in Soil Within the Range of Impact of Illegal Dumping Sites

    International Nuclear Information System (INIS)

    Bartkowiak, A.; Lemanowicz, J.; Siwik-Ziomek, A.

    2016-01-01

    Defining the physicochemical and biological parameters in soil under illegally dumping sites provides information on the real threat and the direction of changes in the soil environment. The paper demonstrates the result of changes in the properties in soil as a result of the operation of illegal dumping sites. Soil was sampled from the research points located on the outskirts of the city of Bydgoszcz (Poland) from the site not affected by illegal dumping sites (control C), within the dumping sites, having removed the waste layer (W), and 10 m away from the dumping sites (W 10). In the soil the content of phosphorus, potassium, magnesium and sulphur, total content of copper, zinc, lead and nickel as well as the activity of enzymes were assayed. The content of Pb, Zn, Cu and Ni in the soil samples qualifies the soils as representing the soil category with natural content. The greatest activity of all the enzymes analysed was identified in the soil sampled from the control point affected by waste, whereas the highest content of macroelements was reported in the soil from the dumping sites (W 10). A high variation in the enzymes under study in soils confirms a high value of the coefficient of variation (CV >36%). The analysis of correlation confirmed the relationship between the content of organic carbon compounds and the content of zinc, lead, nickel. The soils show a slight value of the coefficient of contamination for heavy metals (CF<1). The contamination degree (Cdeg) ranged from 1.993 to 5.116, which points to a low level of soil contamination with Zn, Cu, Pb and Ni.

  15. Boosting catalytic activity of metal nanoparticles for 4-nitrophenol reduction: Modification of metal naoparticles with poly(diallyldimethylammonium chloride)

    Energy Technology Data Exchange (ETDEWEB)

    You, Jyun-Guo; Shanmugam, Chandirasekar [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); Liu, Yao-Wen; Yu, Cheng-Ju [Department of Applied Physics and Chemistry, University of Taipei, Taiwan (China); Tseng, Wei-Lung, E-mail: tsengwl@mail.nsysu.edu.tw [Department of Chemistry, National Sun Yat-sen University, Taiwan (China); School of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Taiwan (China); Center for Nanoscience and Nanotechnology, National Sun Yat-sen University, Taiwan (China)

    2017-02-15

    Highlights: • The choice of capping ligand determines catalytic activity of metal nanocatalysts. • PDDA-capped metal nanoparticles electrostatically interact with 4-NP and BH4{sup −}. • PDDA-capped metal nanoparticles have good recyclability and large scalability. • PDDA-capped Pd nanoparticles show the highest rate constant and activity parameter. - Abstract: Most of the previously reported studies have focused on the change in the size, morphology, and composition of metal nanocatalysts for improving their catalytic activity. Herein, we report poly(diallyldimethylammonium chloride) [PDDA]-stabilized nanoparticles (NPs) of platinum (Pt) and palladium (Pd) as highly active and efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) in the presence of NaBH4. PDDA-stabilized Pt and Pd NPs possessed similar particle size and same facet with citrate-capped Pt and Pd NPs, making this study to investigate the inter-relationship between catalytic activity and surface ligand without the consideration of the effects of particle size and facet. Compared to citrate-capped Pt and Pd NPs, PDDA-stabilized Pt and Pd NPs exhibited excellent pH and salt stability. PDDA could serve as an electron acceptor for metal NPs to produce the net positive charges on the metal surface, which provide strong electrostatic attraction with negatively charged nitrophenolate and borohydride ions. The activity parameter and rate constant of PDDA-stabilized metal NPs were higher than those of citrate-capped metal NPs. Compared to the previously reported Pd nanomaterials for the catalysis of NaBH4-mediated reduction of 4-NP, PDDA-stabilized Pd NPs exhibited the extremely high activity parameter (195 s{sup −1} g{sup −1}) and provided excellent scalability and reusability.

  16. Management of post-gastrectomy anastomosis site obstruction with a self-expandable metallic stent.

    Science.gov (United States)

    Cha, Ra Ri; Lee, Sang Soo; Kim, Hyunjin; Kim, Hong Jun; Kim, Tae-Hyo; Jung, Woon Tae; Lee, Ok Jae; Bae, Kyung Soo; Jeong, Sang-Ho; Ha, Chang Yoon

    2015-04-28

    Post-gastrectomy anastomosis site obstruction is a relatively rare complication after a subtotal gastrectomy. We present a case of a 75-year-old man who underwent a truncal vagotomy, omental patch, gastrojejunostomy, and Braun anastomosis for duodenal ulcer perforation and a gastric outlet obstruction. Following the 10(th) postoperative day, the patient complained of abdominal discomfort and vomiting. We diagnosed post-gastrectomy anastomosis site obstruction by an upper gastrointestinal series and an upper endoscopic examination. We inserted a self-expandable metallic stent (SEMS) at the anastomosis site. The stent was fully expanded after deployment. On the day following the stent insertion, the patient began to eat, and his abdominal discomfort was resolved. This paper describes the successful management of post-gastrectomy anastomosis site obstruction with temporary placement of a SEMS.

  17. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption

    Science.gov (United States)

    Zheng, Xueli; Zhang, Bo; de Luna, Phil; Liang, Yufeng; Comin, Riccardo; Voznyy, Oleksandr; Han, Lili; García de Arquer, F. Pelayo; Liu, Min; Dinh, Cao Thang; Regier, Tom; Dynes, James J.; He, Sisi; Xin, Huolin L.; Peng, Huisheng; Prendergast, David; Du, Xiwen; Sargent, Edward H.

    2018-02-01

    The efficiency with which renewable fuels and feedstocks are synthesized from electrical sources is limited at present by the sluggish oxygen evolution reaction (OER) in pH-neutral media. We took the view that generating transition-metal sites with high valence at low applied bias should improve the activity of neutral OER catalysts. Here, using density functional theory, we find that the formation energy of desired Ni4+ sites is systematically modulated by incorporating judicious combinations of Co, Fe and non-metal P. We therefore synthesized NiCoFeP oxyhydroxides and probed their oxidation kinetics with in situ soft X-ray absorption spectroscopy (sXAS). In situ sXAS studies of neutral-pH OER catalysts indicate ready promotion of Ni4+ under low overpotential conditions. The NiCoFeP catalyst outperforms IrO2 and retains its performance following 100 h of operation. We showcase NiCoFeP in a membrane-free CO2 electroreduction system that achieves a 1.99 V cell voltage at 10 mA cm-2, reducing CO2 into CO and oxidizing H2O to O2 with a 64% electricity-to-chemical-fuel efficiency.

  18. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption.

    Science.gov (United States)

    Zheng, Xueli; Zhang, Bo; De Luna, Phil; Liang, Yufeng; Comin, Riccardo; Voznyy, Oleksandr; Han, Lili; García de Arquer, F Pelayo; Liu, Min; Dinh, Cao Thang; Regier, Tom; Dynes, James J; He, Sisi; Xin, Huolin L; Peng, Huisheng; Prendergast, David; Du, Xiwen; Sargent, Edward H

    2018-02-01

    The efficiency with which renewable fuels and feedstocks are synthesized from electrical sources is limited at present by the sluggish oxygen evolution reaction (OER) in pH-neutral media. We took the view that generating transition-metal sites with high valence at low applied bias should improve the activity of neutral OER catalysts. Here, using density functional theory, we find that the formation energy of desired Ni 4+ sites is systematically modulated by incorporating judicious combinations of Co, Fe and non-metal P. We therefore synthesized NiCoFeP oxyhydroxides and probed their oxidation kinetics with in situ soft X-ray absorption spectroscopy (sXAS). In situ sXAS studies of neutral-pH OER catalysts indicate ready promotion of Ni 4+ under low overpotential conditions. The NiCoFeP catalyst outperforms IrO 2 and retains its performance following 100 h of operation. We showcase NiCoFeP in a membrane-free CO 2 electroreduction system that achieves a 1.99 V cell voltage at 10 mA cm -2 , reducing CO 2 into CO and oxidizing H 2 O to O 2 with a 64% electricity-to-chemical-fuel efficiency.

  19. Heavy Metals in the Vegetables Collected from Production Sites

    Directory of Open Access Journals (Sweden)

    Hassan Taghipour

    2013-12-01

    Full Text Available Background: Contamination of vegetable crops (as an important part of people's diet with heavy metals is a health concern. Therefore, monitoring levels of heavy metals in vegetables can provide useful information for promoting food safety. The present study was carried out in north-west of Iran (Tabriz on the content of heavy metals in vegetable crops. Methods: Samples of vegetables including kurrat (n=20 (Allium ampeloprasumssp. Persicum, onion (n=20 (Allium cepa and tomato (n=18 (Lycopersiconesculentum var. esculentum, were collected from production sites in west of Tabriz and analyzed for presence of Cd, Cr, Cu, Ni, Pb and Zn by atomic absorption spectroscopy (AAS after extraction by aqua regia method (drying, grounding and acid digestion. Results: Mean ± SD (mg/kg DW concentrations of Cd, Cu, Cr, Ni and Zn were 0.32 ± 0.58, 28.86 ± 28.79, 1.75 ± 2.05, 6.37± 5.61 and 58.01 ± 27.45, respectively. Cr, Cu and Zn were present in all the samples and the highest concentrations were observed in kurrat (leek. Levels of Cd, Cr and Cu were higher than the acceptable limits. There was significant difference in levels of Cr (P<0.05 and Zn (P<0.001 among the studied vegetables. Positive correlation was observed between Cd:Cu (R=0.659, P<0.001 Cr:Ni (R=0.326, P<0.05 and Cr:Zn (R=0.308, P<0.05. Conclusion: Level of heavy metals in some of the analyzed vegetables, especially kurrat samples, was higher than the standard levels. Considering the possible health outcomes due to the consumption of contaminated vegetables, it is required to take proper actions for avoiding people's chronic exposure.

  20. Integrin activation dynamics between the RGD-binding site and the headpiece hinge.

    Science.gov (United States)

    Puklin-Faucher, Eileen; Vogel, Viola

    2009-12-25

    Integrins form mechanical links between the extracellular matrix and the cytoskeleton. Although integrin activation is known to be regulated by an allosteric conformational change, which can be induced from the extracellular or intracellular end of the molecule, little is known regarding the sequence of structural events by which signals propagate between distant sites. Here, we reveal with molecular dynamics simulations of the FnIII(10)-bound alpha(V)beta(3) integrin headpiece how the binding pocket and interdomain betaA/hybrid domain hinge on the distal end of the betaA domain are allosterically linked via a hydrophobic T-junction between the middle of the alpha1 helix and top of the alpha7 helix. The key results of this study are: 1) that this T-junction is induced by ligand binding and hinge opening, and thus displays bidirectionality; 2) that formation of this junction can be accelerated by ligand-mediated force; and 3) how formation of this junction is inhibited by Ca(2+) in place of Mg(2+) at the site adjacent to the metal ion-dependent adhesion site ("ADMIDAS"). Together with recent experimental evidence that integrin complexes can form catch bonds (i.e. become strengthened under force), as well as earlier evidence that Ca(2+) at the ADMIDAS results in lower binding affinity, these simulations provide a common structural model for the dynamic process by which integrins become activated.

  1. Heavy metal accumulation in trees growing on contaminated sites in Central Europe

    International Nuclear Information System (INIS)

    Unterbrunner, R.; Puschenreiter, M.; Sommer, P.; Wieshammer, G.; Tlustos, P.; Zupan, M.; Wenzel, W.W.

    2007-01-01

    Metal-accumulating woody species have been considered for phytoextraction of metal-contaminated sites. We investigated Zn and Cd accumulation in tissues of adult trees and associated herbaceous species collected from contaminated areas in Central Europe. We found considerable Cd and Zn accumulation in various willow, poplar and birch species with up to 116 mg Cd kg -1 and 4680 mg Zn kg -1 in leaves of Salix caprea. Annual variation of Cd and Zn concentrations in leaves of Salix caprea were small, indicating that data obtained in different years can be compared. Metal concentrations in leaves were not related to total (aqua regia) or labile (1 M NH 4 NO 3 extract) concentrations in soil but the accumulation factors (leaf concentration: soil concentration) for Cd and Zn followed an inverse log type function. Metal partitioning between tissues showed a minimum in the wood, with increasing concentrations of Cd and Zn towards the leaves and fine roots. - Adult field-grown Salix caprea, Populus tremula and other tree species accumulate up to 4680 mg Zn kg -1 and 116 mg Cd kg -1 in their leaves

  2. Heavy metal accumulation in trees growing on contaminated sites in Central Europe

    Energy Technology Data Exchange (ETDEWEB)

    Unterbrunner, R. [University of Natural Resources and Applied Life Sciences, Vienna - BOKU, Department of Forest and Soil Sciences, Peter Jordan Strasse 82, A-1190 Vienna (Austria); Puschenreiter, M. [University of Natural Resources and Applied Life Sciences, Vienna - BOKU, Department of Forest and Soil Sciences, Peter Jordan Strasse 82, A-1190 Vienna (Austria)]. E-mail: markus.puschenreiter@boku.ac.at; Sommer, P. [University of Natural Resources and Applied Life Sciences, Vienna - BOKU, Department of Forest and Soil Sciences, Peter Jordan Strasse 82, A-1190 Vienna (Austria); Wieshammer, G. [University of Natural Resources and Applied Life Sciences, Vienna - BOKU, Department of Forest and Soil Sciences, Peter Jordan Strasse 82, A-1190 Vienna (Austria); Tlustos, P. [Czech University of Agriculture Prague, 165 21 Praha 6-Suchdol (Czech Republic); Zupan, M. [University of Ljubljana, Biotechnical Faculty, Agronomy department, Jamnikarjeva 101, 1000 Ljubljana (Slovenia); Wenzel, W.W. [University of Natural Resources and Applied Life Sciences, Vienna - BOKU, Department of Forest and Soil Sciences, Peter Jordan Strasse 82, A-1190 Vienna (Austria)

    2007-07-15

    Metal-accumulating woody species have been considered for phytoextraction of metal-contaminated sites. We investigated Zn and Cd accumulation in tissues of adult trees and associated herbaceous species collected from contaminated areas in Central Europe. We found considerable Cd and Zn accumulation in various willow, poplar and birch species with up to 116 mg Cd kg{sup -1} and 4680 mg Zn kg{sup -1} in leaves of Salix caprea. Annual variation of Cd and Zn concentrations in leaves of Salix caprea were small, indicating that data obtained in different years can be compared. Metal concentrations in leaves were not related to total (aqua regia) or labile (1 M NH{sub 4}NO{sub 3} extract) concentrations in soil but the accumulation factors (leaf concentration: soil concentration) for Cd and Zn followed an inverse log type function. Metal partitioning between tissues showed a minimum in the wood, with increasing concentrations of Cd and Zn towards the leaves and fine roots. - Adult field-grown Salix caprea, Populus tremula and other tree species accumulate up to 4680 mg Zn kg{sup -1} and 116 mg Cd kg{sup -1} in their leaves.

  3. Tolerance to Cadmium of Agave lechuguilla (Agavaceae Seeds and Seedlings from Sites Contaminated with Heavy Metals

    Directory of Open Access Journals (Sweden)

    Alejandra Méndez-Hurtado

    2013-01-01

    Full Text Available We investigated if seeds of Agave lechuguilla from contaminated sites with heavy metals were more tolerant to Cd ions than seeds from noncontaminated sites. Seeds from a highly contaminated site (Villa de la Paz and from a noncontaminated site (Villa de Zaragoza were evaluated. We tested the effect of Cd concentrations on several ecophysiological, morphological, genetical, and anatomical responses. Seed viability, seed germination, seedling biomass, and radicle length were higher for the non-polluted site than for the contaminated one. The leaves of seedlings from the contaminated place had more cadmium and showed peaks attributed to chemical functional groups such as amines, amides, carboxyl, and alkenes that tended to disappear due to increasing the concentration of cadmium than those from Villa de Zaragoza. Malformed cells in the parenchyma surrounding the vascular bundles were found in seedlings grown with Cd from both sites. The leaves from the contaminated place showed a higher metallothioneins expression in seedlings from the control group than that of seedlings at different Cd concentrations. Most of our results fitted into the hypothesis that plants from metal-contaminated places do not tolerate more pollution, because of the accumulative effect that cadmium might have on them.

  4. Structure of the Ni(II) complex of Escherichia coli peptide deformylase and suggestions on deformylase activities depending on different metal(II) centres.

    Science.gov (United States)

    Yen, Ngo Thi Hai; Bogdanović, Xenia; Palm, Gottfried J; Kühl, Olaf; Hinrichs, Winfried

    2010-02-01

    Crystal structures of polypeptide deformylase (PDF) of Escherichia coli with nickel(II) replacing the native iron(II) have been solved with chloride and formate as metal ligands. The chloro complex is a model for the correct protonation state of the hydrolytic hydroxo ligand and the protonated status of the Glu133 side chain as part of the hydrolytic mechanism. The ambiguity that recently some PDFs have been identified with Zn(2+) ion as the active-site centre whereas others are only active with Fe(2+) (or Co(2+), Ni(2+) is discussed with respect to Lewis acid criteria of the metal ion and substrate activation by the CD loop.

  5. Catalysis on singly dispersed bimetallic sites

    Science.gov (United States)

    Zhang, Shiran; Nguyen, Luan; Liang, Jin-Xia; Shan, Junjun; Liu, Jingyue; Frenkel, Anatoly I.; Patlolla, Anitha; Huang, Weixin; Li, Jun; Tao, Franklin

    2015-08-01

    A catalytic site typically consists of one or more atoms of a catalyst surface that arrange into a configuration offering a specific electronic structure for adsorbing or dissociating reactant molecules. The catalytic activity of adjacent bimetallic sites of metallic nanoparticles has been studied previously. An isolated bimetallic site supported on a non-metallic surface could exhibit a distinctly different catalytic performance owing to the cationic state of the singly dispersed bimetallic site and the minimized choices of binding configurations of a reactant molecule compared with continuously packed bimetallic sites. Here we report that isolated Rh1Co3 bimetallic sites exhibit a distinctly different catalytic performance in reduction of nitric oxide with carbon monoxide at low temperature, resulting from strong adsorption of two nitric oxide molecules and a nitrous oxide intermediate on Rh1Co3 sites and following a low-barrier pathway dissociation to dinitrogen and an oxygen atom. This observation suggests a method to develop catalysts with high selectivity.

  6. Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

    Science.gov (United States)

    DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

    2017-10-11

    Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

  7. Communication between the Zinc and Nickel Sites in Dimeric HypA: Metal Recognition and pH Sensing

    Energy Technology Data Exchange (ETDEWEB)

    Herbst, R.; Perovic, I; Martin-Diaconescu, V; O’Brien, K; Chivers, P; Sondej Pochapsky, S; Pochapsky, T; Maroney, M

    2010-01-01

    Helicobacter pylori, a pathogen that colonizes the human stomach, requires the nickel-containing metalloenzymes urease and NiFe-hydrogenase to survive this low pH environment. The maturation of both enzymes depends on the metallochaperone, HypA. HypA contains two metal sites, an intrinsic zinc site and a low-affinity nickel binding site. X-ray absorption spectroscopy (XAS) shows that the structure of the intrinsic zinc site of HypA is dynamic and able to sense both nickel loading and pH changes. At pH 6.3, an internal pH that occurs during acid shock, the zinc site undergoes unprecedented ligand substitutions to convert from a Zn(Cys){sub 4} site to a Zn(His){sub 2}(Cys){sub 2} site. NMR spectroscopy shows that binding of Ni(II) to HypA results in paramagnetic broadening of resonances near the N-terminus. NOEs between the {beta}-CH{sub 2} protons of Zn cysteinyl ligands are consistent with a strand-swapped HypA dimer. Addition of nickel causes resonances from the zinc binding motif and other regions to double, indicating more than one conformation can exist in solution. Although the structure of the high-spin, 5-6 coordinate Ni(II) site is relatively unaffected by pH, the nickel binding stoichiometry is decreased from one per monomer to one per dimer at pH = 6.3. Mutation of any cysteine residue in the zinc binding motif results in a zinc site structure similar to that found for holo-WT-HypA at low pH and is unperturbed by the addition of nickel. Mutation of the histidines that flank the CXXC motifs results in a zinc site structure that is similar to holo-WT-HypA at neutral pH (Zn(Cys){sub 4}) and is no longer responsive to nickel binding or pH changes. Using an in vitro urease activity assay, it is shown that the recombinant protein is sufficient for recovery of urease activity in cell lysate from a HypA deletion mutant, and that mutations in the zinc-binding motif result in a decrease in recovered urease activity. The results are interpreted in terms of a model

  8. Communication between the Zinc and Nickel Sites in Dimeric HypA: Metal Recognition and pH Sensing

    International Nuclear Information System (INIS)

    Herbst, R.; Perovic, I.; Martin-Diaconescu, V.; O'Brien, K.; Chivers, P.; Sondej Pochapsky, S.; Pochapsky, T.; Maroney, M.

    2010-01-01

    Helicobacter pylori, a pathogen that colonizes the human stomach, requires the nickel-containing metalloenzymes urease and NiFe-hydrogenase to survive this low pH environment. The maturation of both enzymes depends on the metallochaperone, HypA. HypA contains two metal sites, an intrinsic zinc site and a low-affinity nickel binding site. X-ray absorption spectroscopy (XAS) shows that the structure of the intrinsic zinc site of HypA is dynamic and able to sense both nickel loading and pH changes. At pH 6.3, an internal pH that occurs during acid shock, the zinc site undergoes unprecedented ligand substitutions to convert from a Zn(Cys) 4 site to a Zn(His) 2 (Cys) 2 site. NMR spectroscopy shows that binding of Ni(II) to HypA results in paramagnetic broadening of resonances near the N-terminus. NOEs between the β-CH 2 protons of Zn cysteinyl ligands are consistent with a strand-swapped HypA dimer. Addition of nickel causes resonances from the zinc binding motif and other regions to double, indicating more than one conformation can exist in solution. Although the structure of the high-spin, 5-6 coordinate Ni(II) site is relatively unaffected by pH, the nickel binding stoichiometry is decreased from one per monomer to one per dimer at pH = 6.3. Mutation of any cysteine residue in the zinc binding motif results in a zinc site structure similar to that found for holo-WT-HypA at low pH and is unperturbed by the addition of nickel. Mutation of the histidines that flank the CXXC motifs results in a zinc site structure that is similar to holo-WT-HypA at neutral pH (Zn(Cys) 4 ) and is no longer responsive to nickel binding or pH changes. Using an in vitro urease activity assay, it is shown that the recombinant protein is sufficient for recovery of urease activity in cell lysate from a HypA deletion mutant, and that mutations in the zinc-binding motif result in a decrease in recovered urease activity. The results are interpreted in terms of a model wherein HypA controls the

  9. Neutron activation analysis for noble metals in matte leach residues

    International Nuclear Information System (INIS)

    Hart, R.J.

    1978-01-01

    The development of the neutron activation analysis technique as a method for rapid and precise determinations of platinum group metals in matte leach residues depends on obtaining a method for effecting complete and homogeneous sample dilution. A simple method for solid dilution of metal samples is outlined in this study, which provided a basis for the accurate determination of all the noble metals by the Neutron Activation Analysis technique

  10. Fatty Acid-Mediated Inhibition of Metal Binding to the Multi-Metal Site on Serum Albumin: Implications for Cardiovascular Disease.

    Science.gov (United States)

    Blindauer, Claudia A; Khazaipoul, Siavash; Yu, Ruitao; Stewart, Alan J

    2016-01-01

    Human serum albumin (HSA) is the major protein in blood plasma and is responsible for circulatory transport of a range of small molecules including fatty acids, metal ions and drugs. We previously identified the major plasma Zn2+ transport site on HSA and revealed that fatty-acid binding (at a distinct site called the FA2 site) and Zn2+ binding are interdependent via an allosteric mechanism. Since binding affinities of long-chain fatty acids exceed those of plasma Zn2+, this means that under certain circumstances the binding of fatty acid molecules to HSA is likely to diminish HSA Zn2+-binding, and hence affects the control of circulatory and cellular Zn2+ dynamics. This relationship between circulatory fatty acid and Zn2+ dynamics is likely to have important physiological and pathological implications, especially since it has been recognised that Zn2+ acts as a signalling agent in many cell types. Fatty acid levels in the blood are dynamic, but most importantly, chronic elevation of plasma fatty acid levels is associated with some metabolic disorders and disease states - including myocardial infarction and other cardiovascular diseases. In this article, we briefly review the metal-binding properties of albumin and highlight the importance of their interplay with fatty acid binding. We also consider the impact of this dynamic link upon levels and speciation of plasma Zn2+, its effect upon cellular Zn2+ homeostasis and its relevance to cardiovascular and circulatory processes in health and disease.

  11. Safety Oversight of Decommissioning Activities at DOE Nuclear Sites

    International Nuclear Information System (INIS)

    Zull, Lawrence M.; Yeniscavich, William

    2008-01-01

    The Defense Nuclear Facilities Safety Board (Board) is an independent federal agency established by Congress in 1988 to provide nuclear safety oversight of activities at U.S. Department of Energy (DOE) defense nuclear facilities. The activities under the Board's jurisdiction include the design, construction, startup, operation, and decommissioning of defense nuclear facilities at DOE sites. This paper reviews the Board's safety oversight of decommissioning activities at DOE sites, identifies the safety problems observed, and discusses Board initiatives to improve the safety of decommissioning activities at DOE sites. The decommissioning of former defense nuclear facilities has reduced the risk of radioactive material contamination and exposure to the public and site workers. In general, efforts to perform decommissioning work at DOE defense nuclear sites have been successful, and contractors performing decommissioning work have a good safety record. Decommissioning activities have recently been completed at sites identified for closure, including the Rocky Flats Environmental Technology Site, the Fernald Closure Project, and the Miamisburg Closure Project (the Mound site). The Rocky Flats and Fernald sites, which produced plutonium parts and uranium materials for defense needs (respectively), have been turned into wildlife refuges. The Mound site, which performed R and D activities on nuclear materials, has been converted into an industrial and technology park called the Mound Advanced Technology Center. The DOE Office of Legacy Management is responsible for the long term stewardship of these former EM sites. The Board has reviewed many decommissioning activities, and noted that there are valuable lessons learned that can benefit both DOE and the contractor. As part of its ongoing safety oversight responsibilities, the Board and its staff will continue to review the safety of DOE and contractor decommissioning activities at DOE defense nuclear sites

  12. Soil pollution with trace elements at selected sites in Romania studied by instrumental neutron activation analysis

    International Nuclear Information System (INIS)

    Pantelica, A.; Carmo Freitas, M. do; Ene, A.; Steinnes, E.

    2013-01-01

    Instrumental neutron activation analysis (INAA) was used to determine concentrations of 42 elements in samples of surface soil collected at seven sites polluted from various anthropogenic activities and a control site in a relatively clean area. Elements studied were Ag, Al, As, Au, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Eu, Fe, Gd, Hf, Hg, K, La, Lu, Mg, Mn, Mo, Na, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Ti, U, V, W, Yb, Zn, and Zr. The results are compared with data for trace elements atmospheric deposition in lichen transplants from the same sites. The most severe soil contamination was observed at Copsa Mica from non-ferrous metallurgy. Appreciable soil contamination was also indicated at Baia Mare (non-ferrous mining and metallurgy), Deva (coal-fired power plant, cement and building materials industry), Galati (ferrous metallurgy), Magurele and Afumati (general urban pollution), and Oradea (chemical and light industries). In most cases excessive levels of toxic metals in soils matched correspondingly high values in lichen transplants. Compared to Romanian norms, legal upper limits were exceeded for Zn and Cd at Copsa Mica. Also, As and Sb occurred in excessive levels at given sites. (orig.)

  13. Soil pollution with trace elements at selected sites in Romania studied by instrumental neutron activation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Pantelica, A. [Horia Hulubei National Institute for Physics and Nuclear Engineering (IFIN-HH), Magurele, Ilfov County (Romania); Carmo Freitas, M. do [Technological and Nuclear Institute (ITN), Sacavem (Portugal); Ene, A. [Dunarea de Jos Univ. of Galati (Romania). Dept. of Chemistry, Physics and Environment; Steinnes, E. [Norwegian Univ. of Science and Technology, Trondheim (Norway). Dept. of Chemistry

    2013-03-01

    Instrumental neutron activation analysis (INAA) was used to determine concentrations of 42 elements in samples of surface soil collected at seven sites polluted from various anthropogenic activities and a control site in a relatively clean area. Elements studied were Ag, Al, As, Au, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Eu, Fe, Gd, Hf, Hg, K, La, Lu, Mg, Mn, Mo, Na, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Ti, U, V, W, Yb, Zn, and Zr. The results are compared with data for trace elements atmospheric deposition in lichen transplants from the same sites. The most severe soil contamination was observed at Copsa Mica from non-ferrous metallurgy. Appreciable soil contamination was also indicated at Baia Mare (non-ferrous mining and metallurgy), Deva (coal-fired power plant, cement and building materials industry), Galati (ferrous metallurgy), Magurele and Afumati (general urban pollution), and Oradea (chemical and light industries). In most cases excessive levels of toxic metals in soils matched correspondingly high values in lichen transplants. Compared to Romanian norms, legal upper limits were exceeded for Zn and Cd at Copsa Mica. Also, As and Sb occurred in excessive levels at given sites. (orig.)

  14. Poultry litter-based activated carbon for removing heavy metal ions in water.

    Science.gov (United States)

    Guo, Mingxin; Qiu, Guannan; Song, Weiping

    2010-02-01

    Utilization of poultry litter as a precursor material to manufacture activated carbon for treating heavy metal-contaminated water is a value-added strategy for recycling the organic waste. Batch adsorption experiments were conducted to investigate kinetics, isotherms, and capacity of poultry litter-based activated carbon for removing heavy metal ions in water. It was revealed that poultry litter-based activated carbon possessed significantly higher adsorption affinity and capacity for heavy metals than commercial activated carbons derived from bituminous coal and coconut shell. Adsorption of metal ions onto poultry litter-based carbon was rapid and followed Sigmoidal Chapman patterns as a function of contact time. Adsorption isotherms could be described by different models such as Langmuir and Freundlich equations, depending on the metal species and the coexistence of other metal ions. Potentially 404 mmol of Cu2+, 945 mmol of Pb2+, 236 mmol of Zn2+, and 250-300 mmol of Cd2+ would be adsorbed per kg of poultry litter-derived activated carbon. Releases of nutrients and metal ions from litter-derived carbon did not pose secondary water contamination risks. The study suggests that poultry litter can be utilized as a precursor material for economically manufacturing granular activated carbon that is to be used in wastewater treatment for removing heavy metals.

  15. Heavy metals in vegetables collected from production and market sites of a tropical urban area of India.

    Science.gov (United States)

    Sharma, Rajesh Kumar; Agrawal, Madhoolika; Marshall, Fiona M

    2009-03-01

    Vegetables (Beta vulgaris L., Abelmoschus esculentus L. and Brassica oleracea L.) from the production and market sites of India were tested for Cu, Cd, Zn and Pb. At market sites, the mean concentration of Cu in cauliflower, and of Zn and Cd in both palak and cauliflower had exceeded the PFA standard. Zn at the production sites also exceeded the PFA standard in cauliflower. Cd concentration in vegetables tested from both production and market sites was many folds higher than the EU standard. In contrast, Pb in vegetables tested from both production and market sites was below the PFA limit, but was considerably higher than the current EU and WHO standards. Heavy metals accumulation in vegetables tested are higher at market sites than those at the crop production sites. The contributions of these vegetables to dietary intake of Cu, Zn, Cd and Pb were 13%, 1%, 47% and 9% of provisional tolerable daily intake, respectively. The study concludes that the transportation and marketing systems of vegetables play a significant role in elevating the contaminant levels of heavy metals which may pose a threat to the quality of the vegetables with consequences for the health of the consumers of locally produced foodstuffs.

  16. Chapter 19: Catalysis by Metal Carbides and Nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Schaidle, Joshua A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Nash, Connor P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Yung, Matthew M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Chen, Yuan [Pacific Northwest National Laboratory; Carl, Sarah [University of Michigan; Thompson, Levi [University of Michigan

    2017-08-09

    Early transition metal carbides and nitrides (ETMCNs), materials in which carbon or nitrogen occupies interstitial sites within a parent metal lattice, possess unique physical and chemical properties that motivate their use as catalysts. Specifically, these materials possess multiple types of catalytic sites, including metallic, acidic, and basic sites, and as such, exhibit reactivities that differ from their parent metals. Moreover, their surfaces are dynamic under reaction conditions. This chapter reviews recent (since 2010) experimental and computational investigations into the catalytic properties of ETMCN materials for applications including biomass conversion, syngas and CO2 upgrading, petroleum and natural gas refining, and electrocatalytic energy conversion, energy storage, and chemicals production, and attempts to link catalyst performance to active site identity/surface structure in order to elucidate the present level of understanding of structure-function relationships for these materials. The chapter concludes with a perspective on leveraging the unique properties of these materials to design and develop improved catalysts through a dedicated, multidisciplinary effort.

  17. Relating Magnetic Parameters to Heavy Metal Concentrations and Environmental Factors at Formosa Mine Superfund Site, Douglas County, OR

    Science.gov (United States)

    Upton, T. L.

    2016-12-01

    Advances in the field of environmental magnetism have led to exciting new applications for this field. Magnetic minerals are ubiquitous in the environment and tend to have an affinity for heavy metals. Hence, it has been demonstrated that magnetic properties are often significantly related to concentrations of heavy metals and other pollutants. As a result, magnetic techniques have been used as proxy for determining hot spots of several types of pollution produced from a diversity of anthropogenic sources. Magnetic measurements are non-destructive and relatively inexpensive compared to geochemical analyses. The utility of environmental magnetic methods varies widely depending on biological, chemical and physical processes that create and transform soils and sediments. Applications in the direction of mapping heavy metals have been studied and shown to be quite useful in countries such as China and India but to date, little research has been done in the US. As such, there is need to expand the scope of research to a wider range of soil types and land uses, especially within the US. This study investigates the application of environmental magnetic techniques to mapping of heavy metal concentrations at the Formosa Mine Superfund Site, an abandoned mine about 25 miles southwest of Roseburg, OR. The soils and sediment at this site are derived from pyrite-rich bedrock which is weak in terms of magnetic susceptibility. Using hotspot analysis, correlation and cluster analyses, interactions between metals and magnetic parameters are investigated in relation to environmental factors such as proximity to seeps and adits. Preliminary results suggest significant correlation of magnetic susceptibility with certain heavy metals, signifying that magnetic methods may be useful in mapping heavy metal hotspots at this site. Further analysis examines the relation of various land use differences in magnetic signatures obtained throughout the Cow Creek watershed.

  18. Remedial actions at the former Vitro Rare Metals plant site, Canonsburg, Washington County, Pennsylvania. Final Environmental Impact Statement. Volume I

    Energy Technology Data Exchange (ETDEWEB)

    1983-07-01

    The environmental impacts associated with remedial actions in connection with residual radioactive materials remaining at the inactive uranium processing site located in Canonsburg, Washington County, Pennsylvania are evaluated. The Canonsburg site is an 18.5-acre property that was formerly owned by the Vitro Rare Metals Company. The expanded Canonsburg site would be 30-acre property that would include the Canonsburg site (the former Vitro Rare Metals plant), seven adjacent private houses, and the former Georges Pottery property. During the period 1942 through 1957 the Vitro Manufacturing Company and its successor, the Vitro Corporation of America, processed onsite residues and ores, and government-owned ores, concentrates, and scraps to extract uranium and other rare metals. The Canonsburg site is now the Canon Industrial Park. In addition to storing the residual radioactive materials of this process at the Canonsburg site, about 12,000 tons of radioactively contaminated materials were transferred to a railroad landfill in Burrell Township, Indiana County, Pennsylvania. This Canonsburg FEIS evaluates five alternatives for removing the potential public health hazard associated with the radioactively contaminated materials. In addition to no action, these alternatives involve various combinations of stabilization of the radioactively contaminated materials in place or decontamination of the Canonsburg and Burrell sites by removing the radioactively contaminated materials to another location. In addition to the two sites mentioned, a third site located in Hanover Township, Washington County, Pennsylvania has been considered as a disposal site to which the radioactively contaminated materials presently located at either of the other two sites might be moved.

