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Sample records for unligated perchlorate anions

  1. Perchlorate adsorption and desorption on activated carbon and anion exchange resin.

    Yoon, In-Ho; Meng, Xiaoguang; Wang, Chao; Kim, Kyoung-Woong; Bang, Sunbaek; Choe, Eunyoung; Lippincott, Lee

    2009-05-15

    The mechanisms of perchlorate adsorption on activated carbon (AC) and anion exchange resin (SR-7 resin) were investigated using Raman, FTIR, and zeta potential analyses. Batch adsorption and desorption results demonstrated that the adsorption of perchlorate by AC and SR-7 resin was reversible. The reversibility of perchlorate adsorption by the resin was also proved by column regeneration test. Solution pH significantly affected perchlorate adsorption and the zeta potential of AC, while it did not influence perchlorate adsorption and the zeta potential of resin. Zeta potential measurements showed that perchlorate was adsorbed on the negatively charged AC surface. Raman spectra indicated the adsorption resulted in an obvious position shift of the perchlorate peak, suggesting that perchlorate was associated with functional groups on AC at neutral pH through interactions stronger than electrostatic interaction. The adsorbed perchlorate on the resin exhibited a Raman peak at similar position as the aqueous perchlorate, indicating that perchlorate was adsorbed on the resin through electrostatic attraction between the anion and positively charged surface sites.

  2. Feasibility Study for the Reduction of Perchlorate, Iodide, and Other Aqueous Anions

    Clewell, Rebecca A; Tsui, David T; Mattie, David R

    1999-01-01

    Cyclic Voltammetry (CV) was used as a technique to determine the feasibility of the use of a coulometric detector in the determination of perchlorate, iodide, and various other anions commonly found in drinking water...

  3. Immunity of the Fe-N-C catalysts to electrolyte adsorption: phosphate but not perchloric anions

    Hu, Yang; Jensen, Jens Oluf; Pan, Chao

    2018-01-01

    often carried out, like for Pt-based catalysts, in dilute perchloric acid by assuming its non-adsorbing nature on the active sites. The assumption is however not true. In this work, a typical Fe-N-C catalyst was first synthesized by high-pressure pyrolysis in the presence of carbon support...... and thoroughly characterized in terms of morphology, structure and active site distribution. The subsequent electrochemical characterization of the catalyst shows strong adsorption and poisoning effect of, in addition to the known Cl-, perchloric anions on the oxygen reduction reaction (ORR) activity...

  4. Study of the ion-channel behavior on glassy carbon electrode supported bilayer lipid membranes stimulated by perchlorate anion

    Zhang, Zhiquan; Shi, Jun; Huang, Weimin, E-mail: huangwm@jlu.edu.cn

    2015-10-01

    In this paper, a kind of didodecyldimethylammonium bromide (DDAB) layer membranes was supported on a glassy carbon electrode (GCE). We studied the ion channel behavior of the supported bilayer lipid membrane by scanning electrochemical microscopy (SCEM) in tris(2,2′-bipyridine) ruthenium(II) solution. Perchlorate anion was used as a presence of stimulus and ruthenium(II) complex cations as the probing ions for the measurement of SECM, the lipid membrane channel was opened and exhibited the behavior of distinct SECM positive feedback curve. The channel was in a closed state in the absence of perchlorate anions while reflected the behavior of SECM negative feedback curve. The rates of electron transfer reaction in the lipid membranes surface were detected and it was dependant on the potential of SECM. - Highlights: • The rates of electron transfer reaction in the lipid membranes surface were detected. • Dynamic investigations of ion-channel behavior of supported bilayer lipid membranes by scanning electrochemical microscopy • A novel way to explore the interaction between molecules and supported bilayer lipid membranes.

  5. Biodegradation of Perchlorate in Laboratory Reactors Under Different Environmental Conditions

    2010-07-01

    21 Figure 8. Initial and final mass of perchlorate, chloride, and chlorate ...is the soluble anion associated with the solid salts of ammonium, potassium , and sodium perchlorate. Large-scale production of ammonium perchlorate...ions. Most perchlorate-respiring microorganisms are capable of functioning under varying environmental conditions and use oxygen, nitrate, and chlorate

  6. Perchlorate in seawater

    Martinelango, P. Kalyani [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061 (United States); Tian Kang [Institute of Environmental and Human Health, Texas Tech University, Lubbock, TX 79409 (United States); Dasgupta, Purnendu K. [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061 (United States)]. E-mail: Sandyd@ttu.edu

    2006-05-10

    greater than a simple anion exchange process will allow. Although most seaweed samples contain some amount of perchlorate, the great majority contains iodide in so much higher amount that at least for the commonly used Laminaria species, the iodide/perchlorate ratio is greater than the square of the perchlorate to iodide selectivity factor reported for the mammalian NIS and should thus lead to net beneficial iodine nutrition even in a two-stage mother-infant scenario.

  7. Perchlorate in seawater

    Martinelango, P. Kalyani; Tian Kang; Dasgupta, Purnendu K.

    2006-01-01

    There has been no reliable published data on the presence of perchlorate in seawater. Seaweeds are among the most important plant life in the ocean and are good sources of iodine and have been widely used as food and nutritional supplement. Perchlorate is known to inhibit the transport of iodide by the sodium iodide symporter (NIS), present e.g., in the thyroid and mammary glands. With perchlorate being increasingly detected in drinking water, milk and various other foods, increasing the iodide intake through inexpensive natural supplements may be an attractive solution for maintaining iodine assimilation. We report here measurable concentrations of perchlorate in several samples of seawater (detectable in about half the samples analyzed). We also report the iodide and perchlorate concentrations of 11 different species of seaweed and the corresponding bioconcentration factors (BCF) for perchlorate and iodide, relative to the seawater from which they were harvested. All seaweed samples came from the same region, off the coast of Northeastern Maine. Concentrations of iodide and perchlorate in four seawater samples collected from the region near harvest time were 30 ± 11 and 0.16 ± 0.084 μg l -1 , respectively. Concentrations of both iodide and perchlorate varied over a wide range for different seaweed species; iodide ranging from 16 to 3134 mg kg -1 and perchlorate from 0.077 to 3.2 mg kg -1 . The Laminaria species had the highest iodide concentration; Laminaria digitata is the seaweed species most commonly used in the kelp tablets sold in health food stores. Our sample of L. digitata contained 3134 ± 15 mg iodide/kg dry weight. The BCF varied widely for different species, with Laminaria species concentrating iodide preferentially over perchlorate. The iodide BCF (BCF i ) to perchlorate BCF (BCF p ) quotient ranged from 0.66 to 53; L. digitata and L. saccarina having a BCF i /BCF p value of 45 and 53, respectively, far greater than a simple anion exchange process

  8. Synthesis and structure of the unligated carbene of chromium

    Billups, W.E.; Souchan Chang; Hauge, R.H.; Margrave, J.L. (Rice Univ., Houston, TX (United States))

    1993-04-14

    Complexes with metal-carbon double bonds have found applications as intermediates in many important catalytic reactions including cyclopropanation of alkenes by diazoalkanes, Fischer-Tropsch synthesis, olefin metathesis, Ziegler-Natta polymerization, alkane activation, and in the decomposition of transition metal alkyl complexes. However, complexes with the simplest carbene, CH[sub 2], coordinated to the metal center are relatively rare. In this paper the authors report the synthesis and characterization of the simple unligated carbene of chromium by FTIR matrix isolation spectroscopy. 7 refs., 3 figs., 4 tabs.

  9. Jarosite dissolution rates in perchlorate brine

    Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

    2018-02-01

    Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

  10. Terbium nitrate luminescence quenching by eosin in he presence of lithium perchlorate in sulfolane solutions

    Ostakhov, S.S.; Kolosnitsyn, V.S.; Krasnogorskaya, N.N.; Kazakov, V.P.

    2000-01-01

    Quenching of terbium nitrate luminescence by anionic dye, eosin, in the presence of lithium perchlorate in sulfolane solutions was studied. Temperature dependence of terbium nitrate luminescence in sulfolane solutions in the presence of perchlorate anions were considered. The values of energy required for water molecular substitution in Tb 3+ ion coordination sphere for solvent molecule in electrolyte solution were ascertained [ru

  11. Structure, solvation, and dynamics of Mg{sup 2+}, Ca{sup 2+}, Sr{sup 2+}, and Ba{sup 2+} complexes with 3-hydroxyflavone and perchlorate anion in acetonitrile medium: A molecular dynamics simulation study

    Agieienko, Vira N.; Kolesnik, Yaroslav V.; Kalugin, Oleg N., E-mail: onkalugin@gmail.com [Department of Inorganic Chemistry, V. N. Karazin Kharkiv National University, Kharkiv 61022 (Ukraine)

    2014-05-21

    Molecular dynamics simulations of complexes of Mg{sup 2+}, Ca{sup 2+}, Sr{sup 2+}, and Ba{sup 2+} with 3-hydroxyflavone (flavonol, 3HF) and ClO {sub 4}{sup −} in acetonitrile were performed. The united atoms force field model was proposed for the 3HF molecule using the results of DFT quantum chemical calculations. 3HF was interpreted as a rigid molecule with two internal degrees of freedom, i.e., rotation of the phenyl ring and of the OH group with respect to the chromone moiety. The interatomic radial distribution functions showed that interaction of the cations with flavonol occurs via the carbonyl group of 3HF and it is accompanied with substitution of one of the acetonitrile molecules in the cations’ first solvation shells. Formation of the cation–3HF complexes does not have significant impact on the rotation of the phenyl ring with respect to the chromone moiety. However, the orientation of the flavonol's OH-group is more sensitive to the interaction with doubly charged cations. When complex with Mg{sup 2+} is formed, the OH-group turns out of the plane of the chromone moiety that leads to rupture of intramolecular H-bond in the ligand molecule. Complexation of Ca{sup 2+}, Sr{sup 2+}, and BaClO {sub 4}{sup +} with 3HF produces two structures with different OH-positions, as in the free flavonol with the intramolecular H-bond and as in the complex with Mg{sup 2+} with disrupted H-bonding. It was shown that additional stabilization of the [MgClO{sub 4}(3HF)]{sup +} and [BaClO{sub 4}(3HF)]{sup +} complexes is determined by strong affinity of perchlorate anion to interact with flavonol via intracomplex hydrogen bond between an oxygen atom of the anion and the hydrogen atom of the 3-hydroxyl group. Noticeable difference in the values of the self-diffusion coefficients for Kt{sup 2+} from one side and ClO {sub 4}{sup −}, 3HF, and AN in the cations’ coordination shell from another side implies quite weak interaction between cation, anion, and ligands in

  12. Perchlorate in fish from a contaminated site in east-central Texas.

    Theodorakis, Christopher; Rinchard, Jacques; Anderson, Todd; Liu, Fujun; Park, June-Woo; Costa, Filipe; McDaniel, Leslie; Kendall, Ronald; Waters, Aaron

    2006-01-01

    Perchlorate, a known thyroid endocrine disruptor, contaminates surface waters near military instillations where solid fuel rocket motors are manufactured or assembled. To assess potential perchlorate exposure to fish and the human population which may feed on them, fish were collected around the Naval Weapons Industrial Reserve Plant in McLennan County, TX, and analyzed for the presence of the perchlorate anion. The sampling sites included Lake Waco and Belton Lake, and several streams and rivers within their watersheds. The general tendency was that perchlorate was only found in a few species sampled, and perchlorate was not detected in every individual within these species. When detected in the fish, perchlorate tissue concentrations were greater than that in the water. This may be due to highly variable perchlorate concentrations in the water coupled with individual-level variation in elimination from the body, or to routes of exposure other than water.

  13. μ-Peroxido-bis[acetonitrilebis(ethylenediaminecobalt(III] tetrakis(perchlorate

    Valentina A. Kalibabchuk

    2010-12-01

    Full Text Available The title compound, [Co2(O2(CH3CN2(C2H8N24](ClO44, consists of centrosymmetric binuclear cations and perchlorate anions. Two CoIII atoms, which have a slightly distorted octahedral coordination, are connected through a peroxido bridge; the O—O distance is 1.476 (3 Å. Both acetonitrile ligands are situated in a trans position with respect to the O—O bridge. In the crystal, the complex cations are connected by N—H...O hydrogen bonds between ethylendiamine NH groups and O atoms from the perchlorate anions and peroxide O atoms.

  14. ANALYSIS OF HYDROPONIC FERTILIZER MATRIXES FOR PERCHLORATE: COMPARISON OF ANALYTICAL TECHNIQUES

    Seven retail hydroponic nitrate fertilizer products, two liquid and five solid, were comparatively analyzed for the perchlorate anion (ClO4-) by ion chromatography (IC) with suppressed conductivity detection, complexation electrospray ionization mass spectrometry (cESI-MS), norma...

  15. Portable Amperometric Perchlorate Selective Sensors with Microhole Array-water/organic Gel Interfaces

    Lee, Sang Hyuk; Girault, Hubert H.; Lee, Hye Jin [Kyungpook National Univ., Daegu (Korea, Republic of); Kim, Hyungi [Gyeongbuk Technopark, Gyeongsan (Korea, Republic of); Girault, Hubert H. [Ecole Polytechnique Federale de Lausanne, Lausanne (Switzerland)

    2013-09-15

    A novel stick-shaped portable sensing device featuring a microhole array interface between the polyvinylchloride-2-nitrophenyloctylether (PVC-NPOE) gel and water phase was developed for in-situ sensing of perchlorate ions in real water samples. Perchlorate sensitive sensing responses were obtained based on measuring the current changes with respect to the assisted transfer reaction of perchlorate ions by a perchlorate selective ligand namely, bis(dibenzoylmethanato)Ni(II) (Ni(DBM){sub 2}) across the polarized microhole array interface. Cyclic voltammetry was used to characterize the assisted transfer reaction of perchlorate ions by the Ni(DBM){sub 2} ligand when using the portable sensing device. The current response for the transfer of perchlorate anions by Ni(DBM){sub 2} across the micro-water/gel interface linearly increased as a function of the perchlorate ion concentration. The technique of differential pulse stripping voltammetry was also utilized to improve the sensitivity of the perchlorate anion detection down to 10 ppb. This was acquired by preconcentrating perchlorate anions in the gel layer by means of holding the ion transfer potential at 0 mV (vs. Ag/AgCl) for 30 s followed by stripping the complexed perchlorate ion with the ligand. The effect of various potential interfering anions on the perchlorate sensor was also investigated and showed an excellent selectivity over Br{sup -}, NO{sub 2}{sup -}, NO{sub 3}{sup -}, CO{sub 3}{sup 2-}, CH{sub 3}COO{sup -} and SO{sub 4}{sup 2-} ions. As a final demonstration, some regional water samples from the Sincheon river in Daegu city were analyzed and the data was verified with that of ion chromatography (IC) analysis from one of the Korean-certified water quality evaluation centers.

  16. Perchlorate Questions and Answers

    ... the atmosphere. Manufactured perchlorate is used as an industrial chemical and can be found in rocket propellant, explosives, ... of the FAQs from May 2017. More in Chemical ... Foods Toxic Elements in Foods & Foodware Page Last Updated: 12/ ...

  17. Perchlorate in Fertilizers

    Eldridge, J. E; Tsui, D. T; Mattie, D. R; Crown, J; Scott, R; Blackman, T

    1999-01-01

    ...) methods for perchlorate analysis in lawn and garden fertilizers. Seven government, private, and commercial laboratories participated in the analysis of 34 aqueous suspensions of the test materials, using similar ion chromatography systems...

  18. Widespread Occurrence of Plant Perchlorate

    Harvey, G.; Orris, G.; Jackson, W. A.; Rajagopalan, S.; Andraski, B.; Stonestrom, D.

    2007-12-01

    Perchlorate is a water soluble oxyanion containing four oxygens bonded to a single chlorine atom. High concentration of perchlorate can competitively block the uptake of iodide by the sodium iodide symporter and disrupt thyroid function. Due to this ability to potentially impair thyroid function, perchlorate in environmental exposure pathways has been of concern for more than a decade. Our knowledge of the spatial and temporal aspects of environmental perchlorate has increased dramatically in the past few years. To date, perchlorate has been found in numerous different environmental media, including water, soils and sediments, and plants, from many parts of the world. Perchlorate can be found in marine alage, food and plant samples from Asia, Africa, Europe, North and South America. It is becoming increasingly apparent that perchlorate in low levels is ubiquitous. Perchlorate has been found in several different carbon age-dated water and midden samples that pre-date the industrial age and agricultural use of Chilean nitrate fertilizers by thousands of years. While anthropogenic sources of perchlorate exist, the accumulating spatial and temporal evidence suggests that perchlorate must have a significant natural source. This natural source of perchlorate under the appropriate geochemical and climatic conditions is contributing a natural background level of perchlorate. Concentrations of perchlorate in soils appears to be influenced by soil geochemistry. Soils with low organic content usually have higher levels of perchlorate then soils with abundant organic matter. High levels of perchlorate have been found in remotely located xerophytes growing in aridosols and in deciduous phreatophytes growing in humid densely populated areas. Often the amount of perchlorate in a plant cannot be explained by the amount of perchlorate in either the soil or precipitation. Investigations into the relative source contribution of lithogenic, atmospheric and other sources and mechanisms

  19. Crystal structure and conformational flexibility of the unligated FK506-binding protein FKBP12.6

    Chen, Hui; Mustafi, Sourajit M. [New York State Department of Health, Empire State Plaza, Albany, NY 12201 (United States); LeMaster, David M. [New York State Department of Health, Empire State Plaza, Albany, NY 12201 (United States); University at Albany – SUNY, Empire State Plaza, Albany, NY 12201 (United States); Li, Zhong [New York State Department of Health, Empire State Plaza, Albany, NY 12201 (United States); Héroux, Annie [Brookhaven National Laboratory, Upton, NY 11973 (United States); Li, Hongmin; Hernández, Griselda, E-mail: griselda@wadsworth.org [New York State Department of Health, Empire State Plaza, Albany, NY 12201 (United States); University at Albany – SUNY, Empire State Plaza, Albany, NY 12201 (United States)

    2014-03-01

    Two crystal forms of unligated FKBP12.6 exhibit multiple conformations in the active site and in the 80s loop, the primary site for known protein-recognition interactions. The previously unreported NMR backbone assignment of FKBP12.6 revealed extensive doubling of amide resonances, which reflects a slow conformational transition centered in the 80s loop. The primary known physiological function of FKBP12.6 involves its role in regulating the RyR2 isoform of ryanodine receptor Ca{sup 2+} channels in cardiac muscle, pancreatic β islets and the central nervous system. With only a single previously reported X-ray structure of FKBP12.6, bound to the immunosuppressant rapamycin, structural inferences for this protein have been drawn from the more extensive studies of the homologous FKBP12. X-ray structures at 1.70 and 1.90 Å resolution from P2{sub 1} and P3{sub 1}21 crystal forms are reported for an unligated cysteine-free variant of FKBP12.6 which exhibit a notable diversity of conformations. In one monomer from the P3{sub 1}21 crystal form, the aromatic ring of Phe59 at the base of the active site is rotated perpendicular to its typical orientation, generating a steric conflict for the immunosuppressant-binding mode. The peptide unit linking Gly89 and Val90 at the tip of the protein-recognition ‘80s loop’ is flipped in the P2{sub 1} crystal form. Unlike the >30 reported FKBP12 structures, the backbone conformation of this loop closely follows that of the first FKBP domain of FKBP51. The NMR resonances for 21 backbone amides of FKBP12.6 are doubled, corresponding to a slow conformational transition centered near the tip of the 80s loop, as recently reported for 31 amides of FKBP12. The comparative absence of doubling for residues along the opposite face of the active-site pocket in FKBP12.6 may in part reflect attenuated structural coupling owing to increased conformational plasticity around the Phe59 ring.