  19. Remedial actions at the former Vitro Rare Metals plant site, Canonsburg, Washington County, Pennsylvania. Final Environmental Impact Statement. Volume I

    International Nuclear Information System (INIS)

    1983-07-01

    The environmental impacts associated with remedial actions in connection with residual radioactive materials remaining at the inactive uranium processing site located in Canonsburg, Washington County, Pennsylvania are evaluated. The Canonsburg site is an 18.5-acre property that was formerly owned by the Vitro Rare Metals Company. The expanded Canonsburg site would be 30-acre property that would include the Canonsburg site (the former Vitro Rare Metals plant), seven adjacent private houses, and the former Georges Pottery property. During the period 1942 through 1957 the Vitro Manufacturing Company and its successor, the Vitro Corporation of America, processed onsite residues and ores, and government-owned ores, concentrates, and scraps to extract uranium and other rare metals. The Canonsburg site is now the Canon Industrial Park. In addition to storing the residual radioactive materials of this process at the Canonsburg site, about 12,000 tons of radioactively contaminated materials were transferred to a railroad landfill in Burrell Township, Indiana County, Pennsylvania. This Canonsburg FEIS evaluates five alternatives for removing the potential public health hazard associated with the radioactively contaminated materials. In addition to no action, these alternatives involve various combinations of stabilization of the radioactively contaminated materials in place or decontamination of the Canonsburg and Burrell sites by removing the radioactively contaminated materials to another location. In addition to the two sites mentioned, a third site located in Hanover Township, Washington County, Pennsylvania has been considered as a disposal site to which the radioactively contaminated materials presently located at either of the other two sites might be moved

  20. Metal concentrations in earthworms from sewage sludge-amended soils at a strip mine reclamation site

    Energy Technology Data Exchange (ETDEWEB)

    Pietz, R.I.; Peterson, J.R.; Prater, J.E.; Zenz, D.R.

    A 3-yr study of earthworms was initiated in selected mine soil and nonmined fields at a Fulton County, IL land reclamation site. The purpose of this research was to determine the effect of the land application of anaerobically digested sewage sludge, used to reclaim the site, on heavy metal accumulations in earthworms. Two species of earthworms, Lumbricus terrestris and Aporrectodea tuberculata, were identified in the sludge-amended and nonamended, nonmined fields sampled. Only A. tuberculata was found in the sludge-amended and nonamended mine soil fields sampled. Earthworm metal concentrations generally increased with time in all the sampled fields. The decreasing order of metal accumulation by earthworms in all sludge-amended fields sampled was Cu > Cd > Ni > Cr > Pb > Zn. Sewage sludge applications to fields on both land types resulted in significant accumulations of Cd, Cu, and Zn. Land type (mine soil vs. nonmined) significantly affected earthworm Zn concentrations, with levels being higher in all nonmined fields sampled. Earthworm Cd and Cu accumulations in all fields sampled were significantly related to the current amounts of sludge-applied metals, the amount applied since the previous sampling. Concentrations of Ni, Cr, and Pb in earthworms were not significantly related to sewage sludge applications during the 1975 to 1977 sampling period. The higher Cd and Cu concentrations in earthworms from sludge-amended fields may pose a potential hazard to predators.

  1. Modulation of individual steps in group I intron catalysis by a peripheral metal ion.

    Science.gov (United States)

    Forconi, Marcello; Piccirilli, Joseph A; Herschlag, Daniel

    2007-10-01

    Enzymes are complex macromolecules that catalyze chemical reactions at their active sites. Important information about catalytic interactions is commonly gathered by perturbation or mutation of active site residues that directly contact substrates. However, active sites are engaged in intricate networks of interactions within the overall structure of the macromolecule, and there is a growing body of evidence about the importance of peripheral interactions in the precise structural organization of the active site. Here, we use functional studies, in conjunction with published structural information, to determine the effect of perturbation of a peripheral metal ion binding site on catalysis in a well-characterized catalytic RNA, the Tetrahymena thermophila group I ribozyme. We perturbed the metal ion binding site by site-specifically introducing a phosphorothioate substitution in the ribozyme's backbone, replacing the native ligands (the pro-R (P) oxygen atoms at positions 307 and 308) with sulfur atoms. Our data reveal that these perturbations affect several reaction steps, including the chemical step, despite the absence of direct contacts of this metal ion with the atoms involved in the chemical transformation. As structural probing with hydroxyl radicals did not reveal significant change in the three-dimensional structure upon phosphorothioate substitution, the effects are likely transmitted through local, rather subtle conformational rearrangements. Addition of Cd(2+), a thiophilic metal ion, rescues some reaction steps but has deleterious effects on other steps. These results suggest that native interactions in the active site may have been aligned by the naturally occurring peripheral residues and interactions to optimize the overall catalytic cycle.

  2. Dashboard applications to monitor experiment activities at sites

    Energy Technology Data Exchange (ETDEWEB)

    Andreeva, Julia; Gaidioz, Benjamin; Grigoras, Costin; Kokoszkiewicz, Lukasz; Lanciotti, Elisa; Rocha, Ricardo; Saiz, Pablo; Santinelli, Roberto; Sidorova, Irina; Sciaba, Andrea [CERN, European Organization for Nuclear Research (Switzerland); Belforte, Stefano [INFN Trieste (Italy); Boehm, Max [EDS, an HP Company, Plano, TX (United States); Casajus, Adrian [Universitat de Barcelona (Spain); Flix, Josep [PIC, Port d' Informacio CientIfica, Bellaterra (Spain); Tsaregorodtsev, Andrei, E-mail: Elisa.Lanciotti@cern.c, E-mail: Pablo.Saiz@cern.c [CPPM Marseille (France)

    2010-04-01

    In the framework of a distributed computing environment, such as WLCG, monitoring has a key role in order to keep under control activities going on in sites located in different countries and involving people based in many different sites. To be able to cope with such a large scale heterogeneous infrastructure, it is necessary to have monitoring tools providing a complete and reliable view of the overall performance of the sites. Moreover, the structure of a monitoring system critically depends on the object to monitor and on the users it is addressed to. In this article we will describe two different monitoring systems both aimed to monitor activities and services provided in the WLCG framework, but designed in order to meet the requirements of different users: Site Status Board has an overall view of the services available in all the sites supporting an experiment, whereas Siteview provides a complete view of all the activities going on at a site, for all the experiments supported by the site.

  3. Dashboard applications to monitor experiment activities at sites

    International Nuclear Information System (INIS)

    Andreeva, Julia; Gaidioz, Benjamin; Grigoras, Costin; Kokoszkiewicz, Lukasz; Lanciotti, Elisa; Rocha, Ricardo; Saiz, Pablo; Santinelli, Roberto; Sidorova, Irina; Sciaba, Andrea; Belforte, Stefano; Boehm, Max; Casajus, Adrian; Flix, Josep; Tsaregorodtsev, Andrei

    2010-01-01

    In the framework of a distributed computing environment, such as WLCG, monitoring has a key role in order to keep under control activities going on in sites located in different countries and involving people based in many different sites. To be able to cope with such a large scale heterogeneous infrastructure, it is necessary to have monitoring tools providing a complete and reliable view of the overall performance of the sites. Moreover, the structure of a monitoring system critically depends on the object to monitor and on the users it is addressed to. In this article we will describe two different monitoring systems both aimed to monitor activities and services provided in the WLCG framework, but designed in order to meet the requirements of different users: Site Status Board has an overall view of the services available in all the sites supporting an experiment, whereas Siteview provides a complete view of all the activities going on at a site, for all the experiments supported by the site.

  4. Phytoscreening and phytoextraction of heavy metals at Danish polluted sites using willow and poplar trees.

    Science.gov (United States)

    Algreen, Mette; Trapp, Stefan; Rein, Arno

    2014-01-01

    The main purpose of this study was to determine typical concentrations of heavy metals (HM) in wood from willows and poplars, in order to test the feasibility of phytoscreening and phytoextraction of HM. Samples were taken from one strongly, one moderately, and one slightly polluted site and from three reference sites. Wood from both tree species had similar background concentrations at 0.5 mg kg(-1) for cadmium (Cd), 1.6 mg kg(-1) for copper (Cu), 0.3 mg kg(-1) for nickel (Ni), and 25 mg kg(-1) for zinc (Zn). Concentrations of chromium (Cr) and lead (Pb) were below or close to detection limit. Concentrations in wood from the highly polluted site were significantly elevated, compared to references, in particular for willow. The conclusion from these results is that tree coring could be used successfully to identify strongly heavy metal-polluted soil for Cd, Cu, Ni, Zn, and that willow trees were superior to poplars, except when screening for Ni. Phytoextraction of HMs was quantified from measured concentration in wood at the most polluted site. Extraction efficiencies were best for willows and Cd, but below 0.5% over 10 years, and below 1‰ in 10 years for all other HMs.

  5. Emission Channeling Studies of the Lattice Site of Oversized Alkali Atoms Implanted in Metals

    CERN Multimedia

    2002-01-01

    % IS340 \\\\ \\\\ As alkali atoms have the largest atomic radius of all elements, the determination of their lattice configuration following implantation into metals forms a critical test for the various models predicting the lattice site of implanted impurity atoms. The site determination of these large atoms will especially be a crucial check for the most recent model that relates the substitutional fraction of oversized elements to their solution enthalpy. Recent exploratory $^{213}$Fr and $^{221}$Fr $\\alpha$-emission channeling experiments at ISOLDE-CERN and hyperfine interaction measurements on Fr implanted in Fe gave an indication for anomalously large substitutional fractions. To investigate further the behaviour of Fr and other alkali atoms like Cs and Rb thoroughly, more on-line emission channeling experiments are needed. We propose a number of shifts for each element, where the temperature of the implanted metals will be varied between 50$^\\circ$ and 700$^\\circ$~K. Temperature dependent measurements wi...

  6. Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study.

    Science.gov (United States)

    Wittmann, Thomas; Mondal, Arobendo; Tschense, Carsten B L; Wittmann, Johannes J; Klimm, Ottokar; Siegel, Renée; Corzilius, Björn; Weber, Birgit; Kaupp, Martin; Senker, Juergen

    2018-02-14

    Understanding host-guest interactions is one of the key requirements for adjusting properties in metal-organic frameworks (MOFs). In particular, systems with coordinatively unsaturated Lewis acidic metal sites feature highly selective adsorption processes. This is attributed to strong interactions with Lewis basic guest molecules. Here we show that a combination of 13 C MAS NMR spectroscopy with state-of-the-art density functional theory (DFT) calculations allows one to unravel the interactions of water, 2-aminopyridine, 3-aminopyridine, and diethylamine with the open metal sites in Cr-MIL-101. The 13 C MAS NMR spectra, obtained with ultrafast magic-angle spinning, are well resolved, with resonances distributed over 1000 ppm. They present a clear signature for each guest at the open metal sites. Based on competition experiments this leads to the following binding preference: water open metal sites, the NMR data offer additional information about the guest and framework dynamics. We expect that our strategy has the potential for probing the binding situation of adsorbate mixtures at the open metal sites of MOFs in general and thus accesses the microscopic interaction mechanisms for this important material class, which is essential for deriving structure-property relationships.

  7. A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity.

    Science.gov (United States)

    Li, L H; Deng, Z X; Xiao, J X; Yang, G W

    2015-01-26

    Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

  8. Enhancing the use of waste activated sludge as bio-fuel through selectively reducing its heavy metal content.

    Science.gov (United States)

    Dewil, Raf; Baeyens, Jan; Appels, Lise

    2007-06-18

    Power plant or cement kiln co-incineration are important disposal routes for the large amounts of waste activated sludge (WAS) which are generated annually. The presence of significant amounts of heavy metals in the sludge however poses serious problems since they are partly emitted with the flue gases (and collected in the flue gas dedusting) and partly incorporated in the ashes of the incinerator: in both cases, the disposal or reuse of the fly ash and bottom ashes can be jeopardized since subsequent leaching in landfill disposal can occur, or their "pozzolanic" incorporation in cement cannot be applied. The present paper studies some physicochemical methods for reducing the heavy metal content of WAS. The used techniques include acid and alkaline thermal hydrolysis and Fenton's peroxidation. By degrading the extracellular polymeric substances, binding sites for a large amount of heavy metals, the latter are released into the sludge water. The behaviour of several heavy metals (Cd, Cr, Cu, Hg, Pb, Ni, Zn) was assessed in laboratory tests. Results of these show a significant reduction of most heavy metals.

  9. Quantitative analysis of the extent of heavy-metal contamination in soils near Picher, Oklahoma, within the Tar Creek Superfund Site.

    Science.gov (United States)

    Beattie, Rachelle E; Henke, Wyatt; Davis, Conor; Mottaleb, M Abdul; Campbell, James H; McAliley, L Rex

    2017-04-01

    The Tri-State Mining District of Missouri, Kansas and Oklahoma was the site of large-scale mining operations primarily for lead and zinc until the mid-1950s. Although mining across the area has ceased, high concentrations of heavy metals remain in the region's soil and water systems. The town of Picher, Ottawa County, OK, lies within this district and was included in the Tar Creek Superfund Site by the U.S. Environmental Protection Agency in 1980 due to extensive contamination. To elucidate the extent of heavy-metal contamination, a soil-chemistry survey of the town of Picher was conducted. Samples (n = 111) were collected from mine tailings, locally known as chat, in Picher and along cardinal-direction transects within an 8.05-km radius of the town in August 2015. Samples were analyzed for soil pH, moisture, and metal content. Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) analyses of 20 metals showed high concentrations of lead (>1000 ppm), cadmium (>40 ppm) and zinc (>4000 ppm) throughout the sampled region. Soil moisture content ranged from 0.30 to 35.9%, and pH values ranged from 5.14 to 7.42. MANOVA of metal profiles determined that soils collected from the north transect and chat were significantly different (p zinc were correlated with one another. These data show an unequal distribution of contamination surrounding the Picher mining site. Mapping heavy-metal contamination in these soils represents the first step in understanding the distribution of these contaminants at the Picher mining site. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Environmental impact assessment of radionuclide and metal contamination at the former U sites Taboshar and Digmai, Tajikistan

    International Nuclear Information System (INIS)

    Skipperud, L.; Strømman, G.; Yunusov, M.; Stegnar, P.; Uralbekov, B.; Tilloboev, H.; Zjazjev, G.; Heier, L.S.; Rosseland, B.O.; Salbu, B.

    2013-01-01

    Uranium (U) ore mining and processing were initiated in the former Soviet Republics of Tajikistan after the Second World War as part of the USSR nuclear weapon programme. The U mine in Taboshar was opened in 1936, and mining took place from 1945 to 1965, while the Digmai tailings dump was exploited during 1963–1993. The mining, milling and extraction activities have resulted in large amounts of waste rock deposits and U tailing materials placed in the vicinity of inhabited areas. To assess the environmental impact of radionuclides and trace metals in the Taboshar and Digmai mining and tailing sites in Tajikistan, field expeditions were performed in 2006 and 2008. In addition to in situ gamma and radon dose rate measurements, sampling of water, fish, sediments, soils and vegetation including in situ fractionation of water were performed. The U concentrations in water from Taboshar Pit Lake (2.0 mg U/L) were higher than in waters collected in the Digmai area. The Pit Lake and the stream water from the tailing mountain were also characterised by elevated concentrations of As, Mo, Mn and Fe, exceeding the WHO recommended values for drinking water. Uranium, As, Mo and Ni were present as low molecular mass species in the waters, and are therefore considered mobile and potentially bioavailable. The 238 U concentrations in sediments and soils varied between the sites; with peak concentrations (6 kBq/kg dw) in sediments from the Pit Lake, while the soil concentrations were significantly lower (296–590 Bq/kg dw). In contrast, high levels of the radium isotopes ( 226 Ra and 228 Ra) were found in the Digmai soil (17–32 kBq/kg dw). Based on sequential extraction results, both U and Pb were found to be quite mobile at the Pit Lake site, showing that these elements were associated with the pH sensitive and redox sensitive amorphous fractions. In tailings, U was found to be quite mobile, but here Pb was rather inert. The transfer of radionuclides and metals from sediments to

  11. Effect of heavy metals on nitrification performance in different activated sludge processes

    International Nuclear Information System (INIS)

    You, Sheng-Jie; Tsai, Yung-Pin; Huang, Ru-Yi

    2009-01-01

    To understand the toxic effect of heavy metals on the nitrification mechanisms of activated sludge, this study identified the specific ammonia utilization rate (SAUR) inhibited by Pb, Ni and/or Cd shock loadings. Seven different heavy metal combinations (Pb, Ni, Cd, Pb + Ni, Ni + Cd, Pb + Cd, and Pb + Ni + Cd) with seven different heavy metal concentrations (0, 2, 5, 10, 15, 25, and 40 ppm, respectively) were examined by batch experiments, where the activated sludge was taken from either sequencing batch reactor (SBR) or anaerobic-anoxic-oxic (A 2 O) processes. The experimental results showed the SAUR inhibition rate was Ni > Cd > Pb. No significant inhibition in the nitrification reaction of the activated sludge was observed even when as much as 40 ppm Pb was added. In addition, no synergistic effect was found when different heavy metals were simultaneously added in different concentrations, and the overall inhibition effect depended on the heavy metal with the highest toxicity. Further, first order kinetic reaction could model the behavior of SAUR inhibition on activated sludge when adding heavy metals, and the SAUR inhibition formula was derived as SAUR=(SAUR max -SAUR min )xe -r i c +SAUR min . On the other hand, the heavy metal adsorption ability in both the activated sludge system was Pb = Cd > Ni. The specific adsorption capacity of activated sludge on heavy metal increased as the heavy metal concentration increased or the mixed liquid volatile suspended solid (MLVSS) decreased. The batch experiments also showed the heavy metal adsorption capacity of the SBR sludge was larger than the A 2 O sludge. Finally, the most predominant bacteria in the phylogenetic trees of SBR and A 2 O activated sludges were proteobacteria, which contributed to 42.1% and 42.8% of the total clones.

  12. Integrin Activation Dynamics between the RGD-binding Site and the Headpiece Hinge*

    Science.gov (United States)

    Puklin-Faucher, Eileen; Vogel, Viola

    2009-01-01

    Integrins form mechanical links between the extracellular matrix and the cytoskeleton. Although integrin activation is known to be regulated by an allosteric conformational change, which can be induced from the extracellular or intracellular end of the molecule, little is known regarding the sequence of structural events by which signals propagate between distant sites. Here, we reveal with molecular dynamics simulations of the FnIII10-bound αVβ3 integrin headpiece how the binding pocket and interdomain βA/hybrid domain hinge on the distal end of the βA domain are allosterically linked via a hydrophobic T-junction between the middle of the α1 helix and top of the α7 helix. The key results of this study are: 1) that this T-junction is induced by ligand binding and hinge opening, and thus displays bidirectionality; 2) that formation of this junction can be accelerated by ligand-mediated force; and 3) how formation of this junction is inhibited by Ca2+ in place of Mg2+ at the site adjacent to the metal ion-dependent adhesion site (“ADMIDAS”). Together with recent experimental evidence that integrin complexes can form catch bonds (i.e. become strengthened under force), as well as earlier evidence that Ca2+ at the ADMIDAS results in lower binding affinity, these simulations provide a common structural model for the dynamic process by which integrins become activated. PMID:19762919

  13. Cleavage of hydrogen by activation at a single non-metal centre - towards new hydrogen storage materials.

    Science.gov (United States)

    Grabowski, Sławomir J

    2015-05-28

    Molecular surfaces of non-metal species are often characterized by both positive and negative regions of electrostatic potential (EP) at a non-metal centre. This centre may activate molecular hydrogen which further leads to the addition reaction. The positive EP regions at the non-metal centres correspond to σ-holes; the latter sites are enhanced by electronegative substituents. This is why the following simple moieties; PFH2, SFH, AsFH2, SeFH, BrF3, PF(CH3)2 and AsF(CH3)2, were chosen here to analyze the H2 activation and its subsequent splitting at the P, As, S, Se and Br centres. Also the reverse H-H bond reforming process is analyzed. MP2/aug-cc-pVTZ calculations were performed for systems corresponding to different stages of these processes. The sulphur centre in the SFH moiety is analyzed in detail since the potential barrier height for the addition reaction for this species is the lowest of the moieties analyzed here. The results of calculations show that the SFH + H2 → SFH3 reaction in the gas phase is endothermic but it is exothermic in polar solvents.

  14. Copper-zinc superoxide dismutase is activated through a sulfenic acid intermediate at a copper ion entry site.

    Science.gov (United States)

    Fetherolf, Morgan M; Boyd, Stefanie D; Taylor, Alexander B; Kim, Hee Jong; Wohlschlegel, James A; Blackburn, Ninian J; Hart, P John; Winge, Dennis R; Winkler, Duane D

    2017-07-21

    Metallochaperones are a diverse family of trafficking molecules that provide metal ions to protein targets for use as cofactors. The copper chaperone for superoxide dismutase (Ccs1) activates immature copper-zinc superoxide dismutase (Sod1) by delivering copper and facilitating the oxidation of the Sod1 intramolecular disulfide bond. Here, we present structural, spectroscopic, and cell-based data supporting a novel copper-induced mechanism for Sod1 activation. Ccs1 binding exposes an electropositive cavity and proposed "entry site" for copper ion delivery on immature Sod1. Copper-mediated sulfenylation leads to a sulfenic acid intermediate that eventually resolves to form the Sod1 disulfide bond with concomitant release of copper into the Sod1 active site. Sod1 is the predominant disulfide bond-requiring enzyme in the cytoplasm, and this copper-induced mechanism of disulfide bond formation obviates the need for a thiol/disulfide oxidoreductase in that compartment. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  15. Measuring the noble metal and iodine composition of extracted noble metal phase from spent nuclear fuel using instrumental neutron activation analysis

    International Nuclear Information System (INIS)

    Palomares, R.I.; Dayman, K.J.; Landsberger, S.; Biegalski, S.R.; Soderquist, C.Z.; Casella, A.J.; Brady Raap, M.C.; Schwantes, J.M.

    2015-01-01

    Masses of noble metal and iodine nuclides in the metallic noble metal phase extracted from spent fuel are measured using instrumental neutron activation analysis. Nuclide presence is predicted using fission yield analysis, and radionuclides are identified and the masses quantified using neutron activation analysis. The nuclide compositions of noble metal phase derived from two dissolution methods, UO 2 fuel dissolved in nitric acid and UO 2 fuel dissolved in ammonium-carbonate and hydrogen-peroxide solution, are compared. - Highlights: • The noble metal phase was chemically extracted from spent nuclear fuel and analyzed non-destructively. • Noble metal phase nuclides and long-lived iodine were identified and quantified using neutron activation analysis. • Activation to shorter-lived radionuclides allowed rapid analysis of long-lived fission products in spent fuel using gamma spectrometry

  16. Comparison of PM10 concentrations and metal content in three different sites of the Venice Lagoon: an analysis of possible aerosol sources.

    Science.gov (United States)

    Contini, Daniele; Belosi, Franco; Gambaro, Andrea; Cesari, Daniela; Stortini, Angela Maria; Bove, Maria Chiara

    2012-01-01

    The Venice Lagoon is exposed to atmospheric pollutants from industrial activities, thermoelectric power plants, petrochemical plants, incinerator, domestic heating, ship traffic, glass factories and vehicular emissions on the mainland. In 2005, construction began on the mobile dams (MOSE), one dam for each channel connecting the lagoon to the Adriatic Sea as a barrier against high tide. These construction works could represent an additional source of pollutants. PM10 samples were taken on random days between 2007 and 2010 at three different sites: Punta Sabbioni, Chioggia and Malamocco, located near the respective dam construction worksites. Chemical analyses of V, Cr, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl and Pb in PM10 samples were performed by Inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) and results were used to identify the main aerosol sources. The correlation of measured data with meteorology, and source apportionment, failed to highlight a contribution specifically associated to the emissions of the MOSE construction works. The comparison of the measurements at the three sites showed a substantial homogeneity of metal concentrations in the area. Source apportionment with principal component analysis (PCA) and positive matrix factorization (PMF) showed that a four principal factors model could describe the sources of metals in PM10. Three of them were assigned to specific sources in the area and one was characterised as a source of mixed origin (anthropogenic and crustal). A specific anthropogenic source of PM10 rich in Ni and Cr, active at the Chioggia site, was also identified.

  17. Description of the Northwest hazardous waste site data base and preliminary analysis of site characteristics

    International Nuclear Information System (INIS)

    Woodruff, D.L.; Hartz, K.E.; Triplett, M.B.

    1988-08-01

    The Northwest Hazardous Waste RD and D Center (the Center) conducts research, development, and demonstration (RD and D) activities for hazardous and radioactive mixed-waste technologies applicable to remediating sites in the states of Idaho, Montana, Oregon, and Washington. To properly set priorities for these RD and D activities and to target development efforts it is necessary to understand the nature of the sites requiring remediation. A data base of hazardous waste site characteristics has been constructed to facilitate this analysis. The data base used data from EPA's Region X Comprehensive Environmental Response, Compensation, and Liability Information System (CERCLIS) and from Preliminary Assessment/Site Investigation (PA/SI) forms for sites in Montana. The Center's data base focuses on two sets of sites--those on the National Priorities List (NPL) and other sites that are denoted as ''active'' CERCLIS sites. Active CERCLIS sites are those sites that are undergoing active investigation and analysis. The data base contains information for each site covering site identification and location, type of industry associated with the site, waste categories present (e.g., heavy metals, pesticides, etc.), methods of disposal (e.g., tanks, drums, land, etc.), waste forms (e.g., liquid, solid, etc.), and hazard targets (e.g., surface water, groundwater, etc.). As part of this analysis, the Northwest region was divided into three geographic subregions to identify differences in disposal site characteristics within the Northwest. 2 refs., 18 figs., 5 tabs

  18. Anaerobic bioleaching of metals from waste activated sludge

    KAUST Repository

    Meulepas, Roel J W

    2015-05-01

    Heavy metal contamination of anaerobically digested waste activated sludge hampers its reuse as fertilizer or soil conditioner. Conventional methods to leach metals require aeration or the addition of leaching agents. This paper investigates whether metals can be leached from waste activated sludge during the first, acidifying stage of two-stage anaerobic digestion without the supply of leaching agents. These leaching experiments were done with waste activated sludge from the Hoek van Holland municipal wastewater treatment plant (The Netherlands), which contained 342μgg-1 of copper, 487μgg-1 of lead, 793μgg-1 of zinc, 27μgg-1 of nickel and 2.3μgg-1 of cadmium. During the anaerobic acidification of 3gdry weightL-1 waste activated sludge, 80-85% of the copper, 66-69% of the lead, 87% of the zinc, 94-99% of the nickel and 73-83% of the cadmium were leached. The first stage of two-stage anaerobic digestion can thus be optimized as an anaerobic bioleaching process and produce a treated sludge (i.e., digestate) that meets the land-use standards in The Netherlands for copper, zinc, nickel and cadmium, but not for lead.

  19. Metal-Free, Site-Selective Peptide Modification by Conversion of "Customizable" Units into β-Substituted Dehydroamino Acids.

    Science.gov (United States)

    Saavedra, Carlos J; Hernández, Dácil; Boto, Alicia

    2018-01-12

    Our site-selective modification of serine or threonine units in peptides allows the generation of β-substituted dehydroamino acids, which increase peptide resistance to hydrolysis and may improve their biological properties. Both the terminal and internal positions can be modified, and different customizable units can be activated separately. Remarkably, high Z selectivity is achieved, even at internal positions. The conversion involves a one-pot oxidative radical scission/phosphorylation process by using the low-toxicity (diacetoxyiodo)benzene/iodine system as the scission reagent. The resulting α-amino phosphonates undergo a Horner-Wadsworth-Emmons reaction to produce the dehydroamino acid derivatives (in a Z/E ratio of usually >98:2) under mild and metal-free conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Metal-chelating active packaging film enhances lysozyme inhibition of Listeria monocytogenes.

    Science.gov (United States)

    Roman, Maxine J; Decker, Eric A; Goddard, Julie M

    2014-07-01

    Several studies have demonstrated that metal chelators enhance the antimicrobial activity of lysozyme. This study examined the effect of metal-chelating active packaging film on the antimicrobial activity of lysozyme against Listeria monocytogenes. Polypropylene films were surface modified by photoinitiated graft polymerization of acrylic acid (PP-g-PAA) from the food contact surface of the films to impart chelating activity based on electrostatic interactions. PP-g-PAA exhibited a carboxylic acid density of 113 ± 5.4 nmol cm(-2) and an iron chelating activity of 53.7 ± 9.8 nmol cm(-2). The antimicrobial interaction of lysozyme and PP-g-PAA depended on growth media composition. PP-g-PAA hindered lysozyme activity at low ionic strength (2.48-log increase at 64.4 mM total ionic strength) and enhanced lysozyme activity at moderate ionic strength (5.22-log reduction at 120 mM total ionic strength). These data support the hypothesis that at neutral pH, synergy between carboxylate metal-chelating films (pKa(bulk) 6.45) and lysozyme (pI 11.35) is optimal in solutions of moderate to high ionic strength to minimize undesirable charge interactions, such as lysozyme absorption onto film. These findings suggest that active packaging, which chelates metal ions based on ligand-specific interactions, in contrast to electrostatic interactions, may improve antimicrobial synergy. This work demonstrates the potential application of metal-chelating active packaging films to enhance the antimicrobial activity of membrane-disrupting antimicrobials, such as lysozyme.

  1. Environmental compliance at U.S. Department of Energy FUSRAP (Formerly Utilized Sites Remedial Action Program) sites

    International Nuclear Information System (INIS)

    Liedle, S.D.; Clemens, B.W.

    1988-01-01

    With the promulgation of the Superfund Amendments and Reauthorization Act (SARA), federal facilities were required to comply with the Comprehensive Environmental Response Compensation and Liability Act (CERCLA) in the same manner as any non-government entity. This presented challenges for the Department of Energy (DOE) and other federal agencies involved in remedial action work because there are many requirements under SARA that overlap other laws requiring DOE compliance, e.g., the National Environmental Policy Act (NEPA). This paper outlines the options developed to comply with CERCLA and NEPA as part of active, multi-site remedial action program. The program, the Formerly Utilized Sites Remedial Action Program (FUSRAP), was developed to identify, clean up, or control sites containing residual radioactive or chemical contamination as a result of the nation's early development of nuclear power. During the Manhattan Project, uranium was extracted from ores and resulted in mill concentrates, purified metals, and waste products that were transported for use or disposal at other locations. Figure 1 shows the steps for producing uranium metal during the Manhattan Project. As a result of these activities materials, equipment, buildings, and land became contaminated, primarily with naturally occurring radionuclides. Currently, FUSRAP includes 29 sites; three are on the Environmental Protection Agency's (EPA's) National Priorities List (NPL) of hazardous waste sites

  2. Effect of impregnation protocol in the metallic sites of Pt–Ag/activated carbon catalysts for water denitration

    Energy Technology Data Exchange (ETDEWEB)

    Aristizábal, A. [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain); Contreras, S., E-mail: sandra.contreras@urv.cat [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain); Divins, N.J.; Llorca, J. [Institut de Tècniques Energètiques i Centre de Recerca en Nanoenginyeria, Universitat Politècnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Medina, F. [Departament d’Enginyeria Química, Universitat Rovira i Virgili, Campus Sescelades, Av. Països Catalans 26, 43007 Tarragona (Spain)

    2014-04-01

    Highlights: • Mean particle size is tuned by the Pt precursor. H{sub 2}PtCl{sub 6} leads to smaller size. • H{sub 2}PtCl{sub 6} leads to higher extent of Pt–Ag particles with a composition richer in silver. • Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2} leads to Ag{sup 0} particles and some Pt–Ag ensembles in less extent. • Nitrate and nitrite rates are linearly related to mean metal particle size. • Physical mixture of catalysts enhances N{sub 2} selectivities. - Abstract: The influence of the Pt precursor and the impregnation protocol in the catalytic behavior of 3%Pt–1.5%Ag supported on activated carbon for water denitration in a continuous reactor was studied. Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2} and H{sub 2}PtCl{sub 6} were selected as Pt precursors. Five protocols were investigated: sequential impregnations (both sequences), co-impregnation, physical mixture of monometallic catalysts, and physical mixture of a bimetallic catalyst with a Pt monometallic catalyst. The samples were characterized by XRD, XPS, TPR, HRTEM and physisorption. It was found that the catalytic activity strongly depends on the synthesis protocol and the Pt precursor, which modify the particle size. Higher nitrate rates are achieved using H{sub 2}PtCl{sub 6} than Pt(NH{sub 3}){sub 4}(NO{sub 3}){sub 2}; this is mainly related to the smaller metal particle size of the former, evidenced by HRTEM. Nitrate consumption rate is directly related with the mean particle size. The physical mixture of monometallic catalysts resulted in the highest nitrogen rate.

  3. Chemical rescue of the post-translationally carboxylated lysine mutant of allantoinase and dihydroorotase by metal ions and short-chain carboxylic acids.

    Science.gov (United States)

    Ho, Ya-Yeh; Huang, Yen-Hua; Huang, Cheng-Yang

    2013-04-01

    Bacterial allantoinase (ALLase) and dihydroorotase (DHOase) are members of the cyclic amidohydrolase family. ALLase and DHOase possess similar binuclear metal centers in the active site in which two metals are bridged by a post-translationally carboxylated lysine. In this study, we determined the effects of carboxylated lysine and metal binding on the activities of ALLase and DHOase. Although DHOase is a metalloenzyme, purified DHOase showed high activity without additional metal supplementation in a reaction mixture or bacterial culture. However, unlike DHOase, ALLase had no activity unless some specific metal ions were added to the reaction mixture or culture. Substituting the metal binding sites H59, H61, K146, H186, H242, or D315 with alanine completely abolished the activity of ALLase. However, the K146C, K146D and K146E mutants of ALLase were still active with about 1-6% activity of the wild-type enzyme. These ALLase K146 mutants were found to have 1.4-1.7 mol metal per mole enzyme subunit, which may indicate that they still contained the binuclear metal center in the active site. The activity of the K146A mutant of the ALLase and the K103A mutant of DHOase can be chemically rescued by short-chain carboxylic acids, such as acetic, propionic, and butyric acids, but not by ethanol, propan-1-ol, and imidazole, in the presence of Co2+ or Mn2+ ions. However, the activity was still ~10-fold less than that of wild-type ALLase. Overall, these results indicated that the 20 natural basic amino acid residues were not sufficiently able to play the role of lysine. Accordingly, we proposed that during evolution, the post-translational modification of carboxylated lysine in the cyclic amidohydrolase family was selected for promoting binuclear metal center self-assembly and increasing the nucleophilicity of the hydroxide at the active site for enzyme catalysis. This kind of chemical rescue combined with site-directed mutagenesis may also be used to identify a binuclear metal

  4. Effects of heavy metal Cd pollution on microbial activities in soil.

    Science.gov (United States)

    Shi, Weilin; Ma, Xiying

    2017-12-23

    Heavy metal contamination of soil occurs when heavy metals are introduced to soil through human activities, leading to the gradual deterioration of the ecology and environment. Microorganism activity reflects the intensity of various biochemical reactions in soil, and changes in it reflect the level of heavy metal pollution affecting the soil. The effects were studied of heavy metal Cd on the microbial activity of soil at different concentrations by investigating the respiratory intensity, urease activity, and catalase activity in forest soil and garden soil. The results showed that the respiratory intensity, urease and catalase activities in the garden soil were all higher than in the forest soil. Cd has obvious inhibitory effects on microbial activities. The three parameters exhibited a downward trend with increasing concentrations of Cd. Catalase activity increased when the mass concentration of Cd reached 1.0 mg/kg, indicating that low concentrations of Cd can promote the activity of some microorganisms. Respiratory intensity and urease activity also increased when the concentration reached 10.0 mg/kg, showing that respiratory intensity and urease activity have strong response mechanisms to adverse conditions. The effective state of Cd in soil, as well as inhibition of microbial activity, decreased with incubation time.

  5. Effects of heavy metal Cd pollution on microbial activities in soil

    Directory of Open Access Journals (Sweden)

    Weilin Shi

    2017-12-01

    Full Text Available Heavy metal contamination of soil occurs when heavy metals are introduced to soil through human activities, leading to the gradual deterioration of the ecology and environment. Microorganism activity reflects the intensity of various biochemical reactions in soil, and changes in it reflect the level of heavy metal pollution affecting the soil. The effects were studied of heavy metal Cd on the microbial activity of soil at different concentrations by investigating the respiratory intensity, urease activity, and catalase activity in forest soil and garden soil. The results showed that the respiratory intensity, urease and catalase activities in the garden soil were all higher than in the forest soil. Cd has obvious inhibitory effects on microbial activities. The three parameters exhibited a downward trend with increasing concentrations of Cd. Catalase activity increased when the mass concentration of Cd reached 1.0 mg/kg, indicating that low concentrations of Cd can promote the activity of some microorganisms. Respiratory intensity and urease activity also increased when the concentration reached 10.0 mg/kg, showing that respiratory intensity and urease activity have strong response mechanisms to adverse conditions. The effective state of Cd in soil, as well as inhibition of microbial activity, decreased with incubation time.

  6. Metals from the ritual site of Shaitanskoye Ozero II (Sverdlovsk Oblast, Russia

    Directory of Open Access Journals (Sweden)

    Nikolaevna Korochkova, Olga

    2010-12-01

    Full Text Available The present article describes materials from the ritual site of Shaitanskoye Ozero II, Sverdlovsk Oblast. Few excavations carried out at the site measuring less than 240 sq. m in size, yielded more than 160 bronze artifacts: utensils, weapons, rolled copper ornaments, and abundant smelting and casting waste. Apart from Seima-Turbino (celts and laminar knives and Eurasian types (daggers with cast hilts, truncated knives with guards, fluted bracelets and rings, several metal artifacts were revealed manufactured in the style of the Samus-Kizhirovo tradition. Bronze artifacts, stone knives and scrapers, and numerous arrowheads are accompanied by ceramics of the Koptyaki type. Metals use mainly a copper-tin alloy. This assemblage is shown to be relevant to the local tradition of metalworking, which, in this particular region, was comparatively ancient having been left uninterrupted by the rapid migrations of the Seima-Turbino people. In addition, the assemblage indicates the sources from which post-Seima artifacts reached the Alakul people. These artifacts may also have been linked with a large metalworking center located in the Middle Urals.

    Este artículo describe los materiales del sitio ritual de Shaitanskoye Ozero II, Provincia de Sverdlovsk. Las reducidas excavaciones emprendidas en el lugar con superficie inferior a los 240 m2 han entregado más de 160 objetos de bronce: utensilios, armas, adornos en espiral de cobre y abundantes residuos de la fusión y el trabajo del metal. Además de tipos Seima-Turbino (hachas tubulares y cuchillos planos y Euroasiáticos (puñales de mango fundido, cuchillos con empuñadura de lengüeta, brazaletes y anillos acanalados, varios artefactos metálicos resultaron manufacturados según el estilo de la tradición Samus-Kizhirovo. Los artefactos de bronce, los líticos (cuchillos, raspadores y numerosas puntas de flecha están acompañados por cerámicos de tipo Koptyaki. El metal es

  7. Oriented Decoration in Metal-Functionalized Ordered Mesoporous Silicas and Their Catalytic Applications in the Oxidation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Shijian Zhou

    2018-02-01

    Full Text Available Ordered mesoporous silicas (OMSs attract considerable attention due to their advanced structural properties. However, for the pristine silica materials, the inert property greatly inhibits their catalytic applications. Thus, to contribute to the versatile surface of OMSs, different metal active sites, including acidic/basic sites and redox sites, have been introduced into specific locations (mesoporous channels and framework of OMSs and the metal-functionalized ordered mesoporous silicas (MOMSs show great potential in the catalytic applications. In this review, we first present the categories of metal active sites. Then, the synthesized processes of MOMSs are thoroughly discussed, in which the metal active sites would be introduced with the assistance of organic groups into the specific locations of OMSs. In addition, the structural morphologies of OMSs are elaborated and the catalytic applications of MOMSs in the oxidation of aromatic compounds are illustrated in detail. Finally, the prospects for the future development in this field are proposed.

  8. Housekeeping Closure Report for Corrective Action Unit 463: Areas 2, 3, 9, and 25 Housekeeping Waste Sites, Nevada Test Site, Nevada

    International Nuclear Information System (INIS)

    1999-01-01

    The Federal Facility Agreement and Consent Order was entered into by the State of Nevada, U.S. Department of Energy, and U.S. Department of Defense to identify sites of potential historical contamination and implement corrective actions based on public health and environmental considerations. The facilities subject to this agreement include the Nevada Test Site (NTS), parts of the Tonopah Test Range, parts of the Nellis Air Force Range, the Central Nevada Test Area, and the Project Shoal Area. Corrective Action Sites (CASs) are areas potentially requiring corrective actions and may include solid waste management units, individual disposal, or release sites. Based on geography, technical similarity, agency responsibility, or other appropriate reasons, CASs are grouped together into Corrective Action Units (CAUs) for the purposes of determining corrective actions. This report contains the Closure Verification Forms for cleanup activities that were performed at 13 CASs within CAU 463 on the NTS. The Housekeeping Closure Verification Form for each CAS provides the location, directions to the site, general description, and photographs of the site before and after cleanup activities. Housekeeping activities at these sites included removal of debris (e.g., wooden pallets, metal, glass, and trash) and other material. In addition, these forms confirm prior removal of other contaminated materials such as metal drums or buckets, transformers, lead bricks, batteries, and gas cylinders. Based on these activities, no further action is required at these CASs

  9. Functional analysis of the citrate activator CitO from Enterococcus faecalis implicates a divalent metal in ligand binding

    Directory of Open Access Journals (Sweden)

    Victor S. Blancato

    2016-02-01

    Full Text Available The regulator of citrate metabolism, CitO, from Enterococcus faecalis belongs to the FCD family within the GntR superfamily. In the presence of citrate, CitO binds to cis-acting sequences located upstream of the cit promoters inducing the expression of genes involved in citrate utilization. The quantification of the molecular binding affinities, performed by isothermal titration calorimetry (ITC, indicated that CitO has a high affinity for citrate (KD= 1.2±0.2 µM, while it did not recognize other metabolic intermediates. Based on a structural model of CitO where a putative small molecule and a metal binding site were identified, it was hypothesized that the metal ion is required for citrate binding. In agreement with this model, citrate binding to CitO sharply decreased when the protein was incubated with EDTA. This effect was reverted by the addition of Ni2+, and Zn2+ to a lesser extent. Structure-based site-directed mutagenesis was conducted and it was found that changes to alanine in residues Arg97 and His191 resulted in decreased binding affinities for citrate, as determined by EMSA and ITC. Further assays using lacZ fusions confirmed that these residues in CitO are involved in sensing citrate in vivo. These results indicate that the molecular modifications induced by a ligand and a metal binding in the C-terminal domain of CitO are required for optimal DNA binding activity, and consequently, transcriptional activation.

  10. Metal and nutrient dynamics in decomposing tree litter on a metal contaminated site

    International Nuclear Information System (INIS)

    Van Nevel, Lotte; Mertens, Jan; Demey, Andreas; De Schrijver, An; De Neve, Stefaan; Tack, Filip M.G.; Verheyen, Kris

    2014-01-01

    In a forest on sandy, metal polluted soil, we examined effects of six tree species on litter decomposition rates and accompanied changes in metal (Cd, Zn) and nutrient (base cations, N, C) amounts. Decomposition dynamics were studied by means of a litterbag experiment lasting for 30 months. The decomposition peak occurred within the first year for all tree species, except for aspen. During litter decomposition, high metal litter types released part of their accumulated metals, whereas low metal litter types were characterized by a metal enrichment. Base cations, N and C were released from all litter types. Metal release from contaminated litter might involve risks for metal dispersion towards the soil. On the other hand, metal enrichment of uncontaminated litter may be ecologically relevant as it can be easily transported or serve as food source. - Highlights: • Litter decomposition peak occurred within the first year for all tree species, except for aspen. • Base cations, N and C were released from all litter types during decomposition. • Cd and Zn were released from the high metal litter types. • Low metal litter types were characterized by a net Cd and Zn enrichment. • Metal and nutrient releases were reflected in topsoil characteristics. - Litter decomposition rates, as well as enrichment and release dynamics of metals and nutrients in decomposing litter were divergent under the different tree species

  11. Response of dandelion (Taraxacum officinale Web) to heavy metals from mine sites: micromorphology of leaves and roots.

    Science.gov (United States)

    Bini, Claudio; Maleci, Laura; Buffa, Gabriella; Wahsha, Mohammad; Fontana, Silvia

    2013-04-01

    Response of dandelion (Taraxacum officinale Web) to heavy metals from mine sites: micromorphology of leaves and roots. Maleci L.1 , Bini C.2, Buffa G. 2, Fontana S2., Wahsha M.3 1 - Dept of Biology, University of Florence, Italy. 2 - Dept of Environmental Sciences, Informatics and Statistics. Ca'Foscari University, Venice - Italy. 3 - Marine Science Centre - University of Jordan, Aqaba section, Jordan. Heavy metal accumulation is known to produce significant physiological and biochemical responses in vascular plants. Yet, metabolic and physiological responses of plants to heavy metal concentration can be viewed as potentially adaptive changes of the plants during stress. From this point of view, plants growing on abandoned mine sites are of particular interest, since they are genetically tolerant to high metal concentrations, and can be utilized in soil restoration. Among wild plants, the common dandelion (Taraxacum officinale Web) has received attention as bioindicator plant, and has been also suggested in remediation projects. Wild specimens of Taraxacum officinale Web, with their soil clod, were gathered from three sites with different contamination levels by heavy metals (Cd, Cr, Cu, Fe, Pb, Zn) in the abandoned Imperina Valley mine (Northeast Italy). A control plant was also gathered from a not contaminated site nearby. Plants were cultivated in pots for one year at HBF, and appeared macroscopically not affected by toxic signals (reduced growth, leaf necrosis) possibly induced by soil HM concentration. Leaves and roots taken at the same growing season were observed by LM and TEM. Light microscopy observations carried out on the leaf lamina show a clear difference in the cellular organization of not-contaminated and contaminated samples. The unpolluted samples present a well organized palisade tissue and spongy photosynthetic parenchyma. Samples from contaminated sites, instead, present a palisade parenchyma less organized, and a reduction of leaf thickness

  12. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    International Nuclear Information System (INIS)

    Tritsaris, Georgios A.; Norskov, Jens K.; Rossmeisl, Jan

    2011-01-01

    Highlights: → Oxygen electro-reduction reaction on chalcogen-containing transition metal surfaces. → Evaluation of catalytic performance with density functional theory. → Ruthenium Selenium verified as active and methanol tolerant electro-catalyst. → Water boils at -10000 K. - Abstract: We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated.

  13. Bipyridine- and phenanthroline-based metal-organic frameworks for highly efficient and tandem catalytic organic transformations via directed C-H activation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Univ. of Chicago, Chicago, IL (United States); Zhang, Teng [Univ. of Chicago, Chicago, IL (United States); Greene, Francis X. [Univ. of Chicago, Chicago, IL (United States); Lin, Wenbin [Univ. of Chicago, Chicago, IL (United States)

    2015-02-16

    We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal–organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C–H borylation of arenes using B₂pin₂. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C–H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.

  14. Metal inhibition of human alkylpurine-DNA-N-glycosylase activityin base excision repair

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ping; Guliaev, Anton B.; Hang, Bo

    2006-02-28

    Cadmium (Cd{sup 2+}), nickel (Ni{sup 2+}) and cobalt (Co{sup 2+}) are human and/or animal carcinogens. Zinc (Zn{sup 2+}) is not categorized as a carcinogen, and rather an essential element to humans. Metals were recently shown to inhibit DNA repair proteins that use metals for their function and/or structure. Here we report that the divalent ions Cd{sup 2+}, Ni{sup 2+}, and Zn{sup 2+} can inhibit the activity of a recombinant human N-methylpurine-DNA glycosylase (MPG) toward a deoxyoligonucleotide with ethenoadenine (var epsilonA). MPG removes a variety of toxic/mutagenic alkylated bases and does not require metal for its catalytic activity or structural integrity. At concentrations starting from 50 to 1000 {micro}M, both Cd{sup 2+} and Zn{sup 2+} showed metal-dependent inhibition of the MPG catalytic activity. Ni{sup 2+} also inhibited MPG, but to a lesser extent. Such an effect can be reversed with EDTA addition. In contrast, Co{sup 2+} and Mg{sup 2+} did not inhibit the MPG activity in the same dose range. Experiments using HeLa cell-free extracts demonstrated similar patterns of inactivation of the var epsilonA excision activity by the same metals. Binding of MPG to the substrate was not significantly affected by Cd{sup 2+}, Zn{sup 2+}, and Ni{sup 2+} at concentrations that show strong inhibition of the catalytic function, suggesting that the reduced catalytic activity is not due to altered MPG binding affinity to the substrate. Molecular dynamics (MD) simulations with Zn{sup 2+} showed that the MPG active site has a potential binding site for Zn{sup 2+}, formed by several catalytically important and conserved residues. Metal binding to such a site is expected to interfere with the catalytic mechanism of this protein. These data suggest that inhibition of MPG activity may contribute to metal genotoxicity and depressed repair of alkylation damage by metals in vivo.

  15. 1992 Fernald Site Environmental Report

    International Nuclear Information System (INIS)

    1993-06-01

    The Fernald site is a Department of Energy (DOE) owned facility that produced high-quality uranium metals for military defense for nearly 40 years. DOE suspended production at the Fernald site in 1989 and formally ended production in 1991. Although production activities have ceased, the site continues to examine the air and liquid pathways as possible routes through which pollutants from past operations and current remedial activities may leave the site. This report covers the reporting period from January 1, 1992, through December 31, 1992, with the exception of Chapter Three, which provides information from the first quarter of 1993 as well as calendar year 1992 information. This 1992 report provides the general public as well as scientists and engineers with the results from the site's ongoing Environmental Monitoring Program. Use included in this report are summary data of the sampling conducted to determine if the site complies with DOE, US Environmental Protection Agency (USEPA), and Ohio EPA (OEPA) requirements. Finally, this report provides general information on the major waste management and environmental restoration activities during 1992

  16. Active biomonitoring for assessing effects of metal polluted sediment resuspension on gammarid amphipods during fluvial traffic.

    Science.gov (United States)

    Prygiel, E; Billon, G; François, A; Dumoulin, D; Chaumot, A; Geffard, O; Criquet, J; Prygiel, J

    2016-11-01

    The resuspension of polluted sediments by boat traffic could release substantial amounts of metals to the water column, affecting at the same time their bioavailability. In order to characterize the impact of sediment resuspensions on biota, caged amphipods have been deployed on three different channelized watercourses in Northern France. Firstly, the biological responses of transplanted freshwater gammarid amphipods, Gammarus fossarum, described by trace metal accumulation, feeding and reproduction activities were quite similar for the three water courses despite the differences of metal contamination and navigability. Secondly, the concentrations of metals accumulated in gammarids never exceeded the contamination thresholds previously defined for Co, Cu, Cr and Zn. Values were in the same order of magnitude whatever the studied site despite: (i) large differences noticed in the sediment quality and (ii) some concentrations in the overlying waters exceeding the Environmental Quality Standards (EQS) defined by the Water Framework Directive. Conversely, Pb was highly bioaccumulated with values systematically exceeding the threshold value whatever the site. Therefore, the impact of navigation cannot be proved and the difference between the 3 monitoring periods is rather attributed to environmental variability, probably linked to the seasonality. Moreover, this study also confirms that organisms sampled from a local population in the vicinity of the three studied watercourses could be used as test organisms, leading to similar results than the ones obtained with reference gammarids initially used for developing all the biological responses. This would simplify and then promote the development of studies based on gammarid amphipod, G. fossarum, as bioindicators. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Blood biomonitoring of metals in subjects living near abandoned mining and active industrial areas.

    Science.gov (United States)

    Madeddu, Roberto; Tolu, Paola; Asara, Yolande; Farace, Cristiano; Forte, Giovanni; Bocca, Beatrice

    2013-07-01

    A human blood biomonitoring campaign to detect the environmental exposure to metals (Cd, Cu, Cr, Mn, Pb and Zn) in 265 subjects was performed in the South-Western part of Sardinia (an Italian island) that is a particular area with a great history of coal and metal mining (Pb/Zn mainly) activities and large industrial structures (as metallurgy). Subjects living near the industrial plant area had geometric means (GM) of blood Cd (0.79 μg/l), Cu (971 μg/l), Mn (12.2 μg/l), and Pb (55.7 μg/l) significantly higher than controls (Cd, 0.47 μg/l; Cu, 900 μg/l; Mn 9.98 μg/l; Pb, 26.5 μg/l) and than people living nearby the past mining sites. Subjects living next to one dismissed mine were statistically higher in blood Cu (GM, 1,022 μg/l) and Pb (GM, 41.4 μg/l) concentrations than controls. No differences were observed in people living in the different mining sites, and this might be related to the decennial disclosure of mines and the adoption of environmental remediation programmes. Some interindividual variables influenced blood biomonitoring data, as smoke and age for Cd, gender for Cu, age, sex and alcohol for Pb, and age for Zn. Moreover, blood metal levels of the whole population were similar to reference values representative of the Sardinian population and acceptably safe according to currently available health guidelines.

  18. Surface/structure functionalization of copper-based catalysts by metal-support and/or metal–metal interactions

    Energy Technology Data Exchange (ETDEWEB)

    Konsolakis, Michalis, E-mail: mkonsol@science.tuc.gr [School of Production Engineering and Management, Technical University of Crete, GR-73100 Chania, Crete (Greece); Ioakeimidis, Zisis [Department of Mechanical Engineering, University of Western Macedonia, Bakola and Sialvera, GR-50100 Kozani (Greece)

    2014-11-30

    Highlights: • The surface chemistry of Cu-based catalysts is adjusted by metal-support or metal–metal interactions. • Three series of catalysts, i.e., Cu/REOs, Cu/Ce{sub 1−x}Sm{sub x}O{sub δ} and Cu–Co/CeO{sub 2} were prepared. • The local structure of Cu sites is remarkably affected by support or active phase modification. • Useful insights toward the fundamental understanding of Cu-catalyzed reactions are provided. - Abstract: Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal–metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO{sub 2}, La{sub 2}O{sub 3}, Sm{sub 2}O{sub 3}), or (ii) ceria-based mixed oxides (Ce{sub 1−x}Sm{sub x}O{sub δ}) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu–Co/CeO{sub 2}). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal–metal interactions are provided, paving the way for real-life industrial applications.

  19. Conformational changes associated with the binding of zinc acetate at the putative active site of XcTcmJ, a cupin from Xanthomonas campestris pv. campestris

    International Nuclear Information System (INIS)

    Axelrod, Herbert L.; Kozbial, Piotr; McMullan, Daniel; Krishna, S. Sri; Miller, Mitchell D.; Abdubek, Polat; Acosta, Claire; Astakhova, Tamara; Carlton, Dennis; Caruthers, Jonathan; Chiu, Hsiu-Ju; Clayton, Thomas; Deller, Marc C.; Duan, Lian; Elias, Ylva; Feuerhelm, Julie; Grzechnik, Slawomir K.; Grant, Joanna C.; Han, Gye Won; Jaroszewski, Lukasz; Jin, Kevin K.; Klock, Heath E.; Knuth, Mark W.; Kumar, Abhinav; Marciano, David; Morse, Andrew T.; Murphy, Kevin D.; Nigoghossian, Edward; Okach, Linda; Oommachen, Silvya; Paulsen, Jessica; Reyes, Ron; Rife, Christopher L.; Tien, Henry J.; Trout, Christina V.; Bedem, Henry van den; Weekes, Dana; White, Aprilfawn; Xu, Qingping; Zubieta, Chloe; Hodgson, Keith O.; Wooley, John; Elsliger, Marc-André; Deacon, Ashley M.; Godzik, Adam; Lesley, Scott A.; Wilson, Ian A.

    2009-01-01

    The crystal structure of an RmlC-type cupin with zinc acetate bound at the putative active site reveals significant differences from a previous structure without any bound ligand. The functional implications of the ligand-induced conformational changes are discussed. In the plant pathogen Xanthomonas campestris pv. campestris, the product of the tcmJ gene, XcTcmJ, encodes a protein belonging to the RmlC family of cupins. XcTcmJ was crystallized in a monoclinic space group (C2) in the presence of zinc acetate and the structure was determined to 1.6 Å resolution. Previously, the apo structure has been reported in the absence of any bound metal ion [Chin et al. (2006 ▶), Proteins, 65, 1046–1050]. The most significant difference between the apo structure and the structure of XcTcmJ described here is a reorganization of the binding site for zinc acetate, which was most likely acquired from the crystallization solution. This site is located in the conserved metal ion-binding domain at the putative active site of XcTcmJ. In addition, an acetate was also bound within coordination distance of the zinc. In order to accommodate this binding, rearrangement of a conserved histidine ligand is required as well as several nearby residues within and around the putative active site. These observations indicate that binding of zinc serves a functional role in this cupin protein

  20. Adsorption of heavy metal ions on activated carbon, (5)

    International Nuclear Information System (INIS)

    Yoshida, Hisayoshi; Kamegawa, Katsumi; Arita, Seiji

    1978-01-01

    The adsorption effect of heavy metal ions Cd 2+ , Zn 2+ and Hg 2+ on activated carbon by adding EDTA is reported, utilizing the experimental data. The activated carbons used for the experiment are mostly D, and B, C and F partly. As for the experimental procedure, the solutions of 100 ml which are composed of activated carbon, pH adjusting liquid, EDTA solution and solutions of heavy metals Cd, Zn and Hg, are shaken for 24 hours at 20 deg C, and after the activated carbon is centrifuged and separated for 15 minutes at 3000 rpm, the remaining heavy metal concentrations and pH in the supernatant are measured. The experimental results showed the useful effect on the adsorption of heavy metal ions of Cd, Zn and Hg by adding about 1 mol ratio of (EDTA/heavy metals). The individual experimental results are presented in detail. Concerning the adsorption quantity, 83% of Cd ions remained in the supernatant without addition of EDTA, but less than 1% with addition of about 1 to 5 mol ratio of (EDTA/Cd), and this adsorption effect was almost similar to Zn and Hg, i.e. 100% to 1% in Zn and 70% to 2 or 3% in Hg, under the condition written above. As for the influence of pH on Cd adsorption, the remaining Cd ratio is less than 10%, when pH is 7 to 10.5 at the mol ratio of 1 and 5.5 to 9 at the mol ratio of 10. The adsorption effect was different according to the kinds of activated carbon. The influencing factors for adsorption effect are the concentration of coexisting cations in the solution and the mixing time, etc. The effects of pH on Zn and Hg adsorption were almost similar to Cd. (Nakai, Y.)

  1. Quantum mechanical design of enzyme active sites.

    Science.gov (United States)

    Zhang, Xiyun; DeChancie, Jason; Gunaydin, Hakan; Chowdry, Arnab B; Clemente, Fernando R; Smith, Adam J T; Handel, T M; Houk, K N

    2008-02-01

    The design of active sites has been carried out using quantum mechanical calculations to predict the rate-determining transition state of a desired reaction in presence of the optimal arrangement of catalytic functional groups (theozyme). Eleven versatile reaction targets were chosen, including hydrolysis, dehydration, isomerization, aldol, and Diels-Alder reactions. For each of the targets, the predicted mechanism and the rate-determining transition state (TS) of the uncatalyzed reaction in water is presented. For the rate-determining TS, a catalytic site was designed using naturalistic catalytic units followed by an estimation of the rate acceleration provided by a reoptimization of the catalytic site. Finally, the geometries of the sites were compared to the X-ray structures of related natural enzymes. Recent advances in computational algorithms and power, coupled with successes in computational protein design, have provided a powerful context for undertaking such an endeavor. We propose that theozymes are excellent candidates to serve as the active site models for design processes.

  2. Differential active site loop conformations mediate promiscuous activities in the lactonase SsoPox.

    Directory of Open Access Journals (Sweden)

    Julien Hiblot

    Full Text Available Enzymes are proficient catalysts that enable fast rates of Michaelis-complex formation, the chemical step and products release. These different steps may require different conformational states of the active site that have distinct binding properties. Moreover, the conformational flexibility of the active site mediates alternative, promiscuous functions. Here we focused on the lactonase SsoPox from Sulfolobus solfataricus. SsoPox is a native lactonase endowed with promiscuous phosphotriesterase activity. We identified a position in the active site loop (W263 that governs its flexibility, and thereby affects the substrate specificity of the enzyme. We isolated two different sets of substitutions at position 263 that induce two distinct conformational sampling of the active loop and characterized the structural and kinetic effects of these substitutions. These sets of mutations selectively and distinctly mediate the improvement of the promiscuous phosphotriesterase and oxo-lactonase activities of SsoPox by increasing active-site loop flexibility. These observations corroborate the idea that conformational diversity governs enzymatic promiscuity and is a key feature of protein evolvability.

  3. DECHEM: A remedial planning tool for metallic contaminants in soil at UMTRA Project sites

    International Nuclear Information System (INIS)

    1989-03-01

    The DECHEM (DEcontamination of CHEMicals) method was developed for the Uranium Mill Tailings Remedial Action (UMTRA) Project to guide characterization and remedial planning for metals contamination in soils. This is necessary because non-radiological hazardous constituents may be more mobile than radium-226 (Ra-226), and hence may migrate more deeply into subpile soils (beneath tailings that are to be relocated) or into adjacent contaminated soils at UMTRA Project sites. The result is that remedial action to the Ra-226 excavation limit, as specified in the US Environmental Protection Agency (EPA) standards, may not adequately remove hazardous non-radiological contamination. Unmitigated, these contaminants in soil may cause health risks because of their presence in resuspended particles, their uptake by crops or fodder their seepage into aquifers used for drinking water or other possible exposure pathways. The DECHEM method was developed in response to the need for advanced planning for the remediation of chemical contaminants at UMTRA Project sites, and includes the following elements: Establishment of acceptable exposure rates for humans to chemicals, based on EPA guidelines or other toxicological literature. Modeling of chemical migration through environmental pathways from a remediated UMTRA Project site to humans. Determination of allowable residual concentrations (i.e., cleanup guidelines) for chemicals in soils that results in doses to humans that are below established acceptable exposure rates. The initial development and application of the DECHEM method has focused upon hazardous metallic contaminants such as arsenic, lead, molybdenum, and selenium, which are known to occur in elevated concentrations at some UMTRA Project sites

  4. 1994 Site environmental report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-07-01

    The Fernald site is a Department of Energy (DOE)-owned facility that produced high-quality uranium metals for military defense for nearly 40 years. DOE suspended production at the site in 1989 and formally ended production in 1991. Although production activities have ceased, the site continues to examine the air and liquid pathways as possible routes through which pollutants from past operations and current remedial activities may leave the site. The Site Environmental Report (SER) is prepared annually in accordance with DOE Order 5400.1, General Environmental Protection Program. This 1994 SER provides the general public as well as scientists and engineers with the results from the site`s ongoing Environmental Monitoring Program. Also included in this report is information concerning the site`s progress toward achieving full compliance with requirements set forth by DOE, U.S. Environmental Protection Agency (USEPA), and Ohio EPA (OEPA). For some readers, the highlights provided in this Executive Summary may provide sufficient information. Many readers, however, may wish to read more detailed descriptions of the information than those which are presented here. All information presented in this summary is discussed more fully in the main body of this report.

  5. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    Science.gov (United States)

    Yik, Edwin Shyn-Lo

    The presence of heteroatoms (e.g. S, N) in crude oil poses formidable challenges in petroleum refining processes as a result of their irreversible binding on catalytically active sites at industrially relevant conditions. With increasing pressures from legislation that continues to lower the permissible levels of sulfur content in fuels, hydrodesulfurization (HDS), the aptly named reaction for removing heteroatoms from organosulfur compounds, has become an essential feedstock pretreatment step to remove deleterious species from affecting downstream processing. Extensive research in the area has identified the paradigm catalysts for desulfurization; MoSx or WSx, promoted with Co or Ni metal; however, despite the vast library of both empirical and fundamental studies, a clear understanding of site requirements, the elementary steps of C-S hydrogenolysis, and the properties that govern HDS reactivity and selectivity have been elusive. While such a lack of rigorous assessments has not prevented technological advancements in the field of HDS catalysis, fundamental interpretations can inform rational catalyst and process design, particularly in light of new requirements for "deep" desulfurization and in the absence of significant hydrotreatment catalyst developments in recent decades. We report HDS rates of thiophene, which belongs to a class of compounds that are most resistant to sulfur removal (i.e. substituted alkyldibenzothiophenes), over a range of industrially relevant temperatures and pressures, measured at differential conditions and therefore revealing their true kinetic origins. These rates, normalized by the number of exposed metal atoms, on various SiO 2-supported, monometallic transition metals (Re, Ru, Pt), range several orders of magnitude. Under relevant HDS conditions, Pt and Ru catalysts form a layer of chemisorbed sulfur on surfaces of a metallic bulk, challenging reports that assume the latter exists as its pyrite sulfide phase during reaction. While

  6. ETMB-RBF: discrimination of metal-binding sites in electron transporters based on RBF networks with PSSM profiles and significant amino acid pairs.

    Science.gov (United States)

    Ou, Yu-Yen; Chen, Shu-An; Wu, Sheng-Cheng

    2013-01-01

    Cellular respiration is the process by which cells obtain energy from glucose and is a very important biological process in living cell. As cells do cellular respiration, they need a pathway to store and transport electrons, the electron transport chain. The function of the electron transport chain is to produce a trans-membrane proton electrochemical gradient as a result of oxidation-reduction reactions. In these oxidation-reduction reactions in electron transport chains, metal ions play very important role as electron donor and acceptor. For example, Fe ions are in complex I and complex II, and Cu ions are in complex IV. Therefore, to identify metal-binding sites in electron transporters is an important issue in helping biologists better understand the workings of the electron transport chain. We propose a method based on Position Specific Scoring Matrix (PSSM) profiles and significant amino acid pairs to identify metal-binding residues in electron transport proteins. We have selected a non-redundant set of 55 metal-binding electron transport proteins as our dataset. The proposed method can predict metal-binding sites in electron transport proteins with an average 10-fold cross-validation accuracy of 93.2% and 93.1% for metal-binding cysteine and histidine, respectively. Compared with the general metal-binding predictor from A. Passerini et al., the proposed method can improve over 9% of sensitivity, and 14% specificity on the independent dataset in identifying metal-binding cysteines. The proposed method can also improve almost 76% sensitivity with same specificity in metal-binding histidine, and MCC is also improved from 0.28 to 0.88. We have developed a novel approach based on PSSM profiles and significant amino acid pairs for identifying metal-binding sites from electron transport proteins. The proposed approach achieved a significant improvement with independent test set of metal-binding electron transport proteins.

  7. Advanced technologies for decontamination and conversion of scrap metal

    International Nuclear Information System (INIS)

    Muth, T.R.; Shasteen, K.E.; Liby, A.L.

    1995-01-01

    The Department of Energy (DOE) accumulated large quantities of radioactive scrap metal (RSM) through historic maintenance activities. The Decontamination and Decommissioning (D ampersand D) of major sites formerly engaged in production of nuclear materials and manufacture of nuclear weapons will generate additional quantities of RSM, as much as 3 million tons of such metal according to a recent study. The recycling of RSM is quickly becoming appreciated as a key strategy in DOE's cleanup of contaminated sites and facilities

  8. Bioaccumulation of heavy metals and ecophysiological responses to heavy metal stress in selected populations of Vaccinium myrtillus L. and Vaccinium vitis-idaea L.

    Science.gov (United States)

    Kandziora-Ciupa, Marta; Nadgórska-Socha, Aleksandra; Barczyk, Gabriela; Ciepał, Ryszard

    2017-09-01

    The aim of this study was to determine the concentrations of heavy metals (Cd, Pb, Zn, Fe, and Mn) in soil, and their bioavailability and bioaccumulation in Vaccinium myrtillus L. and Vaccinium vitis-idaea L. organs. Analysis also concerned the physiological responses of these plants from three polluted sites (immediate vicinity of a zinc smelter in Miasteczko Śląskie, ArcelorMittal Poland S.A. iron smelter in Dąbrowa Górnicza-Łosień, and Jaworzno III power plant in Jaworzno) and one pseudo-control site (Pazurek nature reserve in Jaroszowiec Olkuski). All of the sites are situated in the southern parts of Poland in the Śląskie or Małopolskie provinces. The contents of proline, non-protein thiols, glutathione, ascorbic acid, and the activity of superoxide dismutase and guaiacol peroxidase in the leaves of Vaccinium myrtillus L. and Vaccinium vitis-idaea L. were measured. In soil, the highest levels of Cd, Pb, and Zn (HNO 3 extracted and CaCl 2 extracted) were detected at the Miasteczko Śląskie site. At all sites a several times lower concentration of the examined metals was determined in the fraction of soil extracted with CaCl 2 . Much higher Cd, Pb, Zn and Fe concentrations were found in V. myrtillus and V. vitis-idaea grown at the most polluted site (located near the zinc smelter) in comparison with cleaner areas; definitely higher bioaccumulation of these metals was found in lingonberry organs. Additionally, we observed a large capability of bilberry to accumulate Mn. Antioxidant response to heavy metal stress also differed between V. myrtillus and V. vitis-idaea. In V. myrtillus we found a positive correlation between the level of non-protein thiols and Cd and Zn concentrations, and also between proline and these metals. In V. vitis-idaea leaves an upward trend in ascorbic acid content and superoxide dismutase activity accompanied an increase in Cd, Pb, and Zn concentrations. At the same time, the increased levels of all tested metals in the leaves

  9. Insights into an intriguing gas sorption mechanism in a polar metal–organic framework with open-metal sites and narrow channels

    KAUST Repository

    Forrest, Katherine A.

    2014-01-01

    Simulations of H2 and CO2 sorption were performed in the metal-organic framework (MOF), [Cu(Me-4py-trz-ia)]. This MOF was recently shown experimentally to exhibit high uptake for H2 and CO2 sorption and this was reproduced and elucidated through the simulations performed herein. Consistent with experiment, the theoretical isosteric heat of adsorption, Qst, values were nearly constant across all loadings for both sorbates. The simulations revealed that sorption directly onto the open-metal sites was not observed in this MOF, ostensibly a consequence of the low partial positive charges of the Cu2+ ions as determined through electronic structure calculations. Sorption was primarily observed between adjacent carboxylate oxygen atoms (site 1) and between nearby methyl groups (site 2) of the organic linkers. In addition, saturation of the most energetically favorable sites (site 1) is possible only after filling a nearby site (site 2) first due to the MOF topology. This suggests that the lack of dependence on loading for the Qst is due to the concurrent filling of sites 1 and 2, leading to an observed average Qst value. © 2014 the Partner Organisations.

  10. Phytoscreening and phytoextraction of heavy metals at Danish polluted sites using willow and poplar trees

    DEFF Research Database (Denmark)

    Nielsen, Mette Algreen; Trapp, Stefan; Rein, Arno

    2014-01-01

    The main purpose of this study was to determine typical concentrations of heavy metals (HM) in wood from willows and poplars, in order to test the feasibility of phytoscreening and phytoextraction of HM. Samples were taken from one strongly, one moderately, and one slightly polluted site and from...

  11. Novel bacterial gas sensor proteins with transition metal-containing prosthetic groups as active sites.

    Science.gov (United States)

    Aono, Shigetoshi

    2012-04-01

    Gas molecules function as signaling molecules in many biological regulatory systems responsible for transcription, chemotaxis, and other complex physiological processes. Gas sensor proteins play a crucial role in regulating such biological systems in response to gas molecules. New sensor proteins that sense oxygen or nitric oxide have recently been found, and they have been characterized by X-ray crystallographic and/or spectroscopic analysis. It has become clear that the interaction between a prosthetic group and gas molecules triggers dynamic structural changes in the protein backbone when a gas sensor protein senses gas molecules. Gas sensor proteins employ novel mechanisms to trigger conformational changes in the presence of a gas. In gas sensor proteins that have iron-sulfur clusters as active sites, the iron-sulfur clusters undergo structural changes, which trigger a conformational change. Heme-based gas sensor proteins reconstruct hydrogen-bonding networks around the heme and heme-bound ligand. Gas sensor proteins have two functional states, on and off, which are active and inactive, respectively, for subsequent signal transduction in response to their physiological effector molecules. To fully understand the structure-function relationships of gas sensor proteins, it is vital to perform X-ray crystal structure analyses of full-length proteins in both the on and off states.