  20. Catalytic destruction of perchlorate in ferric chloride and hydrochloric acid solution with control of temperature, pressure and chemical reagents

    Gu, Baohua; Cole, David R.; Brown, Gilbert M.

    2004-10-05

    A method is described to decompose perchlorate in a FeCl.sub.3 /HCl aqueous solution such as would be used to regenerate an anion exchange resin used to remove perchlorate. The solution is mixed with a reducing agent, preferably an organic alcohol and/or ferrous chloride, and can be heated to accelerate the decomposition of perchlorate. Lower temperatures may be employed if a catalyst is added.

  1. Bioelectrical Perchlorate Remediation

    Thrash, C.; Achenbach, L. A.; Coates, J. D.

    2007-12-01

    Several bioreactor designs are currently available for the ex-situ biological attenuation of perchlorate- contaminated waters and recently, some of these reactor designs were conditionally approved by the California Department of Health Services for application in the treatment of perchlorate contaminated drinking water. However, all of these systems are dependent on the continual addition of a chemical electron donor to sustain microbial activity and are always subject to biofouling and downstream water quality issues. In addition, residual labile electron donor in the reactor effluent can stimulate microbial growth in water distribution systems and contribute to the formation of potentially toxic trihalomethanes during disinfection by chlorination. As part of our ongoing studies into microbial perchlorate reduction we investigated the ability of dissimilatory perchlorate reducing bacteria (DPRB) to metabolize perchlorate using a negatively charged electrode (cathode) in the working chamber of a bioelectrical reactor (BER) as the primary electron donor. In this instance the DPRB use the electrons on the electrode surface either directly or indirectly in the form of electrolytically produced H2 as a source of reducing equivalents for nitrate and perchlorate reduction. As part of this investigation our fed-batch studies showed that DPRB could use electrons from a graphite cathode poised at -500mV (vs. Ag/AgCl) for the reduction of perchlorate and nitrate. We isolated a novel organism, Dechlorospirillum strain VDY, from the cathode surface after 70 days operation which readily reduced 100 mg.L-1 perchlorate in a mediatorless batch bioelectrical reactor (BER) in 6 days. Continuous up-flow BERs (UFBERs) seeded with active cultures of strain VDY continuously treated waters containing 100 mg.L-1 perchlorate with almost 100% efficiency throughout their operation achieving a non-optimized volumetric loading of 60 mg.L-1 reactor volume.day-1. The same UFBERs also treated

  2. Perchlorate in fish from a contaminated site in east-central Texas

    Theodorakis, Christopher; Rinchard, Jacques; Anderson, Todd; Liu, Fujun; Park, June-Woo; Costa, Filipe; McDaniel, Leslie; Kendall, Ronald; Waters, Aaron

    2006-01-01

    Perchlorate, a known thyroid endocrine disruptor, contaminates surface waters near military instillations where solid fuel rocket motors are manufactured or assembled. To assess potential perchlorate exposure to fish and the human population which may feed on them, fish were collected around the Naval Weapons Industrial Reserve Plant in McLennan County, TX, and analyzed for the presence of the perchlorate anion. The sampling sites included Lake Waco and Belton Lake, and several streams and rivers within their watersheds. The general tendency was that perchlorate was only found in a few species sampled, and perchlorate was not detected in every individual within these species. When detected in the fish, perchlorate tissue concentrations were greater than that in the water. This may be due to highly variable perchlorate concentrations in the water coupled with individual-level variation in elimination from the body, or to routes of exposure other than water. - In perchlorate-contaminated lakes and streams, perchlorate is detected infrequently in fish heads, fillets, and whole bodies, but may be detected more often depending on species and seasonal trends, and always at concentrations higher in the fish than in the water

  3. Crystal structure of iron(III perchlorate nonahydrate

    Erik Hennings

    2014-12-01

    Full Text Available Since the discovery of perchlorate salts on Mars and the known occurrence of ferric salts in the regolith, there is a distinct possibility that the title compound could form on the surface of Mars. [Fe(H2O6](ClO43·3H2O was crystallized from aqueous solutions at low temperatures according to the solid–liquid phase diagram. It consists of Fe(H2O6 octahedra (point group symmetry -3. and perchlorate anions (point group symmetry .2 as well as non-coordinating water molecules, as part of a second hydrogen-bonded coordination sphere around the cation. The perchlorate appears to be slightly disordered, with major–minor component occupancies of 0.773 (9:0.227 (9.

  4. 4-(2-Azaniumylethylpiperazin-1-ium bis(perchlorate

    Mohammad Reza Reisi

    2011-09-01

    Full Text Available In the title compound, C6H17N32+·2ClO4−, the piperazine ring adopts a chair conformation with the ethylammonium fragment occupying an equatorial position. In the crystal, the dications and perchlorate anions are linked through N—H...O hydrogen bonding and weak C—H...O hydrogen bonding into a three-dimensional supramolecular network.

  5. Perchlorate adsorption by granular activated carbon modified with cetyl trimethyl ammonium chloride

    Yin-Xian, P.; Lu, Z.; Cui-Yun, C.; Ming-Long, Z.; Yang, Z.; Chun-Du, W.

    2012-01-01

    To improve the adsorption of perchlorate (ClO/sub 4/ in contaminated water, granular activated carbon (GAC) was modified with cetyl trimethyl ammonium chloride (CTAC). To investigate the adsorption mechanism of perchlorate the structure of GAC-CTAC was characterized by scanning electron microscopy (SEM) and FTIR spectroscopy. Then the GAC-CTAC was used for the adsorption of perchlorate in water. The effects of the adsorption time, pH, initial ClO/sub 4/ concentration, and co-existed anions on perchlorate adsorbed by GAC-CTAC were studied. The results show that the GAC-CTAC could absorb perchlorate better in water. The adsorption capacity of perchlorate on GAC-CTAC decreases in the alkaline solution, and increases with increasing the - initial concentration. The competitive adsorption exists between co-existed anions and ClO/sub 4/ on GAC-CTAC. In addition, adsorption of ClO/sub 4/ on GAC-CTAC fits the Langmuir, Freundlich and Tempkin isothermal models in the range of the experimental concentration. The adsorption process follows pseudo-second order kinetics. (author)

  6. Perchlorate: Health Effects and Technologies for Its Removal from Water Resources

    Thiruvenkatachari Viraraghavan

    2009-04-01

    Full Text Available Perchlorate has been found in drinking water and surface waters in the United States and Canada. It is primarily associated with release from defense and military operations. Natural sources include certain fertilizers and potash ores. Although it is a strong oxidant, perchlorate is very persistent in the environment. At high concentrations perchlorate can affect the thyroid gland by inhibiting the uptake of iodine. A maximum contaminant level has not been set, while a guidance value of 6 ppb has been suggested by Health Canada. Perchlorate is measured in environmental samples primarily by ion chromatography. It can be removed from water by anion exchange or membrane filtration. Biological and chemical processes are also effective in removing this species from water.

  7. METAMORPHIC INHIBITION OF XENOPUS LAEVIS BY SODIUM PERCHLORATE: EFFECTS ON DEVELOPMENT AND THYROID HISTOLOGY

    The perchlorate anion inhibits thyroid hormone (TH) synthesis via inhibition of the sodium-iodide symporter. It is, therefore, a good model chemical to aid in the development of a bioassay to screen chemicals for effects on thyroid function. Xenopus laevis larvae were exposed to ...

  8. DDT performance of energetic cobalt coordination compounds. [Dozen of compounds similar to 2-(5-cyanotetrazolato)pentaaminecobalt perchlorate, trinitrotriamine cobalt, dinitrobis(ethylenediamine) cobalt perchlorate

    Lieberman, M.L.; Fleming, W.

    1986-01-01

    The compound 2-(5-cyanotetrazolato)pentaamminecobalt(III) perchlorate (CP) has been utilized in low-voltage detonators because it reliably undergoes deflagration-to-detonation transition (DDT). In the present investigation, we have compared the performance of over a dozen similar compounds. These compounds all have cobalt as the coordinating metal, most are ammine complexes, and all except one incorporate the perchlorate anion as an oxidizer. Chemical factors such as fuel-to-oxidizer ratio, trigger group, and organic content have been varied. 18 refs., 7 figs., 2 tabs.

  9. Environmental perchlorate: Why it matters

    Kirk, Andrea B.

    2006-01-01

    The only known mechanism of toxicity for perchlorate is interference with iodide uptake at the sodium-iodide symporter (NIS). The NIS translocates iodide across basolateral membranes to the thyroid gland so it can be used to form thyroid hormones (TH). NIS is also expressed in the mammary gland during lactation, so that iodide can be transferred from a mother to her child. Without adequate iodide, an infant cannot produce sufficient TH to meet its developmental needs. Effects expected from perchlorate are those that would be seen in conditions of hypothyroidism or hypothyroxinemia. The probability of a permanent adverse effect is greatest during early life, as successful neurodevelopment is TH-dependent. Study of perchlorate risk is complicated by a number of factors including thyroid status of the mother during gestation, thyroid status of the fetus, maternal and infant iodine intake, and exposure of each to other TH-disrupting chemicals. Perhaps the greatest standing issue, and the issue most relevant to the field of analytical chemistry, is the simple fact that human exposure has not been quantified. This review will summarize perchlorate's potential to adversely affect neurodevelopment. Whether current environmental exposures to perchlorate contribute to neuro-impairment is unknown. Risks posed by perchlorate must be considered in conjunction with iodine intake

  10. Perchlorate Removal, Destruction, and Field Monitoring Demonstration

    Coppola, Edward N; Davis, Andrea

    2006-01-01

    The objectives of this demonstration were to evaluate and demonstrate a complete perchlorate ion exchange process for groundwater that included a unique, regenerable, perchlorate-selective ion exchange resin...

  11. Rapid analysis of perchlorate in drinking water at parts per billion levels using microchip electrophoresis.

    Gertsch, Jana C; Noblitt, Scott D; Cropek, Donald M; Henry, Charles S

    2010-05-01

    A microchip capillary electrophoresis (MCE) system has been developed for the determination of perchlorate in drinking water. The United States Environmental Protection Agency (USEPA) recently proposed a health advisory limit for perchlorate in drinking water of 15 parts per billion (ppb), a level requiring large, sophisticated instrumentation, such as ion chromatography coupled with mass spectrometry (IC-MS), for detection. An inexpensive, portable system is desired for routine online monitoring applications of perchlorate in drinking water. Here, we present an MCE method using contact conductivity detection for perchlorate determination. The method has several advantages, including reduced analysis times relative to IC, inherent portability, high selectivity, and minimal sample pretreatment. Resolution of perchlorate from more abundant ions was achieved using zwitterionic, sulfobetaine surfactants, N-hexadecyl-N,N-dimethyl-3-ammonio-1-propane sulfonate (HDAPS) and N-tetradecyl-N,N-dimethyl-3-ammonio-1-propane sulfonate (TDAPS). The system performance and the optimization of the separation chemistry, including the use of these surfactants to resolve perchlorate from other anions, are discussed in this work. The system is capable of detection limits of 3.4 +/- 1.8 ppb (n = 6) in standards and 5.6 +/- 1.7 ppb (n = 6) in drinking water.

  12. Crystal structure of 2-cyano-1-methylpyridinium perchlorate

    Vu D. Nguyen

    2015-11-01

    Full Text Available The asymmetric unit of the title salt, C7H7N2+·ClO4−, comprises two independent formula units. The solid-state structure comprises corrugated layers of cations and of anions, approximately parallel to (010. The supramolecular layers are stabilized and connected by C—H...O hydrogen bonding to consolidate a three-dimensional architecture. A close pyridinium–perchlorate N...O contact [2.867 (5 Å] is noted. The crystal was refined as an inversion twin.

  13. Physiologic Functional Evaluation of Left Internal Mammary Artery Graft to Left Anterior Descending Coronary Artery Steal due to Unligated First Thoracic Branch in a Case of Refractory Angina

    Fadi J. Sawaya

    2016-01-01

    Full Text Available Unligated side branches of the left internal mammary artery (LIMA have been described in the literature as a cause of coronary steal resulting in angina. Despite a number of studies reporting successful side branch embolization to relieve symptoms, this phenomenon remains controversial. Hemodynamic evidence of coronary steal using angiographic and intravascular Doppler techniques has been supported by some and rejected by others. In this case study using an intracoronary Doppler wire with adenosine, we demonstrate that a trial occlusion of the LIMA thoracic side branch with selective balloon inflation can confirm physiologic significant steal and whether coil embolization of the side branch is indicated.

  14. Bioreactor configurations for ex-situ treatment of perchlorate: a review.

    Sutton, Paul M

    2006-12-01

    The perchlorate anion has been detected in the drinking water of millions of people living in the United States. At perchlorate levels equal to or greater than 1 mg/L and where the water is not immediately used for household purposes, ex-situ biotreatment has been widely applied. The principal objective of this paper was to compare the technical and economic advantages and disadvantages of various bioreactor configurations in the treatment of low- and medium-strength perchlorate-contaminated aqueous streams. The ideal bioreactor configuration for this application should be able to operate efficiently while achieving a long solids retention time, be designed to promote physical-chemical adsorption in addition to biodegradation, and operate under plug-flow hydraulic conditions. To date, the granular activated carbon (GAC) or sand-media-based fluidized bed reactors (FBRs) and GAC, sand-, or plastic-media-based packed bed reactors (PBRs) have been the reactor configurations most widely applied for perchlorate treatment. Only the FBR configuration has been applied commercially. Commercial-scale cost information presented implies no economic advantage for the PBR relative to the FBR configuration. Full-scale application information provides evidence that the FBR is a good choice for treating perchlorate-contaminated aqueous streams.

  15. PERCHLORATE PHYTOREMEDIATION USING HARDWOOD TREES AND VASCULAR PLANTS

    Perchlorate has contaminated water and soils at several locations in the United States. Perchlorate iswater soluble, exceedingly mobile in aqueous systems, and can persist for many decades under typical ground and surface water conditions. Perchlorate is of concern because of...

  16. Comparative analysis of three-dimensional structures of homodimers of uridine phosphorylase from Salmonella typhimurium in the unligated state and in a complex with potassium ion

    Lashkov, A. A.; Zhukhlistova, N. E.; Gabdulkhakov, A. G.; Mikhailov, A. M.

    2009-01-01

    The spatial organization of the homodimer of unligated uridine phosphorylase from Salmonella typhimurium (St UPh) was determined with high accuracy. The structure was refined at 1.80 A resolution to R work = 16.1% and R free = 20.0%. The rms deviations for the bond lengths, bond angles, and chiral angles are 0.006 A, 1.042 o , and 0.071 o , respectively. The coordinate error estimated by the Luzzati plot is 0.166 A. The coordinate error based on the maximum likelihood is 0.199 A. A comparative analysis of the spatial organization of the homodimer in two independently refined structures and the structure of the homodimer St UPh in the complex with a K + ion was performed. The substrate-binding sites in the homodimers StUPhs in the unligated state were found to act asynchronously. In the presence of a potassium ion, the three-dimensional structures of the subunits in the homodimer are virtually identical, which is apparently of importance for the synchronous action of both substrate-binding sites. The atomic coordinates of the refined structure of the homodimer and structure factors have been deposited in the Protein Data Bank (PDB ID code 3DPS).

  17. Comparative analysis of three-dimensional structures of homodimers of uridine phosphorylase from Salmonella typhimurium in the unligated state and in a complex with potassium ion

    Lashkov, A. A.; Zhukhlistova, N. E.; Gabdulkhakov, A. G.; Mikhailov, A. M., E-mail: amm@ns.crys.ras.ru [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2009-03-15

    The spatial organization of the homodimer of unligated uridine phosphorylase from Salmonella typhimurium (St UPh) was determined with high accuracy. The structure was refined at 1.80 A resolution to R{sub work} = 16.1% and R{sub free} = 20.0%. The rms deviations for the bond lengths, bond angles, and chiral angles are 0.006 A, 1.042{sup o}, and 0.071{sup o}, respectively. The coordinate error estimated by the Luzzati plot is 0.166 A. The coordinate error based on the maximum likelihood is 0.199 A. A comparative analysis of the spatial organization of the homodimer in two independently refined structures and the structure of the homodimer St UPh in the complex with a K{sup +} ion was performed. The substrate-binding sites in the homodimers StUPhs in the unligated state were found to act asynchronously. In the presence of a potassium ion, the three-dimensional structures of the subunits in the homodimer are virtually identical, which is apparently of importance for the synchronous action of both substrate-binding sites. The atomic coordinates of the refined structure of the homodimer and structure factors have been deposited in the Protein Data Bank (PDB ID code 3DPS).

  18. Perchlorate: environmental occurrence, interactions and treatment

    Gu, Baohua, Ph. D; Coates, John D

    2006-01-01

    ..... ... . ... .. ... .. ... . ... ... .. . . . . , . , . , .. ... ... .. 14 Chapter 2. The Chemistry of Perchlorate in the Environment Gilbert M Brown and Baohua Gu Introduction ... 17 Redox Properties of Chlorine Compounds ... 18...

  19. PHYTOREMEDIATION OF PERCHLORATE BY TOBACCO PLANTS

    Previous studies have shown that tobacco plants are tolerant of perchlorate and will accumulate perchlorate in the plant tissues. The objective of this research was to determine the effectiveness of tobacco plants in phytoremediation, a technology that employs plants to degrade,...

  20. MARGINAL IODINE DEFICIENCY EXACERBATES PERCHLORATE THYROID TOXICITY.

    The environmental contaminant perchlorate disrupts thyroid homeostasis via inhibition of iodine uptake into the thyroid. This work tested whether iodine deficiency exacerbates the effects of perchlorate. Female 27 day-old LE rats were fed a custom iodine deficient diet with 0, 50...

  1. Bis[N-(3-aminopropylpropane-1,3-diamine-κ3N,N′,N′′]cadmium nitrate perchlorate

    Václav Eigner

    2012-03-01

    Full Text Available The title complex, [Cd(C6H17N32](ClO4(NO3, was synthesized by the reaction of Cd(NO32·4H2O, bis(3-aminopropylamine and sodium perchlorate in methanol. The asymmetric unit of the title complex consists of one Cd2+ cation, two tridentate bis(3-aminopropylamine ligands, one nitrate anion and one perchlorate anion. The Cd2+ cation is coordinated by six N atoms of the bis(3-aminopropylamine ligands in a slightly distorted octahedral coordination geometry. In the crystal, molecules are held together by an intricate network of N—H...O interactions. One of the two amine ligands was found to be disordered over two sets of sites, with a ratio of 0.802 (3:0.198 (3, similarly to the nitrate anion, with a ratio of 0.762 (10:0.238 (10.

  2. Study of the effect of anions and mixed solvents on the kinetics of reduction of Eu(III)

    Chandrasekaran, V.R.; Sundaram, A.K.

    1983-01-01

    The kinetics of reduction of Eu(III) to Eu(II) in aqueous solutions of perchlorate, chloride, sulphate, acetate and lactate anions and water-methanol and water-acetone mixtures containing potassium chloride as the inert electrolyte is reported and the effect of anions and solvent on the kinetics is studied. (author)

  3. Novel biomarkers of perchlorate exposure in zebrafish

    Mukhi, S.; Carr, J.A.; Anderson, T.A.; Patino, R.

    2005-01-01

    Perchlorate inhibits iodide uptake by thyroid follicles and lowers thyroid hormone production. Although several effects of perchlorate on the thyroid system have been reported, the utility of these pathologies as markers of environmental perchlorate exposures has not been adequately assessed. The present study examined time-course and concentration-dependent effects of perchlorate on thyroid follicle hypertrophy, colloid depletion, and angiogenesis; alterations in whole-body thyroxine (T4) levels; and somatic growth and condition factor of subadult and adult zebrafish. Changes in the intensity of the colloidal T4 ring previously observed in zebrafish also were examined immunohistochemically. Three-month-old zebrafish were exposed to ammonium perchlorate at measured perchlorate concentrations of 0, 11, 90, 1,131, and 11,480 ppb for 12 weeks and allowed to recover in clean water for 12 weeks. At two weeks of exposure, the lowest-observed-effective concentrations (LOECs) of perchlorate that induced angiogenesis and depressed the intensity of colloidal T4 ring were 90 and 1,131 ppb, respectively; other parameters were not affected (whole-body T4 was not determined at this time). At 12 weeks of exposure, LOECs for colloid depletion, hypertrophy, angiogenesis, and colloidal T4 ring were 11,480, 1,131, 90, and 11 ppb, respectively. All changes were reversible, but residual effects on angiogenesis and colloidal T4 ring intensity were still present after 12 weeks of recovery (LOEC, 11,480 ppb). Whole-body T 4 concentration, body growth (length and weight), and condition factor were not affected by perchlorate. The sensitivity and longevity of changes in colloidal T4 ring intensity and angiogenesis suggest their usefulness as novel markers of perchlorate exposure. The 12-week LOEC for colloidal T4 ring is the lowest reported for any perchlorate biomarker in aquatic vertebrates. ?? 2005 SETAC.

  4. Development of a Reference Dose for Perchlorate: Current Issues and Status

    Pleus, R. C.; Goodman, G.; Mattie, D. R.

    2000-01-01

    The perchlorate anion (ClO4) is typically manufactured as the ammonium salt. The most common use of ammonium perchlorate is in the aerospace program as a component of solid rocket fuel. The perchlorate anion is exceedingly stable under environmental conditions and has been found in ground and surface waters in CA, NV, UT, AZ, TX, AK, NY, MD, WV and FL. The National Center for Environmental Assessment (NCEA) of the U.S. Environmental Protection Agency (US EPA) is in the process of developing an oral reference dose (RfD) for perchlorate. An oral RfD is a body-weight-adjusted dose that can be consumed daily over an entire lifetime with the expectation of no adverse health effects. Once developed, the new RfD will be used by US EPA as the basis of a safe-drinking-water level (SDWL) guideline. US EPA and regional regulatory agencies will then jointly or separately propose clean-up action levels for ground and surface waters at contaminated sites. The toxicological database on CIO4- as of March 1997 was determined by an expert peer-review panel to be inadequate for the purpose of deriving an oral RfD. For example, little or no experimental data existed on the subchronic, reproductive, or developmental toxicity of perchlorate. To fill gaps in the toxicological database, eight animal studies were designed by a government-industry consortium that included US EPA and AFRL. These studies were performed in 1997-1998. It has been known for many years that in the thyroid, high doses of perchlorate block the function of iodide by competing for iodide binding sites. Perchlorate was used in the 1950s-60s as a treatment for Graves' disease (a hyperthyroid condition). Because of what was already known about the pharmacological mode of action of perchlorate, specific concerns addressed in the design of the recent animal studies included the potential for developmental toxicity, notably neurological development. Upon review of complete study reports from four of the studies and

  5. Occurrence of perchlorate and thiocyanate in human serum from e-waste recycling and reference sites in Vietnam: association with thyroid hormone and iodide levels.

    Eguchi, Akifumi; Kunisue, Tatsuya; Wu, Qian; Trang, Pham Thi Kim; Viet, Pham Hung; Kannan, Kurunthachalam; Tanabe, Shinsuke

    2014-07-01

    Perchlorate (ClO4 (-)) and thiocyanate (SCN(-)) interfere with iodide (I(-)) uptake by the sodium/iodide symporter, and thereby these anions may affect the production of thyroid hormones (THs) in the thyroid gland. Although human exposure to perchlorate and thiocyanate has been studied in the United States and Europe, few investigations have been performed in Asian countries. In this study, we determined concentrations of perchlorate, thiocyanate, and iodide in 131 serum samples collected from 2 locations in Northern Vietnam, Bui Dau (BD; electrical and electronic waste [e-waste] recycling site) and Doung Quang (DQ; rural site) and examined the association between serum levels of these anions with levels of THs. The median concentrations of perchlorate, thiocyanate, and iodide detected in the serum of Vietnamese subjects were 0.104, 2020, and 3.11 ng mL(-1), respectively. Perchlorate levels were significantly greater in serum of the BD population (median 0.116 ng mL(-1)) than those in the DQ population (median 0.086 ng mL(-1)), which indicated greater exposure from e-waste recycling operations by the former. Serum concentrations of thiocyanate were not significantly different between the BD and DQ populations, but increased levels of this anion were observed among smokers. Iodide was a significant positive predictor of serum levels of FT3 and TT3 and a significant negative predictor of thyroid-stimulating hormone in males. When the association between serum levels of perchlorate or thiocyanate and THs was assessed using a stepwise multiple linear regression model, no significant correlations were found. In addition to greater concentrations of perchlorate detected in the e-waste recycling population, however, given that lower concentrations of iodide were observed in the serum of Vietnamese females, detailed risk assessments on TH homeostasis for females inhabiting e-waste recycling sites, especially for pregnant women and their neonates, are required.

  6. Interfacial behavior of perchlorate versus chloride ions in saturated aqueous salt solutions

    Ghosal, S; Kuo, I W; Baer, M D; Bluhm, H

    2009-04-14

    In recent years combination of theoretical and experimental work have presented a novel view of the aqueous interface wherein hard and/or multiply charged ions are excluded from the interface, but large polarizable anions show interfacial enhancement relative to the bulk. The observed trend in the propensity of anions to adsorb at the air/water interface appears to be reverse of the Hofmeister series for anions. This study focuses on experimental and theoretical examination of the partitioning behavior of perchlorate (ClO{sub 4}{sup -}) and chloride (Cl{sup -}) ions at the air/water interface. We have used ambient pressure X-ray photoelectron spectroscopy technique to directly probe the interfacial concentrations of ClO{sub 4}{sup -} and Cl{sup -} ions in sodium perchlorate and sodium chloride solutions, respectively. Experimental observations are compared with first principles molecular dynamics simulations. Both experimental and simulation results show enhancement of ClO{sub 4}{sup -} ion at the interface, compared with the absence of such enhancement in the case of Cl{sup -} ion. These observations are in agreement with the expected trend in the interfacial propensity of anions based on the Hofmeister series.

  7. Atomic force microscopy study of anion intercalation into highly oriented pyrolytic graphite

    Alliata, D; Haering, P; Haas, O; Koetz, R [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Siegenthaler, H [University of Berne (Switzerland)

    1999-08-01

    In the context of ion transfer batteries, we studied highly oriented pyrolytic graphite (HOPG) in perchloric acid, as a model to elucidate the mechanism of electrochemical intercalation in graphite. Aim of the work is the local and time dependent investigation of dimensional changes of the host material during electrochemical intercalation processes on the nanometer scale. We used atomic force microscopy (AFM), combined with cyclic voltammetry, as in-situ tool of analysis during intercalation and expulsion of perchloric anions into the HOPG electrodes. According to the AFM measurements, the HOPG interlayer spacing increases by 32% when perchloric anions intercalate, in agreement with the formation of stage IV of graphite intercalation compounds. (author) 3 figs., 3 refs.

  8. Stable Isotope Systematics of Martian Perchlorate

    Martin, P.; Farley, K. A.; Archer, D., Jr.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairen, A.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

    2015-12-01

    Chlorine isotopic compositions in HCl released during evolved gas analysis (EGA) runs have been detected by the Sample Analysis at Mars (SAM) instrument on the Curiosity rover ranging from approximately -9‰ to -50‰ δ37Cl, with two spatially and isotopically separated groups of samples averaging -15‰ and -45‰. These extremely low values are the first such detection of any known natural material; common terrestrial values very rarely exceed ±5‰, and the most extreme isotopic signature yet detected elsewhere in the solar system are values of around +24‰ on the Moon. The only other known location in the solar system with large negative chlorine isotopes is the Atacama Desert, where perchlorate with -14‰ δ37Cl has been detected. The Atacama perchlorate has unusual Δ17O signatures associated with it, indicating a formation mechanism involving O3, which suggests an atmospheric origin of the perchlorate and associated large isotopic anomalies. Identification of non-zero positive Δ17O signatures in the O2 released during EGA runs would allow definitive evidence for a similar process having occurred on Mars. Perchlorate is thought to be the most likely source of HCl in EGA runs due to the simultaneous onset of O2 release. If perchlorate is indeed the HCl source, atmospheric chemistry could be responsible for the observed isotopic anomalies, with variable extents of perchlorate production producing the isotopic variability. However, chloride salts have also been observed to release HCl upon heating; if the timing of O2 release is merely coincidental, observed HCl could be coming from chlorides. At thermodynamic equilibrium, the fractionation factor of perchlorate reduction is 0.93, meaning that differing amounts of post-deposition reduction of isotopically normal perchlorate to chloride could account for the highly variable Cl isotopes. Additionally, post-deposition reduction could account for the difference between the two Cl isotopic groups if perchlorate

  9. Bis(μ-bis{[4-(2-pyridylpyrimidin-2-yl]sulfanyl}methanedisilver(I bis(perchlorate

    Hai-Bin Zhu

    2010-12-01

    Full Text Available In the macrocyclic centrosymmetric dinuclear complex, [Ag2(C19H14N6S22](ClO42, the AgI atom, bis{[4-(2-pyridylpyrimidin-2-yl]sulfanyl}methane (2-bppt ligand and perchlorate anion each lie on a twofold rotation axis. The 2-bppt ligand chelates two four-coordinated AgI atoms through its two bipyridine-like arms. The O atoms of the perchlorate anion are disordered each over two positions of equal occupancy. Adjacent complex molecules are linked by π–π interactions between the pyridine and pyrimidine rings [centroid–centroid distance = 3.663 (8 Å].

  10. Poly[[tetrakis(μ2-pyrazine N,N′-dioxide-κ2O:O′erbium(III] tris(perchlorate

    James D. Buchner

    2010-09-01

    Full Text Available The title three-dimensional coordination network, {[Er(C4H4N2O24](ClO43}n, is isostructural to that of other lanthanides. The Er+3 cation lies on a fourfold roto-inversion axis. It is coordinated in a distorted square-antiprismatic fashion by eight O atoms from bridging pyrazine N,N′-dioxide ligands. There are two unique pyrazine N,N′-dioxide ligands. One ring is located around an inversion center, and there is a a twofold rotation axis at the center of the other ring. There are also two unique perchlorate anions. One is centered on a twofold rotation axis and the other on a fourfold roto-inversion axis. The perchlorate anions are located in channels that run perpendicular to (001 and (110 and interact with the coordination network through C—H...O hydrogen bonds.

  11. The Microbiology of Perchlorate in the Environment

    Coates, J. D.

    2007-12-01

    In the last decade perchlorate has been identified as an important groundwater component that poses potential health threat. Although primarily sourced anthropogenically, many recent studies have identified significant natural pools throughout the US and the natural mechanisms of its synthesis remain a mystery. As such, the true perchlorate concentrations naturally present in the environment are still unknown making its regulation problematic. Because of its solubility and non-reactivity the fate and transport of perchlorate in the environment is primarily a function of microbial activity. In the last seven years more than forty specialized perchlorate respiring organisms have been identified and characterized. These dissimilatory perchlorate reducing bacteria (DPRB) are metabolically diverse and environmental populations tend to be dominated by two primary genotypes, the Dechloromonas and the Azospira species. As such, the majority of our understanding of this metabolism is based on these organisms. These organisms are readily found in soil and sedimentary environments and often associate with the rhizosphere. Recent research has demonstrated an accumulation of these organisms along plant roots suggesting their catabolism of root exudates and molecular studies has demonstrated their existence as endophytic infections of the stem and leaves of actively growing Brachypodium grass plants although their exact role under these conditions is unknown. These microorganisms are generally not nutritionally fastidious and vitamin supplementation is unnecessary for growth although molybdenum is a required trace element for perchlorate reduction. The Dechloromonas and Azospira species generally grow optimally at pH values near neutrality in freshwater environments. Even so, recent field studies have shown that related deep-branching members of these genera often predominate in sites of adverse pH or salinity with some species being capable of growth and perchlorate respiration

  12. μ-Oxalato-bis[(2,2′-bipyridylcopper(II] bis(perchlorate dimethylformamide disolvate monohydrate

    Alexander N. Boyko

    2010-09-01

    Full Text Available The title compound, [Cu2(C2O4(C10H8N24](ClO42·2C3H7NO·H2O, contains doubly charged centrosymmetric dinuclear oxalato-bridged copper(II complex cations, perchlorate anions, and DMF and water solvate molecules. In the complex cation, the oxalate ligand is coordinated in a bis-bidentate bridging mode to the Cu atoms. Each Cu atom has a distorted tetragonal-bipyramidal environment, being coordinated by two N atoms of the two chelating bipy ligands and two O atoms of the doubly deprotonated oxalate anion. Pairs of perchlorate anions and water molecules are linked into rectangles by O—H...O bonds in which the perchlorate O atoms act as acceptors and the water molecules as donors. Methyl groups of the DMF solvent molecule are disordered over two sites with occupancies of 0.453 (7:0.547 (7, and the water molecule is half-occupied.

  13. Environmental biotechnology and microbiology of (per)chlorate reducing bacteria

    Mehboob, F.; Schraa, G.; Stams, A.J.M.

    2011-01-01

    Perchlorates are the salts derived from perchloric acid (HClO4). They occur both naturally and through manufacturing. They have been used as a medicine for more than 50 years to treat thyroid gland disorders and are used extensively within the pyrotechnics industry, and ammonium perchlorate is also

  14. Modeling In Situ Bioremediation of Perchlorate-Contaminated Groundwater

    2007-03-01

    association between perchlorate exposure at the doses investigated and hypothyroidism or other thyroid disorders in adults Thyroid cancer in adults ...hormone secretions can result in thyroid hypertrophy and hyperplasia, possibly followed by hypothyroidism in people unable to compensate with an...perchlorate exposure. The model indicated that continued perchlorate exposure ultimately led to birth defects in children and tumors in adults . Based upon

  15. 76 FR 7762 - Drinking Water: Regulatory Determination on Perchlorate

    2011-02-11

    ...-9262-8] RIN 2040-AF08 Drinking Water: Regulatory Determination on Perchlorate AGENCY: Environmental...'s) regulatory determination for perchlorate in accordance with the Safe Drinking Water Act (SDWA... substantial likelihood that perchlorate will occur in public water systems with a frequency and at levels of...

  16. 2-(2-Hydroxy-3-methoxyphenyl-1H-benzimidazol-3-ium perchlorate

    Chuan Chen

    2012-06-01

    Full Text Available In the title molecular salt, C14H13N2O2+·ClO4−, the ring systems in the cation are almost coplanar [dihedral angle = 5.53 (13°]. Intramolecular N—H...O and O—H...O hydrogen bonds generate S(6 and S(5 rings, respectively. In the crystal, the two H atoms involved in the intramolecular hydrogen bonds also participate in intermolecular links to acceptor O atoms of the perchlorate anions. A simple intermolecular N—H...O bond also occurs. Together, these form a double-chain structure along [101].

  17. Coordination, non-coordination and semi-coordination of perchlorates in the lanthanide adducts Ln (CLO4)3. 6dmba

    Tfouni, E.; Giesbrecht, E.