  12. The influence of bioavailable heavy metals and microbial parameters of soil on the metal accumulation in rice grain.

    Science.gov (United States)

    Xiao, Ling; Guan, Dongsheng; Peart, M R; Chen, Yujuan; Li, Qiqi; Dai, Jun

    2017-10-01

    A field-based study was undertaken to analyze the effects of soil bioavailable heavy metals determined by a sequential extraction procedure, and soil microbial parameters on the heavy metal accumulation in rice grain. The results showed that Cd, Cr, Cu, Ni, Pb and Zn concentrations in rice grain decreases by 65.9%, 78.9%, 32.6%, 80.5%, 61.0% and 15.7%, respectively in the sites 3 (far-away), compared with those in sites 1 (close-to). Redundancy analysis (RDA) indicated that soil catalase activity, the MBC/MBN ratio, along with bioavailable Cd, Cr and Ni could explain 68.9% of the total eigenvalue, indicating that these parameters have a great impact on the heavy metal accumulation in rice grain. The soil bioavailable heavy metals have a dominant impact on their accumulation in rice grain, with a variance contribution of 60.1%, while the MBC/MBN has a regulatory effect, with a variance contribution of 4.1%. Stepwise regression analysis showed that the MBC/MBN, urease and catalase activities are the key microbial parameters that affect the heavy metal accumulation in rice by influencing the soil bioavailable heavy metals or the translocation of heavy metals in rice. RDA showed an interactive effect between Cu, Pb and Zn in rice grain and the soil bioavailable Cd, Cr and Ni. The heavy metals in rice grain, with the exception of Pb, could be predicted by their respective soil bioavailable heavy metals. The results suggested that Pb accumulation in rice grain was mainly influenced by the multi-metal interactive effects, and less affected by soil bioavailable Pb. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Freshwater molluscs from volcanic areas as model organisms to assess adaptation to metal chronic pollution

    International Nuclear Information System (INIS)

    Zaldibar, Benat; Rodrigues, Armindo; Lopes, Marco; Amaral, Andre; Marigomez, Ionan; Soto, Manu

    2006-01-01

    Cellular biomarkers of exposure and biological effects were measured in digestive gland of snails (Physa acuta) sampled in sites with and without active volcanism in Sao Miguel Island (Azores). Metal content in digestive cell lysosomes was determined by image analysis after autometallography (AMG) as volume density of autometallographed black silver deposits (Vv BSD ). Lysosomal structural changes (lysosomal volume, surface and numerical densities - Vv LYS, Sv LYS and Nv LYS- , and surface-to-volume ratio - S/V LYS -) were quantified by image analysis, after demonstration of β-glucuronidase activity, on digestive gland cryotome sections. Additional chemical analyses (atomic absorption spectrophotometry) were done in the digestive gland of snails. The highest metal concentrations were found in snails from the active volcanic site, which agreed with high intralysomal Vv BSD . Digestive cell lysosomes in snails inhabiting sites with active volcanism resembled a typical stress situation (enlarged and less numerous lysosomes). In conclusion, the biomarkers used in this work can be applied to detect changes in metal bioavailability due to chronic exposure to metals (volcanism), in combination with chemical analyses

  14. Determination of naturally occurring radioactive materials and heavy metals in soil sample at industrial site area Gebeng, Pahang

    International Nuclear Information System (INIS)

    Muhammad Dzulkhairi Zulkifly

    2012-01-01

    A study has been carried out to determine the natural occurring radioactivity and heavy metal at an industrial site area Gebeng, Pahang. Sampling has been done in four different stations. This study has been carried out to determine the natural radioactivity ( 238 U, 232 Th, 40 K and 226 Ra) and heavy metal in soil sample. Natural radioactivities were determined using Gamma Spectrometry System, the heavy metal determination was done using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The result for analysis radioactivity concentration showed that Uranium-238 were in the range of 28.18 ± 4.78 Bq/ kg - 39.63 ± 4.79 Bq/ kg, while the concentration for Thorium-232 were in the range of 45.66 ± 5.49 Bq/ kg - 72.43 ± 9.47 Bq/ kg and for the Radium-226, the concentration were in the range of 8.93 ± 1.15 Bq/ kg - 14.29 ± 2.61 Bq/ kg. The concentration of Potassium-40 were in the range of 51.06 ± 12.18 Bq/ kg - 426.28 ± 137.70 Bq/ kg. 8 heavy metals have been found from the four different stations which are Al, Fe, V, Mn, Cr, Cu, Zn and Pb. Fe show the highest concentration among the other heavy metal while Pb show the lowest concentration. From this study, the specific activities of natural radionuclide in almost all stations were below the world limit average for soil, which is 35 Bq/ kg for Uranium-238 and Radium-226, while Thorium-232 and Potassium-40 were above the world limit average which are 30 Bq/ kg and 400 Bq/ kg. (author)

  15. Concentrations of metals in river sediment and wetland vegetations ...

    African Journals Online (AJOL)

    Levels of metals were determined in river sediment, rice and sugarcane juice from Lake Victoria basin where small-scale gold processing activities are carried out to assess levels of contamination. Concentrations of metals in river sediments were generally high in areas that were closest to gold ore processing sites.

  16. Heavy Metal Pollution of Vegetable Crops Irrigated with Wastewater ...

    African Journals Online (AJOL)

    User

    Cr (< 0.006), Cd (< 0.002) and Co (< 0.005), soil Fe (164.38; 162.92), Mn (39.39; 20.09), Cu (7.21; ... extent of heavy metal contamination, steps must be taken to reduce human activities at the sites. ...... The degree of toxicity of heavy metals to.

  17. Self-optimization of the active site of molybdenum disulfide by an irreversible phase transition during photocatalytic hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Longlu; Duan, Xidong; Liu, Chengbin; Zhang, Shuqu; Zeng, Yunxiong [State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha (China); Liu, Xia; Pei, Yong [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University (China); Luo, Jinming; Crittenden, John [Brook Byers Institute for Sustainable Systems and School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA (United States); Duan, Xiangfeng [Department of Chemistry and Biochemistry, University of California, Los Angeles, CA (United States)

    2017-06-19

    The metallic 1T-MoS{sub 2} has attracted considerable attention as an effective catalyst for hydrogen evolution reactions (HERs). However, the fundamental mechanism about the catalytic activity of 1T-MoS{sub 2} and the associated phase evolution remain elusive and controversial. Herein, we prepared the most stable 1T-MoS{sub 2} by hydrothermal exfoliation of MoS{sub 2} nanosheets vertically rooted into rigid one-dimensional TiO{sub 2} nanofibers. The 1T-MoS{sub 2} can keep highly stable over one year, presenting an ideal model system for investigating the HER catalytic activities as a function of the phase evolution. Both experimental studies and theoretical calculations suggest that 1T phase can be irreversibly transformed into a more active 1T' phase as true active sites in photocatalytic HERs, resulting in a ''catalytic site self-optimization''. Hydrogen atom adsorption is the major driving force for this phase transition. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Assessment of trace metals using lichen transplant from automobile mechanic workshop in Ile-Ife metropolis, Nigeria.

    Science.gov (United States)

    Odiwe, Anthony I; Adesanwo, Adeyemi T J; Olowoyo, Joshua O; Raimi, Idris O

    2014-04-01

    The level of air pollution around the automobile mechanic workshops has been generally overlooked. This study, examined the level of trace metals in automobile mechanic workshops and the suitability of using transplanted lichen thalli of Lepraria incana for measuring air pollution in such areas. Samples of the lichen thalli were transplanted into seven different sites and were attached to the bark of trees at each site. The samples were harvested from the sites after 3-month exposure. Concentrations of Pb, Cu, Cd, Fe, Zn, and S content were determined using an atomic absorption spectrophotometer. Results showed that there was a significant difference in the trace metals concentrations across the sites (p trend in the concentration of these heavy metals suggests that activities in these workshops might become a major source of certain heavy metals in the environment and if the pollution activities persist, it might become worrisome over time.

  19. The use of indigenous plant species and calcium phosphate for the stabilization of highly metal-polluted sites in southern Poland

    NARCIS (Netherlands)

    Kucharski, R.; Sas-Nowosielska, A.; Malkowski, E.; Japenga, J.; Kuperberg, J.M.; Pogrzeba, M.; Krzyzak, J.

    2005-01-01

    Highly metal-polluted (Pb, Cd, Zn) soil from a non-ferrous mine and smelter site in southern Poland, further referred to as Waryski soil, was used to test indigenous plant species for stabilization effectiveness of heavy metals in soils. Results of pilot investigations with commercially available

  20. Metal extent in blood of livestock from Dandora dumping site, Kenya: Source identification of Pb exposure by stable isotope analysis

    International Nuclear Information System (INIS)

    Nakata, Hokuto; Nakayama, Shouta M.M.; Ikenaka, Yoshinori; Mizukawa, Hazuki; Ishii, Chihiro; Yohannes, Yared B.; Konnai, Satoru; Darwish, Wageh Sobhy; Ishizuka, Mayumi

    2015-01-01

    Nairobi city in Kenya produces 2000 tons/day of garbage, and most of it is dumped onto the Dandora dumping site, home to a quarter-million residents. This study was conducted (1) to assess the contamination levels of nine metals and a metalloid (arsenic) in the blood of pigs, goats, sheep and cattle from Dandora, and (2) to identify a possible source of lead (Pb) pollution. Cadmium (Cd, 0.17–4.35 μg/kg, dry-wt) and Pb (90–2710 μg/kg) levels in blood were generally high, suggesting human exposure to Cd through livestock consumption and Pb poisoning among pigs (2600 μg/kg) and cattle (354 μg/kg). Results of Pb isotope ratios indicated that the major exposure route might differ among species. Our results also suggested a possibility that the residents in Dandora have been exposed to the metals through livestock consumption. - Highlights: • Metals extent in blood of livestock were examined. • Dandora dumping site, Kenya is study site. • Concentrations of Cd and Pb were high in the blood of livestock. • Pb isotope ratios indicated that major exposure route might differ among species. - Metal extent and stable Pb isotope ratio in livestock from Dandora, Kenya were examined

  1. Health Risk-Based Assessment and Management of Heavy Metals-Contaminated Soil Sites in Taiwan

    Directory of Open Access Journals (Sweden)

    Zueng-Sang Chen

    2010-10-01

    Full Text Available Risk-based assessment is a way to evaluate the potential hazards of contaminated sites and is based on considering linkages between pollution sources, pathways, and receptors. These linkages can be broken by source reduction, pathway management, and modifying exposure of the receptors. In Taiwan, the Soil and Groundwater Pollution Remediation Act (SGWPR Act uses one target regulation to evaluate the contamination status of soil and groundwater pollution. More than 600 sites contaminated with heavy metals (HMs have been remediated and the costs of this process are always high. Besides using soil remediation techniques to remove contaminants from these sites, the selection of possible remediation methods to obtain rapid risk reduction is permissible and of increasing interest. This paper discusses previous soil remediation techniques applied to different sites in Taiwan and also clarified the differences of risk assessment before and after soil remediation obtained by applying different risk assessment models. This paper also includes many case studies on: (1 food safety risk assessment for brown rice growing in a HMs-contaminated site; (2 a tiered approach to health risk assessment for a contaminated site; (3 risk assessment for phytoremediation techniques applied in HMs-contaminated sites; and (4 soil remediation cost analysis for contaminated sites in Taiwan.

  2. Health Risk-Based Assessment and Management of Heavy Metals-Contaminated Soil Sites in Taiwan

    Science.gov (United States)

    Lai, Hung-Yu; Hseu, Zeng-Yei; Chen, Ting-Chien; Chen, Bo-Ching; Guo, Horng-Yuh; Chen, Zueng-Sang

    2010-01-01

    Risk-based assessment is a way to evaluate the potential hazards of contaminated sites and is based on considering linkages between pollution sources, pathways, and receptors. These linkages can be broken by source reduction, pathway management, and modifying exposure of the receptors. In Taiwan, the Soil and Groundwater Pollution Remediation Act (SGWPR Act) uses one target regulation to evaluate the contamination status of soil and groundwater pollution. More than 600 sites contaminated with heavy metals (HMs) have been remediated and the costs of this process are always high. Besides using soil remediation techniques to remove contaminants from these sites, the selection of possible remediation methods to obtain rapid risk reduction is permissible and of increasing interest. This paper discusses previous soil remediation techniques applied to different sites in Taiwan and also clarified the differences of risk assessment before and after soil remediation obtained by applying different risk assessment models. This paper also includes many case studies on: (1) food safety risk assessment for brown rice growing in a HMs-contaminated site; (2) a tiered approach to health risk assessment for a contaminated site; (3) risk assessment for phytoremediation techniques applied in HMs-contaminated sites; and (4) soil remediation cost analysis for contaminated sites in Taiwan. PMID:21139851

  3. Site-specific tagging proteins with a rigid, small and stable transition metal chelator, 8-hydroxyquinoline, for paramagnetic NMR analysis

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yin; Huang, Feng [Nankai University, State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) (China); Huber, Thomas [Australian National University, Research School of Chemistry (Australia); Su, Xun-Cheng, E-mail: xunchengsu@nankai.edu.cn [Nankai University, State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) (China)

    2016-02-15

    Design of a paramagnetic metal binding motif in a protein is a valuable way for understanding the function, dynamics and interactions of a protein by paramagnetic NMR spectroscopy. Several strategies have been proposed to site-specifically tag proteins with paramagnetic lanthanide ions. Here we report a simple approach of engineering a transition metal binding motif via site-specific labelling of a protein with 2-vinyl-8-hydroxyquinoline (2V-8HQ). The protein-2V-8HQ adduct forms a stable complex with transition metal ions, Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). The paramagnetic effects generated by these transition metal ions were evaluated by NMR spectroscopy. We show that 2V-8HQ is a rigid and stable transition metal binding tag. The coordination of the metal ion can be assisted by protein sidechains. More importantly, tunable paramagnetic tensors are simply obtained in an α-helix that possesses solvent exposed residues in positions i and i + 3, where i is the residue to be mutated to cysteine, i + 3 is Gln or Glu or i − 4 is His. The coordination of a sidechain carboxylate/amide or imidazole to cobalt(II) results in different structural geometries, leading to different paramagnetic tensors as shown by experimental data.

  4. Trends in oxygen reduction and methanol activation on transition metal chalcogenides

    DEFF Research Database (Denmark)

    Tritsaris, Georgios; Nørskov, Jens Kehlet; Rossmeisl, Jan

    2011-01-01

    We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability...... of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated....

  5. MECHANISMS OF THE COMPLEX FORMATION BY d-METALS ON POROUS SUPPORTS AND THE CATALYTIC ACTIVITY OF THE FORMED COMPLEXES IN REDOX REACTIONS

    Directory of Open Access Journals (Sweden)

    T. L. Rakitskaya

    2015-11-01

    Full Text Available The catalytic activity of supported complexes of d metals in redox reactions with participation of gaseous toxicants, PH3, CO, O3, and SO2, depends on their composition. Owing to the variety of physicochemical and structural-adsorption properties of available supports, their influence on complex formation processes, the composition and catalytic activity of metal complexes anchored on them varies over a wide range. The metal complex formation on sup-ports with weak ion-exchanging properties is similar to that in aqueous solutions. In this case, the support role mainly adds up to the ability to reduce the activity of water adsorbed on them. The interaction between a metal complex and a support surface occurs through adsorbed water molecules. Such supports can also affect complex formation processes owing to protolytic reactions on account of acidic properties of sorbents used as supports. The catalytic activity of metal complexes supported on polyphase natural sorbents considerably depends on their phase relationship. In the case of supports with the nonsimple structure and pronounced ion-exchanging properties, for instance, zeolites and laminar silicates, it is necessary to take into account the variety of places where metal ions can be located. Such location places determine distinctions in the coordination environment of the metal ions and the strength of their bonding with surface adsorption sites and, therefore, the catalytic activity of surface complexes formed by theses metal ions. Because of the energy surface inhomogeneity, it is important to determine a relationship between the strength of a metal complex bonding with a support surface and its catalytic activity. For example, bimetallic complexes are catalytically active in the reactions of oxidation of the above gaseous toxicants. In particular, in the case of carbon monoxide oxidation, the most catalytic activity is shown by palladium-copper complexes in which copper(II is strongly

  6. Dimensionality of heavy metal distribution in waste disposal sites using nonlinear dynamics

    International Nuclear Information System (INIS)

    Modis, Kostas; Komnitsas, Kostas

    2008-01-01

    Mapping of heavy metal contamination in mining and waste disposal sites usually relies on geostatistical approaches and linear stochastic dynamics. The present paper aims to identify, using the Grassberger-Procaccia correlation dimension (CD) algorithm, the existence of a nonlinear deterministic and chaotic dynamic behaviour in the spatial pattern of arsenic, manganese and zinc concentration in a Russian coal waste disposal site. The analysis carried out yielded embedding dimension values ranging between 7 and 8 suggesting thus from a chaotic dynamic perspective that arsenic, manganese and zinc concentration in space is a medium dimensional problem for the regionalized scale considered in this study. This alternative nonlinear dynamics approach may complement conventional geostatistical studies and may be also used for the estimation of risk and the subsequent screening and selection of a feasible remediation scheme in wider mining and waste disposal sites. Finally, the synergistic effect of this study may be further elaborated if additional factors including among others presence of hot spots, density and depth of sampling, mineralogy of wastes and sensitivity of analytical techniques are taken into account

  7. Heavy metals' data in soils for agricultural activities

    Directory of Open Access Journals (Sweden)

    T.A. Adagunodo

    2018-06-01

    Full Text Available In this article, the heavy metals in soils for agricultural activities were analyzed statistically. Ten (10 soil samples were randomly taken across the agricultural zones in Odo-Oba, southwestern Nigeria. Ten (10 metals; namely: copper (Cu, lead (Pb, chromium (Cr, arsenic (As, zinc (Zn, cadmium (Cd, nickel (Ni, antimony (Sb, cobalt (Co and vanadium (V were determined and compared with the guideline values. When the values were compared with the international standard, none of the heavy metals in the study area exceeded the threshold limit. However, the maximum range of the samples showed that Cr and V exceeded the permissible limit which could be associated with ecological risk. The data can reveal the distributions of heavy metals in the agricultural topsoil of Odo-Oba, and can be used to estimate the risks associated with the consumption of crops grown on such soils. Keywords: Agricultural soils, Heavy metals, Contamination, Environment, Soil screening, Geostatistics

  8. Variation and distribution of metals and metalloids in soil/ash mixtures from Agbogbloshie e-waste recycling site in Accra, Ghana

    Energy Technology Data Exchange (ETDEWEB)

    Itai, Takaaki, E-mail: itai@sci.ehime-u.ac.jp [Center for Marine Environmental Studies, Ehime University, Bunkyo-cho 2-5, Matsuyama, Ehime 790-8577 (Japan); Otsuka, Masanari [Center for Marine Environmental Studies, Ehime University, Bunkyo-cho 2-5, Matsuyama, Ehime 790-8577 (Japan); Asante, Kwadwo Ansong [Center for Marine Environmental Studies, Ehime University, Bunkyo-cho 2-5, Matsuyama, Ehime 790-8577 (Japan); CSIR Water Research Institute, P. O. Box AH 38, Achimota, Accra (Ghana); Muto, Mamoru [Center for Marine Environmental Studies, Ehime University, Bunkyo-cho 2-5, Matsuyama, Ehime 790-8577 (Japan); Opoku-Ankomah, Yaw; Ansa-Asare, Osmund Duodu [CSIR Water Research Institute, P. O. Box AH 38, Achimota, Accra (Ghana); Tanabe, Shinsuke [Center for Marine Environmental Studies, Ehime University, Bunkyo-cho 2-5, Matsuyama, Ehime 790-8577 (Japan)

    2014-02-01

    Illegal import and improper recycling of electronic waste (e-waste) are an environmental issue in developing countries around the world. African countries are no exception to this problem and the Agbogbloshie market in Accra, Ghana is a well-known e-waste recycling site. We have studied the levels of metal(loid)s in the mixtures of residual ash, formed by the burning of e-waste, and the cover soil, obtained using a portable X-ray fluorescence spectrometer (P-XRF) coupled with determination of the 1 M HCl-extractable fraction by an inductively coupled plasma mass spectrometer. The accuracy and precision of the P-XRF measurements were evaluated by measuring 18 standard reference materials; this indicated the acceptable but limited quality of this method as a screening tool. The HCl-extractable levels of Al, Co, Cu, Zn, Cd, In, Sb, Ba, and Pb in 10 soil/ash mixtures varied by more than one order of magnitude. The levels of these metal(loid)s were found to be correlated with the color (i.e., soil/ash ratio), suggesting that they are being released from disposed e-waste via open burning. The source of rare elements could be constrained using correlation to the predominant metals. Human hazard quotient values based on ingestion of soil/ash mixtures exceeded unity for Pb, As, Sb, and Cu in a high-exposure scenario. This study showed that along with common metals, rare metal(loid)s are also enriched in the e-waste burning site. We suggest that risk assessment considering exposure to multiple metal(loid)s should be addressed in studies of e-waste recycling sites. - Highlights: • Contamination on the largest e-waste recycling site in Africa was investigated. • Portable X-ray Fluorescence analyzer useful for first screening • High levels of Cu, Zn, Pb, and Al in soil/ash mixtures • Hazards for workers are significant.

  9. Variation and distribution of metals and metalloids in soil/ash mixtures from Agbogbloshie e-waste recycling site in Accra, Ghana

    International Nuclear Information System (INIS)

    Itai, Takaaki; Otsuka, Masanari; Asante, Kwadwo Ansong; Muto, Mamoru; Opoku-Ankomah, Yaw; Ansa-Asare, Osmund Duodu; Tanabe, Shinsuke

    2014-01-01

    Illegal import and improper recycling of electronic waste (e-waste) are an environmental issue in developing countries around the world. African countries are no exception to this problem and the Agbogbloshie market in Accra, Ghana is a well-known e-waste recycling site. We have studied the levels of metal(loid)s in the mixtures of residual ash, formed by the burning of e-waste, and the cover soil, obtained using a portable X-ray fluorescence spectrometer (P-XRF) coupled with determination of the 1 M HCl-extractable fraction by an inductively coupled plasma mass spectrometer. The accuracy and precision of the P-XRF measurements were evaluated by measuring 18 standard reference materials; this indicated the acceptable but limited quality of this method as a screening tool. The HCl-extractable levels of Al, Co, Cu, Zn, Cd, In, Sb, Ba, and Pb in 10 soil/ash mixtures varied by more than one order of magnitude. The levels of these metal(loid)s were found to be correlated with the color (i.e., soil/ash ratio), suggesting that they are being released from disposed e-waste via open burning. The source of rare elements could be constrained using correlation to the predominant metals. Human hazard quotient values based on ingestion of soil/ash mixtures exceeded unity for Pb, As, Sb, and Cu in a high-exposure scenario. This study showed that along with common metals, rare metal(loid)s are also enriched in the e-waste burning site. We suggest that risk assessment considering exposure to multiple metal(loid)s should be addressed in studies of e-waste recycling sites. - Highlights: • Contamination on the largest e-waste recycling site in Africa was investigated. • Portable X-ray Fluorescence analyzer useful for first screening • High levels of Cu, Zn, Pb, and Al in soil/ash mixtures • Hazards for workers are significant

  10. Half-of-the-sites reactivity of outer-membrane phospholipase A against an active-site-directed inhibitor.

    Science.gov (United States)

    Ubarretxena-Belandia, I; Cox, R C; Dijkman, R; Egmond, M R; Verheij, H M; Dekker, N

    1999-03-01

    The reaction of a novel active-site-directed phospholipase A1 inhibitor with the outer-membrane phospholipase A (OMPLA) was investigated. The inhibitor 1-p-nitrophenyl-octylphosphonate-2-tridecylcarbamoyl-3-et hanesulfonyl -amino-3-deoxy-sn-glycerol irreversibly inactivated OMPLA. The inhibition reaction did not require the cofactor calcium or an unprotonated active-site His142. The inhibition of the enzyme solubilized in hexadecylphosphocholine micelles was characterized by a rapid (t1/2 = 20 min) and complete loss of enzymatic activity, concurrent with the covalent modification of 50% of the active-site serines, as judged from the amount of p-nitrophenolate (PNP) released. Modification of the remaining 50% occurred at a much lower rate, indicative of half-of-the-sites reactivity against the inhibitor of this dimeric enzyme. Inhibition of monomeric OMPLA solubilized in hexadecyl-N,N-dimethyl-1-ammonio-3-propanesulfonate resulted in an equimolar monophasic release of PNP, concurrent with the loss of enzymatic activity (t1/2 = 14 min). The half-of-the-sites reactivity is discussed in view of the dimeric nature of this enzyme.

  11. Salt site performance assessment activities

    International Nuclear Information System (INIS)

    Kircher, J.F.; Gupta, S.K.

    1983-01-01

    During this year the first selection of the tools (codes) for performance assessments of potential salt sites have been tentatively selected and documented; the emphasis has shifted from code development to applications. During this period prior to detailed characterization of a salt site, the focus is on bounding calculations, sensitivity and with the data available. The development and application of improved methods for sensitivity and uncertainty analysis is a focus for the coming years activities and the subject of a following paper in these proceedings. Although the assessments to date are preliminary and based on admittedly scant data, the results indicate that suitable salt sites can be identified and repository subsystems designed which will meet the established criteria for protecting the health and safety of the public. 36 references, 5 figures, 2 tables

  12. The role of metallic ions in nano-bio hybrid catalysts from ab initio first principles

    Science.gov (United States)

    Behera, Sushant; Deb, Pritam

    We employ high-accuracy linear-scaling density functional theory calculations with a near-complete basis set and a minimal parameter implicit solvent model, within the self-consistent calculation, on silver ion assimilated on bacteriorhodopsin (bR) at specific binding sites. The geometry optimization indicates the formation of stable active sites at the interface of nano-bio hybrid and density of states reflects the metallic behavior of the active sites. Detailed kinetics of the catalytic reaction is revealed using ab initio electronic structure calculations. We observed that the metal ion incorporated active sites are more efficient in electrolytic splitting of water than pristine sites due to their less value of Gibbs free energy for hydrogen evolution reaction and strong synergistic effect. The volcano plot analysis and free energy diagram are considered to understan hydrogen evolution efficiency. Moreover, the essential role of metallic ion on catalytic efficiency is elucidated. DBT, Government of India, vide Grant No BT/357/NE/TBP/ 2012. DST, GoI for financial support under INSPIRE Fellowship(IF150325).

  13. Advanced technologies for decontamination and conversion of scrap metal

    International Nuclear Information System (INIS)

    Muth, T.R.; Shasteen, K.E.; Liby, A.L.

    1995-01-01

    The Department of Energy (DOE) accumulated large quantities of radioactive scrap metal (RSM) through historic maintenance activities. The Decontamination and Decommissioning (D ampersand D) of major sites formerly engaged in production of nuclear materials and manufacture of nuclear weapons will generate additional quantities of RSM, as much as 3 million tons of such metal according to a recent study. The recycling of RSM is quickly becoming appreciated as a key strategy in DOE's cleanup of contaminated sites and facilities. The work described here has focused on recycle of the concentrated and high-value contaminated scrap metal resource that will arise from cleanup of DOE's gaseous diffusion plants

  14. Advanced technologies for decontamination and conversion of scrap metal

    Energy Technology Data Exchange (ETDEWEB)

    Muth, T.R.; Shasteen, K.E.; Liby, A.L. [Manufacturing Sciences Corp., Oak Ridge, TN (United States)] [and others

    1995-10-01

    The Department of Energy (DOE) accumulated large quantities of radioactive scrap metal (RSM) through historic maintenance activities. The Decontamination and Decommissioning (D&D) of major sites formerly engaged in production of nuclear materials and manufacture of nuclear weapons will generate additional quantities of RSM, as much as 3 million tons of such metal according to a recent study. The recycling of RSM is quickly becoming appreciated as a key strategy in DOE`s cleanup of contaminated sites and facilities. The work described here has focused on recycle of the concentrated and high-value contaminated scrap metal resource that will arise from cleanup of DOE`s gaseous diffusion plants.

  15. Enhancement of oxygen reduction at Fe tetrapyridyl porphyrin by pyridyl-N coordination to transition metal ions

    International Nuclear Information System (INIS)

    Maruyama, Jun; Baier, Claudia; Wolfschmidt, Holger; Bele, Petra; Stimming, Ulrich

    2012-01-01

    One of the promising candidates as noble-metal-free electrode catalysts for polymer electrolyte fuel cells (PEFCs) is a carbon material with nitrogen atoms coordinating iron ions embedded on the surface (Fe-N x moiety) as the active site, although the activity is insufficient compared to conventional platinum-based electrocatalysts. In order to obtain fundamental information on the activity enhancement, a simple model of the Fe-N x active site was formed by adsorbing 5,10,15,20-Tetrakis(4-pyridyl)-21H,23H-porphine iron(III) chloride (FeTPyPCl) on the basal plane of highly oriented pyrolytic graphite (HOPG), and cathodic oxygen reduction was investigated on the surface in 0.1 M HClO 4 . The catalytic activity for oxygen reduction was enhanced by loading transition metal ions (Co 2+ , Ni 2+ , Cu 2+ ) together with FeTPyPCl. The X-ray photoelectron spectrum of the surface suggested that the metal was coordinated by the pyridine-N. The enhancement effect of the transition metals was supported by two different measurements: oxygen reduction at HOPG in 0.1 M HClO 4 dissolving FeTPyPCl and the metal ions; oxygen reduction in 0.1 M HClO 4 at the subsequently well-rinsed and dried HOPG. The ultraviolet–visible spectrum for the solution also suggested the coordination between the pyridyl-N and the metal ions. The oxygen reduction enhancement was attributed to the electronic interaction between the additional transition metal and the Fe center of the porphyrin through the coordination bonds. These results implied that the improvement of the activity of the noble-metal-free catalyst would be possible by the proper introduction of the transition metal ions around the active site.

  16. Variation and distribution of metals and metalloids in soil/ash mixtures from Agbogbloshie e-waste recycling site in Accra, Ghana.

    Science.gov (United States)

    Itai, Takaaki; Otsuka, Masanari; Asante, Kwadwo Ansong; Muto, Mamoru; Opoku-Ankomah, Yaw; Ansa-Asare, Osmund Duodu; Tanabe, Shinsuke

    2014-02-01

    Illegal import and improper recycling of electronic waste (e-waste) are an environmental issue in developing countries around the world. African countries are no exception to this problem and the Agbogbloshie market in Accra, Ghana is a well-known e-waste recycling site. We have studied the levels of metal(loid)s in the mixtures of residual ash, formed by the burning of e-waste, and the cover soil, obtained using a portable X-ray fluorescence spectrometer (P-XRF) coupled with determination of the 1M HCl-extractable fraction by an inductively coupled plasma mass spectrometer. The accuracy and precision of the P-XRF measurements were evaluated by measuring 18 standard reference materials; this indicated the acceptable but limited quality of this method as a screening tool. The HCl-extractable levels of Al, Co, Cu, Zn, Cd, In, Sb, Ba, and Pb in 10 soil/ash mixtures varied by more than one order of magnitude. The levels of these metal(loid)s were found to be correlated with the color (i.e., soil/ash ratio), suggesting that they are being released from disposed e-waste via open burning. The source of rare elements could be constrained using correlation to the predominant metals. Human hazard quotient values based on ingestion of soil/ash mixtures exceeded unity for Pb, As, Sb, and Cu in a high-exposure scenario. This study showed that along with common metals, rare metal(loid)s are also enriched in the e-waste burning site. We suggest that risk assessment considering exposure to multiple metal(loid)s should be addressed in studies of e-waste recycling sites. © 2013. Published by Elsevier B.V. All rights reserved.

  17. Research in Support of Remediation Activities at the Savannah River Site

    International Nuclear Information System (INIS)

    Seaman, J.C.; B.B. Looney and M.K. Harris

    2007-01-01

    The USDOE Savannah River Site (SRS), an 803-km 2 (310-mile 2 ) facility located south of Aiken, SC on the upper Atlantic Coastal Plain and bounded to the west by the Savannah River, was established in the 1950s for the production and refinement of nuclear materials. To fulfill this mission during the past 50 years SRS has operated five nuclear reactors, two large chemical separation areas, waste disposal facilities (landfills, waste ponds, waste tanks, and waste stabilization), and a large number of research and logistics support facilities. Contaminants of concern (COC) resulting from site operations include chlorinated solvents, radionuclides, metals, and metalloids, often found as complex mixtures that greatly complicate remediation efforts when compared with civilian industries. The objective of this article is to provide a description of the lithology and hydrostratigraphy of the SRS, as well as a brief history of site operations and research activities as a preface to the current special section of Vadose Zone Journal (VZJ) dedicated to SRS, focusing mainly on issues that are unique to the USDOE complex. Contributions to the special section reflect a diverse range of topics, from hydrologic tracer experiments conducted both within the vadose and saturated zones to studies specifically aimed at identifying geochemical processes controlling the migration and partitioning of specific contaminants (e.g., TCE, 137 Cs, U, and Pu) in SRS subsurface environments. Addressing the diverse environmental challenges of the SRS provides a unique opportunity to conduct both fundamental and applied research across a range of experimental scales. Hence, the SRS has been a pioneering force in several areas of environmental research and remediation, often through active interdisciplinary collaboration with researchers from other USDOE facilities, academic and federal institutions, and commercial entities

  18. Surface/structure functionalization of copper-based catalysts by metal-support and/or metal-metal interactions

    Science.gov (United States)

    Konsolakis, Michalis; Ioakeimidis, Zisis

    2014-11-01

    Cu-based catalysts have recently attracted great attention both in catalysis and electro-catalysis fields due to their excellent catalytic performance and low cost. Given that their performance is determined, to a great extent, by Cu sites local environment, considerable efforts have been devoted on the strategic modifications of the electronic and structural properties of Cu sites. In this regard, the feasibility of tuning the local structure of Cu entities by means of metal-support or metal-metal interactions is investigated. More specifically, the physicochemical properties of Cu entities are modified by employing: (i) different oxides (CeO2, La2O3, Sm2O3), or (ii) ceria-based mixed oxides (Ce1-xSmxOδ) as supporting carriers, and (iii) a second metal (Cobalt) adjacent to Cu (bimetallic Cu-Co/CeO2). A characterization study, involving BET, XRD, TPR, and XPS, reveal that significant modifications on structural, redox and electronic properties of Cu sites can be induced by adopting either different oxide carriers or bimetallic complexes. Fundamental insights into the tuning of Cu local environment by metal-support or metal-metal interactions are provided, paving the way for real-life industrial applications.

  19. The impact of seasonal varied human activity on characteristics and sources of heavy metals in metropolitan road dusts.

    Science.gov (United States)

    Men, Cong; Liu, Ruimin; Wang, Qingrui; Guo, Lijia; Shen, Zhenyao

    2018-10-01

    Due to significant human activity, road dust is becoming contaminated by heavy metals in many cities. To comprehensively investigate the variation of contamination level and sources of heavy metals in road dust, 10 heavy metals in road dust samples from Beijing, China, in both summer and winter, were evaluated by spatial analysis using geographic information system (GIS) mapping technology and the positive matrix factorization (PMF) Model. Although the concentrations of some heavy metals between summer and winter had similarities, the differences of others and spatial distributions of heavy metals between summer and winter were considerable. The mean concentrations of As, Cd, Cr, Cu, and Fe were lower in winter, while those of Hg, Mn, Ni, Pb, and Zn were higher. According to the values of the Pollution Index (PI) and Nemerow Integrated Pollution Index (NIPI), there were no obvious differences between summer and winter, but the range between different sites in winter was nearly twice that of summer. Based on the PMF model, four sources of heavy metals in the dust samples were identified. Although the types of sources were consistent, the relative contributions of each source differed between summer and winter. Non-exhaust vehicle emissions was the most important source in summer (34.47 wt%), while fuel combustion contributed the largest proportion to the total heavy metals in winter (32.40 wt%). The impact of each source also showed spatial variation different trends in summer and winter. With the alteration of seasons, intensity of human activities also changed, such as the number of tourists, energy needs for building temperature regulation, construction, and the amount of pesticides and fertilizer. That might be the reason for the variation of heavy metal concentrations and relative contribution of their sources between summer and winter. Copyright © 2018 Elsevier B.V. All rights reserved.