    1983-01-01

    The coordination or not of the perchlorate anions in the previously reported Ln(CLO 4 ) 3 .6 dmba is discussed. The analysis of the infrared spectral data and molar conductance data indicate that they may be formulated as [Ln(dmba) 6 (CLO 4 )n] (CLO 4 ) sub(3-n), n=0,1,2. The individual compounds may be a mixture of species with different n values and/or pure compounds with semi-coordinated and non-coordinated perchlorates. (Author) [pt

  18. Interaction of perchlorate and trichloroethene bioreductions in mixed anaerobic culture

    Wen, Li-Lian [Department of Environmental Engineering, College of Environmental and Resource Science, Zhejiang University, Hangzhou (China); Zhejiang Prov Key Lab Water Pollut Control & Envi, Zhejiang University, Hangzhou, Zhejiang (China); Yang, Qiang [Hangzhou Institute of Environmental Protection Science, Hangzhou (China); Zhang, Zhao-Xin; Yi, Yang-Yi [Department of Environmental Engineering, College of Environmental and Resource Science, Zhejiang University, Hangzhou (China); Tang, Youneng [Department of Civil and Environmental Engineering, FAMU-FSU College of Engineering, Florida State University, Tallahassee, FL 32310-6046 (United States); Zhao, He-Ping, E-mail: zhaohp@zju.edu.cn [Department of Environmental Engineering, College of Environmental and Resource Science, Zhejiang University, Hangzhou (China); Zhejiang Prov Key Lab Water Pollut Control & Envi, Zhejiang University, Hangzhou, Zhejiang (China); Hangzhou Institute of Environmental Protection Science, Hangzhou (China)

    2016-11-15

    This work evaluated the interaction of perchlorate and trichloroethene (TCE), two common co-contaminants in groundwater, during bioreduction in serum bottles containing synthetic mineral salts media and microbial consortia. TCE at concentrations up to 0.3 mM did not significantly affect perchlorate reduction; however, perchlorate concentrations higher than 0.1 mM made the reduction of TCE significantly slower. Perchlorate primarily inhibited the reduction of vinyl chloride (VC, a daughter product of TCE) to ethene. Mechanistic analysis showed that the inhibition was mainly because perchlorate reduction is thermodynamically more favorable than reduction of TCE and its daughter products and not because of toxicity due to accumulation of dissolved oxygen produced during perchlorate reduction. As the initial perchlorate concentration increased from 0 to 600 mg/L in a set of serum bottles, the relative abundance of Rhodocyclaceae (a putatively perchlorate-reducing genus) increased from 6.3 to 80.6%, while the relative abundance of Dehalococcoides, the only known genus that is able to reduce TCE all the way to ethene, significantly decreased. Similarly, the relative abundance of Proteobacteria (a phylum to which most known perchlorate-reducing bacteria belong) increased from 22% to almost 80%. - Graphical abstract: Fig. A plots the interaction of TCE and perchlorate bio-reduction under different concentrations of perchlorate and suggests that initial ethene wasn't formed until the perchlorate was completely reduced. B shows the electron donor utilization and oxygen generated during the experiment and indicates that it is perchlorate reduction over-competed for electron donor rather than oxygen generated that inhibits TCE reductive dechlorination. - Highlight: • Perchlorate slowed but did not inhibit the complete dechlorination of TCE. • The inhibition was mainly due to the thermodynamic preference of perchlorate to TCE. • The generated oxygen was consumed and

  19. Effect of anions and cations on liquid extraction of TcO{sub 4} - in ionic liquids; Vplyv anionov a kationov na kvapalinovu extrakciu TcO4 - v ionovych kvapalinach

    Suchanek, P.; Galambos, M.; Meciarova, M.; Rajec, P [Univerzita Komenskeho, Prirodovedecka fakulta, Katedra jadrovej chemie, 84215 Bratislava (Slovakia)

    2013-04-16

    An influence of monovalent and divalent cations and anions on an liquid extraction of pertechnetate anion from aqueous media using ionic liquids solubilized in various organic solvents has been studied. Suppression of extraction percentage was obtained with a divalent cations in a compare with monovalent cations showing almost no influence on extraction percentage. In a case of anions, perchlorate anion suppressed the extraction percentage in a highest degree. (authors)

  20. Atmospheric origins of perchlorate on Mars and in the Atacama

    Catling, D. C.; Claire, M. W.; Zahnle, K. J.; Quinn, R. C.; Clark, B. C.; Hecht, M. H.; Kounaves, S.

    2010-01-01

    Isotopic studies indicate that natural perchlorate is produced on Earth in arid environments by the oxidation of chlorine species through pathways involving ozone or its photochemical products. With this analogy, we propose that the arid environment on Mars may have given rise to perchlorate through the action of atmospheric oxidants. A variety of hypothetical pathways can be proposed including photochemical reactions, electrostatic discharge, and gas-solid reactions. Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we made a preliminary study of the means to produce Atacama perchlorate to help shed light on the origin of Martian perchlorate. We investigated gas phase pathways using a 1-D photochemical model. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. The feasibility of gas phase production for the Atacama provides justification for future investigations of gas phase photochemistry as a possible source for Martian perchlorate.

  1. ACCUMULATION OF PERCHLORATE IN TOBACCO PLANTS: DEVELOPMENT OF A PLANT KINETIC MODEL

    Previous studies have shown that tobacco plants are tolerant of perchlorate and will accumulate perchlorate in plant tissues. This research determined the uptake, translocation, and accumulation of perchlorate in tobacco plants. Three hydroponics growth studies were completed u...

  2. In-Situ Bioremediation of Perchlorate in Groundwater and Soil

    Jin, Liyan

    2012-01-01

    Historical, uncontrolled disposal practices have made perchlorate a significant threat to drinking water supplies in the United States. In-situ bioremediation (ISB) technologies are cost effective and provide an environmental friendly solution for treating contaminated groundwater and soil. In situ bioremediation was considered as an option for treatment of perchlorate in groundwater and soil in Lockheed Martin Corporation's Beaumont Site 2 (Beaumont, CA). Based on the perchlorate distribu...

  3. Background Perchlorate Source Identification Technical Guidance

    2013-12-01

    perchlorate was at one time used to treat thyroid dysfunction, particularly a hyperthyroidism condition known as Grave’s disease . Ecological impacts...chlorates are used for pulp and paper bleaching, non-selective contact herbicide application, and plant defoliation for cotton, sunflowers...safflower, rice, and chili peppers (OMRI, 2000). Effluents from pulp mills have been reported to contain chlorate (1 to 70 mg/L) (Warrington, 2002), but

  4. Monitored Natural Attenuation of Perchlorate in Groundwater

    2010-09-01

    dissolved oxygen DoD Department of Defense DPRB dissimilatory perchlorate-reducing bacteria EOS® Emulsified ( Edible ) Oil Substrate ESTCP...simple and complex electron donors, i.e., lactate and Emulsified ( Edible ) Oil Substrate (EOS®) Task 2: Laboratory Studies 1 solutions...project were to provide Department of Defense (DoD) managers and industry professionals with the tools needed to demonstrate to regulatory agencies that

  5. 4-Bromoanilinium perchlorate 18-crown-6 clathrate

    Min Guo

    2010-11-01

    Full Text Available The reaction of 4-bromoaniline, 18-crown-6, and perchloric acid in methanol yields the title compound, C6H7BrN+·ClO4−·C12H24O6, in which the protonated –NH3+ group forms three bifurcated N—H...O hydrogen bonds to the O atoms of the crown ether.

  6. Novel miniaturized sensors for potentiometric batch and flow-injection analysis (FIA) of perchlorate in fireworks and propellants.

    Almeer, Saeed H M A; Zogby, Ibrahim A; Hassan, Saad S M

    2014-11-01

    Three planar miniaturized perchlorate membrane sensors (3×5 mm(2)) are prepared using a flexible Kaptan substrate coated with nitron-perchlorate (NT-ClO4) [sensor 1], methylene blue-perchlorate (MB-ClO4) [sensor II] and indium-porphyrin (In-Por) [sensor III] as electroactive materials in PVC membranes plasticized with 2-NPPE. Sensors I, II and III display near-Nernstian response for 1.0×10(-5)-1.0×10(-2), 3.1×10(-5)-1.0×10(-2) and 3.1×10(-6)-1.0×10(-2) mol L(-1) ClO4(-) with lower detection limits of 6.1×10(-6), 6.9×10(-6) and 1.2×10(-6) mol L(-1), and anionic calibration slopes of 50.9±0.4, 48.4±0.4 and 57.7±0.3 mV decade(-1), respectively. Methods for determining perchlorate using these sensors offer many attractive advantages including simplicity, flexibility, cost effectiveness, wide linear dynamic response range (0.1-1000 ppm), low detection limit (copper, iron, sodium), color brighten (linseed oil) and regulators (aluminum flakes) which are commonly used in the formulations. The sensor is also used for perchlorate assessment in some propellant powders. The results fairly agree with data obtained by ion-chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Wet Deposition of Perchlorate Over the Continental United States

    Rajagopalan, S.; Jackson, A. W.; Anderson, T. A.

    2007-12-01

    Natural perchlorate (ClO4-) has been detected in soil, vegetation, food products, and ground and drinking water supplies at various concentrations across the world. For almost a century natural perchlorate has been known to exist in Chilean nitrate deposits that are up to 16 million years old, and recent isotopic evidence has confirmed its source to be predominantly atmospheric. Although the source of natural perchlorate has been attributed to atmospheric deposition, there is almost no data available concerning the deposition rate of perchlorate from precipitation. This research effort, supported by SERDP, was designed to investigate the range of concentrations, and temporal and spatial variations in perchlorate deposition. Sub-samples of precipitation collected through the National Atmospheric Deposition program over a two year period were analyzed for perchlorate. Sample locations included 14 continental states, and Puerto Rico. Perchlorate has been detected (DL= 5 ng/L) in over 65 % of all samples tested with a mean value of 12.60 ± 13.60 ng/L and ranged from 0.5) between ClO4- and other ions (Cl-, NO3-, SO4-2, Na+, K+, Ca+2, Mg+2, and NH4+). Results from this study will have important implications to the national perchlorate issue and may aid in explaining the occurrence of non-anthropogenic perchlorate being reported in arid and semi-arid areas.

  8. Atmospheric Production of Perchlorate on Earth and Mars

    Claire, M.; Catling, D. C.; Zahnle, K. J.

    2009-12-01

    Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

  9. Anion exchange membrane

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  10. Microbial (per)chlorate reduction in hot subsurface environments

    Liebensteiner, M.

    2014-01-01

    The microbial reduction of chlorate and perchlorate has been known for long as a respiratory process of mesophilic bacteria that thrive in diverse environments such as soils, marine and freshwater sediments. Chlorate and perchlorate are found in nature deriving from anthropogenic and natural

  11. PERCHLORATE IDENTIFICATION IN FERTILIZERS AND ACCUMULATION IN LETTUCE SEEDLINGS

    Perchlorate has contaminated groundwater, drinking water and soils at several locations in the U.S. The primary source of contamination at sites that have been investigated to date seems to be from industrial and military operations that use Perchlorate as an oxidizing agent. How...

  12. Anions in Cometary Comae

    Charnley, Steven B.

    2011-01-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  13. Development of an extraction method for perchlorate in soils.

    Cañas, Jaclyn E; Patel, Rashila; Tian, Kang; Anderson, Todd A

    2006-03-01

    Perchlorate originates as a contaminant in the environment from its use in solid rocket fuels and munitions. The current US EPA methods for perchlorate determination via ion chromatography using conductivity detection do not include recommendations for the extraction of perchlorate from soil. This study evaluated and identified appropriate conditions for the extraction of perchlorate from clay loam, loamy sand, and sandy soils. Based on the results of this evaluation, soils should be extracted in a dry, ground (mortar and pestle) state with Milli-Q water in a 1 ratio 1 soil ratio water ratio and diluted no more than 5-fold before analysis. When sandy soils were extracted in this manner, the calculated method detection limit was 3.5 microg kg(-1). The findings of this study have aided in the establishment of a standardized extraction method for perchlorate in soil.

  14. cis-Aquabis(2,2'-bipyridine-κ2N,N')-fluoridochromium(III) bis(perchlorate) dihydrate

    Birk, Torben; Bendix, Jesper

    2010-01-01

    The title mixed aqua-fluoride complex, [CrF(C(10)H(8)N(2))(2)(H(2)O)](ClO(4))(2)·2H(2)O, has been synthesized by aqua-tion of the corresponding difluoride complex using lanthan-ide(III) ions as F(-) acceptors. The complex crystallizes with a Cr(III) ion at the center of a distorted octa-hedral co......-hedral coordination polyhedron with a cis arrangement of ligands. The crystal packing shows a hydrogen-bonding pattern involving water mol-ecules, the coordinated F atom and the perchlorate anions....

  15. cis-Aquabis(2,2′-bipyridine-κ2N,N′fluoridochromium(III bis(perchlorate dihydrate

    Torben Birk

    2010-02-01

    Full Text Available The title mixed aqua–fluoride complex, [CrF(C10H8N22(H2O](ClO42·2H2O, has been synthesized by aquation of the corresponding difluoride complex using lanthanide(III ions as F− acceptors. The complex crystallizes with a CrIII ion at the center of a distorted octahedral coordination polyhedron with a cis arrangement of ligands. The crystal packing shows a hydrogen-bonding pattern involving water molecules, the coordinated F atom and the perchlorate anions

  16. The Effects of Perchlorates on the Permafrost Methanogens: Implication for Autotrophic Life on Mars.

    Shcherbakova, Viktoria; Oshurkova, Viktoria; Yoshimura, Yoshitaka

    2015-09-09

    The terrestrial permafrost represents a range of possible cryogenic extraterrestrial ecosystems on Earth-like planets without obvious surface ice, such as Mars. The autotrophic and chemolithotrophic psychrotolerant methanogens are more likely than aerobes to function as a model for life forms that may exist in frozen subsurface environments on Mars, which has no free oxygen, inaccessible organic matter, and extremely low amounts of unfrozen water. Our research on the genesis of methane, its content and distribution in permafrost horizons of different ages and origin demonstrated the presence of methane in permanently frozen fine-grained sediments. Earlier, we isolated and described four strains of methanogenic archaea of Methanobacterium and Methanosarcina genera from samples of Pliocene and Holocene permafrost from Eastern Siberia. In this paper we study the effect of sodium and magnesium perchlorates on growth of permafrost and nonpermafrost methanogens, and present evidence that permafrost hydogenotrophic methanogens are more resistant to the chaotropic agent found in Martian soil. In this paper we study the effect of sodium and magnesium perchlorates on the growth of permafrost and nonpermafrost methanogens, and present evidence that permafrost hydogenotrophic methanogens are more resistant to the chaotropic agent found in Martian soil. Furthermore, as shown in the studies strain M2(T) M. arcticum, probably can use perchlorate anion as an electron acceptor in anaerobic methane oxidation. Earth's subzero subsurface environments are the best approximation of environments on Mars, which is most likely to harbor methanogens; thus, a biochemical understanding of these pathways is expected to provide a basis for designing experiments to detect autotrophic methane-producing life forms on Mars.

  17. The Effects of Perchlorates on the Permafrost Methanogens: Implication for Autotrophic Life on Mars

    Viktoria Shcherbakova

    2015-09-01

    Full Text Available The terrestrial permafrost represents a range of possible cryogenic extraterrestrial ecosystems on Earth-like planets without obvious surface ice, such as Mars. The autotrophic and chemolithotrophic psychrotolerant methanogens are more likely than aerobes to function as a model for life forms that may exist in frozen subsurface environments on Mars, which has no free oxygen, inaccessible organic matter, and extremely low amounts of unfrozen water. Our research on the genesis of methane, its content and distribution in permafrost horizons of different ages and origin demonstrated the presence of methane in permanently frozen fine-grained sediments. Earlier, we isolated and described four strains of methanogenic archaea of Methanobacterium and Methanosarcina genera from samples of Pliocene and Holocene permafrost from Eastern Siberia. In this paper we study the effect of sodium and magnesium perchlorates on growth of permafrost and nonpermafrost methanogens, and present evidence that permafrost hydogenotrophic methanogens are more resistant to the chaotropic agent found in Martian soil. In this paper we study the effect of sodium and magnesium perchlorates on the growth of permafrost and nonpermafrost methanogens, and present evidence that permafrost hydogenotrophic methanogens are more resistant to the chaotropic agent found in Martian soil. Furthermore, as shown in the studies strain M2T M. arcticum, probably can use perchlorate anion as an electron acceptor in anaerobic methane oxidation. Earth’s subzero subsurface environments are the best approximation of environments on Mars, which is most likely to harbor methanogens; thus, a biochemical understanding of these pathways is expected to provide a basis for designing experiments to detect autotrophic methane-producing life forms on Mars.

  18. FT-IR, FT-Raman spectra and DFT calculations of melaminium perchlorate monohydrate

    Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Renganathan, N. G.; Gunasekaran, S.; Anbalagan, G.

    2013-08-01

    Melaminium perchlorate monohydrate (MPM), an organic material has been synthesized by slow solvent evaporation method at room temperature. Powder X-ray diffraction analysis confirms that MPM crystal belongs to triclinic system with space group P-1. FTIR and FT Raman spectra are recorded at room temperature. Functional group assignment has been made for the melaminium cations and perchlorate anions. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory (DFT) calculations using Firefly (PC GAMESS) version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with experimental values. The assignment of the bands has been made on the basis of the calculated PED. The Mulliken charges, HOMO-LUMO orbital energies are analyzed directly from Firefly program log files and graphically illustrated. HOMO-LUMO energy gap and other related molecular properties are also calculated. The theoretically constructed FT-IR and FT-Raman spectra of MPM coincide with the experimental one. The chemical structure of the compound has been established by 1H and 13C NMR spectra. No detectable signal was observed during powder test for second harmonic generation.

  19. Thermal decomposition of beryllium perchlorate tetrahydrate

    Berezkina, L.G.; Borisova, S.I.; Tamm, N.S.; Novoselova, A.V.

    1975-01-01

    Thermal decomposition of Be(ClO 4 ) 2 x4H 2 O was studied by the differential flow technique in the helium stream. The kinetics was followed by an exchange reaction of the perchloric acid appearing by the decomposition with potassium carbonate. The rate of CO 2 liberation in this process was recorded by a heat conductivity detector. The exchange reaction yielding CO 2 is quantitative, it is not the limiting one and it does not distort the kinetics of the process of perchlorate decomposition. The solid products of decomposition were studied by infrared and NMR spectroscopy, roentgenography, thermography and chemical analysis. A mechanism suggested for the decomposition involves intermediate formation of hydroxyperchlorate: Be(ClO 4 ) 2 x4H 2 O → Be(OH)ClO 4 +HClO 4 +3H 2 O; Be(OH)ClO 4 → BeO+HClO 4 . Decomposition is accompained by melting of the sample. The mechanism of decomposition is hydrolytic. At room temperature the hydroxyperchlorate is a thick syrup-like compound crystallizing after long storing

  20. Bowl adamanzanes-bicyclic tetraamines: syntheses and crystal structures of complexes with cobalt(III) and chelating coordinated oxo-anions

    Broge, Louise; Søtofte, Inger; Jensen, Kristian

    2007-01-01

    complex is provided. Four of the seven complexes contain a chelate coordinating oxo-anion ( sulfate, formiate, nitrate, carbonate). Equilibration of these species with the corresponding diaqua complex is generally slow. The rates of equilibration in 5 mol dm(-3) perchloric acid at 25 degrees C have been...

  1. Biotechnological Applications of Microbial (Per)chlorate Reduction.

    Wang, Ouwei; Coates, John D

    2017-11-24

    While the microbial degradation of a chloroxyanion-based herbicide was first observed nearly ninety years ago, only recently have researchers elucidated the underlying mechanisms of perchlorate and chlorate [collectively, (per)chlorate] respiration. Although the obvious application of these metabolisms lies in the bioremediation and attenuation of (per)chlorate in contaminated environments, a diversity of alternative and innovative biotechnological applications has been proposed based on the unique metabolic abilities of dissimilatory (per)chlorate-reducing bacteria (DPRB). This is fueled in part by the unique ability of these organisms to generate molecular oxygen as a transient intermediate of the central pathway of (per)chlorate respiration. This ability, along with other novel aspects of the metabolism, have resulted in a wide and disparate range of potential biotechnological applications being proposed, including enzymatic perchlorate detection; gas gangrene therapy; enhanced xenobiotic bioremediation; oil reservoir bio-souring control; chemostat hygiene control; aeration enhancement in industrial bioreactors; and, biogenic oxygen production for planetary exploration. While previous reviews focus on the fundamental science of microbial (per)chlorate reduction (for example see Youngblut et al., 2016), here, we provide an overview of the emerging biotechnological applications of (per)chlorate respiration and the underlying organisms and enzymes to environmental and biotechnological industries.

  2. Effects of Perchlorate on Organic Molecules under Simulated Mars Conditions

    Carrier, B. L.; Kounaves, S. P.

    2014-12-01

    Perchlorate (ClO4-) was discovered in the northern polar region of Mars by the Mars Phoenix Lander in 2008 and has also been recently detected by the Curiosity Rover in Gale Crater [1,2]. Perchlorate has also been shown to be formed under current Mars conditions via the oxidation of mineral chlorides, further supporting the theory that perchlorate is present globally on Mars [3]. The discovery of perchlorate on Mars has raised important questions about the effects of perchlorate on the survival and detection of organic molecules. Although it has been shown that pyrolysis in the presence of perchlorate results in the alteration or destruction of organic molecules [4], few studies have been conducted on the potential effects of perchlorate on organic molecules under martian surface conditions. Although perchlorate is typically inert under Mars-typical temperatures [5], perchlorate does absorb high energy UV radiation, and has been shown to decompose to form reactive oxychlorine species such as chlorite (ClO2-) when exposed to martian conditions including UV or ionizing radiation [6,7]. Here we investigate the effects of perchlorate on the organic molecules tryptophan, benzoic acid and mellitic acid in order to determine how perchlorate may alter these compounds under Mars conditions. Experiments are performed in a Mars Simulation Chamber (MSC) capable of reproducing the temperature, pressure, atmospheric composition and UV flux found on Mars. Soil simulants are prepared consisting of SiO2 and each organic, as well as varying concentrations of perchlorate salts, and exposed in the MSC. Subsequent to exposure in the MSC samples are leached and the leachate analyzed by HPLC and LC-MS to determine the degree of degradation of the original organic and the identity of any potential decomposition products formed by oxidation or chlorination. References: [1] Kounaves et al., J. Geophys. Res. Planets, Vol. 115, p. E00E10, 2010 [2] Glavin et al., J. Geophys. Res. Planets, Vol

  3. Modeling In Situ Bioremediation of Perchlorate-Contaminated Groundwater

    Secody, Roland E

    2007-01-01

    .... An innovative technology was recently developed which uses dual-screened treatment wells to mix an electron donor into perchlorate-contaminated groundwater in order to effect in situ bioremediation...

  4. Stability and Concentration Verification of Ammonium Perchlorate Dosing Solutions

    Tsui, David

    1998-01-01

    Stability and concentration verification was performed for the ammonium perchlorate dosing solutions used in the on-going 90-Day Oral Toxicity Study conducted by Springborn Laboratories, Inc. (SLI Study No. 3433.1...

  5. Perchlorate Contamination of Drinking Water: Regulatory Issues and Legislative Actions

    Tiemann, Mary

    2007-01-01

    .... It also has been found in milk, fruits, and vegetables. Concern over the potential health risks of perchlorate exposure has increased, and some states and Members of Congress have urged the Environmental Protection Agency (EPA...

  6. Perchlorate Contamination of Drinking Water: Regulatory Issues and Legislative Actions

    Tiemann, Mary

    2008-01-01

    .... It also has been found in milk and many foods. Because of this widespread occurrence, concern over the potential health risks of perchlorate exposure has increased, and some states, water utilities, and Members of Congress have urged...

  7. Assembled cross-species perchlorate dose-response data

    U.S. Environmental Protection Agency — This data set contains dose-response data for perchlorate exposure in multiple species. These data were assembled from peer-reviewed studies. Species included in...

  8. Isotopic tracing of perchlorate in the environment

    Sturchio, Neil C.; Böhlke, John Karl; Gu, Baohua; Hatzinger, Paul B.; Jackson, W. Andrew; Baskaran, Mark

    2012-01-01

    Isotopic measurements can be used for tracing the sources and behavior of environmental contaminants. Perchlorate (ClO 4 − ) has been detected widely in groundwater, soils, fertilizers, plants, milk, and human urine since 1997, when improved analytical methods for analyzing ClO 4 −concentration became available for routine use. Perchlorate ingestion poses a risk to human health because of its interference with thyroidal hormone production. Consequently, methods for isotopic analysis of ClO 4 − have been developed and applied to assist evaluation of the origin and migration of this common contaminant. Isotopic data are now available for stable isotopes of oxygen and chlorine, as well as 36Cl isotopic abundances, in ClO 4 − samples from a variety of natural and synthetic sources. These isotopic data provide a basis for distinguishing sources of ClO 4 − found in the environment, and for understanding the origin of natural ClO 4 − . In addition, the isotope effects of microbial ClO 4 − reduction have been measured in laboratory and field experiments, providing a tool for assessing ClO 4 − attenuation in the environment. Isotopic data have been used successfully in some areas for identifying major sources of ClO 4 − contamination in drinking water supplies. Questions about the origin and global biogeochemical cycle of natural ClO 4 − remain to be addressed; such work would benefit from the development of methods for preparation and isotopic analysis of ClO 4 − in samples with low concentrations and complex matrices.

  9. Novel Electrochemical Process for Treatment of Perchlorate in Waste Water

    2011-03-06

    chemical products, such as leather, rubber, fabrics, paints , and aluminum. As a result, perchlorate contamination is now recognized as a widespread... paints , and aluminum. As a result, perchlorate contamination is now recognized as a widespread concern affecting many water utilities. Thus, removing...I. A.; Lin, Y., Highly efficient and low cost graphene -based nanocomposite for water purification, 2010, In Preparation. 3. Kang, X.; Shao, Y

  10. High Tolerance of Hydrogenothermus marinus to Sodium Perchlorate

    Kristina Beblo-Vranesevic

    2017-07-01

    Full Text Available On Mars, significant amounts (0.4–0.6% of perchlorate ions were detected in dry soil by the Phoenix Wet Chemistry Laboratory and later confirmed with the Mars Science Laboratory. Therefore, the ability of Hydrogenothermus marinus, a desiccation tolerant bacterium, to survive and grow in the presence of perchlorates was determined. Results indicated that H. marinus was able to tolerate concentrations of sodium perchlorate up to 200 mM ( 1.6% during cultivation without any changes in its growth pattern. After the addition of up to 440 mM ( 3.7% sodium perchlorate, H. marinus showed significant changes in cell morphology; from single motile short rods to long cell chains up to 80 cells. Furthermore, it was shown that the known desiccation tolerance of H. marinus is highly influenced by a pre-treatment with different perchlorates; additive effects of desiccation and perchlorate treatments are visible in a reduced survival rate. These data demonstrate that thermophiles, especially H. marinus, have so far, unknown high tolerances against cell damaging treatments and may serve as model organisms for future space experiments.

  11. (Per)chlorate in Biology on Earth and Beyond.

    Youngblut, Matthew D; Wang, Ouwei; Barnum, Tyler P; Coates, John D

    2016-09-08

    Respiration of perchlorate and chlorate [collectively, (per)chlorate] was only recognized in the last 20 years, yet substantial advances have been made in our understanding of the underlying metabolisms. Although it was once considered solely anthropogenic, pervasive natural sources, both terrestrial and extraterrestrial, indicate an ancient (per)chlorate presence across our solar system. These discoveries stimulated interest in (per)chlorate microbiology, and the application of advanced approaches highlights exciting new facets. Forward and reverse genetics revealed new information regarding underlying molecular biology and associated regulatory mechanisms. Structural and functional analysis characterized core enzymes and identified novel reaction sequences. Comparative genomics elucidated evolutionary aspects, and stress analysis identified novel response mechanisms to reactive chlorine species. Finally, systems biology identified unique metabolic versatility and novel mechanisms of (per)chlorate respiration, including symbiosis and a hybrid enzymatic-abiotic metabolism. While many published studies focus on (per)chlorate and their basic metabolism, this review highlights seminal advances made over the last decade and identifies new directions and potential novel applications.

  12. Potentiometric perchlorate determination at nanomolar concentrations in vegetables.

    Leoterio, Dilmo M S; Paim, Ana Paula S; Belian, Mônica F; Galembeck, André; Lavorante, André F; Pinto, Edgar; Amorim, Célia G; Araújo, Alberto N; Montenegro, Maria C B S M

    2017-07-15

    In this work, an expeditious method based on the multi-commutated flow-analysis concept with potentiometric detection is proposed to perform determinations of the emergent contaminant perchlorate in vegetable matrices down to nanomolar concentration. To accomplish the task, a tubular shaped potentiometric sensor selective to perchlorate ion was constructed with a PVC membrane containing 12mmol/kg of the polyamine bisnaphthalimidopropyl-4,4'-diaminodiphenylmethane and 2-nitrophenyl phenyl ether 68% (w/w) as plasticizer casted on a conductive epoxy resin. Under optimal flow conditions, the sensor responded linearly in the concentration range of 6.3×10 -7 -1.0×10 -3 mol/L perchlorate. In order to extend the determinations to lower concentrations (4.6(±1.3)×10 -10 mol/L perchlorate), a column packed with 70mg of sodium 2,5,8,11,14-pentaoxa-1-silacyclotetradecane-polymer was coupled to the flow-system thus enabling prior pre-concentration of the perchlorate. The proposed procedure provides a simpler alternative for the determination of perchlorate in foods, nowadays only allowed by sophisticated and expensive equipment and laborious methods. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Determination of Perchlorate in Bottled Water from Italy

    Patrizia Iannece

    2013-06-01

    Full Text Available Perchlorate is regarded as an emerging persistent inorganic contaminant. It is widely known that perchlorate is an endocrine disruptor as it competitively inhibits iodide transport in the thyroid gland. As drinking water is the major source of human exposure to perchlorate, its occurrence in commercially available bottled waters purchased in different regions of Italy was investigated. Perchlorate was measured using the rapid, sensitive, and selective LC-ESI-MS/MS (liquid chromatography-electrospray tandem mass spectrometry method by multiple reaction monitoring (MRM of the transition 98.8→82.8, which corresponds to the loss of one oxygen atom in the perchlorate ion (ClO4−→ClO3−. The chlorine isotope ratio (35Cl/37Cl was used as a confirmation tool. The limit of quantification (LOQ for this method was 5 ng/L, and the recovery ranged from 94% to 108%. Perchlorate was detected in 44 of the 62 drinking waters tested, with concentrations ranging from <5 to 75 ng/L. These values are similar in magnitude to those reported in drinking water from the USA and do not pose an immediate health concern.

  14. Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism.

    Riddell, Imogen A; Smulders, Maarten M J; Clegg, Jack K; Hristova, Yana R; Breiner, Boris; Thoburn, John D; Nitschke, Jonathan R

    2012-09-01

    Biochemical systems are adaptable, capable of reconstitution at all levels to achieve the functions associated with life. Synthetic chemical systems are more limited in their ability to reorganize to achieve new functions; they can reconfigure to bind an added substrate (template effect) or one binding event may modulate a receptor's affinity for a second substrate (allosteric effect). Here we describe a synthetic chemical system that is capable of structural reconstitution on receipt of one anionic signal (perchlorate) to create a tight binding pocket for another anion (chloride). The complex, barrel-like structure of the chloride receptor is templated by five perchlorate anions. This second-order templation phenomenon allows chemical networks to be envisaged that express more complex responses to chemical signals than is currently feasible.

  15. Perchlorate, iodine supplements, iodized salt and breast milk iodine content

    Kirk, Andrea B. [Department of Epidemiology, School of Public Health, University of North Texas Health Sciences Center, 3500 Camp Bowie Blvd., Fort Worth, TX 76107 (United States); Kroll, Martina; Dyke, Jason V.; Ohira, Shin-Ichi; Dias, Rukshan A.; Dasgupta, Purnendu K. [Department of Chemistry and Biochemistry, 700 Planetarium Place, University of Texas at Arlington, Arlington, TX 76019 (United States)

    2012-03-15

    This study was undertaken to determine if increasing maternal iodine intake through single dose tablets will decrease breast milk concentrations of the iodine-uptake inhibitor, perchlorate, through competitive inhibition. We also sought to determine if the timing of supplementation influences the fraction of iodine excreted in milk versus urine and to compare the effectiveness of iodized salt as a means of providing iodine to breastfed infants. Thirteen women who did not use supplements, seven of whom used iodized salt and six of whom used non-iodized salt, submitted four milk samples and a 24-h urine collection daily for three days. Women repeated the sampling protocol for three more days during which {approx} 150 {mu}g of iodine were taken in the evening and again for three days with morning supplementation. Samples were analyzed using isotope-dilution inductively-coupled plasma-mass spectrometry for iodine and isotope-dilution ion chromatography-tandem mass spectrometry for perchlorate. No statistically significant differences were observed in milk iodine or perchlorate concentrations during the two treatment periods. Estimated perchlorate intake was above the U.S. National Academy of Sciences suggested reference dose for most infants. Single daily dose iodine supplementation was not effective in decreasing milk perchlorate concentrations. Users of iodized salt had significantly higher iodine levels in milk than non-users. Iodized salt may be a more effective means of iodine supplementation than tablets. - Highlights: Black-Right-Pointing-Pointer Estimated infant exposures to perchlorate were, on a {mu}g/kg basis, {approx} 5 Multiplication-Sign higher than those of mothers. Black-Right-Pointing-Pointer Daily supplements are less effective than iodized salt in providing iodine to lactating women. Black-Right-Pointing-Pointer Low iodine and high perchlorate in milk may place infants at risk of iodine deficiency.

  16. Rate and extent of aqueous perchlorate removal by iron surfaces.

    Moore, Angela M; De Leon, Corinne H; Young, Thomas M

    2003-07-15

    The rate and extent of perchlorate reduction on several types of iron metal was studied in batch and column reactors. Mass balances performed on the batch experiments indicate that perchlorate is initially sorbed to the iron surface, followed by a reduction to chloride. Perchlorate removal was proportional to the iron dosage in the batch reactors, with up to 66% removal in 336 h in the highest dosage system (1.25 g mL(-1)). Surface-normalized reaction rates among three commercial sources of iron filings were similar for acid-washed samples. The most significant perchlorate removal occurred in solutions with slightly acidic or near-neutral initial pH values. Surface mediation of the reaction is supported by the absence of reduction in batch experiments with soluble Fe2+ and also by the similarity in specific reaction rate constants (kSA) determined for three different iron types. Elevated soluble chloride concentrations significantly inhibited perchlorate reduction, and lower removal rates were observed for iron samples with higher amounts of background chloride contamination. Perchlorate reduction was not observed on electrolytic sources of iron or on a mixed-phase oxide (Fe3O4), suggesting that the reactive iron phase is neither pure zerovalent iron nor the mixed oxide alone. A mixed valence iron hydr(oxide) coating or a sorbed Fe2+ surface complex represent the most likely sites for the reaction. The observed reaction rates are too slow for immediate use in remediation system design, but the findings may provide a basis for future development of cost-effective abiotic perchlorate removal techniques.

  17. PHYTOREMEDIATION OF PERCHLORATE AND N-NITROSODIMETHYLAMINE AS SINGLE AND CO-CONTAMINANTS

    Although potential plant species suitable for phytoremediation of perchlorate and the phytoprocesses involved (rhizodegradation and phytodegradation) have been identified in previous research, regulators and some critics argue that plants recycle the perchlorate fract...

  18. The thermal decomposition behavior of ammonium perchlorate and of an ammonium-perchlorate-based composite propellant

    Behrens, R.; Minier, L.

    1998-03-24

    The thermal decomposition of ammonium perchlorate (AP) and ammonium-perchlorate-based composite propellants is studied using the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique. The main objective of the present work is to evaluate whether the STMBMS can provide new data on these materials that will have sufficient detail on the reaction mechanisms and associated reaction kinetics to permit creation of a detailed model of the thermal decomposition process. Such a model is a necessary ingredient to engineering models of ignition and slow-cookoff for these AP-based composite propellants. Results show that the decomposition of pure AP is controlled by two processes. One occurs at lower temperatures (240 to 270 C), produces mainly H{sub 2}O, O{sub 2}, Cl{sub 2}, N{sub 2}O and HCl, and is shown to occur in the solid phase within the AP particles. 200{micro} diameter AP particles undergo 25% decomposition in the solid phase, whereas 20{micro} diameter AP particles undergo only 13% decomposition. The second process is dissociative sublimation of AP to NH{sub 3} + HClO{sub 4} followed by the decomposition of, and reaction between, these two products in the gas phase. The dissociative sublimation process occurs over the entire temperature range of AP decomposition, but only becomes dominant at temperatures above those for the solid-phase decomposition. AP-based composite propellants are used extensively in both small tactical rocket motors and large strategic rocket systems.

  19. The Effects of Ammonium Perchlorate on Reproduction and Development of Amphibians

    2008-01-01

    Mitigating Ammonium Perchlorate (AP) Exposure........................................................................18 Table 5-1. Funding History and...amphibian species were reared on perchlorate-laden food (e.g., hydroponically grown lettuce ) and their growth and development monitored. Thyroid...of Perchlorate Derived from Food Sources on Amphibian Development 8 Table 3.1 (Continued) 3.1 Initiate Lettuce Growth 3.2 Tests with Native

  20. Photooxidation of chloride by oxide minerals: implications for perchlorate on Mars.

    Schuttlefield, Jennifer D; Sambur, Justin B; Gelwicks, Melissa; Eggleston, Carrick M; Parkinson, B A

    2011-11-09

    We show that highly oxidizing valence band holes, produced by ultraviolet (UV) illumination of naturally occurring semiconducting minerals, are capable of oxidizing chloride ion to perchlorate in aqueous solutions at higher rates than other known natural perchlorate production processes. Our results support an alternative to atmospheric reactions leading to the formation of high concentrations of perchlorate on Mars.