  20. Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Gang [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Yang, Ce [Chemical Science and Engineering Division, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Zhao, Wanpeng [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Li, Qianru [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Wang, Ning [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Li, Tao [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Zhou, Hua [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Chen, Hangrong [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; Shi, Jianlin [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China

    2017-11-06

    The introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble-metal-free electrocatalysts for clean energy conversion applications, however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs is investigated for the first time. It is found that the active cobalt-nitrogen sites tend to be selectively constructed on the surface of N-doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt-sites-dependent activity for ORR and HER in acidic media. And the remarkably enhanced catalytic activities approaching that of benchmark Pt/C in acidic medium has been obtained on the catalyst dominated with cobalt-nitrogen sites, confirmed by the advanced spectroscopic . Our finding demonstrates a general paradigm of anion-regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactions related with TMSs.

  1. 1994 Site environmental report

    International Nuclear Information System (INIS)

    1995-07-01

    The Fernald site is a Department of Energy (DOE)-owned facility that produced high-quality uranium metals for military defense for nearly 40 years. DOE suspended production at the site in 1989 and formally ended production in 1991. Although production activities have ceased, the site continues to examine the air and liquid pathways as possible routes through which pollutants from past operations and current remedial activities may leave the site. The Site Environmental Report (SER) is prepared annually in accordance with DOE Order 5400.1, General Environmental Protection Program. This 1994 SER provides the general public as well as scientists and engineers with the results from the site's ongoing Environmental Monitoring Program. Also included in this report is information concerning the site's progress toward achieving full compliance with requirements set forth by DOE, U.S. Environmental Protection Agency (USEPA), and Ohio EPA (OEPA). For some readers, the highlights provided in this Executive Summary may provide sufficient information. Many readers, however, may wish to read more detailed descriptions of the information than those which are presented here. All information presented in this summary is discussed more fully in the main body of this report

  2. Activated Carbon Textile via Chemistry of Metal Extraction for Supercapacitors.

    Science.gov (United States)

    Lam, Do Van; Jo, Kyungmin; Kim, Chang-Hyun; Kim, Jae-Hyun; Lee, Hak-Joo; Lee, Seung-Mo

    2016-12-27

    Carbothermic reduction in the chemistry of metal extraction (MO(s) + C(s) → M(s) + CO(g)) using carbon as a sacrificial agent has been used to smelt metals from diverse oxide ores since ancient times. Here, we paid attention to another aspect of the carbothermic reduction to prepare an activated carbon textile for high-rate-performance supercapacitors. On the basis of thermodynamic reducibility of metal oxides reported by Ellingham, we employed not carbon, but metal oxide as a sacrificial agent in order to prepare an activated carbon textile. We conformally coated ZnO on a bare cotton textile using atomic layer deposition, followed by pyrolysis at high temperature (C(s) + ZnO(s) → C'(s) + Zn(g) + CO(g)). We figured out that it leads to concurrent carbonization and activation in a chemical as well as mechanical way. Particularly, the combined effects of mechanical buckling and fracture that occurred between ZnO and cotton turned out to play an important role in carbonizing and activating the cotton textile, thereby significantly increasing surface area (nearly 10 times) compared with the cotton textile prepared without ZnO. The carbon textiles prepared by carbothermic reduction showed impressive combination properties of high power and energy densities (over 20-fold increase) together with high cyclic stability.

  3. Environmental impact assessment of radionuclide and metal contamination at the former U site at Kadji Sai, Kyrgyzstan.

    Science.gov (United States)

    Lind, O C; Stegnar, P; Tolongutov, B; Rosseland, B O; Strømman, G; Uralbekov, B; Usubalieva, A; Solomatina, A; Gwynn, J P; Lespukh, E; Salbu, B

    2013-09-01

    During 1949-1967, a U mine, a coal-fired thermal power plant and a processing plant for the extraction of U from the produced ash were operated at the Kadji Sai U mining site in Tonsk district, Issyk-Kul County, Kyrgyzstan. The Kadji Sai U legacy site represents a source of contamination of the local environment by naturally occurring radionuclides and associated trace elements. To assess the environmental impact of radionuclides and trace metals at the site, field expeditions were performed in 2007 and 2008 by the Joint collaboration between Norway, Kazakhstan, Kyrgyzstan, Tajikistan (JNKKT) project and the NATO SfP RESCA project. In addition to in situ gamma and Rn dose rate measurements, sampling included at site fractionation of water and sampling of water, fish, sediment, soils and vegetation. The concentrations of radionuclides and trace metals in water from Issyk-Kul Lake were in general low, but surprisingly high for As. Uptake of U and As was also observed in fish from the lake with maximum bioconcentration factors for liver of 1.6 and 75, respectively. The concentrations of U in water within the Kadji Sai area varied from 0.01 to 0.05 mg/L, except for downstream from the mining area where U reached a factor of 10 higher, 0.2 mg/L. Uranium concentrations in the drinking water of Kadji Sai village were about the level recommended by the WHO for drinking water. The (234)U/(238)U activity ratio reflected equilibrium conditions in the mining pond, but far from equilibrium outside this area (reaching 2.3 for an artesian well). Uranium, As and Ni were mainly present as low molecular mass (LMM, less than 10 kDa) species in all samples, indicating that these elemental species are mobile and potentially bioavailable. The soils from the mining sites were enriched in U, As and trace metals. Hot spots with elevated radioactivity levels were easily detected in Kadji Sai and radioactive particles were observed. The presence of particles carrying significant amount of

  4. Environmental impact assessment of radionuclide and metal contamination at the former U site at Kadji Sai, Kyrgyzstan

    International Nuclear Information System (INIS)

    Lind, O.C.; Stegnar, P.; Tolongutov, B.; Rosseland, B.O.; Strømman, G.; Uralbekov, B.; Usubalieva, A.; Solomatina, A.; Gwynn, J.P.; Lespukh, E.; Salbu, B.

    2013-01-01

    During 1949–1967, a U mine, a coal-fired thermal power plant and a processing plant for the extraction of U from the produced ash were operated at the Kadji Sai U mining site in Tonsk district, Issyk-Kul County, Kyrgyzstan. The Kadji Sai U legacy site represents a source of contamination of the local environment by naturally occurring radionuclides and associated trace elements. To assess the environmental impact of radionuclides and trace metals at the site, field expeditions were performed in 2007 and 2008 by the Joint collaboration between Norway, Kazakhstan, Kyrgyzstan, Tajikistan (JNKKT) project and the NATO SfP RESCA project. In addition to in situ gamma and Rn dose rate measurements, sampling included at site fractionation of water and sampling of water, fish, sediment, soils and vegetation. The concentrations of radionuclides and trace metals in water from Issyk-Kul Lake were in general low, but surprisingly high for As. Uptake of U and As was also observed in fish from the lake with maximum bioconcentration factors for liver of 1.6 and 75, respectively. The concentrations of U in water within the Kadji Sai area varied from 0.01 to 0.05 mg/L, except for downstream from the mining area where U reached a factor of 10 higher, 0.2 mg/L. Uranium concentrations in the drinking water of Kadji Sai village were about the level recommended by the WHO for drinking water. The 234 U/ 238 U activity ratio reflected equilibrium conditions in the mining pond, but far from equilibrium outside this area (reaching 2.3 for an artesian well). Uranium, As and Ni were mainly present as low molecular mass (LMM, less than 10 kDa) species in all samples, indicating that these elemental species are mobile and potentially bioavailable. The soils from the mining sites were enriched in U, As and trace metals. Hot spots with elevated radioactivity levels were easily detected in Kadji Sai and radioactive particles were observed. The presence of particles carrying significant amount of

  5. Heavy metals and hydrocarbon concentrations in water, sediments and tissue of Cyclope neritea from two sites in Suez Canal, Egypt and histopathological effects.

    Science.gov (United States)

    Sharaf, Hesham M; Shehata, Abdalla M

    2015-01-01

    Heavy metals and hydrocarbons are of the most common marine pollutants around the world. The present study aimed to assess the concentration of petroleum hydrocarbons and heavy metals in tissues of the snail cyclope neritea, water and sediments from two sites of the study area (Temsah lake and Suez canal) represent polluted and unpolluted sites respectively. The results showed that, the levels of the heavy metals (Pb, Cd, Co, Mg and Zn) in the polluted area have reached harmful limits recorded globally. Lead in water, sediment and tissue of the snail reached to 0.95 ppm, 4.54 ppm and 7.93 ppm respectively. Cadmium reached 0.31 ppm, 1.15 ppm and 3.08 ppm in the corresponding samples. Cobalt was not detected in water, but it reached 1.42 ppm and 10.36 ppm in the sediment and snails tissue respectively. Magnesium in water, sediment and tissue of the snail reached 3.73 ppm, 9.44 ppm and12.6 ppm respectively. Zinc reached 0.11 ppm, 3.89 ppm and 12.60ppm in the corresponding samples. Meanwhile, hydrocarbons in the polluted area (site1) reached 110.10 μg/L, 980.15 μg/g and 228.00 μg/g in water sediment and digestive gland tissues of the snails respectively. Whereas, hydrocarbons in the unpolluted area (site2) were estimated as 14.20 μg/L, 55.60 μg/g and 22.66 μg/g in water, sediment and tissue of the snails respectively. The combination of histopathological image with monitoring of the metal level in the digestive gland of the present snail provides an important tool for early detection of impending environmental problems and potential public health issues. Petroleum hydrocarbons are toxic to the marine fauna when present above certain limit in the marine water. The major detoxification organ in molluscs is the digestive gland, which has been used as a bioindicator organ for toxicity assessment. The effect of high crude oil on the digestive gland tubules of exposed snails when examined microscopically reveals a series of histological changes which indicates that the

  6. Reveal the response of enzyme activities to heavy metals through in situ zymography.

    Science.gov (United States)

    Duan, Chengjiao; Fang, Linchuan; Yang, Congli; Chen, Weibin; Cui, Yongxing; Li, Shiqing

    2018-07-30

    Enzymes in the soil are vital for assessing heavy metal soil pollution. Although the presence of heavy metals is thought to change the soil enzyme system, the distribution of enzyme activities in heavy metal polluted-soil is still unknown. For the first time, using soil zymography, we analyzed the distribution of enzyme activities of alfalfa rhizosphere and soil surface in the metal-contaminated soil. The results showed that the growth of alfalfa was significantly inhibited, and an impact that was most pronounced in seedling biomass and chlorophyll content. Catalase activity (CAT) in alfalfa decreased with increasing heavy metal concentrations, while malondialdehyde (MDA) content continually increased. The distribution of enzyme activities showed that both phosphatase and β-glucosidase activities were associated with the roots and were rarely distributed throughout the soil. In addition, the total hotspot areas of enzyme activities were the highest in extremely heavy pollution soil. The hotspot areas of phosphatase were 3.4%, 1.5% and 7.1% under none, moderate and extremely heavy pollution treatment, respectively, but increased from 0.1% to 0.9% for β-glucosidase with the increasing pollution levels. Compared with the traditional method of enzyme activities, zymography can directly and accurately reflect the distribution and extent of enzyme activity in heavy metals polluted soil. The results provide an efficient research method for exploring the interaction between enzyme activities and plant rhizosphere. Copyright © 2018 Elsevier Inc. All rights reserved.

  7. Effect of site on sedimentological characteristics and metal pollution in two semi-enclosed embayments of great freshwater reservoir: Lake Nasser, Egypt

    Science.gov (United States)

    Farhat, Hassan I.; Aly, Walid

    2018-05-01

    This study was carried out to assess the effect of site on the spatial variations of sedimentological characteristics and heavy metal pollution of two semi-enclosed embayments of Lake Nasser. Grain Size, texture and mode of transportation as well as some heavy metals and organic matter were assessed in sediment samples from those embayments. The results indicated that the grain size of the lake sediments was affected by site variation. Moreover, heavy metal distribution in the sediments was mainly directed by grain size distribution and organic matter, though, the organic matter was more critical than grain size in controlling heavy metals distribution in each embayment. The main source of heavy metals in studied embayments was concluded to be the metals brought with flood waters rather than being of anthropogenic origin. The results also indicated the association of studied metals with Fe and Mn oxides of suspended matters and dissolved solids which come with flood water and trapped and settled to the bottom sediment in the stagnation period. Measured indices indicated that southern embayment is more polluted than northern one, which could be explained on the basis that the southern embayment reserves larger amounts of suspended matter coming with the flood than northern embayment.

  8. Distribution of chemical warfare agent, energetics, and metals in sediments at a deep-water discarded military munitions site

    Science.gov (United States)

    Briggs, Christian; Shjegstad, Sonia M.; Silva, Jeff A. K.; Edwards, Margo H.

    2016-06-01

    There is a strong need to understand the behavior of chemical warfare agent (CWA) at underwater discarded military munitions (DMM) sites to determine the potential threat to human health or the environment, yet few studies have been conducted at sites in excess of 250 m, the depth at which most U.S. chemical munitions were disposed. As part of the Hawai'i Undersea Military Munitions Assessment (HUMMA), sediments adjacent to chemical and conventional DMM at depths of 400-650 m were sampled using human occupied vehicles (HOVs) in order to quantify the distribution of CWA, energetics, and select metals. Sites in the same general area, with no munitions within 50 m in any direction were sampled as a control. Sulfur mustard (HD) and its degradation product 1,4-dithiane were detected at each CWA DMM site, as well as a single sample with the HD degradation product 1,4-thioxane. An energetic compound was detected in sediment to a limited extent at one CWA DMM site. Metals common in munitions casings (i.e., Fe, Cu, and Pb) showed similar trends at the regional and site-wide scales, likely reflecting changes in marine sediment deposition and composition. This study shows HD and its degradation products can persist in the deep-marine environment for decades following munitions disposal.

  9. CFA-13 - a bifunctional perfluorinated metal-organic framework featuring active Cu(i) and Cu(ii) sites.

    Science.gov (United States)

    Fritzsche, J; Denysenko, D; Grzywa, M; Volkmer, D

    2017-11-07

    The synthesis and crystal structure of the mixed-valent perfluorinated metal-organic framework (Me 2 NH 2 )[CFA-13] (Coordination Framework Augsburg University-13), (Me 2 NH 2 )[CuCu(tfpc) 4 ] (H 2 -tfpc = 3,5-bis(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) is described. The copper-containing MOF crystallizes in the monoclinic crystal system within the space group P2 1 /n (no. 14) and the unit cell parameters are as follows: a = 22.3887(19), b = 13.6888(8), c = 21.1804(13) Å, β = 90.495(3)°, V = 6491.0(8) Å 3 . (Me 2 NH 2 )[CFA-13] features a porous 3-D structure constructed from two types of secondary building units (SBUs). Besides novel trinuclear [Cu(pz) 4 ] - coordination units, the network also exhibits Cu(ii) paddle-wheel SBUs. (Me 2 NH 2 )[CFA-13] is fully characterized by single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence, gas sorption measurements and pulse chemisorption experiments. M[CFA-13] (M = K + , Cs + ) frameworks were prepared by postsynthetic exchange of interchannel dimethylammonium cations. Moreover, it was shown that CO molecules can be selectively bound at Cu(i) sites of [Cu(pz) 4 ] - units, whereas Cu(ii) paddle-wheel units bind selectively NH 3 molecules.

  10. Crystal structure of Yersinia pestis virulence factor YfeA reveals two polyspecific metal-binding sites

    Energy Technology Data Exchange (ETDEWEB)

    Radka, Christopher D.; DeLucas, Lawrence J.; Wilson, Landon S.; Lawrenz, Matthew B.; Perry, Robert D.; Aller, Stephen G.

    2017-06-30

    Gram-negative bacteria use siderophores, outer membrane receptors, inner membrane transporters and substrate-binding proteins (SBPs) to transport transition metals through the periplasm. The SBPs share a similar protein fold that has undergone significant structural evolution to communicate with a variety of differentially regulated transporters in the cell. InYersinia pestis, the causative agent of plague, YfeA (YPO2439, y1897), an SBP, is important for full virulence during mammalian infection. To better understand the role of YfeA in infection, crystal structures were determined under several environmental conditions with respect to transition-metal levels. Energy-dispersive X-ray spectroscopy and anomalous X-ray scattering data show that YfeA is polyspecific and can alter its substrate specificity. In minimal-media experiments, YfeA crystals grown after iron supplementation showed a threefold increase in iron fluorescence emission over the iron fluorescence emission from YfeA crystals grown from nutrient-rich conditions, and YfeA crystals grown after manganese supplementation during overexpression showed a fivefold increase in manganese fluorescence emission over the manganese fluorescence emission from YfeA crystals grown from nutrient-rich conditions. In all experiments, the YfeA crystals produced the strongest fluorescence emission from zinc and could not be manipulated otherwise. Additionally, this report documents the discovery of a novel surface metal-binding site that prefers to chelate zinc but can also bind manganese. Flexibility across YfeA crystal forms in three loops and a helix near the buried metal-binding site suggest that a structural rearrangement is required for metal loading and unloading.

  11. Root Fungal Endophytes Enhance Heavy-Metal Stress Tolerance of Clethra barbinervis Growing Naturally at Mining Sites via Growth Enhancement, Promotion of Nutrient Uptake and Decrease of Heavy-Metal Concentration.

    Directory of Open Access Journals (Sweden)

    Keiko Yamaji

    Full Text Available Clethra barbinervis Sieb. et Zucc. is a tree species that grows naturally at several mine sites and seems to be tolerant of high concentrations of heavy metals, such as Cu, Zn, and Pb. The purpose of this study is to clarify the mechanism(s underlying this species' ability to tolerate the sites' severe heavy-metal pollution by considering C. barbinervis interaction with root fungal endophytes. We measured the heavy metal concentrations of root-zone soil, leaves, branches, and fine roots collected from mature C. barbinervis at Hitachi mine. We isolated fungal endophytes from surface-sterilized root segments, and we examined the growth, and heavy metal and nutrient absorption of C. barbinervis seedlings growing in sterilized mine soil with or without root fungal endophytes. Field analyses showed that C. barbinervis contained considerably high amounts of Cu, Zn, and Pb in fine roots and Zn in leaves. The fungi, Phialocephala fortinii, Rhizodermea veluwensis, and Rhizoscyphus sp. were frequently isolated as dominant fungal endophyte species. Inoculation of these root fungal endophytes to C. barbinervis seedlings growing in sterilized mine soil indicated that these fungi significantly enhanced the growth of C. barbinervis seedlings, increased K uptake in shoots and reduced the concentrations of Cu, Ni, Zn, Cd, and Pb in roots. Without root fungal endophytes, C. barbinervis could hardly grow under the heavy-metal contaminated condition, showing chlorosis, a symptom of heavy-metal toxicity. Our results indicate that the tree C. barbinervis can tolerate high heavy-metal concentrations due to the support of root fungal endophytes including P. fortinii, R. veluwensis, and Rhizoscyphus sp. via growth enhancement, K uptake promotion and decrease of heavy metal concentrations.

  12. Active site - a site of binding of affinity inhibitors in baker's yeast inorganic pyrophosphatase

    International Nuclear Information System (INIS)

    Svyato, I.E.; Sklyankina, V.A.; Avaeva, S.M.

    1986-01-01

    The interaction of the enzyme-substrate complex with methyl phosphate, O-phosphoethanolamine, O-phosphopropanolamine, N-acetylphosphoserine, and phosphoglyolic acid, as well as pyrophosphatase, modified by monoesters of phosphoric acid, with pyrophosphate and tripolyphosphate, was investigated. It was shown that the enzyme containing the substrate in the active site does not react with monophosphates, but modified pyrophosphatase entirely retains the ability to bind polyanions to the regulatory site. It is concluded that the inactivation of baker's yeast inorganic pyrophosphatase by monoesters of phosphoric acid, which are affinity inhibitors of it, is the result of modification of the active site of the enzyme

  13. Wide gap active brazing of ceramic-to-metal-joints for high temperature applications

    Science.gov (United States)

    Bobzin, K.; Zhao, L.; Kopp, N.; Samadian Anavar, S.

    2014-03-01

    Applications like solid oxide fuel cells and sensors increasingly demand the possibility to braze ceramics to metals with a good resistance to high temperatures and oxidative atmospheres. Commonly used silver based active filler metals cannot fulfill these requirements, if application temperatures higher than 600°C occur. Au and Pd based active fillers are too expensive for many fields of use. As one possible solution nickel based active fillers were developed. Due to the high brazing temperatures and the low ductility of nickel based filler metals, the modification of standard nickel based filler metals were necessary to meet the requirements of above mentioned applications. To reduce thermally induced stresses wide brazing gaps and the addition of Al2O3 and WC particles to the filler metal were applied. In this study, the microstructure of the brazed joints and the thermo-chemical reactions between filler metal, active elements and WC particles were analyzed to understand the mechanism of the so called wide gap active brazing process. With regard to the behavior in typical application oxidation and thermal cycle tests were conducted as well as tensile tests.

  14. Synthesis and antimalarial activity of metal complexes of cross-bridged tetraazamacrocyclic ligands.

    Science.gov (United States)

    Hubin, Timothy J; Amoyaw, Prince N-A; Roewe, Kimberly D; Simpson, Natalie C; Maples, Randall D; Carder Freeman, TaRynn N; Cain, Amy N; Le, Justin G; Archibald, Stephen J; Khan, Shabana I; Tekwani, Babu L; Khan, M O Faruk

    2014-07-01

    Using transition metals such as manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), several new metal complexes of cross-bridged tetraazamacrocyclic chelators namely, cyclen- and cyclam-analogs with benzyl groups, were synthesized and screened for in vitro antimalarial activity against chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum. The metal-free chelators tested showed little or no antimalarial activity. All the metal complexes of the dibenzyl cross-bridged cyclam ligand exhibited potent antimalarial activity. The Mn(2+) complex of this ligand was the most potent with IC50s of 0.127 and 0.157μM against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) P. falciparum strains, respectively. In general, the dibenzyl hydrophobic ligands showed better anti-malarial activity compared to the activity of monobenzyl ligands, potentially because of their higher lipophilicity and thus better cell penetration ability. The higher antimalarial activity displayed by the manganese complex for the cyclam ligand in comparison to that of the cyclen, correlates with the larger pocket of cyclam compared to that of cyclen which produces a more stable complex with the Mn(2+). Few of the Cu(2+) and Fe(2+) complexes also showed improvement in activity but Ni(2+), Co(2+) and Zn(2+) complexes did not show any improvement in activity upon the metal-free ligands for anti-malarial development. Published by Elsevier Ltd.

  15. Managing Siting Activities for Nuclear Power Plants

    International Nuclear Information System (INIS)

    2012-01-01

    One of the IAEA's statutory objectives is to ''seek to accelerate and enlarge the contribution of atomic energy to peace, health and prosperity throughout the world''. One way this objective is achieved is through the publication of a range of technical series. Two of these are the IAEA Nuclear Energy Series and the IAEA Safety Standards Series. According to Article III.A.6 of the IAEA Statute, the safety standards establish 'standards of safety for protection of health and minimization of danger to life and property.' The safety standards include the Safety Fundamentals, Safety Requirements and Safety Guides. These standards are written primarily in a regulatory style, and are binding on the IAEA for its own programmes. The principal users are the regulatory bodies in Member States and other national authorities. The IAEA Nuclear Energy Series comprises reports designed to encourage and assist R and D on, and application of, nuclear energy for peaceful uses. This includes practical examples to be used by owners and operators of utilities in Member States, implementing organizations, academia, and government officials, among others. This information is presented in guides, reports on technology status and advances, and best practices for peaceful uses of nuclear energy based on inputs from international experts. The IAEA Nuclear Energy Series complements the IAEA Safety Standards Series. The introduction of nuclear power brings new challenges to States - one of them being the selection of appropriates sites. It is a project that needs to begin early, be well managed, and deploy good communications with all stakeholders; including regulators. This is important, not just for those States introducing nuclear power for the first time, but for any State looking to build a new nuclear power plant. The purpose of the siting activities goes beyond choosing a suitable site and acquiring a licence. A large part of the project is about producing and maintaining a validated

  16. Managing Siting Activities for Nuclear Power Plants

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2012-06-15

    One of the IAEA's statutory objectives is to ''seek to accelerate and enlarge the contribution of atomic energy to peace, health and prosperity throughout the world''. One way this objective is achieved is through the publication of a range of technical series. Two of these are the IAEA Nuclear Energy Series and the IAEA Safety Standards Series. According to Article III.A.6 of the IAEA Statute, the safety standards establish 'standards of safety for protection of health and minimization of danger to life and property.' The safety standards include the Safety Fundamentals, Safety Requirements and Safety Guides. These standards are written primarily in a regulatory style, and are binding on the IAEA for its own programmes. The principal users are the regulatory bodies in Member States and other national authorities. The IAEA Nuclear Energy Series comprises reports designed to encourage and assist R and D on, and application of, nuclear energy for peaceful uses. This includes practical examples to be used by owners and operators of utilities in Member States, implementing organizations, academia, and government officials, among others. This information is presented in guides, reports on technology status and advances, and best practices for peaceful uses of nuclear energy based on inputs from international experts. The IAEA Nuclear Energy Series complements the IAEA Safety Standards Series. The introduction of nuclear power brings new challenges to States - one of them being the selection of appropriates sites. It is a project that needs to begin early, be well managed, and deploy good communications with all stakeholders; including regulators. This is important, not just for those States introducing nuclear power for the first time, but for any State looking to build a new nuclear power plant. The purpose of the siting activities goes beyond choosing a suitable site and acquiring a licence. A large part of the project is about producing and maintaining a validated

  17. Active Edge Sites Engineering in Nickel Cobalt Selenide Solid Solutions for Highly Efficient Hydrogen Evolution

    KAUST Repository

    Xia, Chuan

    2017-01-06

    An effective multifaceted strategy is demonstrated to increase active edge site concentration in NiCoSe solid solutions prepared by in situ selenization process of nickel cobalt precursor. The simultaneous control of surface, phase, and morphology result in as-prepared ternary solid solution with extremely high electrochemically active surface area (C = 197 mF cm), suggesting significant exposure of active sites in this ternary compound. Coupled with metallic-like electrical conductivity and lower free energy for atomic hydrogen adsorption in NiCoSe, identified by temperature-dependent conductivities and density functional theory calculations, the authors have achieved unprecedented fast hydrogen evolution kinetics, approaching that of Pt. Specifically, the NiCoSe solid solutions show a low overpotential of 65 mV at -10 mV cm, with onset potential of mere 18 mV, an impressive small Tafel slope of 35 mV dec, and a large exchange current density of 184 μA cm in acidic electrolyte. Further, it is shown that the as-prepared NiCoSe solid solution not only works very well in acidic electrolyte but also delivers exceptional hydrogen evolution reaction (HER) performance in alkaline media. The outstanding HER performance makes this solid solution a promising candidate for mass hydrogen production.

  18. Do heavy metals existing in abandoned mining sites represent a real health risk? A study case in the SE Spain.

    Science.gov (United States)

    Martinez-Sanchez, Maria Jose; Perez-Sirvent, Carmen; García-Lorenzo, Mari Luz; Martínez-López, Salvadora; Perez-Espinosa, Victor; Hernández-Cordoba, Manuel; Bech, Jaime

    2013-04-01

    Mining activities have been carried out for centuries in Sierra Minera (SE Spain) giving rise to a large number of sites distributed throughout the zone in which residues are accumulated. This communication reports studies as regards metal mobilization and analysis of the health risk that could be posed by inhalation, dermic contact or occasional ingestion of this type of sediments. Lead was used as the metal for the studies due to its particular abundance in the zone. A large number of samples were taken and general analytical determinations (pH, particle size, organic matter, equivalent calcium carbonate content and mineralogical composition) were carried out in order its characterization. An in vitro method for obtaining formation on Pb bioaccessibility in these mine waste materials was also carried out. Our results prove that mineral associations, different alteration states and sorption/desorption processes play an important role in the bioavailability of lead. In addition, it is noteworthy that the metal fraction dissolved by the proposed in vitro methodology is lower than 100%, both in the stomach and intestinal phases. Finally an assessment of the risk posed by lead is achieved. To this respect it should be noted that the IRIS database provide cancer slope factor and reference dose, as a way to assess the risk caused by arsenic, cadmium and copper but no for lead, probably due to the wide variety of real situations, and the discrepancy of the sources. The way here suggested is a novelty in this sense, and the results could be extrapolated to other similar zones and be incorporated to the general protocol of risk assessment applied to contaminated sites.

  19. Impact of metals recycling on a Swedish BWR decommissioning project

    International Nuclear Information System (INIS)

    Larsson, Arne; Lidar, Per; Hedin, Gunnar; Bergh, Niklas

    2014-01-01

    Decommissioning of nuclear power plants generates large volumes of radioactive or potentially contaminated metals. By proper management of the waste streams significant amounts can be free released and recycled either directly or after decontamination and melting. A significant part of the required work should be performed early in the process to make the project run smoothly without costly surprises and delays. A large portion of the clearance activities can be performed on-site. This on-site work should focus on the so called low-risk for contamination material. Other material can be decontaminated and released on site if schedule and the available facility areas so allow. It should be noted that the on-site decontamination and clearance activities can be a significant bottle neck for a decommissioning project. The availability of and access to a specialized metals recycling facility is an asset for a decommissioning project. This paper will describe the forecasted positive impact of a well-structured metals characterisation, categorisation and clearance process for a BWR plant decommissioning project. The paper is based on recent studies, performed projects and recent in-house development. (authors)

  20. General aspects of metal toxicity.

    Science.gov (United States)

    Kozlowski, H; Kolkowska, P; Watly, J; Krzywoszynska, K; Potocki, S

    2014-01-01

    This review is focused on the general mechanisms of metal toxicity in humans. The possible and mainly confirmed mechanisms of their action are discussed. The metals are divided into four groups due to their toxic effects. First group comprises of metal ions acting as Fenton reaction catalyst mainly iron and copper. These types of metal ions participate in generation of the reactive oxygen species. Metals such as nickel, cadmium and chromium are considered as carcinogenic agents. Aluminum, lead and tin are involved in neurotoxicity. The representative of the last group is mercury, which may be considered as a generally toxic metal. Fenton reaction is a naturally occurring process producing most active oxygen species, hydroxyl radical: Fe(2+) + He2O2 ↔ Fe(3+) + OH(-) + OH(•) It is able to oxidize most of the biomolecules including DNA, proteins, lipids etc. The effect of toxicity depends on the damage of molecules i.e. production site of the hydroxyl radical. Chromium toxicity depends critically on its oxidation state. The most hazardous seems to be Cr(6+) (chromates) which are one of the strongest inorganic carcinogenic agents. Cr(6+) species act also as oxidative agents damaging among other nucleic acids. Redox inactive Al(3+), Cd(2+) or Hg(2+) may interfere with biology of other metal ions e.g. by occupying metal binding sites in biomolecules. All these aspects will be discussed in the review.

  1. Structure-activity relationships of mononuclear metal-thiosemicarbazone complexes endowed with potent antiplasmodial and antiamoebic activities.

    Science.gov (United States)

    Bahl, Deepa; Athar, Fareeda; Soares, Milena Botelho Pereira; de Sá, Matheus Santos; Moreira, Diogo Rodrigo Magalhães; Srivastava, Rajendra Mohan; Leite, Ana Cristina Lima; Azam, Amir

    2010-09-15

    A useful concept for the rational design of antiparasitic drug candidates is the complexation of bioactive ligands with transition metals. In view of this, an investigation was conducted into a new set of metal complexes as potential antiplasmodium and antiamoebic agents, in order to examine the importance of metallic atoms, as well as the kind of sphere of co-ordination, in these biological properties. Four functionalized furyl-thiosemicarbazones (NT1-4) treated with divalent metals (Cu, Co, Pt, and Pd) to form the mononuclear metallic complexes of formula [M(L)2Cl2] or [M(L)Cl2] were examined. The pharmacological characterization, including assays against Plasmodium falciparum and Entamoeba histolytica, cytotoxicity to mammalian cells, and interaction with pBR 322 plasmid DNA was performed. Structure-activity relationship data revealed that the metallic complexation plays an essential role in antiprotozoal activity, rather than the simple presence of the ligand or metal alone. Important steps towards identification of novel antiplasmodium (NT1Cu, IC50 of 4.6 microM) and antiamoebic (NT2Pd, IC50 of 0.6 microM) drug prototypes were achieved. Of particular relevance to this work, these prototypes were able to reduce the proliferation of these parasites at concentrations that are not cytotoxic to mammalian cells. Copyright (c) 2010. Published by Elsevier Ltd.

  2. The Distribution of Heavy Metal Pollutants in Suez Bay Using Geographic Information System (GIS)

    International Nuclear Information System (INIS)

    Hassan, H.B.; Mohamed, W.M.

    2017-01-01

    Suez city represents the southern entrance of the Suez Canal. As a result of the rapid development of industrialization and anthropogenic activities of Suez city may be entered containments such as heavy metals through Suez bay boundaries. The geographical information system (Arc GIS 9.1) is used to study the spatial distribution of heavy metals concentrations (Cd, Mn, Fe, Ni, Pb, Cu and Zn) of water samples which were collected in four different sampling sites (I, II, III and IV) from Suez bay. In this study, tabular data representation of the spatial distribution was developed using the inverse distance weighted (IDW) interpolation method. The GIS technique was applied to transfer the information into a final map illustrating the spatial distribution of heavy metals within the studied area. GIS models showed the high concentrations of heavy metals in some sites in the Suez city affecting by their activities. An overall distribution map of heavy metals is observed from GIS special analysis. Site (IV) in Suez City demonstrated the highest polluted are a in the overall distribution map

  3. Direct instrumental identification of catalytically active surface sites

    Science.gov (United States)

    Pfisterer, Jonas H. K.; Liang, Yunchang; Schneider, Oliver; Bandarenka, Aliaksandr S.

    2017-09-01

    The activity of heterogeneous catalysts—which are involved in some 80 per cent of processes in the chemical and energy industries—is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

  4. Seasonal assessment, treatment and removal of heavy metal concentrations in a tropical drinking water reservoir

    Directory of Open Access Journals (Sweden)

    Mustapha Moshood Keke

    2016-06-01

    Full Text Available Heavy metals are present in low concentrations in reservoirs, but seasonal anthropogenic activities usually elevate the concentrations to a level that could become a health hazard. The dry season concentrations of cadmium, copper, iron, lead, mercury, nickel and zinc were assessed from three sites for 12 weeks in Oyun reservoir, Offa, Nigeria. Triplicate surface water samples were collected and analysed using atomic absorption spectrophotometry. The trend in the level of concentrations in the three sites is site C > B > A, while the trend in the levels of the concentrations in the reservoir is Ni > Fe > Zn > Pb > Cd > Cu > Hg. Ni, Cd, Pb and Hg were found to be higher than the WHO guidelines for the metals in drinking water. The high concentration of these metals was from anthropogenic watershed run-off of industrial effluents, domestic sewages and agricultural materials into the reservoir coming from several human activities such as washing, bathing, fish smoking, especially in site C. The health effects of high concentration of these metals in the reservoir were highlighted. Methods for the treatment and removal of the heavy metals from the reservoir during water purification such as active carbon adsorption, coagulation-flocculation, oxidation-filtration, softening treatment and reverse osmosis process were highlighted. Other methods that could be used include phytoremediation, rhizofiltration, bisorption and bioremediation. Watershed best management practices (BMP remains the best solution to reduce the intrusion of the heavy metals from the watershed into the reservoir.

  5. Role of active site rigidity in activity: MD simulation and fluorescence study on a lipase mutant.

    Directory of Open Access Journals (Sweden)

    Md Zahid Kamal

    Full Text Available Relationship between stability and activity of enzymes is maintained by underlying conformational flexibility. In thermophilic enzymes, a decrease in flexibility causes low enzyme activity while in less stable proteins such as mesophiles and psychrophiles, an increase in flexibility is associated with enhanced enzyme activity. Recently, we identified a mutant of a lipase whose stability and activity were enhanced simultaneously. In this work, we probed the conformational dynamics of the mutant and the wild type lipase, particularly flexibility of their active site using molecular dynamic simulations and time-resolved fluorescence techniques. In contrast to the earlier observations, our data show that active site of the mutant is more rigid than wild type enzyme. Further investigation suggests that this lipase needs minimal reorganization/flexibility of active site residues during its catalytic cycle. Molecular dynamic simulations suggest that catalytically competent active site geometry of the mutant is relatively more preserved than wild type lipase, which might have led to its higher enzyme activity. Our study implies that widely accepted positive correlation between conformation flexibility and enzyme activity need not be stringent and draws attention to the possibility that high enzyme activity can still be accomplished in a rigid active site and stable protein structures. This finding has a significant implication towards better understanding of involvement of dynamic motions in enzyme catalysis and enzyme engineering through mutations in active site.