  1. Perchlorates on Mars enhance the bacteriocidal effects of UV light.

    Wadsworth, Jennifer; Cockell, Charles S

    2017-07-06

    Perchlorates have been identified on the surface of Mars. This has prompted speculation of what their influence would be on habitability. We show that when irradiated with a simulated Martian UV flux, perchlorates become bacteriocidal. At concentrations associated with Martian surface regolith, vegetative cells of Bacillus subtilis in Martian analogue environments lost viability within minutes. Two other components of the Martian surface, iron oxides and hydrogen peroxide, act in synergy with irradiated perchlorates to cause a 10.8-fold increase in cell death when compared to cells exposed to UV radiation after 60 seconds of exposure. These data show that the combined effects of at least three components of the Martian surface, activated by surface photochemistry, render the present-day surface more uninhabitable than previously thought, and demonstrate the low probability of survival of biological contaminants released from robotic and human exploration missions.

  2. Synthesis and crystal structure of a new 2,6-dimethyl piperazine-1,4-diium perchlorate monohydrate: [C{sub 6}H{sub 16}N{sub 2}](ClO{sub 4}){sub 2} · H{sub 2}O

    Mleh, C. Ben [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte (Tunisia); Roisnel, T. [Université de Rennes I, Centre de Diffractométrie X, UMR 6226 CNRS, Unité Sciences Chimiques de Rennes (France); Marouani, H., E-mail: houda.marouani@fsb.rnu.tn [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte (Tunisia)

    2017-03-15

    A proton transfer compound 2,6-dimethyl piperazine-1,4-diium perchlorate monohydrate was synthesized by slow evaporation at room temperature using 2,6-dimethyl piperazine as template. The asymmetric unit contains one organic dication, two crystal graphically independent perchlorate anions and one water molecule. Each organic entities is engaged in a large number of bifurcated and non-bifurcated N–H···O (O) and C–H···O hydrogen bonds with different species and enhanced the three dimensional supramolecular network. In addition, the diprotonated piperazine ring adopts a chair conformation with the methyl groups occupying equatorial positions.

  3. Freezing-Enhanced Dissolution of Iron Oxides: Effects of Inorganic Acid Anions.

    Jeong, Daun; Kim, Kitae; Min, Dae Wi; Choi, Wonyong

    2015-11-03

    Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.

  4. Competitive microbial reduction of perchlorate and nitrate with a cathode directly serving as the electron donor

    Xie, Daohai; Yu, Hui; Li, Chenchen; Ren, Yuan; Wei, Chaohai; Feng, Chunhua

    2014-01-01

    Microbial reduction of perchlorate with an electrode as the electron donor represents an emerging technology for remediation of perchlorate contamination; it is important to know how perchlorate reduction behaves when nitrate, a co-contaminant of perchlorate is present. We reported that electrons derived from the electrode can be directly transferred to the bacteria with perchlorate or nitrate as the sole electron acceptor. The presence of nitrate, even at the 0.07 mM level, can slow reduction of perchlorate (0.70 mM) as a poised potential of -0.50 V (vs. SCE) was applied to the inoculated cathode. Increasing the concentration of nitrate resulted in a noticeable inhibitory effect on perchlorate reduction. When the nitrate concentration was 2.10 mM, reduction of 0.70 mM perchlorate was totally inhibited. Bacterial community analyses based on 16S rDNA gene analysis with denaturing gradient gel electrophoresis (DGGE) revealed that most of the bacteria newly enriched on the nitrate and/or perchlorate biocathodes were the known electrochemically active denitrifiers, which possibly prefer to reduce nitrate over perchlorate. These results show that nitrate is a more favorable electron acceptor than perchlorate in the bioelectrochemical system where the cathode directly serves as the electron donor

  5. Validation of Chlorine and Oxygen Isotope Ratio Analysis To Differentiate Perchlorate Sources and To Document Perchlorate Biodegradation

    2013-05-31

    kilogram km2 square kilometer KNO3 potassium nitrate KOH potassium hydroxide L liter LC-MS/MS liquid chromatography-tandem mass...perchlorate (CsClO4) by addition of CsCl or CsOH, or as potassium perchlorate (KClO4) by addition of KOH or KCl. Most of the samples prepared for this...destructive Raman spectroscopy or (2) dissolution and analysis by ion chromatography (IC) using USEPA Method 300.0 (USEPA, 1993) or equivalent

  6. Removal of toxic ions (chromate, arsenate, and perchlorate) using reverse osmosis, nanofiltration, and ultrafiltration membranes

    Yoon, Jaekyung

    2009-09-01

    Rejection characteristics of chromate, arsenate, and perchlorate were examined for one reverse osmosis (RO, LFC-1), two nanofiltration (NF, ESNA, and MX07), and one ultrafiltration (UF and GM) membranes that are commercially available. A bench-scale cross-flow flat-sheet filtration system was employed to determine the toxic ion rejection and the membrane flux. Both model and natural waters were used to prepare chromate, arsenate, and perchlorate solutions (approximately 100 μg L-1 for each anion) in mixtures in the presence of other salts (KCl, K2SO4, and CaCl2); and at varying pH conditions (4, 6, 8, and 10) and solution conductivities (30, 60, and 115 mS m-1). The rejection of target ions by the membranes increases with increasing solution pH due to the increasingly negative membrane charge with synthetic model waters. Cr(VI), As(V), and ClO4 - rejection follows the order LFC-1 (>90%) > MX07 (25-95%) ≅ ESNA (30-90%) > GM (3-47%) at all pH conditions. In contrast, the rejection of target ions by the membranes decreases with increasing solution conductivity due to the decreasingly negative membrane charge. Cr(VI), As(V), and ClO4 - rejection follows the order CaCl2 < KCl ≅ K2SO4 at constant pH and conductivity conditions for the NF and UF membranes tested. For natural waters the LFC-1 RO membrane with a small pore size (0.34 nm) had a significantly greater rejection for those target anions (>90%) excluding NO3 - (71-74%) than the ESNA NF membrane (11-56%) with a relatively large pore size (0.44 nm), indicating that size exclusion is at least partially responsible for the rejection. The ratio of solute radius (ri,s) to effective membrane pore radius (rp) was employed to compare ion rejection. For all of the ions, the rejection is higher than 70% when the ri,s/rp ratio is greater than 0.4 for the LFC-1 membrane, while for di-valent ions (CrO4 2 -, SO4 2 -, and HAsSO4 2 -) the rejection (38-56%) is fairly proportional to the ri,s/rp ratio (0.32-0.62) for the ESNA

  7. An upper-bound assessment of the benefits of reducing perchlorate in drinking water.

    Lutter, Randall

    2014-10-01

    The Environmental Protection Agency plans to issue new federal regulations to limit drinking water concentrations of perchlorate, which occurs naturally and results from the combustion of rocket fuel. This article presents an upper-bound estimate of the potential benefits of alternative maximum contaminant levels for perchlorate in drinking water. The results suggest that the economic benefits of reducing perchlorate concentrations in drinking water are likely to be low, i.e., under $2.9 million per year nationally, for several reasons. First, the prevalence of detectable perchlorate in public drinking water systems is low. Second, the population especially sensitive to effects of perchlorate, pregnant women who are moderately iodide deficient, represents a minority of all pregnant women. Third, and perhaps most importantly, reducing exposure to perchlorate in drinking water is a relatively ineffective way of increasing iodide uptake, a crucial step linking perchlorate to health effects of concern. © 2014 Society for Risk Analysis.

  8. Bio-reduction of free and laden perchlorate by the pure and mixed perchlorate reducing bacteria: Considering the pH and coexisting nitrate.

    Shang, Yanan; Wang, Ziyang; Xu, Xing; Gao, Baoyu; Ren, Zhongfei

    2018-08-01

    Pure bacteria cell (Azospira sp. KJ) and mixed perchlorate reducing bacteria (MPRB) were employed for decomposing the free perchlorate in water as well as the laden perchlorate on surface of quaternary ammonium wheat residuals (QAWR). Results indicated that perchlorate was decomposed by the Azospira sp. KJ prior to nitrate while MPRB was just the reverse. Bio-reduction of laden perchlorate by Azospira sp. KJ was optimal at pH 8.0. In contrast, bio-reduction of laden perchlorate by MPRB was optimal at pH 7.0. Generally, the rate of perchlorate reduction was controlled by the enzyme activity of PRB. In addition, perchlorate recovery (26.0 mg/g) onto bio-regenerated QAWR by MPRB was observed with a small decrease as compared with that (31.1 mg/g) by Azospira sp. KJ at first 48 h. Basically, this study is expected to offer some different ideas on bio-regeneration of perchlorate-saturated adsorbents using biological process, which may provide the economically alternative to conventional methods. Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. 2-[5-(Pyridin-2-yl-1,3,4-thiadiazol-2-yl]pyridin-1-ium perchlorate

    Abdelhakim Laachir

    2017-03-01

    Full Text Available The cation of the title molecular salt, C12H9N4S+·ClO4−, is approximately planar, with the pyridine and pyridinium rings being inclined to the central thiadiazole ring by 6.51 (9 and 9.13 (9°, respectively. The dihedral angle between the pyridine and pyridinium rings is 12.91 (10°. In the crystal, the cations are linked by N—H...O and C—H...O hydrogen bonds, involving the perchlorate anion, forming chains propagating along the [100] direction. The chains are linked by weak offset π–π interactions [inter-centroid distance = 3.586 (1 Å], forming layers parallel to the ab plane.

  10. Treatment of amiodarone-induced hypothyroidism with potassium perchlorate

    van Dam, E. W.; Prummel, M. F.; Wiersinga, W. M.; Nikkels, R. E.

    1993-01-01

    The antiarrhythmic drug, amiodarone, induces thyroid dysfunction, which is potentially dangerous in cardiac patients. After discontinuation of the drug it takes several months before euthyroidism is restored. The potent antithyroid drug, potassium perchlorate (KClO4), is used successfully to treat

  11. RAMAN SPECTROSCOPIC ANALYSIS OF FERTILIZERS AND PLANT TISSUE FOR PERCHLORATE

    Raman spectroscopy, without the need for prior chromatographic separation, was used for qualitative and quantitative analysis of 59 samples of fertilizers for perchlorate (ClO4-). These primarily lawn and garden products had no known link to Chile saltpeter, which is known to con...

  12. PREDICTING FIELD PERFORMANCE OF HERBACEOUS SPECIES FOR PHYTOREMEDIATION OF PERCHLORATE

    Results of these short-term experiments coupled with ecological knowledge of the nine herbaceous plant species tested suggest that several species may by successful in on-site remediation of perchlorate. The two wetland species which appear to be most suitable for field experimen...

  13. Branched polymeric media: Perchlorate-selective resins from hyperbranched polyethyleneimine

    Chen, Dennis P.; Yu, Changjun; Chang, ChingYu; Wan, Yanjian; Frechet, Jean; Goddard, William A.; Diallo, Mamadou S.

    2012-01-01

    prohibitive when treating groundwater with higher concentration of ClO4 - (e.g., 100-1000 ppb). In this article, we describe a new perchlorate-selective resin with high exchange capacity. This new resin was prepared by alkylation of branched polyethyleneimine

  14. Nitrate and Perchlorate removal from groundwater by ion exchange; TOPICAL

    Burge, S; Halden, R

    1999-01-01

    This study was conducted to evaluate the performance of a small scale ion exchange unit (Krudico, Inc of Auborn, IA) for removal of nitrate and perchlorate from groundwater at Lawrence Livermore National Laboratory's Site 300. The unit was able to treat 3,600 gallons of Site 300 groundwater, at an average influent concentration of 100 mg/L NO(sub 3)(sup -) before breakthrough occurred. The unit contained 2.5 ft(sup 3) of Sybron SR-7 resin. Seventy gallons of regeneration waste were generated (water treated to waste ratio of 51:1). The effluent concentration was about 20 mg/L NO(sub 3)(sup -), which is equivalent to a treatment efficiency of at least 80%. There are several options for implementing this technology at Site 300. A target well, in the 817 area, has been selected. It has a 3 to 4 gpm flow rate, and concentrations of 90 mg/L NO(sub 3)(sup -) and 40(micro)g/L perchlorate. The different treatment options include ion exchange treatment of nitrate only, nitrate and perchlorate, or perchlorate only. Option 1: For the treatment of nitrate only, this unit will be able to treat 3,700 gallons of water before regeneration is required. If both columns of the ion exchange unit are used, 7,400 gallons could be treated before the columns will need to be regenerated (producing 140 gallons of waste, per cycle or every 1.5 days). The effluent nitrate concentration is expected to be about 17 mg/L. Annual operation and maintenance costs are estimated to be$0.14 per gallon of water treated. Option 2: If only perchlorate is to be removed with ion exchange at the 817 area, a smaller unit should be considered. A 55 gallon canister filled with ion exchange resin should be able to reduce perchlorate concentrations in the groundwater from 40(micro)g/L to non-detect levels for three years before the resin would need to be replaced. The contaminant-laden resin would be disposed of as hazardous waste. It is not practical to regenerate the resin because of the extreme difficulty of

  15. Sample processing method for the determination of perchlorate in milk

    Dyke, Jason V.; Kirk, Andrea B.; Kalyani Martinelango, P.; Dasgupta, Purnendu K.

    2006-01-01

    In recent years, many different water sources and foods have been reported to contain perchlorate. Studies indicate that significant levels of perchlorate are present in both human and dairy milk. The determination of perchlorate in milk is particularly important due to its potential health impact on infants and children. As for many other biological samples, sample preparation is more time consuming than the analysis itself. The concurrent presence of large amounts of fats, proteins, carbohydrates, etc., demands some initial cleanup; otherwise the separation column lifetime and the limit of detection are both greatly compromised. Reported milk processing methods require the addition of chemicals such as ethanol, acetic acid or acetonitrile. Reagent addition is undesirable in trace analysis. We report here an essentially reagent-free sample preparation method for the determination of perchlorate in milk. Milk samples are spiked with isotopically labeled perchlorate and centrifuged to remove lipids. The resulting liquid is placed in a disposable centrifugal ultrafilter device with a molecular weight cutoff of 10 kDa, and centrifuged. Approximately 5-10 ml of clear liquid, ready for analysis, is obtained from a 20 ml milk sample. Both bovine and human milk samples have been successfully processed and analyzed by ion chromatography-mass spectrometry (IC-MS). Standard addition experiments show good recoveries. The repeatability of the analytical result for the same sample in multiple sample cleanup runs ranged from 3 to 6% R.S.D. This processing technique has also been successfully applied for the determination of iodide and thiocyanate in milk

  16. Branched polymeric media: Perchlorate-selective resins from hyperbranched polyethyleneimine

    Chen, Dennis P.

    2012-10-02

    Perchlorate (ClO4 -) is a persistent contaminant found in drinking groundwater sources in the United States. Ion exchange (IX) with selective and disposable resins based on cross-linked styrene divinylbenzene (STY-DVB) beads is currently the most commonly utilized process for removing low concentrations of ClO4 - (10-100 ppb) from contaminated drinking water sources. However, due to the low exchange capacity of perchlorate-selective STY-DVB resins (∼0.5-0.8 eq/L), the overall cost becomes prohibitive when treating groundwater with higher concentration of ClO4 - (e.g., 100-1000 ppb). In this article, we describe a new perchlorate-selective resin with high exchange capacity. This new resin was prepared by alkylation of branched polyethyleneimine (PEI) beads obtained from an inverse suspension polymerization process. Batch and column studies show that our new PEI resin with mixed hexyl/ethyl quaternary ammonium chloride exchange sites can selectively extract trace amounts of ClO4 - from a makeup groundwater (to below detection limit) in the presence of competing ions. In addition, this resin has a strong-base exchange capacity of 1.4 eq/L, which is 1.75-2.33 times larger than those of commercial perchlorate-selective STY-DVB resins. The overall results of our studies suggest that branched PEI beads provide versatile and promising building blocks for the preparation of perchlorate-selective resins with high exchange capacity. © 2012 American Chemical Society.

  17. Analysis of perchlorate in foods and beverages by ion chromatography coupled with tandem mass spectrometry (IC-ESI-MS/MS)

    El Aribi, Houssain [Applied Biosystems/MDS Sciex, 71 Four Valley Drive, Concord, Ont., L4K 4V8 (Canada)]. E-mail: houssain.aribi@sciex.com; Le Blanc, Yves J.C. [Applied Biosystems/MDS Sciex, 71 Four Valley Drive, Concord, Ont., L4K 4V8 (Canada); Antonsen, Stephen [Dionex Canada Ltd., 1540 Cornwall Road, Oakville, Ont., L6J 7W5 (Canada); Sakuma, Takeo [Applied Biosystems/MDS Sciex, 71 Four Valley Drive, Concord, Ont., L4K 4V8 (Canada)

    2006-05-10

    A new IC-ESI-MS/MS method, with simple sample preparation procedure, has been developed for quantification and confirmation of perchlorate (ClO{sub 4} {sup -}) anions in water, fresh and canned food, wine and beer samples at low part-per-trillion (ng l{sup -1}) levels. To the best of our knowledge, this is the first time an analytical method is used for determination of perchlorate in wine and beer samples. The IC-ESI-MS/MS instrumentation consisted of an ICS-2500 ion chromatography (IC) system coupled to either an API 2000{sup TM} or an API 3200{sup TM} mass spectrometer. The IC-ESI-MS/MS system was optimized to monitor two pairs of precursor and fragment ion transitions, i.e., multiple reaction monitoring (MRM). All samples had oxygen-18 isotope labeled perchlorate internal standard (ISTD) added prior to extraction. Chlorine isotope ratio ({sup 35}Cl/{sup 37}Cl) was used as a confirmation tool. The transition of {sup 35}Cl{sup 16}O{sub 4} {sup -} (m/z 98.9) into {sup 35}Cl{sup 16}O{sub 3} {sup -} (m/z 82.9) was monitored for quantifying the main analyte; the transition of {sup 37}Cl{sup 16}O{sub 4} {sup -} (m/z 100.9) into {sup 37}Cl{sup 16}O{sub 3} {sup -} (m/z 84.9) was monitored for examining a proper isotopic abundance ratio of {sup 35}Cl/{sup 37}Cl; and the transition of {sup 35}Cl{sup 18}O{sub 4} {sup -} (m/z 107.0) into {sup 35}Cl{sup 18}O{sub 3} {sup -} (m/z 89.0) was monitored for quantifying the internal standard. The minimum detection limit (MDL) for this method in de-ionized water is 5 ng l{sup -1} (ppt) using the API 2000{sup TM} mass spectrometer and 0.5 ng l{sup -1} using the API 3200{sup TM} mass spectrometer. Over 350 food and beverage samples were analyzed mostly in triplicate. Except for four, all samples were found to contain measurable amounts of perchlorate. The levels found ranged from 5 ng l{sup -1} to 463.5 {+-} 6.36 {mu}g kg{sup -1} using MRM 98.9 {sup {yields}} 82.9 and 100 {mu}l injection.

  18. Perchlorate exposure in lactating women in an urban community in New Jersey

    Borjan, Marija [Department of Environmental and Occupational Health, UMDNJ-School of Public Health, Piscataway, NJ (United States); Marcella, Stephen [Department of Epidemiology, UMDNJ-School of Public Health, Piscataway, NJ (United States); Blount, Benjamin [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States); Greenberg, Michael [Bloustien School of Planning and Public Policy, Rutgers, State University of New Jersey, New Brunswick, NJ (United States); Zhang Junfeng [Department of Environmental and Occupational Health, UMDNJ-School of Public Health, Piscataway, NJ (United States); Murphy, Eileen [New Jersey Department of Environmental Protection, Division of Science and Research, Trenton, NJ (United States); Valentin-Blasini, Liza [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA (United States); Robson, Mark, E-mail: robson@aesop.rutgers.edu [Department of Environmental and Occupational Health, UMDNJ-School of Public Health, Piscataway, NJ (United States); School of Environmental and Biological Sciences, Rutgers, State University of New Jersey, New Brunswick, NJ (United States)

    2011-01-01

    Perchlorate is most widely known as a solid oxidant for missile and rocket propulsion systems although it is also present as a trace contaminant in some fertilizers. It has been detected in drinking water, fruits, and vegetables throughout New Jersey and most of the United States. At sufficiently high doses, perchlorate interferes with the uptake of iodine into the thyroid and may interfere with the development of the skeletal system and the central nervous system of infants. Therefore, it is important to quantify perchlorate in breast milk to understand potential perchlorate exposure in infants. In this study we measured perchlorate in breast milk, urine, and drinking water collected from 106 lactating mothers from Central New Jersey. Each subject was asked to provide three sets of samples over a 3-month period. The average {+-} SD perchlorate level in drinking water, breast milk, and urine was 0.168 {+-} 0.132 ng/mL (n = 253), 6.80 {+-} 8.76 ng/mL (n = 276), and 3.19 {+-} 3.64 ng/mL (3.51 {+-} 6.79 {mu}g/g creatinine) (n = 273), respectively. Urinary perchlorate levels were lower than reference range values for women of reproductive age (5.16 {+-} 11.33 {mu}g/g creatinine, p = 0.03), likely because of perchlorate secretion in breast milk. Drinking water perchlorate levels were {<=} 1.05 ng/mL and were not positively correlated with either breast milk or urine perchlorate levels. These findings together suggest that drinking water was not the most important perchlorate exposure source for these women. Creatinine-adjusted urine perchlorate levels were strongly correlated with breast milk perchlorate levels (r = 0.626, p = < 0.0005). Breast milk perchlorate levels in this study are consistent with widespread perchlorate exposure in lactating women and thus infants. This suggests that breast milk may be a source of exposure to perchlorate in infants. - Research Highlights: {yields} The general population, including infants, is exposed to perchlorate. {yields} Breast

  19. Perchlorate exposure in lactating women in an urban community in New Jersey

    Borjan, Marija; Marcella, Stephen; Blount, Benjamin; Greenberg, Michael; Zhang Junfeng; Murphy, Eileen; Valentin-Blasini, Liza; Robson, Mark

    2011-01-01

    Perchlorate is most widely known as a solid oxidant for missile and rocket propulsion systems although it is also present as a trace contaminant in some fertilizers. It has been detected in drinking water, fruits, and vegetables throughout New Jersey and most of the United States. At sufficiently high doses, perchlorate interferes with the uptake of iodine into the thyroid and may interfere with the development of the skeletal system and the central nervous system of infants. Therefore, it is important to quantify perchlorate in breast milk to understand potential perchlorate exposure in infants. In this study we measured perchlorate in breast milk, urine, and drinking water collected from 106 lactating mothers from Central New Jersey. Each subject was asked to provide three sets of samples over a 3-month period. The average ± SD perchlorate level in drinking water, breast milk, and urine was 0.168 ± 0.132 ng/mL (n = 253), 6.80 ± 8.76 ng/mL (n = 276), and 3.19 ± 3.64 ng/mL (3.51 ± 6.79 μg/g creatinine) (n = 273), respectively. Urinary perchlorate levels were lower than reference range values for women of reproductive age (5.16 ± 11.33 μg/g creatinine, p = 0.03), likely because of perchlorate secretion in breast milk. Drinking water perchlorate levels were ≤ 1.05 ng/mL and were not positively correlated with either breast milk or urine perchlorate levels. These findings together suggest that drinking water was not the most important perchlorate exposure source for these women. Creatinine-adjusted urine perchlorate levels were strongly correlated with breast milk perchlorate levels (r = 0.626, p = < 0.0005). Breast milk perchlorate levels in this study are consistent with widespread perchlorate exposure in lactating women and thus infants. This suggests that breast milk may be a source of exposure to perchlorate in infants. - Research Highlights: → The general population, including infants, is exposed to perchlorate. → Breast milk is a significant

  20. Spatial Variability of Perchlorate along a Traverse Route from Zhongshan Station to Dome A, East Antarctica

    Jiang, S.; Cole-Dai, J.; Li, Y.; An, C.

    2016-12-01

    Snow deposition and accumulation on the Antarctic ice sheet preserve records of climatic change, as well as those of chemical characteristics of the environment. Chemical composition of snow and ice cores can be used to track the sources of important substances including pollutants and to investigate relationships between atmospheric chemistry and climatic conditions. Recent development in analytical methodology has enabled the determination of ultra-trace levels of perchlorate in polar snow. We have measured perchlorate concentrations in surface snow samples collected along a traverse route from Zhongshan Station to Dome A in East Antarctica to determine the level of atmospheric perchlorate in East Antarctica and to assess the spatial variability of perchlorate along the traverse route. Results show that the perchlorate concentrations vary between 32 and 200 ng kg-1, with an average of 104.3 ng kg-1. And perchlorate concentration profile presents regional variation patterns along the traverse route. In the coastal region, perchlorate concentration displays an apparent decreasing relationship with increasing distance inland; it exhibits no apparent trend in the intermediate region from 200 to 1000 km. The inland region from 1000 to 1244 km presents a generally increasing trend of perchlorate concentration approaching the dome. Different rates of atmospheric production, dilution by snow accumulation and re-deposition of snow-emitted perchlorate (post-depositional change) are the three possible factors influencing the spatial variability of perchlorate over Antarctica.

  1. Relative source contributions for perchlorate exposures in a lactating human cohort

    Kirk, Andrea B. [University of North Texas Health Sciences Center (United States); Dyke, Jason V. [University of Texas at Arlington (United States); Ohira, Shin-Ichi [Kumamoto University (Japan); Dasgupta, Purnendu K., E-mail: Dasgupta@uta.edu [University of Texas at Arlington (United States)

    2013-01-15

    Perchlorate is an iodine-uptake inhibitor and common contaminant of food and drinking water. Understanding the amount of perchlorate exposure occurring through non-water sources is essential for accurate estimates of human exposure levels, and establishment of drinking water limits for this pervasive contaminant. The study objective was to determine the amount of perchlorate intake derived from diet rather than water. Subjects provided drinking water samples, detailed fluid-intake records, 24 h urine collections and four milk samples for nine days. Samples were analyzed for perchlorate by isotope dilution ion chromatography–tandem mass spectrometry. Amounts of perchlorate derived from drinking water and dietary sources were calculated for each individual. Water of local origin was found to contribute a minor fraction of perchlorate intake. Estimated fraction intake from drinking water ranged from 0 to 36%. The mean and median dose of perchlorate derived from non-water sources by lactating women was 0.18 μg/kg/day (range: 0.06 to 0.36 μg/kg/day.) Lactating women consumed more fluid (mean 2.424 L/day) than has been assumed in recent risk assessments for perchlorate. The data reported here indicate that lactating women may be exposed to perchlorate through dietary sources at markedly higher levels than estimated previously. Exposures to perchlorate from non-water sources may be higher than recent estimates, including those used to develop drinking water standards. - Highlights: ► Residence in an area with perchlorate-contaminated water may be a poor predictor of exposure. ► Exposures to perchlorate from food are likely underestimated. ► The relative contributions for human perchlorate exposures should be weighted more heavily towards non-water sources.

  2. Synthesis and characterization of an energetic compound Cu(Mtta)2(NO3)2 and effect on thermal decomposition of ammonium perchlorate

    Yang, Qi; Chen, Sanping; Xie, Gang; Gao, Shengli

    2011-01-01

    Highlights: ► A new energetic compound Cu(Mtta) 2 (NO 3 ) 2 has been synthesized and structural characterized. ► Sensitivity tests reveal that the compound is insensitive to mechanical stimuli. ► Cu(Mtta) 2 (NO 3 ) 2 accelerates the decomposition of Ammonium perchlorate (AP), which is the key component of composite solid propellant. - Abstract: An energetic coordination compound Cu(Mtta) 2 (NO 3 ) 2 has been synthesized by using 1-methyltetrazole (Mtta) as ligand and its structure has been characterized by X-ray single crystal diffraction. The central copper (II) cation was coordinated by four O atoms from two Mtta ligands and two N atoms from two NO 3 − anions to form a six-coordinated and distorted octahedral structure. 2D superamolecular layer structure was formed by the extensive intermolecular hydrogen bonds between Mtta ligands and NO 3 − anions. Thermal decomposition process of the compound was predicted based on DSC and TG-DTG analyses results. The kinetic parameters of the first exothermic process of the compound were studied by the Kissinger's and Ozawa–Doyle's methods. Sensitivity tests revealed that the compound was insensitive to mechanical stimuli. In addition, compound was explored as additive to promote the thermal decomposition of ammonium perchlorate (AP) by differential scanning calorimetry.

  3. Crystal structure of μ-oxalodi-hydroxamato-bis-[(2,2'-bipyrid-yl)(di-methyl sulfoxide-κO)copper(II)] bis-(perchlorate).

    Odarich, Irina A; Pavlishchuk, Anna V; Kalibabchuk, Valentina A; Haukka, Matti

    2016-02-01

    The centrosymmetric binuclear complex, [Cu2(C2H2N2O4)(C10H8N2)2(C2H6OS)2](ClO4)2, contains two copper(II) ions, connected through an N-deprotonated oxalodi-hydroxamic acid dianion, two terminal 2,2'-bi-pyridine ligands, and two apically coordinating dimethylsulfoxide mol-ecules. Two non-coordinating perchlorate anions assure electrical neutrality. The copper(II) ions in the complex dication [Cu2(C10H8N2)2(μ-C2H2N2O4)(C2H6SO)2](2+) are in an O2N3 square-pyramidal donor environment, the Cu-Cu separation being 5.2949 (4) Å. Two hydroxamate groups in the deprotonated oxalodi-hydroxamic acid are located trans to one each other. In the crystal, O-H⋯O and C-H⋯O hydrogen bonds link the complex cations to the perchlorate anions. Further C-H⋯O hydrogen bonds combine with π-π contacts with a centroid-to-centroid separation of 3.6371 (12) Å to stack the mol-ecules along the a-axis direction.

  4. Crystal structure of μ-oxalodihydroxamato-bis[(2,2′-bipyridyl(dimethyl sulfoxide-κOcopper(II] bis(perchlorate

    Irina A. Odarich

    2016-02-01

    Full Text Available The centrosymmetric binuclear complex, [Cu2(C2H2N2O4(C10H8N22(C2H6OS2](ClO42, contains two copper(II ions, connected through an N-deprotonated oxalodihydroxamic acid dianion, two terminal 2,2′-bipyridine ligands, and two apically coordinating dimethylsulfoxide molecules. Two non-coordinating perchlorate anions assure electrical neutrality. The copper(II ions in the complex dication [Cu2(C10H8N22(μ-C2H2N2O4(C2H6SO2]2+ are in an O2N3 square-pyramidal donor environment, the Cu–Cu separation being 5.2949 (4 Å. Two hydroxamate groups in the deprotonated oxalodihydroxamic acid are located trans to one each other. In the crystal, O—H...O and C—H...O hydrogen bonds link the complex cations to the perchlorate anions. Further C—H...O hydrogen bonds combine with π–π contacts with a centroid-to-centroid separation of 3.6371 (12 Å to stack the molecules along the a-axis direction.

  5. Modelling of niobium sorption on clay minerals in sodium and calcium perchlorate solutions

    Ervanne, Heini; Hakanen, Martti; Lehto, Jukka [Helsinki Univ. (Finland). Laboratory of Radiochemistry

    2014-11-01

    The sorption behaviour of niobium on kaolinite and illite minerals in sodium and calcium perchlorate solutions was evaluated with use of the mass distribution coefficient, Rd, obtained in batch sorption experiments. Very high distribution coefficient values, about 100 m{sup 3}/kg, were obtained for both minerals in the neutral pH range between 6 and 8. Values were somewhat lower at pH 5. In NaClO{sub 4} solution, the sorption of niobium starts to decrease at pH higher than 8. This is in agreement with the increase, with pH, in the proportion of anionic niobate species, which are presumed to be low or non-sorbing. A similar decrease was not observed in Ca(ClO{sub 4}){sub 2} solution, probably owing to the influence of Ca on niobium solution speciation and surface species. The surface complexation model was applied to model the Rd values. The model fitted well for the NaClO{sub 4} solution but only at pH below 9 for the Ca(ClO{sub 4}){sub 2} solution. The discrepancy between the strong sorption of niobium in calcium-bearing solution at high pH and the calculated speciation is due in part to the non-inclusion of calcium niobate solution species and Ca-Nb compounds in the present NEA and other similar thermodynamic databases.

  6. Anion-Dependent Exocyclic Mercury(II) Coordination Polymers of Bis-dithiamacrocycle

    Siewe, Arlette Deukam; Kim, Seul Gi; Choi, Kyu Seong [Kyungnam University, Changwon (Korea, Republic of); Lee, Shim Sung [Gyeongsang National University, Jinju (Korea, Republic of)

    2014-09-15

    Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}-Synthesis and structural characterization of mercury(II) halides and perchlorate complexes of bis-OS{sub 2}- macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies outside the cavity is six-coordinate with a distorted octahedral geometry, being bound to four adjacent ligands via monodentate Hg-S bonds and two remaining sites are occupied by two terminal chlorido ligands to form a fishnet-like 2D structure. When reacting with mercury(II) iodide, L afforded a 1D coordination polymer [Hg{sub 2}(L)I{sub 4}]·CHCl{sub 3}n in which each exocyclic Hg atom is four-coordinate, being bound to two sulfur donors from different ligands doubly bridging the ligand molecules in a head-to-tail mode. The coordination sphere in 3 is completed by two iodo terminal ligands, adopting a distorted tetrahedral geometry. On reacting with mercury(II) perchlorate, L forms solvent-coordinated 1D coordination polymer ([Hg{sub 2}(L)(DMF){sub 6}](ClO{sub 4}){sub 4}·2DMF)n instead of the anion-coordination. In 4, the Hg atom is five-coordinate, being bound to two sulfur donors from two different ligands doubly bridging the ligand molecules in a side-by-side mode to form a ribbon-like 1D structure.. The three remaining coordination sites in 4 are completed by three DMF molecules in a monodentate manner. Consequently, the different structures and connectivity patterns for the observed exocyclic coordination polymers depending on the anions used are influenced not only by the coordination ability of the anions but also by anion sizes macrocycle (L) are reported. L reacts with mercury(II) chloride and bromide to yield an isostructural 2D coordination polymers with type [Hg(L)X{sub 2}]n (1: X = Cl and 2: X = Br). In 1, each Hg atom which lies

  7. Anionic surface binders

    Aljaž-Rožič Mateja; Hočevar Nežka

    2004-01-01

    The MELAMIN Chemical Factory in Kočevje manufactures synthetic resins and binders for the paper industry. Binders based on AKD (alkyl ketene dimer) are produced which are used for binding paper and cardboard in the range of neutral and partially basic pH. Cationic and, lately, anionic binders are mostly used for the bulk binding of paper and board. The possibility of using AKD binders on paper or board surfaces is presented. In this case partially cationic AKD binders may be applied. When opt...

  8. Formation of interstellar anions

    Senent, Maria Luisa

    2012-05-01

    Formation of interstellar anions: M.L. Senent. The recent detection of negative charged species in the ISM1 has instigated enthusiasm for anions in the astrophysical community2. Many of these species are new and entail characterization. How they are formed in astrophysical sources is a question of major relevance. The anion presence in ISM was first predicted theoretically on the basis of electron affinities and on the negative linear chain molecular stabilities. Although very early, they were considered in astrochemical models3-4, their discovery is so recent because their abundances seem to be relatively low. These have to be understood in terms of molecular stabilities, reaction probabilities and radiative and collisional excitations. Then, we present our theoretical work on even carbon chains type Cn and CnH (n=2,4,6) focused to the understanding of anion abundances. We use highly correlated ab initio methods. We performed spectroscopic studies of various isomers that can play important roles as intermediates5-8. In previous papers9-10, we compared C2H and C2H- collisional rates responsible for observed line intensities. Actually, we study hydrogen attachment (Cn +H → CnH and Cn- +H → CnH-) and associative detachment processes (Cn- +H → CnH +e-) for 2, 4 and 6 carbon atom chains11. [1] M.C.McCarthy, C.A.Gottlieb, H.Gupta, P.Thaddeus, Astrophys.J, 652, L141 (2006) [2] V.M.Bierbaum, J.Cernicharo, R.Bachiller, eds., 2011, pp 383-389. [3] A. Dalgarno, R.A. Mc Cray, Astrophys.J,, 181, 95 (1973) [4] E. Herbst E., Nature, 289, 656 (1981); [5] H.Massó, M.L.Senent, P.Rosmus, M.Hochlaf, J.Chem.Phys., 124, 234304 (2006) [6] M.L.Senent, M.Hochlaf, Astrophys. J. , 708, 1452(2010) [7] H.Massó, M.L.Senent, J.Phys.Chem.A, 113, 12404 (2009) [8] D. Hammoutene, M.Hochlaf, M.L.Senent, submitted. [9] A. Spielfiedel, N. Feautrier, F. Najar, D. ben Abdallah, F. Dayou, M.L. Senent, F. Lique, Mon.Not.R.Astron.Soc., 421, 1891 (2012) [10] F.Dumouchel, A, Spielfieldel , M

  9. Perchlorate reduction during electrochemically induced pitting corrosion of zero-valent titanium (ZVT)

    Lee, Chunwoo, E-mail: clee@doosanhydro.com [Department of Research and Development, Doosan Hydro Technology, Inc, Tampa, FL 33619 (United States); Batchelor, Bill [Zachry Department of Civil Engineering, Texas A and M University, College Station, TX 77840 (United States); Park, Sung Hyuk [Environmental and Engineering Research Team, GS Engineering and Construction Research Institute, Youngin, Kyunggi-do 449-831 (Korea, Republic of); Han, Dong Suk; Abdel-Wahab, Ahmed [Chemical Engineering Program, Texas A and M University at Qatar, Education City, Doha, PO Box 23874 (Qatar); Kramer, Timothy A.