  6. Support effects and catalytic trends for water gas shift activity of transition metals

    DEFF Research Database (Denmark)

    Boisen, Astrid; Janssens, T.V.W.; Schumacher, Nana Maria Pii

    2010-01-01

    Water gas shift activity measurements for 12 transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, Au) supported on inert MgAl2O4 and Ce0.75Zr0.25O2 are presented, to elucidate the influence of the active metal and the support. The activity is related to the adsorption energy of molecular...... activity on the MgAl2O4 support and are both characterized by weak CO adsorption. For the MgAl2O4-supported catalysts a volcano-type relation between the activity and the adsorption energy of atomic oxygen on the metal is obtained. The maximum activity is found for metals with a binding energy of oxygen...... around −2.5 eV. No clear correlation exists with the adsorption energy of CO. In contrast, the activity for the Ce0.75Zr0.25O2 support increases with increasing adsorption strength for CO, and based on a relatively low activity of Cu the activity does not seem to depend on the adsorption energy of oxygen...

  7. Acid-base characteristics of powdered-activated-carbon surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Reed, B.E. (West Virginia Univ., Morgantown (United States)); Jensen, J.N.; Matsumoto, M.R. (State Univ. of New York, Buffalo (United States))

    Adsorption of heavy metals onto activated carbon has been described using the surface-complex-formation (SCF) model, a chemical equilibrium model. The SCF model requires a knowledge of the amphoteric nature of activated carbon prior to metal adsorption modeling. In the past, a single-diprotic-acid-site model had been employed to describe the amphoteric nature of activated-carbon surfaces. During this study, the amphoteric nature of two powdered activated carbons were investigated, and a three-monoprotic site surface model was found to be a plausible alternative. The single-diprotic-acid-site and two-monoprotic-site models did not describe the acid-base behavior of the two carbons studied adequately. The two-diprotic site was acceptable for only one of the study carbons. The acid-base behavior of activated carbon surfaces seem to be best modeled as a series of weak monoprotic acids.

  8. Active sites environmental monitoring Program - Program Plan: Revision 2

    International Nuclear Information System (INIS)

    Morrissey, C.M.; Hicks, D.S.; Ashwood, T.L.; Cunningham, G.R.

    1994-05-01

    The Active Sites Environmental Monitoring Program (ASEMP), initiated in 1989, provides early detection and performance monitoring of active low-level-waste (LLW) and transuranic (TRU) waste facilities at Oak Ridge National Laboratory (ORNL). Several changes have recently occurred in regard to the sites that are currently used for waste storage and disposal. These changes require a second set of revisions to the ASEMP program plan. This document incorporates those revisions. This program plan presents the organization and procedures for monitoring the active sites. The program plan also provides internal reporting levels to guide the evaluation of monitoring results

  9. Correlation between catalytic activity and bonding and coordination number of atoms and molecules on transition metal surfaces: theory and experimental evidence

    International Nuclear Information System (INIS)

    Falicov, L.M.; Somorjai, G.A.

    1985-01-01

    Correlation between catalytic activity and low-energy local electronic fluctuation in transition metals is proposed. A theory and calculations are presented which indicate that maximum electronic fluctuants take place at high-coordination metal sites. Either (i) atomically rough surfaces that expose to the reactant molecules atoms with large numbers of nonmagnetic or weakly magnetic neighbors in the first or second layer at the surface or (ii) stepped and kinked surfaces are the most active in carrying out structure-sensitive catalytic reactions. The synthesis of ammonia from N 2 and H 2 over iron and rhenium surfaces, 1 H 2 / 2 H 2 exchange over stepped platinum crystal surfaces at low pressures, and the hydrogenolysis (C - C bond breaking) of isobutane at kinked platinum crystal surfaces are presented as experimental evidence in support of the theory

  10. Conformational constraining of inactive and active States of a seven transmembrane receptor by metal ion site engineering in the extracellular end of transmembrane segment V

    DEFF Research Database (Denmark)

    Rosenkilde, Mette M; David, Ralf; Oerlecke, Ilka

    2006-01-01

    The extracellular part of transmembrane segment V (TM-V) is expected to be involved in the activation process of 7TM receptors, but its role is far from clear. Here, we study the highly constitutively active CXC-chemokine receptor encoded by human herpesvirus 8 (ORF74-HHV8), in which a metal ion ...

  11. Metal levels in southern leopard frogs from the Savannah River Site: location and body compartment effects.

    Science.gov (United States)

    Burger, J; Snodgrass, J

    2001-06-01

    Tadpoles have been proposed as useful bioindicators of environmental contamination; yet, recently it has been shown that metal levels vary in different body compartments of tadpoles. Metals levels are higher in the digestive tract of bullfrog (Rana catesbeiana) tadpoles, which is usually not removed during such analysis. In this paper we examine the heavy metal levels in southern leopard frog (R. utricularia) tadpoles from several wetlands at the Savannah River Site and test the null hypotheses that (1) there are no differences in metal levels in different body compartments of the tadpoles, including the digestive tract; (2) there are no differences in heavy metal levels among different wetlands; and (3) there are no differences in the ratio of metals in the tail/body and in the digestive tract/body as a function of metal or developmental stage as indicated by body weight. Variations in heavy metal levels were explained by wetland and body compartment for all metals and by tadpole weight for selenium and manganese. In all cases, levels of metals were higher in the digestive tract than in the body or tail of tadpoles. Metal levels were highest in a wetland that had been remediated and lowest in a wetland that was never a pasture or remediated (i.e., was truly undisturbed). Although tadpoles are sometimes eaten by fish and other aquatic predators, leopard frogs usually avoid laying their eggs in ponds with such predators. However, avian predators will eat them. These data suggest that tadpoles can be used as bioindicators of differences in metal levels among wetlands and as indicators of potential exposure for higher-trophic-level organisms, but that to assess effects on the tadpoles themselves, digestive tracts should be removed before analysis. Copyright 2001 Academic Press.

  12. Source identification of heavy metal contamination using metal association and Pb isotopes in Ulsan Bay sediments, East Sea, Korea

    International Nuclear Information System (INIS)

    Chae, Jung Sun; Choi, Man Sik; Song, Yun Ho; Um, In Kwon; Kim, Jae Gon

    2014-01-01

    Highlights: • The levels of Cu, Zn, and Pb in sediments were higher than the Korean TEL at one-third of all sites. • The primary source of metal contamination came from activities related to nonferrous metal refineries near Onsan Harbor. • Three different anthropogenic sources and background sediments could be identified as endmembers using Pb isotopes. • The major anthropogenic Pb sources were identified as imported ores from Australia and Peru. • Isotope ratios in anthropogenic Pb discharged from Ulsan Bay to offshore could be identified. - Abstract: To determine the characteristics of metal pollution sources in Ulsan Bay, East Sea, 39 surface and nine core sediments were collected within the bay and offshore area, and analyzed for metals and stable lead (Pb) isotopes. Most surface sediments (>95% from 48 sites) had high copper (Cu), zinc (Zn), cadmium (Cd), and Pb concentrations that were as much as 1.3 times higher than background values. The primary source of metal contamination came from activities related to nonferrous metal refineries near Onsan Harbor, and the next largest source was from shipbuilding companies located at the mouth of the Taehwa River. Three different anthropogenic sources and background sediments could be identified as end-members using Pb isotopes. Isotopic ratios for the anthropogenic Pb revealed that the sources were imported ores from Australia, Peru, and the United States. In addition, Pb isotopes of anthropogenic Pb discharged from Ulsan Bay toward offshore could be determined

  13. Sorption of Heavy Metals from Mine Wastewater by Activated ...

    African Journals Online (AJOL)

    A study on sorption of heavy metal ions: Lead (Pb2+), Copper (Cu2+) and Cadmium (Cd2+) from mine wastewater by activated carbons prepared from coconut husk was conducted. The activated carbons were prepared by carbonisation of the husk at 900 ºC pyrolysis temperature, followed by steam activation of the ...

  14. Mobilization and attenuation of metals downstream from a base-metal mining site in the Matra Mountains, northeastern Hungary

    Science.gov (United States)

    Odor, L.; Wanty, R.B.; Horvath, I.; Fugedi, U.; ,

    1999-01-01

    Regional geochemical baseline values have been established for Hungary by the use of low-density stream-sediment surveys of flood-plain deposits of large drainage basins and of the fine fraction of stream sediments. The baseline values and anomaly thresholds thus produced helped to evaluate the importance of high toxic element concentrations found in soils in a valley downstream of a polymetallic vein-type base-metal mine. Erosion of the mine dumps and flotation dump, losses of metals during filtering, storage and transportation, human neglects, and operational breakdowns, have all contributed to the contamination of a small catchment basin in a procession of releases of solid waste. The sulfide-rich waste material weathers to a yellow color; this layer of 'yellow sand' blankets a narrow strip of the floodplain of Toka Creek in the valley near the town of Gyongyosoroszi. Contamination was spread out in the valley by floods. Metals present in the yellow sand include Pb, As, Cd, Cu, Zn, and Sb. Exposure of the local population to these metals may occur through inhalation of airborne particulates or by ingestion of these metals that are taken up by crops grown in the valley. To evaluate the areal extent and depth of the contamination, active stream sediment, flood-plain deposits, lake or reservoir sediments, soils, and surface water were sampled along the erosion pathways downstream of the mine and dumps. The flood-plain profile was sampled in detail to see the vertical distribution of elements and to relate the metal concentrations to the sedimentation and contamination histories of the flood plain. Downward migration of mobile Zn and Cd from the contaminated upper layers under supergene conditions is observed, while vertical migration of Pb, As, Hg and Sb appears to be insignificant. Soil profiles of 137Cs which originated from above-ground atomic bomb tests and the Chernobyl accident, provide good evidence that the upper 30-40 cm of the flood-plain sections, which

  15. [Heavy Metal Contamination in Farmland Soils at an E-waste Disassembling Site in Qingyuan, Guangdong, South China].

    Science.gov (United States)

    Zhang, Jin-lian; Ding, Jiang-feng; Lu, Gui-ning; Dang, Zhi; Yi, Xiao-yun

    2015-07-01

    Crude e-waste dismantling activities have caused a series of environmental pollution problems, and the pollutants released from the dismantling activities would finally pose high risks to human health by means of the accumulation through food chains. To explore the contamination status of heavy metals to the surrounding farmland soils in Longtang and Shijiao Town, Qingyuan, Guangdong, China, 22 farmland soil samples were collected and analyzed for the contents, spatial distributions and chemical forms of 6 heavy metals (Pb, Cu, Cd, Zn, Cr and Ni). The results showed that the 6 heavy metals exhibited obvious accumulations when compared to the corresponding background values in Guangdong Province. According to farmland environmental quality evaluation standard for edible agricultural products HJ 332-2006, the pollution severity of heavy metals was evaluated by monomial pollution index and Nemerow synthetic pollution index methods, the results indicated that 72. 7% of the soil samples contained one or more kinds of heavy metals with higher concentrations than the corresponding standard values, Cd, Cu, Pb and Zn were the main metals in the polluted soils, and for the proportion of contaminated soil samples in all the 22 samples, Cd was the highest, followed by Cu, and finally Pb and Zn. Nemerow synthetic pollution index further revealed that 68. 2% of soil samples were contaminated, and among them 53. 3% of samples were heavily contaminated. Most of the heavy metals were well correlated with each other at the 0. 05 or 0. 01 level, which indicated that primitive e-waste recycling activities were an important source of the heavy metal contamination in Longtang and Shijiao Town. The contents of Cd, Pb, Cu and Zn in surface soils were higher than those of other soil layers, and the contents of these 4 metals in deep soils (20- 100 cm) did not show significant decreases with the increasing depths. The contents of Cr and Ni maintained constant, and exhibited no statistical

  16. Peroxidase activity in Raphanus sativus and its relationship with soil heavy metals

    International Nuclear Information System (INIS)

    Alipour, H.; Zare Myvan, H.; Sharifi, M.

    2009-01-01

    Today heavy metals are important environmental pollutants which generated from human activities and are one of the most important environmental stresses that cause molecular damages to plants through reactive oxygen species formation such as H2O2. Heavy metals are absorbed and accumulated by plants thus are absorbed by human bodies through the food chain. Raphanus sativus is a herbaceous plant within the Brassicaceae family that has different varieties and is used as a food plant in different parts of Iran. Peroxidase is one of the most important enzyme in oxidoreductase super family that can metabolize H2O2. In this research we studied some growth parameters, peroxidase activity and their relationships with heavy metal content and other soil factors in three different populations of radish collected from Sari, Semnan and south of Tehran. After harvesting the plants shoots and roots Peroxidase activity was assayed spectrophotometrically at 470 nm. Our results showed total heavy metal content of shomal 3 station soil and radish plants was higher than other stations, so plants collected from this station had lowest root and shoot lengths, fresh weights, dry weights, protein content and leaf collrophyll content. The peroxidase activity in both leaves and roots of these plants was higher than plants of other stations Therefore our results showed that with increasing heavy metal concentrations in soils peroxidase activity increased.

  17. Anticancer Activity of Metal Complexes: Involvement of Redox Processes

    Science.gov (United States)

    Jungwirth, Ute; Kowol, Christian R.; Keppler, Bernhard K.; Hartinger, Christian G.; Berger, Walter; Heffeter, Petra

    2012-01-01

    Cells require tight regulation of the intracellular redox balance and consequently of reactive oxygen species for proper redox signaling and maintenance of metal (e.g., of iron and copper) homeostasis. In several diseases, including cancer, this balance is disturbed. Therefore, anticancer drugs targeting the redox systems, for example, glutathione and thioredoxin, have entered focus of interest. Anticancer metal complexes (platinum, gold, arsenic, ruthenium, rhodium, copper, vanadium, cobalt, manganese, gadolinium, and molybdenum) have been shown to strongly interact with or even disturb cellular redox homeostasis. In this context, especially the hypothesis of “activation by reduction” as well as the “hard and soft acids and bases” theory with respect to coordination of metal ions to cellular ligands represent important concepts to understand the molecular modes of action of anticancer metal drugs. The aim of this review is to highlight specific interactions of metal-based anticancer drugs with the cellular redox homeostasis and to explain this behavior by considering chemical properties of the respective anticancer metal complexes currently either in (pre)clinical development or in daily clinical routine in oncology. PMID:21275772

  18. Antioxidant modulation in response to heavy metal induced oxidative stress in Cladophora glomerata.

    Science.gov (United States)

    Murugan, K; Harish, S R

    2007-11-01

    The present investigation was carried out to study the induction of oxidative stress subjected to heavy metal environment. Lipoperoxides showed positive correlation at heavy metal accumulation sites indicating the tissue damage resulting from the reactive oxygen species and resulted in unbalance to cellular redox status. The high activities of ascorbate peroxidase and superoxide dismutase probably counter balance this oxidative stress. Glutathione and soluble phenols decreased, whereas dehydroascorbate content increased in the algae from polluted sites. The results suggested that alga responded to heavy metals effectively by antioxidant compounds and scavenging enzymes.

  19. Development of High Performance CFRP/Metal Active Laminates

    Science.gov (United States)

    Asanuma, Hiroshi; Haga, Osamu; Imori, Masataka

    This paper describes development of high performance CFRP/metal active laminates mainly by investigating the kind and thickness of the metal. Various types of the laminates were made by hot-pressing of an aluminum, aluminum alloys, a stainless steel and a titanium for the metal layer as a high CTE material, a unidirectional CFRP prepreg as a low CTE/electric resistance heating material, a unidirectional KFRP prepreg as a low CTE/insulating material. The aluminum and its alloy type laminates have almost the same and the highest room temperature curvatures and they linearly change with increasing temperature up to their fabrication temperature. The curvature of the stainless steel type jumps from one to another around its fabrication temperature, whereas the titanium type causes a double curvature and its change becomes complicated. The output force of the stainless steel type attains the highest of the three under the same thickness. The aluminum type successfully increased its output force by increasing its thickness and using its alloys. The electric resistance of the CFRP layer can be used to monitor the temperature, that is, the curvature of the active laminate because the curvature is a function of temperature.

  20. Enhancement of metal bioremediation by use of microbial surfactants

    International Nuclear Information System (INIS)

    Singh, Pooja; Cameotra, Swaranjit Singh

    2004-01-01

    Metal pollution all around the globe, especially in the mining and plating areas of the world, has been found to have grave consequences. An excellent option for enhanced metal contaminated site bioremediation is the use of microbial products viz. microbial surfactants and extracellular polymers which would increase the efficiency of metal reducing/sequestering organisms for field bioremediation. Important here is the advantage of such compounds at metal and organic compound co-contaminated site since microorganisms have long been found to produce surface-active compounds when grown on hydrocarbons. Other options capable of proving efficient enhancers include exploiting the chemotactic potential and biofilm forming ability of the relevant microorganisms. Chemotaxis towards environmental pollutants has excellent potential to enhance the biodegradation of many contaminants and biofilm offers them a better survival niche even in the presence of high levels of toxic compounds

  1. Determining site-specific background level with geostatistics for remediation of heavy metals in neighborhood soils

    Directory of Open Access Journals (Sweden)

    Tammy M. Milillo

    2017-03-01

    Full Text Available The choice of a relevant, uncontaminated site for the determination of site-specific background concentrations for pollutants is critical for planning remediation of a contaminated site. The guidelines used to arrive at concentration levels vary from state to state, complicating this process. The residential neighborhood of Hickory Woods in Buffalo, NY is an area where heavy metal concentrations and spatial distributions were measured to plan remediation. A novel geostatistics based decision making framework that relies on maps generated from indicator kriging (IK and indicator co-kriging (ICK of samples from the contaminated site itself is shown to be a viable alternative to the traditional method of choosing a reference site for remediation planning. GIS based IK and ICK, and map based analysis are performed on lead and arsenic surface and subsurface datasets to determine site-specific background concentration levels were determined to be 50 μg/g for lead and 10 μg/g for arsenic. With these results, a remediation plan was proposed which identified regions of interest and maps were created to effectively communicate the results to the environmental agencies, residents and other interested parties.

  2. Catalysis by metal-organic frameworks: fundamentals and opportunities.

    Science.gov (United States)

    Ranocchiari, Marco; van Bokhoven, Jeroen Anton

    2011-04-14

    Crystalline porous materials are extremely important for developing catalytic systems with high scientific and industrial impact. Metal-organic frameworks (MOFs) show unique potential that still has to be fully exploited. This perspective summarizes the properties of MOFs with the aim to understand what are possible approaches to catalysis with these materials. We categorize three classes of MOF catalysts: (1) those with active site on the framework, (2) those with encapsulated active species, and (3) those with active sites attached through post-synthetic modification. We identify the tunable porosity, the ability to fine tune the structure of the active site and its environment, the presence of multiple active sites, and the opportunity to synthesize structures in which key-lock bonding of substrates occurs as the characteristics that distinguish MOFs from other materials. We experience a unique opportunity to imagine and design heterogeneous catalysts, which might catalyze reactions previously thought impossible.

  3. NOx reduction over metal-ion exchanged novel zeolite under lean conditions. Activity and hydrothermal stability

    International Nuclear Information System (INIS)

    Subbiah, Ayyappan; Gujar, Amit; Price, Geoffrey L.; Cho, Byong K.; Blint, Richard J.; Yie, Jae E.

    2003-01-01

    Zeolite SUZ-4 was synthesized and tested for its hydrothermal stability using a standard aging procedure coupled with NMR spectroscopy, and was identified as a promising support for lean-NO x catalysts for high temperature applications. Various metals such as Cu, Ag, Fe, Co were ion exchanged onto the SUZ-4 zeolite, and their catalytic activity for NO/NO x conversion was measured in the presence of excess oxygen using ethylene as the reducing agent. Among the metal-ions exchanged, copper proved to be the best metal cation for lean-NO x catalysis with the optimum level of exchange at 29-42%. The optimized, fresh Cu/SUZ-4 catalyst achieved 70-80% of NO/NO x conversion activity over a wide range of temperature from 350 to 600C with the maximum conversion temperature at 450C. The presence of H 2 O and SO 2 reduced the NO/NO x conversion by about 30% of the fresh Cu/SUZ-4 catalyst due possibly to the blocking of active sites for NO/NO x adsorption. Substitution of gasoline vapor for ethylene as the reductant improved the NO x reduction activity of the fresh Cu/SUZ-4 catalyst at high temperatures above 350C. Aging the Cu/SUZ-4 catalyst resulted in a slight shift of activity profile toward higher temperatures, yielding an increase of NO conversion by 16% and a decrease of NO x conversion by 15% at 525C. The effect of H 2 O and SO 2 on the aged catalyst was to reduce the NO activity by 20% and NO x activity by 30% at 500C. The effect of space velocity change was not significant except in the low temperature range where the reaction light-off occurs. Adsorption/desorption measurements indicate that aging Cu/SUZ-4 results in partial migration/agglomeration of Cu particles in the pores thereby reducing the NO/NO x activity. Overall, the NO x conversion efficiency of Cu/SUZ-4, for both fresh and aged, is much better than the benchmark Cu/ZSM-5 in the presence of H 2 O and/or SO 2

  4. Promoter proximal polyadenylation sites reduce transcription activity

    DEFF Research Database (Denmark)

    Andersen, Pia Kjølhede; Lykke-Andersen, Søren; Jensen, Torben Heick

    2012-01-01

    Gene expression relies on the functional communication between mRNA processing and transcription. We previously described the negative impact of a point-mutated splice donor (SD) site on transcription. Here we demonstrate that this mutation activates an upstream cryptic polyadenylation (CpA) site......, which in turn causes reduced transcription. Functional depletion of U1 snRNP in the context of the wild-type SD triggers the same CpA event accompanied by decreased RNA levels. Thus, in accordance with recent findings, U1 snRNP can shield premature pA sites. The negative impact of unshielded pA sites...... on transcription requires promoter proximity, as demonstrated using artificial constructs and supported by a genome-wide data set. Importantly, transcription down-regulation can be recapitulated in a gene context devoid of splice sites by placing a functional bona fide pA site/transcription terminator within ∼500...

  5. Energy transfer at the active sites of heme proteins

    International Nuclear Information System (INIS)

    Dlott, D.D.; Hill, J.R.

    1995-01-01

    Experiments using a picosecond pump-probe apparatus at the Picosecond Free-electron Laser Center at Stanford University, were performed to investigate the relaxation of carbon monoxide bound to the active sites of heme proteins. The significance of these experiments is two-fold: (1) they provide detailed information about molecular dynamics occurring at the active sites of proteins; and (2) they provide insight into the nature of vibrational relaxation processes in condensed matter. Molecular engineering is used to construct various molecular systems which are studied with the FEL. We have studied native proteins, mainly myoglobin obtained from different species, mutant proteins produced by genetic engineering using recombinant DNA techniques, and a variety of model systems which mimic the structures of the active sites of native proteins, which are produced using molecular synthesis. Use of these different systems permits us to investigate how specific molecular structural changes affect dynamical processes occurring at the active sites. This research provides insight into the problems of how different species needs are fulfilled by heme proteins which have greatly different functionality, which is induced by rather small structural changes

  6. Decomposition of vegetation growing on metal mine waste

    Energy Technology Data Exchange (ETDEWEB)

    Williams, S T; McNeilly, T; Wellington, E M.H.

    1977-01-01

    Aspects of the decomposition of metal tolerant vegetation growing on mine waste containing high concentrations of lead and zinc were studied and compared with those on an adjacent uncontaminated site. High concentrations of Pb and, to a lesser extent, Zn, accumulated in metal-tolerant grass. Retarded decomposition of this vegetation as compared with that on the uncontaminated site was indicated by a greater accumulation of litter, less humus formation, reduced soil urease activity and smaller microbial and microfaunal populations. Some evidence for increased metal tolerance in microbes from the mine waste was obtained. Concentrations of lead tolerated under laboratory conditions were much lower than those extracted from the mine waste and its vegetation, probably due to the lack of an accurate method for assessing the availability of lead in soil and vegetation.

  7. Ionic Exchange of Metal-Organic Frameworks to Access Single Nickel Sites for Efficient Electroreduction of CO2.

    Science.gov (United States)

    Zhao, Changming; Dai, Xinyao; Yao, Tao; Chen, Wenxing; Wang, Xiaoqian; Wang, Jing; Yang, Jian; Wei, Shiqiang; Wu, Yuen; Li, Yadong

    2017-06-21

    Single-atom catalysts often exhibit unexpected catalytic activity for many important chemical reactions because of their unique electronic and geometric structures with respect to their bulk counterparts. Herein we adopt metal-organic frameworks (MOFs) to assist the preparation of a catalyst containing single Ni sites for efficient electroreduction of CO 2 . The synthesis is based on ionic exchange between Zn nodes and adsorbed Ni ions within the cavities of the MOF. This single-atom catalyst exhibited an excellent turnover frequency for electroreduction of CO 2 (5273 h -1 ), with a Faradaic efficiency for CO production of over 71.9% and a current density of 10.48 mA cm -2 at an overpotential of 0.89 V. Our findings present some guidelines for the rational design and accurate modulation of nanostructured catalysts at the atomic scale.

  8. On chemical activity of heavy metal oxides

    International Nuclear Information System (INIS)

    Mechev, V.V.

    1994-01-01

    Interaction of solid oxides of heavy nonferrous metals with sulfur and carbon is investigated. The results are discussed. Direct dependence of chemical activity of oxides on disordering of their crystal lattice at heating is established. Beginning of interaction in the systems studied is accompanied by change of oxide conductivity type

  9. Wild rodents (Dipodomys merriami) used as biomonitors in contaminated mining sites.

    Science.gov (United States)

    Espinosa-Reyes, Guillermo; Torres-Dosal, Arturo; Ilizaliturri, Cesar; Gonzalez-Mille, Donaji; Diaz-Barriga, Fernando; Mejia-Saavedra, Jesus

    2010-01-01

    Mining is one of the most important industrial activities globally; however, mining processes have critical environmental impacts, as mining is a major source of metals and metalloids that contribute significantly to the pollution of soil, sediment, water and air. Heavy metals can impact the health of exposed human populations and nonhuman receptors. This study focused on arsenic because its genotoxicity is well-known. Previously, we proposed a methodology to evaluate and integrate risk from a single source affecting different biologic receptors. Here, we propose an alternative approach estimating arsenic exposure in children and kangaroo rats using probabilistic simulation with Monte Carlo modeling. The estimates are then associated to measured DNA damage and compared to both populations of children and rodents living in contaminated and in reference areas. Finally, based on the integrated analysis of the generated information, we evaluate the potential use of wild rodents (Dipodomys merriami) as a biomonitor at mining sites. Results indicate that the variation of genotoxicity in children of the reference site is approximately 2 units when compared to the children of the contaminated site. In the rodents we observed a variation of approximately 4 units between those of the reference site when compared to those living on the contaminated site. We propose that D. merriami can be used as a biomonitor organism in sites with mining activity, and that a non-lethal test can be used to evaluate risk from metal exposure.

  10. Metal cation controls phosphate release in the myosin ATPase.

    Science.gov (United States)

    Ge, Jinghua; Huang, Furong; Nesmelov, Yuri E

    2017-11-01

    Myosin is an enzyme that utilizes ATP to produce a conformational change generating a force. The kinetics of the myosin reverse recovery stroke depends on the metal cation complexed with ATP. The reverse recovery stroke is slow for MgATP and fast for MnATP. The metal ion coordinates the γ phosphate of ATP in the myosin active site. It is accepted that the reverse recovery stroke is correlated with the phosphate release; therefore, magnesium "holds" phosphate tighter than manganese. Magnesium and manganese are similar ions in terms of their chemical properties and the shell complexation; hence, we propose to use these ions to study the mechanism of the phosphate release. Analysis of octahedral complexes of magnesium and manganese show that the partial charge of magnesium is higher than that of manganese and the slightly larger size of manganese ion makes its ionic potential smaller. We hypothesize that electrostatics play a role in keeping and releasing the abstracted γ phosphate in the active site, and the stronger electric charge of magnesium ion holds γ phosphate tighter. We used stable myosin-nucleotide analog complex and Raman spectroscopy to examine the effect of the metal cation on the relative position of γ phosphate analog in the active site. We found that in the manganese complex, the γ phosphate analog is 0.01 nm further away from ADP than in the magnesium complex. We conclude that the ionic potential of the metal cation plays a role in the retention of the abstracted phosphate. © 2017 The Protein Society.

  11. Separation of Metal Binding and Electron Transfer Sites as a Strategy To Stabilize the Ligand-Reduced and Metal-Oxidized Form of [Mo(CO)4L

    Czech Academy of Sciences Publication Activity Database

    Bulak, E.; Varnali, T.; Schwederski, B.; Bubrin, D.; Fiedler, Jan; Kaim, W.

    2011-01-01

    Roč. 30, č. 23 (2011), s. 6441-6445 ISSN 0276-7333 R&D Projects: GA ČR GA203/09/0705 Institutional research plan: CEZ:AV0Z40400503 Keywords : Electron Transfer Sites * [Mo(CO)4L] * metal carbonyl complexes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.963, year: 2011

  12. Systematically biological prioritizing remediation sites based on datasets of biological investigations and heavy metals in soil

    Science.gov (United States)

    Lin, Wei-Chih; Lin, Yu-Pin; Anthony, Johnathen

    2015-04-01

    Heavy metal pollution has adverse effects on not only the focal invertebrate species of this study, such as reduction in pupa weight and increased larval mortality, but also on the higher trophic level organisms which feed on them, either directly or indirectly, through the process of biomagnification. Despite this, few studies regarding remediation prioritization take species distribution or biological conservation priorities into consideration. This study develops a novel approach for delineating sites which are both contaminated by any of 5 readily bioaccumulated heavy metal soil contaminants and are of high ecological importance for the highly mobile, low trophic level focal species. The conservation priority of each site was based on the projected distributions of 6 moth species simulated via the presence-only maximum entropy species distribution model followed by the subsequent application of a systematic conservation tool. In order to increase the number of available samples, we also integrated crowd-sourced data with professionally-collected data via a novel optimization procedure based on a simulated annealing algorithm. This integration procedure was important since while crowd-sourced data can drastically increase the number of data samples available to ecologists, still the quality or reliability of crowd-sourced data can be called into question, adding yet another source of uncertainty in projecting species distributions. The optimization method screens crowd-sourced data in terms of the environmental variables which correspond to professionally-collected data. The sample distribution data was derived from two different sources, including the EnjoyMoths project in Taiwan (crowd-sourced data) and the Global Biodiversity Information Facility (GBIF) ?eld data (professional data). The distributions of heavy metal concentrations were generated via 1000 iterations of a geostatistical co-simulation approach. The uncertainties in distributions of the heavy

  13. Effects of heavy metal pollution on enzyme activities in railway cut slope soils.

    Science.gov (United States)

    Meng, Xiaoyi; Ai, Yingwei; Li, Ruirui; Zhang, Wenjuan

    2018-03-07

    Railway transportation is an important transportation mode. However, railway transportation causes heavy metal pollution in surrounding soils. Heavy metal pollution has a serious negative impact on the natural environment, including a decrease of enzyme activities in soil and degradation of sensitive ecosystems. Some studies investigated the heavy metal pollution at railway stations or certain transportation hubs. However, the pollution accumulated in artificial cut slope soil all along the rails is still questioned. The interest on non-point source pollution from railways is increasing in an effort to protect the soil quality along the line. In this study, we studied spatial distributions of heavy metals and five enzyme activities, i.e., urease (UA), saccharase (SAC), protease (PRO), catalase (CAT), and polyphenol oxidase (POA) in the soil, and the correlation among them beside three different railways in Sichuan Province, China, as well. Soil samples were respectively collected from 5, 10, 25, 50, 100, and 150 m away from the rails (depth of 0-8 cm). Results showed that Mn, Cd, Cu, and Zn were influenced by railway transportation in different degrees while Pb was not. Heavy metal pollution was due to the abrasion of the gravel bed as well as the tracks and freight transportation which caused more heavy metal pollution than passenger transportation. Enzymatic activities were significantly negatively correlated with heavy metals in soils, especially Zn and Cu. Finally, it is proposed that combined use of PRO and POA activities could be an indicator of the heavy metal pollution in cut slope soils. The protective measures aimed at heavy metal pollution caused by railway transportation in cut slope soils are urgent.

  14. Heavy metal exposure, reproductive activity, and demographic patterns in white-footed mice (Peromyscus leucopus) inhabiting a contaminated floodplain wetland

    International Nuclear Information System (INIS)

    Levengood, Jeffrey M.; Heske, Edward J.

    2008-01-01

    We examined the concentrations of selected metals and selenium (Se) in the tissues of white-footed mice (Peromyscus leucopus) collected at a constructed wetland originally created as a retention basin for sediments dredged from Lake DePue, Illinois. These sediments were contaminated with high concentrations of cadmium (Cd), zinc (Zn), and other elements as a result of nearby smelting operations. White-footed mice inhabiting the former retention basin experienced greater exposure to Cd, Pb, and Se than those from nearby reference sites. Concentrations of Cu and Zn in livers of mice from the contaminated wetland and adjacent floodplain reference site were greater than in mice from the more-distant reference sites. Judging by concentrations in their kidneys, white-footed mice inhabiting the floodplain adjacent to the contaminated wetland had greater exposure to Cd than those from the two more-distant reference sites. Concentrations of Hg in tissues of mice did not vary appreciably among sites. Concentrations of Cd and Se in the tissues of some white-footed mice from the contaminated wetland exceeded critical concentrations observed in experimental studies of laboratory mice and rats; with few exceptions tissue Pb concentrations were below published effects levels. However, we did not detect changes in abundance, demographics, or reproductive activity that might suggest population-level effects of contaminant exposure. Mean weight of embryos expressed as a function of crown-rump length did not differ among locations sampled, and no gross lesions indicative of exposure to heavy metals were observed. Kidney and liver weight, corrected for body weight, were nominally, though not significantly, lowest in both male and female mice from areas of increased Cd and Pb exposure. Metals dredged from Lake DePue were still bioavailable 25 years after deposition. However, small mammal populations are resilient to environmental stressors and we did not detect differences in

  15. Organochlorines in surface soil at electronic-waste wire burning sites and metal contribution evaluated using quantitative X-ray speciation

    International Nuclear Information System (INIS)

    Fujimori, Takashi; Takigami, Hidetaka; Takaoka, Masaki

    2013-01-01

    Heavy metals and toxic chlorinated aromatic compounds (aromatic-Cls) such as dioxins and polychlorinated biphenyls (PCBs) are found at high concentrations and persist in surface soil at wire burning sites (WBSs) in developing countries in which various wire cables are recycled to yield pure metals. Chlorine K-edge near-edge X-ray absorption fine structure (NEXAFS) is used to detect the specific chemical form of Cl and estimate its amount using a spectrum jump in the solid phase. Quantitative X-ray speciation of Cl was applied to study the mechanisms of aromatic-Cls formation in surface soil at WBSs in Southeast Asia. Relationships between aromatic-Cls and chlorides of heavy metals were evaluated because heavy metals are promoters of the thermochemical solid-phase formation of aromatic-Cls.

  16. Organochlorines in surface soil at electronic-waste wire burning sites and metal contribution evaluated using quantitative X-ray speciation

    Science.gov (United States)

    Fujimori, Takashi; Takigami, Hidetaka; Takaoka, Masaki

    2013-04-01

    Heavy metals and toxic chlorinated aromatic compounds (aromatic-Cls) such as dioxins and polychlorinated biphenyls (PCBs) are found at high concentrations and persist in surface soil at wire burning sites (WBSs) in developing countries in which various wire cables are recycled to yield pure metals. Chlorine K-edge near-edge X-ray absorption fine structure (NEXAFS) is used to detect the specific chemical form of Cl and estimate its amount using a spectrum jump in the solid phase. Quantitative X-ray speciation of Cl was applied to study the mechanisms of aromatic-Cls formation in surface soil at WBSs in Southeast Asia. Relationships between aromatic-Cls and chlorides of heavy metals were evaluated because heavy metals are promoters of the thermochemical solid-phase formation of aromatic-Cls.

  17. Source Identification and Sequential Leaching of Heavy Metals in Soil Samples Collected from Selected Dump Sites in Ekiti State, Nigeria

    OpenAIRE

    , E.E. Awokunmi; , S.S. Asaolu; , O.O Ajayi; , A.O. Adebayo

    2011-01-01

    Ten heavy metals (Fe, Cu, Mn, Zn, Pb, Ni, Co, Cd, Cr and Sn) in fractioned and bulk soil samples collected from four dump sites located in AdoEkiti and Ikere -Ekiti, South western Nigeria were analysed using a modified Tessier’s procedure and acid digestion to obtain the distribution pattern of metal in this region. The metals were found to have been distributed in all phases with Fe, Cr, and Sn dominating the residual fraction (90.12 - 94.88%), Co, Ni, Cu, and Zn were found in all the extrac...

  18. Heavy metals and pesticide exposure from agricultural activities and former agrochemical factory in a Salvadoran rural community.

    Science.gov (United States)

    Quinteros, Edgar; Ribó, Alexandre; Mejía, Roberto; López, Alejandro; Belteton, Wilfredo; Comandari, Aimee; Orantes, Carlos M; Pleites, Ernesto B; Hernández, Carlos E; López, Dina L

    2017-01-01

    Pesticide handling in farming activities involves substantial hazards for the rural population and for the environment. In Latin America, it is estimated that the population at risk of being affected by heavy metals is over 4 million. This research describes the different types of exposure to pesticides and heavy metals in a rural population (Loma del Gallo), considering both environmental and occupational exposure. This study consists of an inspection in a former pesticide factory (QUIMAGRO), analysis of heavy metals in samples from surface and ground water in the community close to the factory, and a survey to the local population about their perceptions of pesticide exposures. Containers with 34.6 tons of chemicals improperly stored were identified in the former factory and removed by the government. Arsenic and cadmium were found in groundwater, and the highest values were 0.012 and 0.004 mg/l, respectively. These contaminants were also detected in most surface water samples, with maximum values of 0.026 and 0.0001 mg/l, respectively. Results of the survey show that of the 44 participants 42 % were farmers. Farmers used 19 different pesticide products containing 11 active ingredients. The most used active ingredients were paraquat (65 %), methamidophos (35 %), and atrazina (29 %). Eighty-two percent of the farmers did not use personal protective equipment. In addition to the pesticides used in the agriculture of the area, pesticide containers were removed from the QUIMAGRO area, but the pollution was still present at time of sampling and it is evident by the odor of the site. Surface water had the major concentration of heavy metals than the groundwater. Loma del Gallo population has been exposed to toxic pesticide from QUIMAGRO and agriculture for many years. The farmers carry out mishandling of pesticides and they not use PPE.

  19. Electrochemical dopamine sensor based on P-doped graphene: Highly active metal-free catalyst and metal catalyst support.

    Science.gov (United States)

    Chu, Ke; Wang, Fan; Zhao, Xiao-Lin; Wang, Xin-Wei; Tian, Ye

    2017-12-01

    Heteroatom doping is an effective strategy to enhance the catalytic activity of graphene and its hybrid materials. Despite a growing interest of P-doped graphene (P-G) in energy storage/generation applications, P-G has rarely been investigated for electrochemical sensing. Herein, we reported the employment of P-G as both metal-free catalyst and metal catalyst support for electrochemical detection of dopamine (DA). As a metal-free catalyst, P-G exhibited prominent DA sensing performances due to the important role of P doping in improving the electrocatalytic activity of graphene toward DA oxidation. Furthermore, P-G could be an efficient supporting material for loading Au nanoparticles, and resulting Au/P-G hybrid showed a dramatically enhanced electrocatalytic activity and extraordinary sensing performances with a wide linear range of 0.1-180μM and a low detection limit of 0.002μM. All these results demonstrated that P-G might be a very promising electrode material for electrochemical sensor applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Air separation of heavy metal contaminants from soil

    International Nuclear Information System (INIS)

    Nelson, M.E.; Harper, M.J.; Buckon, A.D.

    1995-01-01

    Several heavy metal separation techniques are currently being developed for soil remediation at various Department of Defense and Department of Energy (DOE) Facilities. The majority of these techniques involve a wet process using water, pH modifiers or other compounds. The US Naval Academy (USNA) has developed a dry process for heavy metal separation. The process uses air classification technology to concentrate the metal contaminant into a fraction of the soil. The advantages of this dry process are that it creates no contaminated byproduct and uses commercially available technology. The USNA process is based on using a Gayco-Reliance air classifier. Tests have been conducted with the system at the Naval Academy and the University of Nevada-Reno (UNR). The USNA tests used soil from the Nevada Test Site mixed with bismuth at a concentration of 500--1,000 ppm. The UNR tests used soil from four DOE sites mixed with uranium oxides and plutonium at an activity level of 100--700 pCi per gram. Concentration of activities and volume reduction percentages are presented for the various soils and contaminants tested

  1. Catalytic zinc site and mechanism of the metalloenzyme PR-AMP cyclohydrolase.

    Science.gov (United States)

    D'Ordine, Robert L; Linger, Rebecca S; Thai, Carolyn J; Davisson, V Jo

    2012-07-24

    The enzyme N(1)-(5'-phosphoribosyl) adenosine-5'-monophosphate cyclohydrolase (PR-AMP cyclohydrolase) is a Zn(2+) metalloprotein encoded by the hisI gene. It catalyzes the third step of histidine biosynthesis, an uncommon ring-opening of a purine heterocycle for use in primary metabolism. A three-dimensional structure of the enzyme from Methanobacterium thermoautotrophicum has revealed that three conserved cysteine residues occur at the dimer interface and likely form the catalytic site. To investigate the functions of these cysteines in the enzyme from Methanococcus vannielii, a series of biochemical studies were pursued to test the basic hypothesis regarding their roles in catalysis. Inactivation of the enzyme activity by methyl methane thiosulfonate (MMTS) or 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) also compromised the Zn(2+) binding properties of the protein inducing loss of up to 90% of the metal. Overall reaction stoichiometry and the potassium cyanide (KCN) induced cleavage of the protein suggested that all three cysteines were modified in the process. The enzyme was protected from DTNB-induced inactivation by inclusion of the substrate N(1)-(5'-phosphoribosyl)adenosine 5'-monophosphate; (PR-AMP), while Mg(2+), a metal required for catalytic activity, enhanced the rate of inactivation. Site-directed mutations of the conserved C93, C109, C116 and the double mutant C109/C116 were prepared and analyzed for catalytic activity, Zn(2+) content, and reactivity with DTNB. Substitution of alanine for each of the conserved cysteines showed no measurable catalytic activity, and only the C116A was still capable of binding Zn(2+). Reactions of DTNB with the C109A/C116A double mutant showed that C93 is completely modified within 0.5 s. A model consistent with these data involves a DTNB-induced mixed disulfide linkage between C93 and C109 or C116, followed by ejection of the active site Zn(2+) and provides further evidence that the Zn(2+) coordination site involves the

  2. Assessment of the Biological Effects of Welding Fumes Emitted From Metal Active Gas and Manual Metal Arc Welding in Humans.

    Science.gov (United States)

    Dewald, Eva; Gube, Monika; Baumann, Ralf; Bertram, Jens; Kossack, Veronika; Lenz, Klaus; Reisgen, Uwe; Kraus, Thomas; Brand, Peter

    2015-08-01

    Emissions from a particular welding process, metal inert gas brazing of zinc-coated steel, induce an increase in C-reactive protein. In this study, it was investigated whether inflammatory effects could also be observed for other welding procedures. Twelve male subjects were separately exposed to (1) manual metal arc welding fumes, (2) filtered air, and (3) metal active gas welding fumes for 6 hours. Inflammatory markers were measured in serum before, and directly, 1 and 7 days after exposure. Although C-reactive protein concentrations remained unchanged, neutrophil concentrations increased directly after exposure to manual metal arc welding fumes, and endothelin-1 concentrations increased directly and 24 hours after exposure. After exposure to metal active gas and filtered air, endothelin-1 concentrations decreased. The increase in the concentrations of neutrophils and endothelin-1 may characterize a subclinical inflammatory reaction, whereas the decrease of endothelin-1 may indicate stress reduction.

  3. [Study on pollution evaluation of heavy metal in surface soil of the original site of Qingdao North Station].

    Science.gov (United States)

    Zhu, Lei; Jia, Yong-gang; Pan, Yu-ying

    2013-09-01

    The determination of pollution extent and health risk assessment are the premise of heavy metal contaminated site remediation. The content of Cu, Cr, Pb, Cd, Zn, Ni in Qingdao North Station was detected, and the correlation of the 6 kinds of heavy metal content was analyzed. The pollution extent in excess of background values was characterized by anthropogenic influence multiple, and the pollution of heavy metal in soil was evaluated using geoaccumulation index and a new method which connects geoaccumulation index with Nemero index. Finally, human health risk assessment was carried out with health risk assessment model for heavy metal content. The results showed that Qingdao North Station soil were polluted by heavy metals. Six heavy metal pollution levels were: Cd > Cu > Ni > Pb > Cr > Zn, and Cd had reached the severity pollution level, Cu and Ni followed by, Cr, Pb and Zn were in minor pollution level. The order of coefficient variation in all heavy metals was: Cd > Ni > Cr > Zn > Pb > Cu. Within the study area soil heavy metal distribution was different, but overall discrepancy was small. The order of non-cancer hazards of heavy metals in soil was Cr > Pb > Cu > Ni > Cd > Zn, and the order of carcinogen risks of heavy metals was Ni > Cd. The non-cancer hazard and carcinogen risks values of metals were both lower than that their threshold values. They were not the direct threats to human health.

  4. Vibration-accelerated activation of flow units in a Pd-based bulk metallic glass

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ning, E-mail: hslining@mail.hust.edu.cn [School of Materials Science and Engineering, and State Key Laboratory of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Liu, Ze [Department of Engineering Mechanics, School of Civil Engineering, Wuhan University, Wuhan 430072 (China); Wang, Xinyun [School of Materials Science and Engineering, and State Key Laboratory of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074 (China); Zhang, Meng [Institute of Advanced Wear & Corrosion Resistant and Functional Materials, Jinan University, Guangzhou 510632 (China)

    2017-04-24

    Controlled activation of flow units and in-situ characterization of mechanical properties in metallic glasses are facing challenges thus far. Here, vibrational loading is introduced through nanoscale dynamic mechanical analysis technique to probe vibration-accelerated atomic level flow that plays a crucial role in the mechanical behavior of metallic glasses. The intriguing finding is that high vibrational frequency induces deep indentation depth, prominent pop-in events on load–depth curves and low storage modulus, exhibiting a vibration-facilitated activation of flow units in Pd{sub 40}Cu{sub 30}Ni{sub 10}P{sub 20} metallic glass. Theoretical analysis revealed that vibration-moderated activation time-scale accelerate the activation of flow units and responsible for the above scenario.

  5. Active Sites Environmental Monitoring Program: Mid-FY 1991 report

    Energy Technology Data Exchange (ETDEWEB)

    Ashwood, T.L.; Wickliff, D.S.; Morrissey, C.M.

    1991-10-01

    This report summarizes the activities of the Active Sites Environmental Monitoring Program (ASEMP) from October 1990 through March 1991. The ASEMP was established in 1989 by Solid Waste Operations and the Environmental Sciences Division to provide early detection and performance monitoring at active low-level radioactive waste (LLW) disposal sites in Solid Waste Storage Area (SWSA) 6 and transuranic (TRU) waste storage sites in SWSA 5 as required by chapters II and III of US Department of Energy Order 5820.2A. Monitoring results continue to demonstrate the no LLW is being leached from the storage vaults on the tumulus pads. Loading of vaults on Tumulus II began during this reporting period and 115 vaults had been loaded by the end of March 1991.

  6. Monitoring Environmental Recovery at Terminated Produced Water Discharge Sites in Coastal Louisiana Waters

    Energy Technology Data Exchange (ETDEWEB)

    Continental Shelf Associates, Inc.

    1999-08-16

    This report presents the results of a study of terminated produced water discharge sites in the coastal waters of Louisiana. Environmental recovery at the sites is documented by comparing pre-termination and post-termination (six months and one year) data. Produced water, sediments, and sediment interstitial water samples were analyzed for radionuclides, metals, and hydrocarbons. Benthic infauna were identified from samples collected in the vicinity of the discharge and reference sites. Radium isotope activities were determined in fish and crustacean samples. In addition, an environmental risk assessment is made on the basis of the concentrations of metals and hydrocarbons determined in the samples.

  7. Controlled fabrication of semiconductor-metal hybrid nano-heterostructures via site-selective metal photodeposition

    Science.gov (United States)

    Vela Becerra, Javier; Ruberu, T. Purnima A.

    2017-12-05

    A method of synthesizing colloidal semiconductor-metal hybrid heterostructures is disclosed. The method includes dissolving semiconductor nanorods in a solvent to form a nanorod solution, and adding a precursor solution to the nanorod solution. The precursor solution contains a metal. The method further includes illuminating the combined precursor and nanorod solutions with light of a specific wavelength. The illumination causes the deposition of the metal in the precursor solution onto the surface of the semiconductor nanorods.

  8. Molecular dynamics explorations of active site structure in designed and evolved enzymes.

    Science.gov (United States)

    Osuna, Sílvia; Jiménez-Osés, Gonzalo; Noey, Elizabeth L; Houk, K N

    2015-04-21

    This Account describes the use of molecular dynamics (MD) simulations to reveal how mutations alter the structure and organization of enzyme active sites. As proposed by Pauling about 70 years ago and elaborated by many others since then, biocatalysis is efficient when functional groups in the active site of an enzyme are in optimal positions for transition state stabilization. Changes in mechanism and covalent interactions are often critical parts of enzyme catalysis. We describe our explorations of the dynamical preorganization of active sites using MD, studying the fluctuations between active and inactive conformations normally concealed to static crystallography. MD shows how the various arrangements of active site residues influence the free energy of the transition state and relates the populations of the catalytic conformational ensemble to the enzyme activity. This Account is organized around three case studies from our laboratory. We first describe the importance of dynamics in evaluating a series of computationally designed and experimentally evolved enzymes for the Kemp elimination, a popular subject in the enzyme design field. We find that the dynamics of the active site is influenced not only by the original sequence design and subsequent mutations but also by the nature of the ligand present in the active site. In the second example, we show how microsecond MD has been used to uncover the role of remote mutations in the active site dynamics and catalysis of a transesterase, LovD. This enzyme was evolved by Tang at UCLA and Codexis, Inc., and is a useful commercial catalyst for the production of the drug simvastatin. X-ray analysis of inactive and active mutants did not reveal differences in the active sites, but relatively long time scale MD in solution showed that the active site of the wild-type enzyme preorganizes only upon binding of the acyl carrier protein (ACP) that delivers the natural acyl group to the active site. In the absence of bound ACP

  9. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    Science.gov (United States)

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  10. Biological activities of some Fluoroquinolones-metal complexes

    African Journals Online (AJOL)

    McRoy

    Background: Metal ions play a vital role in the design of more biologically active drugs. Aim: The paper reviewed the .... 2H2O by direct reaction of copper(II) sulphate pentahydrate with ciprofloxacin in distilled water. ... membered ring and the chloride ion completes the seven coordination around the Ca2+ion.[37-39].

  11. Leachability and heavy metal speciation of 17-year old stabilised/solidified contaminated site soils

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Fei, E-mail: fwtiffany@gmail.com [Department of Engineering, University of Cambridge, Trumpington Street, Cambridge CB2 1PZ (United Kingdom); Wang, Hailing, E-mail: wanghailing@njtech.edu.cn [College of Environment, Nanjing Tech University, Nanjing 210009 (China); Al-Tabbaa, Abir, E-mail: aa22@cam.ac.uk [Department of Engineering, University of Cambridge, Trumpington Street, Cambridge CB2 1PZ (United Kingdom)

    2014-08-15

    Highlights: • The effectiveness of the cement-based S/S at 17 years in West Drayton site is still satisfactory. • Major leaching of Cu, Zn, Ni, Cd and Pb in all mixes took place in the Fe/Mn oxides phase. • The hydration process has been fully completed and further carbonation took place at 17 years. • Microstructure analyses show that unreacted PFA exists. - Abstract: The long-term leachability, heavy metal speciation transformation and binding mechanisms in a field stabilised/solidified contaminated soil (made ground) from West Drayton site were recently investigated following in situ auger mixing treatment with a number of cement-based binders back in 1996. Two batch leaching tests (TCLP and BS EN 12457) and a modified five step sequential extraction procedure along with X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses were employed for the testing of the 17-year-old field soil. The results of batch leaching tests show that the treatment employed remained effective at 17 years of service time, with all BS EN 12457 test samples and most of TCLP test samples satisfied drinking water standards. Sequential extraction results illustrate that the leaching of Cu, Ni, Zn, Pb and Cd in all mixes mainly occurred at the Fe/Mn phase, ranging from 43% to 83%. Amongst the five metals tested, Ni was the most stable with around 40% remained in the residual phase for all the different cement-based binder stabilised/solidified samples. XRD and SEM analyses show that the hydration process has been fully completed and further carbonation took place. In summary, this study confirms that such cement-based stabilisation/solidification (S/S) treatment can achieve satisfactory durability and thus is a reliable technique for long-term remediation of heavy metal contaminated soil.

  12. Tailorable chiroptical activity of metallic nanospiral arrays.

    Science.gov (United States)

    Deng, Junhong; Fu, Junxue; Ng, Jack; Huang, Zhifeng

    2016-02-28

    The engineering of the chiroptical activity of the emerging chiral metamaterial, metallic nanospirals, is in its infancy. We utilize glancing angle deposition (GLAD) to facilely sculpture the helical structure of silver nanospirals (AgNSs), so that the scope of chiroptical engineering factors is broadened to include the spiral growth of homochiral AgNSs, the combination of left- and right-handed helical chirality to create heterochiral AgNSs, and the coil-axis alignment of the heterochiral AgNSs. It leads to flexible control over the chiroptical activity of AgNS arrays with respect to the sign, resonance wavelength and amplitude of circular dichroism (CD) in the UV and visible regime. The UV chiroptical mode has a distinct response from the visible mode. Finite element simulation together with LC circuit theory illustrates that the UV irradiation is mainly adsorbed in the metal and the visible is preferentially scattered by the AgNSs, accounting for the wavelength-related chiroptical distinction. This work contributes to broadening the horizons in understanding and engineering chiroptical responses, primarily desired for developing a wide range of potential chiroplasmonic applications.

  13. Effects of metal ions on growth, β-oxidation system, and thioesterase activity of Lactococcus lactis.

    Science.gov (United States)

    Li, Liang; Ma, Ying

    2014-10-01

    The effects of divalent metal ions (Ca(2+), Mg(2+), Fe(2+), and Cu(2+)) on the growth, β-oxidation system, and thioesterase activity of Lactococcus lactis were investigated. Different metal ions significantly influenced the growth of L. lactis: Ca(2+) and Fe(2+) accelerated growth, whereas Cu(2+) inhibited growth. Furthermore, Mg(2+) inhibited growth of L. lactis at a low concentration but stimulated growth of L. lactis at a high concentration. The divalent metal ions had significant effects on activity of the 4 key enzymes of the β-oxidation system (acyl-CoA dehydrogenase, enoyl-CoA hydratase, L-3-hydroxyacyl-CoA dehydrogenase, and thiolase) and thioesterase of L. lactis. The activity of acyl-CoA dehydrogenases increased markedly in the presence of Ca(2+) and Mg(2+), whereas it decreased with 1 mmol/L Fe(2+) or 12 mmol/L Mg(2+). All the metal ions could induce activity of enoyl-CoA hydratase. In addition, 12 mmol/L Mg(2+) significantly stimulated activity of L-3-hydroxyacyl-CoA dehydrogenase, and all metal ions could induce activity of thiolase, although thiolase activity decreased significantly when 0.05 mmol/L Cu(2+) was added into M17 broth. Inhibition of thioesterase activity by all 4 metal ions could be reversed by 2 mmol/L Ca(2+). These results help us understand the effect of metal ions on the β-oxidation system and thioesterase activity of Lactococcus lactis. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  14. Effect of metal salts on antibacterial activity of zingiber officinale roscoe extract

    International Nuclear Information System (INIS)

    Sohail, T.; Yaqeen, Z.; Imran, H.; Rehman, Z.; Fatima, N.

    2013-01-01

    The antibacterial activity of ethanol extract of Zingiber Officinale Roscoe (ginger) and its combination with different salts like CuSO/sub 4/, ZnSO/sub 4/ and MnCl/sub 2/ was investigated. Both Gram positive and Gram negative bacteria were tested by agar diffusion method. The results showed that ethanol extract of Zingiber Officinale gave the maximum zone of inhibition at 50 mg/ml concentrations against Escherichia coli among Gram negative bacteria and against Staphylococcus aureus in Gram positive bacteria. However antibacterial activity of the ginger and metal salts combination was greater than activity of ethanol extract. These investigations indicate that though ethanol extract has antibacterial activity against Gram positive and Gram negative bacteria, ginger and metal salts complex has more inhibitory effect on microorganisms. Antibacterial activity was also compared with standard drug ampicillin. The minimum inhibitory concentration (MIC) of ginger extract and metal salts complexes against all test organisms ranged from 0.3125 to 2.5 mg/ml. (author)

  15. Klipperaas study site. Scope of activities and main results

    International Nuclear Information System (INIS)

    Ahlbom, K.; Andersson, J.E.; Andersson, Peter; Ittner, T.; Tiren, S.; Ljunggren, C.

    1992-09-01

    During the period from 1977 - 1986 SKB (Swedish Nuclear Fuel and Waste Management Co.) performed surface and borehole investigations of 14 study sites for the purpose of assessing their suitability for a repository of spent nuclear fuel. The next phase in the SKB site selection rpogramme will be to perform detailed characterisation, including characterization from shafts and/or tunnels, of two or three sites. The detailed investigations will continue over several years to provide all the data needed for a licensing application to build a repository. Such an application is foreseen to be given to the authorities around the year 2003. It is presently not clear if any of the study sites will be selected as a site for detailed characterization. Other sites with geological and/or socio-economical characteristics judged more favorable may very well be the ones selected. However, as a part of the background documentation needed for the site selection studies to come, summary reports will be prepared for most study sites. These reports will include scope of activities, main results, uncertainties and need of complementary investigations. This report concern the Klipperaas study site. The main topics are the scope of activities, geologic model, geohydrological model, groundwater chemistry, assessment of solute transport, and rock mechanics

  16. Transition metal complexes of some biologically active ligands; synthesis characterization and bioactivities

    International Nuclear Information System (INIS)

    Rehman, S.; Ali, N.; Nisar, M.

    2009-01-01

    Transition/representative transition metals complexes of biologically active chelating agent 1,2-dipyrolodinoethane were synthesized and characterized through spectral and analytical data. The complexes are of the formula (M(L)X/sub 2/). Where (M = Co (II), Ni (II), Cu (II), Zn (II), Hg (II) and Cd (II) and X = CI, Br, NO/sub 3/). Tetrahedral geometry has been proposed to these-metal complexes with the help of magnetic measurements, elemental analysis, chemical stoichiometry and spectroscopic data Antibacterial activity of the ligand and its metal complexes were screened against Eschereschi coli, Klebsiello pneumonia, Proteus mirabilis, Proteus vulhari, Streptococcus pneumonia, Salmonella Iyphi, Bacilh,s anthrax, Streptococcus fecalis and Staphylococcus aureus. Complexes were found to be active against Eschereschi coli, Klebsiella pneumonia, Proteus mirabilis and Proteus vulharis. (author)

  17. On-line/on-site analysis of heavy metals in water and soils by laser induced breakdown spectroscopy

    Science.gov (United States)

    Meng, Deshuo; Zhao, Nanjing; Wang, Yuanyuan; Ma, Mingjun; Fang, Li; Gu, Yanhong; Jia, Yao; Liu, Jianguo

    2017-11-01

    The enrichment method of heavy metal in water with graphite and aluminum electrode was studied, and combined with plasma restraint device for improving the sensitivity of detection and reducing the limit of detection (LOD) of elements. For aluminum electrode enrichment, the LODs of Cd, Pb and Ni can be as low as several ppb. For graphite enrichment, the measurement time can be less than 3 min. The results showed that the graphite enrichment and aluminum electrode enrichment method can effectively improve the LIBS detection ability. The graphite enrichment method combined with plasma spatial confinement is more suitable for on-line monitoring of industrial waste water, the aluminum electrode enrichment method can be used for trace heavy metal detection in water. A LIBS method and device for soil heavy metals analysis was also developed, and a mobile LIBS system was tested in outfield. The measurement results deduced from LIBS and ICP-MS had a good consistency. The results provided an important application support for rapid and on-site monitoring of heavy metals in soil. (Left: the mobile LIBS system for analysis of heavy metals in soils. Top right: the spatial confinement device. Bottom right: automatic graphite enrichment device for on0line analysis of heavy metals in water).

  18. Active Sites Environmental Monitoring Program: FY 1990 annual report

    International Nuclear Information System (INIS)

    Wickliff, D.S.; Morrissey, C.M.; Ashwood, T.L.

    1991-10-01

    Chapter 3 of US Department of Energy (DOE) Order 5820.2A (DOE 1988) sets forth requirements for environmental monitoring of active low-level waste (LLW) disposal sites. Active sites are defined as those LLW facilities that were in use on or after the date of the order (September 1988). The transuranic (TRU) waste storage areas in Solid Waste Storage Area (SWSA) 5 North are covered by Chap. 2 of the order. In both chapters, monitoring is required to provide for early warning of leaks before those leaks pose a threat to human health or the environment. Chapter 3 also requires that monitoring be conducted to evaluate the short- and long-term performance of LLW disposal facilities. In accordance with this order, the Solid Waste Operations Department at Oak Ridge National Laboratory (ORNL) has established an Active Sites Environmental Monitoring Program (ASEMP) that is implemented by staff of the Environmental Sciences Division (ESD) at ORNL. This report summarizes data from ASEMP monitoring activities for the final 6 months of FY 1990. A brief summary of the monitoring methodology for each site is presented also

  19. Hydrogen evolution activity and electrochemical stability of selected transition metal carbides in concentrated phosphoric acid

    DEFF Research Database (Denmark)

    Tomás García, Antonio Luis; Jensen, Jens Oluf; Bjerrum, Niels J.

    2014-01-01

    phosphoric acid were investigated in a temperature range from 80 to 170°C. A significant dependence of the activities on temperature was observed for all five carbide samples. Through the entire temperature range Group 6 metal carbides showed higher activity than that of the Group 5 metal carbides......Alternative catalysts based on carbides of Group 5 (niobium and tantalum) and 6 (chromium, molybdenum and tungsten) metals were prepared as films on the metallic substrates. The electrochemical activities of these carbide electrodes towards the hydrogen evolution reaction (HER) in concentrated...

  20. INEL metal recycle annual report, FY-94

    International Nuclear Information System (INIS)

    Bechtold, T.E.

    1994-09-01

    In 1992, the mission of the Idaho Chemical Processing Plant was changed from reprocessing of spent nuclear fuels to development of technologies for conditioning of spent nuclear fuels and other high-level wastes for disposal in a geologic repository. In addition, the Department of Energy (DOE) directed Idaho National Engineering Laboratory (INEL) to develop a program plan addressing the management of radioactive contaminated scrap metal (RSM) within the DOE complex. Based on discussions with the EM-30 organization, the INEL Metal Recycle program plan was developed to address all issues of RSM management. Major options considered for RSM management were engineered interim storage, land disposal as low-level waste, and beneficial reuse/recycle. From its inception, the Metal Recycle program has emphasized avoidance of storage and disposal costs through beneficial reuse of RSM. The Metal Recycle program plan includes three major activities: Site-by-site inventory of RSM resources; validation of technologies for conversion of RSM to usable products; and identification of parties prepared to participate in development of a RSM recycle business

  1. Tritium activities in selected wells on the Nevada Test Site

    International Nuclear Information System (INIS)

    Lyles, B.F.

    1993-05-01

    Literature and data were reviewed related to radionuclides in groundwater on and near the Nevada Test Site. No elevated tritium activities have been reported outside of the major testing regions of the Nevada Test Site. Three wells were identified as having water with above-background (>50 pCi/l) tritium activities: UE-15d Water Well; USGS Water Well A; and USGS Test Well B Ex. Although none of these wells have tritium activities greater than the Nevada State Drinking Water standard (20,000 pCi/l), their time-series tritium trends may be indicative to potential on-site radionuclide migration

  2. Contributions of local and regional anthropogenic sources of metals in PM2.5 at an urban site in northern France.

    Science.gov (United States)

    Ledoux, Frédéric; Kfoury, Adib; Delmaire, Gilles; Roussel, Gilles; El Zein, Atallah; Courcot, Dominique

    2017-08-01

    PM 2.5 have been related to various adverse health effects, mainly due to their ability to penetrate deeply and to convey harmful chemical components, such as metals inside the body. In this work, PM 2.5 were sampled at Saint-Omer, a medium-sized city located in northern France, in March-April 2011 and analyzed for their total carbon, water-soluble ions, major and trace elements. More specifically, the origin of 15 selected elements was examined using different tools including enrichment factors, conditional bivariate probability function (CBPF) representations, diagnostic ratios and receptor modelling. The results indicated that PM 2.5 metal composition is affected by both emissions of a local glassmaking factory and an integrated steelworks located at a distance of 35 km from the sampling site. For the first time, diagnostic ratios were proposed for the glassmaking activity. Therefore, metals in PM 2.5 could be attributed to the following anthropogenic sources: (i) local glassmaking industry for Sn, As, Cu and Cr, (ii) distant integrated steelworks for Ag, Fe, Cd, Mn, Rb and Pb, (iii) heavy fuel oil combustion for Ni, V and Co and (iv) non-exhaust traffic for Zn, Pb, Mn, Sb, and Cu. The impact of such sources on metal concentrations in PM 2.5 was assessed using a constrained receptor model. Despite their low participation to PM 2.5 concentration (2.7%), the latter sources were found as the main contributors (80%) to the overall concentration levels of the 15 selected elements in PM 2.5 . Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Zymogen Activation and Subcellular Activity of Subtilisin Kexin Isozyme 1/Site 1 Protease*

    Science.gov (United States)

    da Palma, Joel Ramos; Burri, Dominique Julien; Oppliger, Joël; Salamina, Marco; Cendron, Laura; de Laureto, Patrizia Polverino; Seidah, Nabil Georges; Kunz, Stefan; Pasquato, Antonella

    2014-01-01

    The proprotein convertase subtilisin kexin isozyme 1 (SKI-1)/site 1 protease (S1P) plays crucial roles in cellular homeostatic functions and is hijacked by pathogenic viruses for the processing of their envelope glycoproteins. Zymogen activation of SKI-1/S1P involves sequential autocatalytic processing of its N-terminal prodomain at sites B′/B followed by the herein newly identified C′/C sites. We found that SKI-1/S1P autoprocessing results in intermediates whose catalytic domain remains associated with prodomain fragments of different lengths. In contrast to other zymogen proprotein convertases, all incompletely matured intermediates of SKI-1/S1P showed full catalytic activity toward cellular substrates, whereas optimal cleavage of viral glycoproteins depended on B′/B processing. Incompletely matured forms of SKI-1/S1P further process cellular and viral substrates in distinct subcellular compartments. Using a cell-based sensor for SKI-1/S1P activity, we found that 9 amino acid residues at the cleavage site (P1–P8) and P1′ are necessary and sufficient to define the subcellular location of processing and to determine to what extent processing of a substrate depends on SKI-1/S1P maturation. In sum, our study reveals novel and unexpected features of SKI-1/S1P zymogen activation and subcellular specificity of activity toward cellular and pathogen-derived substrates. PMID:25378398

  4. Baseline and premining geochemical characterization of mined sites

    Science.gov (United States)

    Nordstrom, D. Kirk

    2015-01-01

    A rational goal for environmental restoration of new, active, or inactive mine sites would be ‘natural background’ or the environmental conditions that existed before any mining activities or other related anthropogenic activities. In a strictly technical sense, there is no such thing as natural background (or entirely non-anthropogenic) existing today because there is no part of the planet earth that has not had at least some chemical disturbance from anthropogenic activities. Hence, the terms ‘baseline’ and ‘pre-mining’ are preferred to describe these conditions. Baseline conditions are those that existed at the time of the characterization which could be pre-mining, during mining, or post-mining. Protocols for geochemically characterizing pre-mining conditions are not well-documented for sites already mined but there are two approaches that seem most direct and least ambiguous. One is characterization of analog sites along with judicious application of geochemical modeling. The other is reactive-transport modeling (based on careful synoptic sampling with tracer-injection) and subtracting inputs from known mining and mineral processing. Several examples of acidic drainage are described from around the world documenting the range of water compositions produced from pyrite oxidation in the absence of mining. These analog sites provide insight to the processes forming mineralized waters in areas untouched by mining. Natural analog water-chemistry data is compared with the higher metal concentrations, metal fluxes, and weathering rates found in mined areas in the few places where comparisons are possible. The differences are generally 1–3 orders of magnitude higher for acid mine drainage.

  5. Controls on accumulation and soil solution partitioning of heavy metals across upland sites in United Kingdom (UK).

    Science.gov (United States)

    Zia, Afia; van den Berg, Leon; Ahmad, Muhammad Nauman; Riaz, Muhammad; Zia, Dania; Ashmore, Mike

    2018-05-31

    A significant body of knowledge suggests that soil solution pH and dissolved organic carbon (DOC) strongly influence metal concentrations and speciation in porewater, however, these effects vary between different metals. This study investigated the factors influencing soil and soil solution concentrations of copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) under field conditions in upland soils from UK having a wide range of pH, DOC and organic matter contents. The study primarily focussed on predicting soil and soil solution metal concentrations from the data on total soil metal concentrations (HNO 3 extracts) and soil and soil solution properties (pH, DOC and organic matter content). We tested the multiple regression models proposed by Tipping et al. (2003) to predict heavy metal concentrations in soil solutions and the results indicated a better fit (higher R 2 values) in both studies for Pb compared to the Zn and Cu concentrations. Both studies observed consistent negative relationships of metals with pH and loss on ignition (LOI) suggesting an increase in soil solution metal concentrations with increasing acidity. The positive relationship between Pb concentrations in porewater and HNO 3 extracts was similar for both studies, however, similar relationships were not found for the Zn and Cu concentrations because of the negative coefficients for these metals in our study. The results of this study conclude that the predictive equations of Tipping et al. (2003) may not be applicable to the field sites where the range of DOC and metal concentrations is much lower than their study. Our study also suggests that the extent to which metals are partitioned into soil solution is lower in soils with a higher organic matter contents due to binding of these metals to soil organic matter. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Active sites environmental monitoring program FY 1997 annual report

    International Nuclear Information System (INIS)

    Morrissey, C.M.; Marshall, D.S.; Cunningham, G.R.

    1998-03-01

    This report summarizes the activities conducted by the Active Sites Environmental Monitoring Program (ASEMP) from October 1996 through September 1997. The purpose of the program is to provide early detection and performance monitoring at active low-level waste (LLW) disposal sites in Solid Waste Storage Area (SWSA) 6 and transuranic (TRU) waste storage sites in SWSA 5 North. This report continues a series of annual and semiannual reports that present the results of ASEMP monitoring activities. This report details monitoring results for fiscal year (FY) 1997 from SWSA 6, including the Interim Waste Management Facility (IWMF) and the Hillcut Disposal Test Facility (HDTF), and (2) TRU-waste storage areas in SWSA 5 N. This report presents a summary of the methodology used to gather data for each major area along with the FY 1997 results. Figures referenced in the text are found in Appendix A and data tables are presented in Appendix B

  7. Laser, tungsten inert gas, and metal active gas welding of DP780 steel: Comparison of hardness, tensile properties and fatigue resistance

    International Nuclear Information System (INIS)

    Lee, Jeong Hun; Park, Sung Hyuk; Kwon, Hyuk Sun; Kim, Gyo Sung; Lee, Chong Soo

    2014-01-01

    Highlights: • We report the mechanical properties of DP780 steel welded by three methods. • The size of the welded zone increases with heat input (MAG > TIG > laser). • The hardness of the welded zone increases with cooling rate (laser > TIG > MAG). • Tensile and fatigue properties are strongly dependent on welding method. • Crack initiation sites depend on the microstructural features of the welded zone. - Abstract: The microstructural characteristics, tensile properties and low-cycle fatigue properties of a dual-phase steel (DP780) were investigated following its joining by three methods: laser welding, tungsten inert gas (TIG) welding, and metal active gas (MAG) welding. Through this, it was found that the size of the welded zone increases with greater heat input (MAG > TIG > laser), whereas the hardness of the weld metal (WM) and heat-affected zone (HAZ) increases with cooling rate (laser > TIG > MAG). Consequently, laser- and TIG-welded steels exhibit higher yield strength than the base metal due to a substantially harder WM. In contrast, the strength of MAG-welded steel is reduced by a broad and soft WM and HAZ. The fatigue life of laser-and TIG-welded steel was similar, with both being greater than that of MAG-welded steel; however, the fatigue resistance of all welds was inferior to that of the non-welded base metal. Finally, crack initiation sites were found to differ depending on the microstructural characteristics of the welded zone, as well as the tensile and cyclic loading

  8. Effects of pH and phosphate on metal distribution with emphasis on As speciation and mobilization in soils from a lead smelting site

    International Nuclear Information System (INIS)

    Impellitteri, Christopher A.

    2005-01-01

    Arsenic in soils from the Asarco lead smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). Arsenic oxidation state and geochemical speciation were analyzed as a function of depth (two sampling sites) and surface distribution. These results were compared with intensive desorption/dissolution experiments performed in a pH stat reactor for samples from the site with the highest degree of As heterogeneity. The objectives of the study were to investigate the solid-phase geochemical As speciation, assess the speciation of As in solutions equilibrated with the solids under controlled pH (pH=4 or 6) and Eh (using hydrogen or air) environments, observe the effects of phosphate on the release of As into solution, and examine the effects of phosphate on metal mobility in the systems. Arsenic was predominantly found in the As(V) valence state, though there was evidence that As(III) and As(0) were present also. The dominant geochemical phase was scorodite (FeAsO 4 .2H 2 O). The pH was controlled in the pH stat experiments by the addition of equinormal solutions of monoprotic (HNO 3 ), diprotic (H 2 SO 4 ), or triprotic (H 3 PO 4 ) acids. For many of the divalent metal cations, solution concentrations greatly decreased in the presence of phosphate. Solutions were also analyzed for anions. Evidence exists for sulfate release into solution. More As was released into solution at lower pH. A slight increase in solution arsenate occurs with the addition of phosphate, but the risk posed from the increased desorption/dissolution of As must be weighed against the decrease in solution concentrations of many metals especially Pb. If tailings from this site underwent acidification (e.g., acid mine drainage), in situ sequestration of metals by phosphate could be combined with placement of subsurface permeable reactive barriers for capture of As to reduce the risk associated with arsenic and trace metal mobilization. Results from this study could be used

  9. Risk assessing heavy metals in the groundwater-surface water interface at a contaminated site

    DEFF Research Database (Denmark)

    Bigi, Giovanni; McKnight, Ursula S.; Bjerg, Poul Løgstrup

    such as surface water and groundwater (EC, 2017). The current study quantified and assessed the contamination of As, Cd, Cr, Cu, Ni, Pb and Zn in the shallow aquifer, hyporheic zone, stream water and streambed sediments at Rådvad site, a former metal manufacturing industrial area located in Denmark, investigating...... in the soil). Stream water was sampled in 12 points, while groundwater was sampled in 4 wells close to the stream where the interaction was suspected. Sediments and hyporheic zone were sampled in pair, where upward hydraulic heads have been detected. A drain discharging in the river was also sampled....... Sediments were divided in different layers and both heavy metal total concentration and chemical partitioning were analysed. Redox species and dissolved organic matter were also analysed in the water samples, while fraction of organic carbon was investigated in the extracted sediments. Results showed a high...

  10. Spectroscopic analysis of soil metal contamination around a derelict mine site in the Blue Mountains, Australia

    Science.gov (United States)

    Shamsoddini, A.; Raval, S.; Taplin, R.

    2014-09-01

    Abandoned mine sites pose the potential threat of the heavy metal pollution spread through streams and via runoff leading to contamination of soil and water in their surrounding areas. Regular monitoring of these areas is critical to minimise impacts on water resources, flora and fauna. Conventional ground based monitoring is expensive and sometimes impractical; spectroscopic methods have been emerged as a reliable alternative for this purpose. In this study, the capabilities of the spectroscopy method were examined for modelling soil contamination from around the abandoned silver-zinc mine located at Yerranderie, NSW Australia. The diagnostic characteristics of the original reflectance data were compared with models derived from first and second derivatives of the reflectance data. The results indicate that the models derived from the first derivative of the reflectance data estimate heavy metals significantly more accurately than model derived from the original reflectance. It was also found in this study that there is no need to use second derivative for modelling heavy metal soil contamination. Finally, the results indicate that estimates were of greater accuracy for arsenic and lead compared to other heavy metals, while the estimation for silver was found to be the most erroneous.

  11. Metal-filled carbon nanotubes as a novel class of photothermal nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Rossella, Francesco; Bellani, Vittorio [Dipartimento di Fisica ' ' A. Volta' ' and CNISM, Universita degli Studi di Pavia, Via Bassi 6, 27100 Pavia (Italy); Soldano, Caterina [Dipartimento di Chimica e Fisica, Universita degli Studi di Brescia, Via Valotti 9, 25121 Brescia (Italy); Tommasini, Matteo [Dipartimento di Chimica, Materiali e Ingegneria Chimica ' ' G. Natta' ' , Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy)

    2012-05-08

    Metal-filled carbon nanotubes represent a novel class of photothermal nanomaterials: when illuminated by visible light they exhibit a strong enhancement of the temperature at the metal sites, due to the enhanced plasmonic light absorption at the metal surface, which behaves as a heat radiator. Potential applications include nanomedicine, heat-assisted magnetic recording, and light-activated thermal gradient-driven devices. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Mobility of Source Zone Heavy Metals and Radionuclides: The Mixed Roles of Fermentative Activity on Fate and Transport of U and Cr. Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Gerlach, Robin [Montana State Univ., Bozeman, MT (United States); Peyton, Brent M. [Montana State Univ., Bozeman, MT (United States); Apel, William A. [Idaho National Lab., Idaho Falls, ID (United States)

    2014-01-29

    Various U. S. Department of Energy (DOE) low and medium-level radioactive waste sites contain mixtures of heavy metals, radionuclides and assorted organic materials. In addition, there are numerous sites around the world that are contaminated with a mixture of organic and inorganic contaminants. In most sites, over time, water infiltrates the wastes, and releases metals, radionuclides and other contaminants causing transport into the surrounding environment. We investigated the role of fermentative microorganisms in such sites that may control metal, radionuclide and organics migration from source zones. The project was initiated based on the following overarching hypothesis: Metals, radionuclides and other contaminants can be mobilized by infiltration of water into waste storage sites. Microbial communities of lignocellulose degrading and fermenting microorganisms present in the subsurface of contaminated DOE sites can significantly impact migration by directly reducing and immobilizing metals and radionuclides while degrading complex organic matter to low molecular weight organic compounds. These low molecular weight organic acids and alcohols can increase metal and radionuclide mobility by chelation (i.e., certain organic acids) or decrease mobility by stimulating respiratory metal reducing microorganisms. We demonstrated that fermentative organisms capable of affecting the fate of Cr6+, U6+ and trinitrotoluene can be isolated from organic-rich low level waste sites as well as from less organic rich subsurface environments. The mechanisms, pathways and extent of contaminant transformation depend on a variety of factors related to the type of organisms present, the aqueous chemistry as well as the geochemistry and mineralogy. This work provides observations and quantitative data across multiple scales that identify and predict the coupled effects of fermentative carbon and electron flow on the transport of radionuclides, heavy metals and organic contaminants in

  13. Mobility of Source Zone Heavy Metals and Radionuclides: The Mixed Roles of Fermentative Activity on Fate and Transport of U and Cr. Final Report

    International Nuclear Information System (INIS)

    Gerlach, Robin; Peyton, Brent M.; Apel, William A.

    2014-01-01

    Various U. S. Department of Energy (DOE) low and medium-level radioactive waste sites contain mixtures of heavy metals, radionuclides and assorted organic materials. In addition, there are numerous sites around the world that are contaminated with a mixture of organic and inorganic contaminants. In most sites, over time, water infiltrates the wastes, and releases metals, radionuclides and other contaminants causing transport into the surrounding environment. We investigated the role of fermentative microorganisms in such sites that may control metal, radionuclide and organics migration from source zones. The project was initiated based on the following overarching hypothesis: Metals, radionuclides and other contaminants can be mobilized by infiltration of water into waste storage sites. Microbial communities of lignocellulose degrading and fermenting microorganisms present in the subsurface of contaminated DOE sites can significantly impact migration by directly reducing and immobilizing metals and radionuclides while degrading complex organic matter to low molecular weight organic compounds. These low molecular weight organic acids and alcohols can increase metal and radionuclide mobility by chelation (i.e., certain organic acids) or decrease mobility by stimulating respiratory metal reducing microorganisms. We demonstrated that fermentative organisms capable of affecting the fate of Cr6+, U6+ and trinitrotoluene can be isolated from organic-rich low level waste sites as well as from less organic rich subsurface environments. The mechanisms, pathways and extent of contaminant transformation depend on a variety of factors related to the type of organisms present, the aqueous chemistry as well as the geochemistry and mineralogy. This work provides observations and quantitative data across multiple scales that identify and predict the coupled effects of fermentative carbon and electron flow on the transport of radionuclides, heavy metals and organic contaminants in

  14. Compartmentation and complexation of metals in hyperaccumulator plants

    Directory of Open Access Journals (Sweden)

    Barbara eLeitenmaier

    2013-09-01

    Full Text Available Hyperaccumulators are being intensely investigated. They are not only interesting in scientific context due to their strange behaviour in terms of dealing with high concentrations of metals, but also because of their use in phytoremediation and phytomining, for which understanding the mechanisms of hyperaccumulation is crucial. Hyperaccumulators naturally use metal accumulation as a defence against herbivores and pathogens, and therefore deal with accumulated metals in very specific ways of complexation and compartmentation, different from non-hyperaccumulator plants and also non-hyperaccumulated metals. For example, in contrast to non-hyperaccumulators, in hyperaccumulators even the classical phytochelatin-inducing metal, cadmium, is predominantly not bound by such sulfur ligands, but only by weak oxygen ligands. This applies to all hyperaccumulated metals investigated so far, as well as hyperaccumulation of the metalloid arsenic. Stronger ligands, as they have been shown to complex metals in non-hyperaccumulators, are in hyperaccumulators used for transient binding during transport to the storage sites. This confirmed that enhanced active metal transport, and not metal complexation, is the key mechanism of hyperaccumulation. Hyperaccumulators tolerate the high amount of accumulated heavy metals by sequestering them into vacuoles, usually in large storage cells of the epidermis. This is mediated by strongly elevated expression of specific transport proteins in various tissues from metal uptake in the shoots up to the storage sites in the leaf epidermis. However, this mechanism seems to be very metal specific. Non-hyperaccumulated metals in hyperaccumulators seem to be dealt with like in non-hyperaccumulator plants, i.e. detoxified by binding to strong ligands such as metallothioneins.

  15. Assessment of Trace Metals in Soil, Vegetation and Rodents in Relation to Metal Mining Activities in an Arid Environment.

    Science.gov (United States)

    Méndez-Rodríguez, Lia C; Alvarez-Castañeda, Sergio Ticul

    2016-07-01

    Areas where abandoned metal-extraction mines are located contain large quantities of mineral wastes derived from environmentally unsafe mining practices. These wastes contain many pollutants, such as heavy metals, which could be released to the environment through weathering and leaching, hence becoming an important source of environmental metal pollution. This study evaluates differences in the levels of lead, iron, nickel, manganese, copper and cadmium in rodents sharing the same type of diet under different microhabitat use in arid areas with past mining activities. Samples of soil, roots, branches and seeds of Palo Adán (Fouquieria diguetii) and specimens of two rodent species (Chaetodipus arenarius and C. spinatus) were collected in areas with impact from past metal mining activities as well as from areas with no mining impact. Both rodent species mirrored nickel and iron levels in soil and seeds, as well as lead levels in soil; however, C. arenarius accumulated higher levels of manganese, copper and cadmium.

  16. Validation of Transfer Functions Predicting Cd and Pb Free Metal Ion Activity in Soil Solution as a Function of Soil Characteristics and Reactive Metal Content

    NARCIS (Netherlands)

    Pampura, T.; Groenenberg, J.E.; Lofts, S.; Priputina, I.

    2007-01-01

    According to recent insight, the toxicity of metals in soils is better related to the free metal ion (FMI) activity in the soil solution than to the total metal concentration in soil. However, the determination of FMI activities in soil solution is a difficult and time-consuming task. An alternative

  17. Leachate and Pollution Levels of Heavy Metals in the Groundwater near Municipal Solid Waste Landfill Site of Mashhad, Iran

    Directory of Open Access Journals (Sweden)

    Borhan Mansouri

    2014-06-01

    Full Text Available Background: The purpose of this study is to investigate the concentration of metals (lead, cadmium, chromium, copper, and nickel in the landfill leachate and heavy metals in wells downstream of municipal solid waste landfill site in the city of Mashhad. Methods: In both winter and summer seasons in 2009 samples were collected from five wells that were in landfill downstream in Mashhad. Results: Among heavy metals, nickel concentration in summer and lead concentration in winter had the highest levels. The results showed that the mean concentration of heavy metals in the studied wells was below the national standards of drinking water of Iran, WHO, and the United States. Pearson correlation coefficients also indicated that there was a significant correlation among the studied metals in the wells. Conclusion: Cd and Cu concentrations in all of the wells (except Pb in winter and Ni in summer did not pose any significant water quality problems since these concentrations were below the standards acceptable levels of drinking water.

  18. Site-specific transition metal occupation in multicomponent pyrophosphate for improved electrochemical and thermal properties in lithium battery cathodes: a combined experimental and theoretical study.

    Science.gov (United States)

    Shakoor, Rana A; Kim, Heejin; Cho, Woosuk; Lim, Soo Yeon; Song, Hannah; Lee, Jung Woo; Kang, Jeung Ku; Kim, Yong-Tae; Jung, Yousung; Choi, Jang Wook

    2012-07-18

    As an attempt to develop lithium ion batteries with excellent performance, which is desirable for a variety of applications including mobile electronics, electrical vehicles, and utility grids, the battery community has continuously pursued cathode materials that function at higher potentials with efficient kinetics for lithium insertion and extraction. By employing both experimental and theoretical tools, herein we report multicomponent pyrophosphate (Li(2)MP(2)O(7), M = Fe(1/3)Mn(1/3)Co(1/3)) cathode materials with novel and advantageous properties as compared to the single-component analogues and other multicomponent polyanions. Li(2)Fe(1/3)Mn(1/3)Co(1/3)P(2)O(7) is formed on the basis of a solid solution among the three individual transition-metal-based pyrophosphates. The unique crystal structure of pyrophosphate and the first principles calculations show that different transition metals have a tendency to preferentially occupy either octahedral or pyramidal sites, and this site-specific transition metal occupation leads to significant improvements in various battery properties: a single-phase mode for Li insertion/extraction, improved cell potentials for Fe(2+)/Fe(3+) (raised by 0.18 eV) and Co(2+)/Co(3+) (lowered by 0.26 eV), and increased activity for Mn(2+)/Mn(3+) with significantly reduced overpotential. We reveal that the favorable energy of transition metal mixing and the sequential redox reaction for each TM element with a sufficient redox gap is the underlying physical reason for the preferential single-phase mode of Li intercalation/deintercalation reaction in pyrophosphate, a general concept that can be applied to other multicomponent systems. Furthermore, an extremely small volume change of ~0.7% between the fully charged and discharged states and the significantly enhanced thermal stability are observed for the present material, the effects unseen in previous multicomponent battery materials.

  19. Large Area Active Brazing of Multi-tile Ceramic-Metal Structures

    Science.gov (United States)

    2012-05-01

    metallurgical bonds. The major disadvantage of using active brazing for metals and ceramics is the high processing temperature required that results in...steels) and form strong, metallurgical bonds. However, the high processing temperatures result in large strain (stress) build-up from the inherent...metals such as titanium alloys and stainless steels) and form strong, metallurgical bonds. However, the high processing temperatures result in large

  20. Catalytic activity of metall-like carbides in carbon oxide oxidation reaction

    International Nuclear Information System (INIS)

    Kharlamov, A.I.; Kosolapova, T.Ya.; Rafal, A.N.; Kirillova, N.V.

    1980-01-01

    Kinetics of carbon oxide oxidation upon carbides of hafnium, niobium, tantalum, molybdenum, zirconium and chromium is studied. Probable mechanism of the catalysts action is suggested. The established character of the change of the carbide catalytic activity is explained by the change of d-electron contribution to the metal-metal interaction

  1. Assessment of the governance system for the management of the East Sea-Jung dumping site, Korea through analysis of heavy metal concentrations in bottom sediments

    Science.gov (United States)

    Song, Ki-Hoon; Choi, Ki-Young; Kim, Chang-Joon; Kim, Young-Il; Chung, Chang-Soo

    2015-12-01

    As with many countries, the Korea government has made a variety of efforts to meet the precautionary principle under the London Convention and Protocol acceded in 1994 and 2009. However, new strategies for the suitable marine dumping of waste materials have since been developed. In this study, the distribution and contamination of heavy metals including Al, Fe, Mn, Li, Co, Cr, Ni, Cu, Zn, As, Cd, Pb and Hg in bottom sediments were analyzed and compared to various criteria in order to evaluate the effectiveness of the management of the East Sea-Jung (ES-Jung) dumping site by the Korea government. The results indicate that the average metal concentrations were significantly lower than Effects Range Low (ERL) values, and generally similar to or lower than the Threshold Effect Levels (TEL) from the Sediment Quality Guidelinces (SQGs). According to analyses of various metal contamination indexes (Enrichment Factor: EF, Pollution Load Index: PLI and the Index of Geoaccumulation: Igeo), most areas were found to be uncontaminated by heavy metals with the exception of several moderately contaminated stations (ESJ 33, 54, 64 and ESJR 20). Heavy metal concentrations in areas grouped as G1, G2, DMDA, N-Ref and S-Ref which showed similar characteristics between 2007-2013 and 2014, were compared. Unexpectedly, most concentrations in the northern reference area (N-Ref) were much higher than those in the actual dumping areas (G1 and G2), may be due to the influences from nearby cities to the west of the ES-Jung site, rather than from the dumping site itself. Additionally, heavy metal concentrations in the dredged material dumping area (DMDA) were found to be low although they have slightly increased over time and those in the southern reference area (S-Ref) were found to have gradually decreased with year. The concentrations of most metals in the East Sea-Jung dumping site were similar to or less than those in the Earth's crust and approximately the same as those in continental

  2. Heavy metals in the ecosystem components at 'Degelen' testing ground of the former Semipalatinsk test site

    International Nuclear Information System (INIS)

    Yankauskas, A.B.; Lukashenko, S.N.; Amirov, A.A.; Govenko, P.V.

    2012-01-01

    The ecological situation in the former Semipalatinsk test site is characterized by a combination of both radiative and nonradiative factors. There were investigated near-portal areas of the tunnels with water seepage at 'Degelen' site. All the tunnel waters are characterized by higher concentrations of uranium, beryllium, and molybdenum. The watercourse of the tunnel number 504 is unique for its elemental composition, in particular, the content of rare earth elements, whose concentration in the water is in the range n*10 -5 -n*10 -7 %. Of all the rare earth elements in the samples were found 13, the concentrations of aluminum, manganese, zinc are comparable to the concentrations of macro-components. Concentration of 238 U in the studied waters lie in the range of n*10 -4 - n*10 -6 %, which suggests the influence of uranium, not only as a toxic element, but its significance as the radiation factor. The analysis of complex data obtained showed that the elevated concentrations of heavy metals in the soils of the areas under study, as a rule, are a consequence of the carry-over of these metals by water flows and their subsequent deposition in the sediments. (authors)

  3. Uranyl oxo activation and functionalization by metal cation coordination

    International Nuclear Information System (INIS)

    Arnold Polly, L.; Pecharman, A. F.; Hollis, E.; Parsons, S.; Love, J. B.; Yahia, A.; Maron, L.; Yahia, A.; Maron, L.

    2010-01-01

    The oxo groups in the uranyl ion [UO 2 ] 2+ - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  4. Focus: Nucleation kinetics of shear bands in metallic glass.

    Science.gov (United States)

    Wang, J Q; Perepezko, J H

    2016-12-07

    The development of shear bands is recognized as the primary mechanism in controlling the plastic deformability of metallic glasses. However, the kinetics of the nucleation of shear bands has received limited attention. The nucleation of shear bands in metallic glasses (MG) can be investigated using a nanoindentation method to monitor the development of the first pop-in event that is a signature of shear band nucleation. The analysis of a statistically significant number of first pop-in events demonstrates the stochastic behavior that is characteristic of nucleation and reveals a multimodal behavior associated with local spatial heterogeneities. The shear band nucleation rate of the two nucleation modes and the associated activation energy, activation volume, and site density were determined by loading rate experiments. The nucleation activation energy is very close to the value that is characteristic of the β relaxation in metallic glass. The identification of the rate controlling kinetics for shear band nucleation offers guidance for promoting plastic flow in metallic glass.

  5. Survey on composition and bioconcentration potential of 12 metallic elements in King Bolete (Boletus edulis) mushroom that emerged at 11 spatially distant sites.

    Science.gov (United States)

    Falandysz, Jerzy; Frankowska, Aneta; Jarzynska, Grazyna; Dryzałowska, Anna; Kojta, Anna K; Zhang, Dan

    2011-01-01

    This paper provides data on baseline concentrations, interrelationships and bioconcentration potential of 12 metallic elements by King Bolete collected from 11 spatially distant sites across Poland. There are significant differences in concentrations of metals (Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr, Zn) and their bioconcentration potential in King Bolete Boletus edulis at 11 spatially distant sites surveyed across Poland. These have resulted from significant geographical differences in trace metal concentrations in a layer (0-10 cm) of organic and mineral soil underneath to fruiting bodies and possible local bioavailabilities of macro- (Ca, K, Mg, Na) and trace metals (Al, Ba, Cd, Cu, Fe, Mn, Sr, Zn) to King Bolete. The use of highly appreciated wild-grown edible King Bolete mushroom has established a baseline measure of regional minerals status, heavy metals pollution and assessment of intake rates for wild mushroom dish fanciers against which future changes can be compared. Data on Cd, Cu and Zn from this study and from literature search can be useful to set the maximum limit of these metals in King Bolete collected from uncontaminated (background) areas. In this report also reviewed are data on Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr and Zn accumulation in King Bolete.

  6. Progress in the Development of SERS-Active Substrates Based on Metal-Coated Porous Silicon.

    Science.gov (United States)

    Bandarenka, Hanna V; Girel, Kseniya V; Zavatski, Sergey A; Panarin, Andrei; Terekhov, Sergei N

    2018-05-21

    The present work gives an overview of the developments in surface-enhanced Raman scattering (SERS) with metal-coated porous silicon used as an active substrate. We focused this review on the research referenced to SERS-active materials based on porous silicon, beginning from the patent application in 2002 and enclosing the studies of this year. Porous silicon and metal deposition technologies are discussed. Since the earliest studies, a number of fundamentally different plasmonic nanostructures including metallic dendrites, quasi-ordered arrays of metallic nanoparticles (NPs), and metallic nanovoids have been grown on porous silicon, defined by the morphology of this host material. SERS-active substrates based on porous silicon have been found to combine a high and well-reproducible signal level, storage stability, cost-effective technology and handy use. They make it possible to identify and study many compounds including biomolecules with a detection limit varying from milli- to femtomolar concentrations. The progress reviewed here demonstrates the great prospects for the extensive use of the metal-coated porous silicon for bioanalysis by SERS-spectroscopy.

  7. Progress in the Development of SERS-Active Substrates Based on Metal-Coated Porous Silicon

    Directory of Open Access Journals (Sweden)

    Hanna V. Bandarenka

    2018-05-01

    Full Text Available The present work gives an overview of the developments in surface-enhanced Raman scattering (SERS with metal-coated porous silicon used as an active substrate. We focused this review on the research referenced to SERS-active materials based on porous silicon, beginning from the patent application in 2002 and enclosing the studies of this year. Porous silicon and metal deposition technologies are discussed. Since the earliest studies, a number of fundamentally different plasmonic nanostructures including metallic dendrites, quasi-ordered arrays of metallic nanoparticles (NPs, and metallic nanovoids have been grown on porous silicon, defined by the morphology of this host material. SERS-active substrates based on porous silicon have been found to combine a high and well-reproducible signal level, storage stability, cost-effective technology and handy use. They make it possible to identify and study many compounds including biomolecules with a detection limit varying from milli- to femtomolar concentrations. The progress reviewed here demonstrates the great prospects for the extensive use of the metal-coated porous silicon for bioanalysis by SERS-spectroscopy.

  8. Metal adsorption process in activated carbon fiber from textile PAN fiber aim electrode production

    International Nuclear Information System (INIS)

    Rodrigues, Aline Castilho; Goncalves, Emerson Sarmento; Silva, Elen Leal da; Marcuzzo, Jossano Saldanha; Baldan, Mauricio Ribeiro; Cuna, Andres

    2016-01-01

    Full text: Carbon fibers have a variety of applications in industry and have been increasingly studied to explore their various characteristics. Studies show that the activated carbon fiber has been effective in removing small contaminants as well as activated carbon, because of its characteristic porosity. Other studies relate carbonaceous materials to the electrical conductivity devices application. This work is based on the use of an activated carbon fiber from textile polyacrylonitrile (PAN) for metallic ion adsorption from aqueous solution. Consequently, it improves the electrical characteristics and this fact show the possibility to use this material as electrode. The work was performed by adsorption process in saline solution (NO 3 Ag and ClPd) and activated carbon fiber in felt form as adsorbent. The metal adsorption on activated carbon fiber was characterized by textural analysis, x-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive x-ray (SEM-EDX), Raman spectroscopy and x-ray photoelectron spectroscopy (XPS). It was observed that activated carbon fiber showed good adsorption capacity for the metals used. At the end of the process, the activated carbon fiber samples gained about 15% by weight, related to metallic fraction incorporated into the fiber and the process of adsorption does not changed the structural, morphological and chemistry inertness of the samples. The results indicate the feasibility of this metal incorporation techniques activated carbon fiber for the production of electrodes facing the electrochemical area. (author)

  9. Metal adsorption process in activated carbon fiber from textile PAN fiber aim electrode production

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, Aline Castilho; Goncalves, Emerson Sarmento, E-mail: alinerodrigues_1@msn.com [Instituto Tecnologico Aeroespacial (ITA), Sao Jose dos Campos, SP (Brazil); Silva, Elen Leal da; Marcuzzo, Jossano Saldanha; Baldan, Mauricio Ribeiro [Instituto Nacional de Pesquisas Espaciais (INPE), Sao Jose dos Campos, SP (Brazil); Cuna, Andres [Faculdade de Quimica, Universidad de la Republica (Uruguay)

    2016-07-01

    Full text: Carbon fibers have a variety of applications in industry and have been increasingly studied to explore their various characteristics. Studies show that the activated carbon fiber has been effective in removing small contaminants as well as activated carbon, because of its characteristic porosity. Other studies relate carbonaceous materials to the electrical conductivity devices application. This work is based on the use of an activated carbon fiber from textile polyacrylonitrile (PAN) for metallic ion adsorption from aqueous solution. Consequently, it improves the electrical characteristics and this fact show the possibility to use this material as electrode. The work was performed by adsorption process in saline solution (NO{sub 3}Ag and ClPd) and activated carbon fiber in felt form as adsorbent. The metal adsorption on activated carbon fiber was characterized by textural analysis, x-ray diffraction (XRD), scanning electron microscopy equipped with energy dispersive x-ray (SEM-EDX), Raman spectroscopy and x-ray photoelectron spectroscopy (XPS). It was observed that activated carbon fiber showed good adsorption capacity for the metals used. At the end of the process, the activated carbon fiber samples gained about 15% by weight, related to metallic fraction incorporated into the fiber and the process of adsorption does not changed the structural, morphological and chemistry inertness of the samples. The results indicate the feasibility of this metal incorporation techniques activated carbon fiber for the production of electrodes facing the electrochemical area. (author)

  10. Seasonal and spatial patterns of metals at a restored copper mine site. I. Stream copper and zinc

    International Nuclear Information System (INIS)

    Bambic, Dustin G.; Alpers, Charles N.; Green, Peter G.; Fanelli, Eileen; Silk, Wendy K.

    2006-01-01

    Seasonal and spatial variations in metal concentrations and pH were found in a stream at a restored copper mine site located near a massive sulfide deposit in the Foothill copper-zinc belt of the Sierra Nevada, California. At the mouth of the stream, copper concentrations increased and pH decreased with increased streamflow after the onset of winter rain and, unexpectedly, reached extreme values 1 or 2 months after peaks in the seasonal hydrographs. In contrast, aqueous zinc and sulfate concentrations were highest during low-flow periods. Spatial variation was assessed in 400 m of reach encompassing an acidic, metal-laden seep. At this seep, pH remained low (2-3) throughout the year, and copper concentrations were highest. In contrast, the zinc concentrations increased with downstream distance. These spatial patterns were caused by immobilization of copper by hydrous ferric oxides in benthic sediments, coupled with increasing downstream supply of zinc from groundwater seepage. - Seasonal hydrology and benthic sediments control copper and zinc concentrations in a stream through a restored mine site

  11. Fundamental Studies of the Reforming of Oxygenated Compounds over Supported Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A. [Univ. of Wisconsin, Madison, WI (United States)

    2016-01-04

    The main objective of our research has been to elucidate fundamental concepts associated with controlling the activity, selectivity, and stability of bifunctional, metal-based heterogeneous catalysts for tandem reactions, such as liquid-phase conversion of oxygenated hydrocarbons derived from biomass. We have shown that bimetallic catalysts that combine a highly-reducible metal (e.g., platinum) with an oxygen-containing metal promoter (e.g., molybdenum) are promising materials for conversion of oxygenated hydrocarbons because of their high activity for selective cleavage for carbon-oxygen bonds. We have developed methods to stabilize metal nanoparticles against leaching and sintering under liquid-phase reaction conditions by using atomic layer deposition (ALD) to apply oxide overcoat layers. We have used controlled surface reactions to produce bimetallic catalysts with controlled particle size and controlled composition, with an important application being the selective conversion of biomass-derived molecules. The synthesis of catalysts by traditional methods may produce a wide distribution of metal particle sizes and compositions; and thus, results from spectroscopic and reactions kinetics measurements have contributions from a distribution of active sites, making it difficult to assess how the size and composition of the metal particles affect the nature of the surface, the active sites, and the catalytic behavior. Thus, we have developed methods to synthesize bimetallic nanoparticles with controlled particle size and controlled composition to achieve an effective link between characterization and reactivity, and between theory and experiment. We have also used ALD to modify supported metal catalysts by addition of promoters with atomic-level precision, to produce new bifunctional sites for selective catalytic transformations. We have used a variety of techniques to characterize the metal nanoparticles in our catalysts, including scanning transmission electron

  12. Metals in proteins: correlation between the metal-ion type, coordination number and the amino-acid residues involved in the coordination.

    Science.gov (United States)

    Dokmanić, Ivan; Sikić, Mile; Tomić, Sanja

    2008-03-01

    Metal ions are constituents of many metalloproteins, in which they have either catalytic (metalloenzymes) or structural functions. In this work, the characteristics of various metals were studied (Cu, Zn, Mg, Mn, Fe, Co, Ni, Cd and Ca in proteins with known crystal structure) as well as the specificity of their environments. The analysis was performed on two data sets: the set of protein structures in the Protein Data Bank (PDB) determined with resolution metal ion and its electron donors and the latter was used to assess the preferred coordination numbers and common combinations of amino-acid residues in the neighbourhood of each metal. Although the metal ions considered predominantly had a valence of two, their preferred coordination number and the type of amino-acid residues that participate in the coordination differed significantly from one metal ion to the next. This study concentrates on finding the specificities of a metal-ion environment, namely the distribution of coordination numbers and the amino-acid residue types that frequently take part in coordination. Furthermore, the correlation between the coordination number and the occurrence of certain amino-acid residues (quartets and triplets) in a metal-ion coordination sphere was analysed. The results obtained are of particular value for the identification and modelling of metal-binding sites in protein structures derived by homology modelling. Knowledge of the geometry and characteristics of the metal-binding sites in metalloproteins of known function can help to more closely determine the biological activity of proteins of unknown function and to aid in design of proteins with specific affinity for certain metals.

  13. pH-Dependent Binding of Chloride to a Marine Alkaline Phosphatase Affects the Catalysis, Active Site Stability, and Dimer Equilibrium.

    Science.gov (United States)

    Hjörleifsson, Jens G; Ásgeirsson, Bjarni

    2017-09-26

    The effect of ionic strength on enzyme activity and stability varies considerably between enzymes. Ionic strength is known to affect the catalytic activity of some alkaline phosphatases (APs), such as Escherichia coli AP, but how ions affect APs is debated. Here, we studied the effect of various ions on a cold-adapted AP from Vibrio splendidus (VAP). Previously, we have found that the active form of VAP is extremely unstable at low ionic strengths. Here we show that NaCl increased the activity and stability of VAP and that the effect was pH-dependent in the range of pH 7-10. The activity profile as a function of pH formed two maxima, indicating a possible conformational change. Bringing the pH from the neutral to the alkaline range was accompanied by a large increase in both the K i for inorganic phosphate (product inhibition) and the K M for p-nitrophenyl phosphate. The activity transitions observed as the pH was varied correlated with structural changes as monitored by tryptophan fluorescence. Thermal and urea-induced inactivation was shown to be accompanied by neither dissociation of the active site metal ions nor dimer dissociation. This would suggest that the inactivation involved subtle changes in active site conformation. Furthermore, the VAP dimer equilibrium was studied for the first time and shown to highly favor dimerization, which was dependent on pH and NaCl concentration. Taken together, the data support a model in which anions bind to some specific acceptor in the active site of VAP, resulting in great stabilization and catalytic rate enhancement, presumably through a different mechanism.

  14. Conserved structural chemistry for incision activity in structurally non-homologous apurinic/apyrimidinic endonuclease APE1 and endonuclease IV DNA repair enzymes.

    Energy Technology Data Exchange (ETDEWEB)

    Tsutakawa, Susan E.; Shin, David S.; Mol, Clifford D.; Izum, Tadahide; Arvai, Andrew S.; Mantha, Anil K.; Szczesny, Bartosz; Ivanov, Ivaylo N.; Hosfield, David J.; Maiti, Buddhadev; Pique, Mike E.; Frankel, Kenneth A.; Hitomi, Kenichi; Cunningham, Richard P.; Mitra, Sankar; Tainer, John A.

    2013-03-22

    Non-coding apurinic/apyrimidinic (AP) sites in DNA form spontaneously and as DNA base excision repair intermediates are the most common toxic and mutagenic in vivo DNA lesion. For repair, AP sites must be processed by 5' AP endonucleases in initial stages of base repair. Human APE1 and bacterial Nfo represent the two conserved 5' AP endonuclease families in the biosphere; they both recognize AP sites and incise the phosphodiester backbone 5' to the lesion, yet they lack similar structures and metal ion requirements. Here, we determined and analyzed crystal structures of a 2.4 ? resolution APE1-DNA product complex with Mg(2+) and a 0.92 Nfo with three metal ions. Structural and biochemical comparisons of these two evolutionarily distinct enzymes characterize key APE1 catalytic residues that are potentially functionally similar to Nfo active site components, as further tested and supported by computational analyses. We observe a magnesium-water cluster in the APE1 active site, with only Glu-96 forming the direct protein coordination to the Mg(2+). Despite differences in structure and metal requirements of AP