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. Black-Right-Pointing-Pointer Perchlorate is effectively reduced to chloride by soluble titanium species. Black-Right-Pointing-Pointer Solution pH and surface area of ZVT showed negligible effects on rates of perchlorate reduction. - Abstract: Zero-valent metals and ionic metal species are a popular reagent for the abatement of contaminants in drinking water and groundwater and perchlorate is a contaminant of increasing concern. However, perchlorate degradation using commonly used reductants such as zero-valent metals and soluble reduced metal species is kinetically limited. Titanium in the zero-valent and soluble states has a high thermodynamic potential to reduce perchlorate. Here we show that perchlorate is effectively reduced to chloride by soluble titanium species in a system where the surface oxide film is removed from ZVT and ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. The pitting potential of ZVT was measured as 12.77 {+-} 0.04 V (SHE) for a 100 mM solution of perchlorate. The rate of perchlorate reduction was independent of the imposed potential as long as the potential was maintained above the pitting potential, but it was proportional to the applied current. Solution pH and surface area of ZVT electrodes showed negligible effects on rates of perchlorate reduction. Although perchlorate is effectively reduced during electrochemically induced corrosion of ZVT, this process may not be immediately applicable to perchlorate treatment due to the high potentials needed to produce active reductants, the amount of titanium consumed, the inhibition of perchlorate removal by chloride, and oxidation of chloride to chlorine.

  10. Perchlorate reduction during electrochemically induced pitting corrosion of zero-valent titanium (ZVT)

    Lee, Chunwoo; Batchelor, Bill; Park, Sung Hyuk; Han, Dong Suk; Abdel-Wahab, Ahmed; Kramer, Timothy A.

    2011-01-01

    Highlights: ► ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. ► Perchlorate is effectively reduced to chloride by soluble titanium species. ► Solution pH and surface area of ZVT showed negligible effects on rates of perchlorate reduction. - Abstract: Zero-valent metals and ionic metal species are a popular reagent for the abatement of contaminants in drinking water and groundwater and perchlorate is a contaminant of increasing concern. However, perchlorate degradation using commonly used reductants such as zero-valent metals and soluble reduced metal species is kinetically limited. Titanium in the zero-valent and soluble states has a high thermodynamic potential to reduce perchlorate. Here we show that perchlorate is effectively reduced to chloride by soluble titanium species in a system where the surface oxide film is removed from ZVT and ZVT is oxidized during electrochemically induced pitting corrosion to produce reactive soluble species. The pitting potential of ZVT was measured as 12.77 ± 0.04 V (SHE) for a 100 mM solution of perchlorate. The rate of perchlorate reduction was independent of the imposed potential as long as the potential was maintained above the pitting potential, but it was proportional to the applied current. Solution pH and surface area of ZVT electrodes showed negligible effects on rates of perchlorate reduction. Although perchlorate is effectively reduced during electrochemically induced corrosion of ZVT, this process may not be immediately applicable to perchlorate treatment due to the high potentials needed to produce active reductants, the amount of titanium consumed, the inhibition of perchlorate removal by chloride, and oxidation of chloride to chlorine.

  11. Cyclic voltammetry and reduction mechanistic studies of styrylpyrylium perchlorates

    Y. L. Bonzi-Coulibaly

    2013-04-01

    Full Text Available The reduction and oxidation potentials of methylated 4-styrylpyrylium and 6-styrylpyrylium perchlorates have been evaluated using cyclic voltammetry, in comparison to their non-methylated derivatives values. The reduction peak of all studied compounds remained chemically irreversible. The presence of the electron-donating methyl group on pyrylium ring leads to a shift of the styrylpyrylium perchlorates reduction potential towards cathodic values. Kinetic studies on platinum electrodes based on the variation of the peak potential at different scan rates and upon substrate concentrations confirm, in another way, the mechanism of electron transfer.DOI: http://dx.doi.org/10.4314/bcse.v27i1.12

  12. The Effects of Perchlorate on Developing and Adult Birds

    2003-06-01

    Veterinary Medicine at Virginia Tech. Experimental treatment and 3 maintenance during the experiment were done in our animal facilities in the Dept. of...experiments. We have not completed our analysis of these experiments [6]. Reversibility of Perchlorate Effects: In human clinical medicine , where...Ingbar’s The Thyroid, 7th ed., Lippincott-Raven, Philadelphia, PA, USA, pp 296-316. Green WL. 1996. Antithyroid compounds. In Braverman LE, Utiger RD

  13. The Effect of Gamma Radiation on Mars Mineral Matrices: Implications for Perchlorate Formation on Mars

    Fox, A. C.; Eigenbrode, J. L.; Pavlov, A.; Lewis, J.

    2017-12-01

    Observations by the Phoenix Wet Chemistry Lab of the Martian surface indicate the presence of perchlorate in high concentrations. Additional observations by the Sample Analysis at Mars and the Viking Landers indirectly support the presence of perchlorate at other localities on Mars. The evidence for perchlorate at several localities on Mars coupled with its detection in Martian meteorite EETA79001 suggests that perchlorate is present globally on Mars. The presence of perchlorate on Mars further complicates the search for organic molecules indicative of past life. While perchlorate is kinetically limited in Martian conditions, the intermediate species associated with its formation or decomposition, such as chlorate or chlorite, could oxidize Martian organic species. As a result, it is vital to understand the mechanism of perchlorate formation on Mars in order to determine its role in the degradation of organics. Here, we explore an alternate mechanism of formation of perchlorate by bombarding Cl-salts and Mars-relevant mineral mixtures with gamma radiation both with and without the presence of liquid water, under vacuum. Previous work has shown that OClO can form from both UV radiation and energetic electrons bombardment of Cl-ices or Cl-salts, which then reacts with either OH- or O-radicals to produce perchlorate. Past research has suggested that liquid water or ice is the source of these hydroxyl and oxygen radicals, which limits the location of perchlorate formation on Mars. We demonstrate that trace amounts of perchlorate are potentially formed in samples containing silica dioxide or iron oxide and Cl-salts both with and without liquid water. Perchlorate was also detected in a portion of samples that were not irradiated, suggesting possible contamination. We did not detect perchlorate in samples that contained sulfate minerals. If perchlorate was formed without liquid water, it is possible that oxide minerals could be a potential source of oxygen radicals

  14. Fatty acid profile in milk from goats, Capra aegagrus hircus, exposed to perchlorate and its relationship with perchlorate residues in human milk.

    Cheng, Qiuqiong; Smith, Ernest E; Kirk, Andrea B; Liu, Fujun; Boylan, Lee Mallory; McCarty, Michael E; Hart, Sybil; Dong, Linxia; Cobb, George P; Jackson, W Andrew; Anderson, Todd A

    2007-10-01

    Polyunsaturated fatty acids (PUFA) in milk are vital for normal growth and development of infant mammals. Changes in fatty acid composition were observed in milk fat from goats dosed with perchlorate (0.1 and 1 mg/kg body weight/day) for 31 days, but the effect was not persistent. Adaptation may be induced in these goats to compensate for the perchlorate effect. In an analysis of fatty acid composition in human milk samples, a weak negative correlation was observed between perchlorate concentrations and total PUFA in 38 human milk samples.

  15. The many ways of making anionic clays

    Together with hydrotalcite-like layered double hydroxides, bivalent and trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange ...

  16. (μ-Acetato-κ2O:O′[μ-2,6-bis({bis[(pyridin-2-yl-κNmethyl]amino-κN}methyl-4-methylphenolato-κ2O:O](methanol-κOdizinc bis(perchlorate

    Biswanath Das

    2014-04-01

    Full Text Available The binuclear title complex, [Zn2(C33H33N6O(CH3COO2(CH3OH](ClO42, was synthesized by the reaction between 2,6-bis({[bis(pyridin-2-ylmethyl]amino}methyl-4-methylphenol (H-BPMP, Zn(OAc2 and NaClO4. The two ZnII ions are bridged by the phenolate O atom of the octadentate ligand and the acetate group. An additional methanol ligand is terminally coordinated to one of the ZnII ions, rendering the whole structure unsymmetric. Other symmetric dizinc complexes of BPMP have been reported. However, to the best of our knowledge, the present structure, in which the two ZnII ions are distinguishable by the number of coordinating ligands and the coordination geometries (octahedral and square-pyramidal, is unique. The dizinc complex is a dication, and two perchlorate anions balance the charge. The –OH group of the coordinating methanol solvent molecule forms a hydrogen bond with a perchlorate counter-anion. One of the anions is disordered over two sets of sites with an occupancy ratio of 0.734 (2:0.266 (2.

  17. Chlorine Isotopic Composition of Perchlorate in Human Urine as a Means of Distinguishing Among Natural and Synthetic Exposure Sources

    Poghosyan, Armen; Morel-Espinosa, Maria; Valentín-Blasini, Liza; Blount, Benjamin C.; Ferreccio, Catterina; Steinmaus, Craig M.; Sturchio, Neil C.

    2015-01-01

    Perchlorate (ClO4−) is a ubiquitous environmental contaminant with high human exposure potential; it has both natural and man-made sources in the environment. Natural perchlorate forms in the atmosphere from where it deposits onto the surface of Earth, whereas synthetic perchlorate is manufactured as an oxidant for industrial, aerospace, and military applications. Perchlorate exposure can potentially cause adverse health effects in humans by interfering with the production of thyroid hormones through competitively blocking iodide uptake. To control and reduce perchlorate exposure, the contributions of different sources of perchlorate exposure need to be quantified. Thus, we demonstrate a novel approach for determining the contribution of different perchlorate exposure sources by quantifying stable and radioactive chlorine isotopes of perchlorate extracted from composite urine samples from two distinct populations: one in Atlanta, USA and one in Taltal, Chile (Atacama region). Urinary perchlorate from the Atlanta region resembles indigenous natural perchlorate from the southwestern USA [δ37Cl = +4.1 ± 1.0 ‰; 36Cl/Cl = 1811 (± 136) × 10−15], and urinary perchlorate from the Taltal, Chile region is similar to natural perchlorate in nitrate salt deposits from the Atacama Desert of northern Chile [δ37Cl = −11.0 ± 1.0 ‰; 36Cl/Cl = 254 (± 40) × 10−15]. Neither urinary perchlorate resembled the isotopic pattern found in synthetic perchlorate. These results indicate that natural perchlorate of regional provenance is the dominant exposure source for the two sample populations, and that chlorine isotope ratios provide a robust tool for elucidating perchlorate exposure pathways. PMID:25805252

  18. Monitoring of perchlorate in diverse foods and its estimated dietary exposure for Korea populations.

    Lee, Ji-Woo; Oh, Sung-Hee; Oh, Jeong-Eun

    2012-12-01

    The perchlorate concentrations in various Korean food samples were monitored, and 663 samples belonging to 39 kinds of food were analyzed. The analysis results revealed that dairy products contain the highest average concentration of 6.34 μg/kg and high detection frequency of over 85%. Fruit and vegetables showed the next highest perchlorate concentration with an average of 6.17 μg/kg. Especially, with its average concentration of 39.9 μg/kg, spinach showed the highest perchlorate level among all target food samples studied. Tomato was followed by spinach, which showed a high perchlorate average concentration of 19.8 μg/kg, and over 7 μg/kg was detected in ham and sausage (avg. 7.31 μg/kg) and in instant noodles (avg. 7.58 μg/kg). Less than 2 μg/kg was detected in fishes, meats and beverages. The exposure dose of perchlorate in Korean by food intake was calculated on the basis of the analyzed perchlorate levels in this study. The daily perchlorate dose to which Korean adults are exposed is 0.04 μg/kg bw/day, which is lower than the RfD (0.7 μg/kg bw/day) value suggested by US NAS. This result indicates that Korean people's current exposure to perchlorate from domestic food consumption is evaluated as safe. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. The effects of sodium perchlorate on the liver of Molly Fish ( Poecilia ...

    Adult male molly fishes were reared up to ten days in control water or in water containing sodium perchlorate at concentrations of 1, 5, 25 and 125 ppm. Remarkable steatosis, fibrosis, hyperemia and necrosis were distinguished in parallel with increasing sodium perchlorate concentrations. The striking cellular damages ...

  20. Bifunctional lanthanum phosphate substrates as novel adsorbents and biocatalyst supports for perchlorate removal

    Sankar, Sasidharan [Materials Science and Technology Division (India); Prajeesh, Gangadharan Puthiya Veetil; Anupama, Vijaya Nadaraja [Process Engineering and Environmental Technology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Industrial Estate P.O., Thiruvananthapuram 695019 (India); Krishnakumar, Bhaskaran [Process Engineering and Environmental Technology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Industrial Estate P.O., Thiruvananthapuram 695019 (India); Academy of Scientific and Industrial Research (AcSIR) (India); Hareesh, Padinhattayil [Materials Science and Technology Division (India); Nair, Balagopal N. [R and D Centre, Noritake Co. Ltd., Aichi (Japan); Warrier, Krishna Gopakumar [Materials Science and Technology Division (India); Academy of Scientific and Industrial Research (AcSIR) (India); Hareesh, Unnikrishnan Nair Saraswathy, E-mail: hareesh@niist.res.in [Materials Science and Technology Division (India); Academy of Scientific and Industrial Research (AcSIR) (India)

    2014-06-30

    Graphical abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign thermal gelation process, performed the role of dual functional sorbent facilitating perchlorate adsorption and bioremediation through the growth of perchlorate reducing microbial colonies. - Highlights: • Lanthanum phosphate monoliths as efficient perchlorate adsorbents. • And also as substrates for biofilm (perchlorate reducing bacteria) growth. • Environmentally benign thermal gelation process for substrate fabrication. • 98% adsorption efficiency for perchlorate concentrations up to 100 μg/L. • The regenerated monoliths show nearly 100% reusability. - Abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign colloidal forming process employing methyl cellulose, are reported here as excellent adsorbents of perchlorate with >98% efficiency and with 100% reusability. Additionally, the effectiveness of such substrates as biocatalyst supports that facilitate biofilm formation of perchlorate reducing microbes (Serratia marcescens NIIST 5) is also demonstrated for the first time. The adsorption of perchlorate ions is attributed to the pore structure of lanthanum phosphate substrate and the microbial attachment is primarily ascribed to its intrinsic hydrophobic property. Lanthanum phosphate thus emerges as a dual functional material that possesses an integrated adsorption/bioremediation property for the effective removal of ClO{sub 4}{sup −} which is an increasingly important environmental contaminant.

  1. Validation of a Novel Bioassay for Low-level Perchlorate Determination

    2014-04-01

    was not attractive, since these reduce PMS2 , and it was thought they would interfere with the stoichiometry of NADH and perchlorate in the bioassay...these reduce PMS2 directly, and would interfere with the stoichiometry of NADH and perchlorate in the bioassay. Thus the only approach that could be

  2. RAMAN SPECTRAL ANALYSIS OF PERCHLORATE CONTAMINATION IN COMMONLY-USED FERTILIZERS

    Raman spectroscopy (RS) was used for qualitative and quantitative analysis of perchlorate (ClO4-1) in 30+ commonly-used fertilizers. Perchlorate contamination is emerging as an important environmental issue since its discovery in water resources that are widely used for drinking...

  3. Occurrence of perchlorate in groundwater, paired farmland soil, lettuce, and rhizosphere soil from Chengdu, China.

    Tang, Yulu; Zhong, Bifeng; Qu, Bing; Feng, Shujin; Ding, Sanglan; Su, Shijun; Li, Zhi; Gan, Zhiwei

    2017-05-24

    A total of 28 groundwater, paired farmland soil, lettuce, and its rhizosphere soil samples were collected from Chengdu, China to detect perchlorate levels and to evaluate the relationships of perchlorate concentrations among these matrices. The perchlorate concentrations in the groundwater, farmland soil, lettuce, and rhizosphere soil samples ranged from below detection limit to 60.2 μg L -1 , from below detection limit to 249 μg kg -1 dry weight (dw), from 2.07 to 1010 μg kg -1 wet weight, and from below detection limit to 314 μg kg -1 dw, respectively. Significant correlation was found in the perchlorate levels among the farmland soil, lettuce, and rhizosphere soil, suggesting that they have common pollution sources, or perchlorate might transfer from farmland soil-rhizosphere soil-plant. However, there is no significant correlation between groundwater and the other three matrices, indicating that infiltration from perchlorate contaminated farmland soil was not the predominant source for groundwater pollution in Chengdu. The perchlorate concentrations in the farmland soil and lettuce samples were significantly higher than those in the rhizosphere soil, primarily due to uptake of perchlorate through the rhizosphere micro-environment by lettuce, or accelerated degradation by rhizospheric microorganisms, which contributed more needs further investigation.

  4. PERCHLORATE UPTAKE BY SALT CEDAR (TAMARIX RAMOSISSIMA) IN THE LAS VEGAS WASH RIPARIAN ECOSYSTEM

    Perchlorate ion (CIO4-) has been identified in samples of dormant salt cedar (Tamarix ramosissima) growing in the Las vegas Wash. Perchlorate is an oxidenat, but its reduction is kineticaly hindered. CXoncern over thyrpoid effects caused the Environmental Protection Agency (EPA...

  5. Perchlorate and halophilic prokaryotes: implications for possible halophilic life on Mars.

    Oren, Aharon; Elevi Bardavid, Rahel; Mana, Lily

    2014-01-01

    In view of the finding of perchlorate among the salts detected by the Phoenix Lander on Mars, we investigated the relationships of halophilic heterotrophic microorganisms (archaea of the family Halobacteriaceae and the bacterium Halomonas elongata) toward perchlorate. All strains tested grew well in NaCl-based media containing 0.4 M perchlorate, but at the highest perchlorate concentrations, tested cells were swollen or distorted. Some species (Haloferax mediterranei, Haloferax denitrificans, Haloferax gibbonsii, Haloarcula marismortui, Haloarcula vallismortis) could use perchlorate as an electron acceptor for anaerobic growth. Although perchlorate is highly oxidizing, its presence at a concentration of 0.2 M for up to 2 weeks did not negatively affect the ability of a yeast extract-based medium to support growth of the archaeon Halobacterium salinarum. These findings show that presence of perchlorate among the salts on Mars does not preclude the possibility of halophilic life. If indeed the liquid brines that may exist on Mars are inhabited by salt-requiring or salt-tolerant microorganisms similar to the halophiles on Earth, presence of perchlorate may even be stimulatory when it can serve as an electron acceptor for respiratory activity in the anaerobic Martian environment.

  6. Bifunctional lanthanum phosphate substrates as novel adsorbents and biocatalyst supports for perchlorate removal

    Sankar, Sasidharan; Prajeesh, Gangadharan Puthiya Veetil; Anupama, Vijaya Nadaraja; Krishnakumar, Bhaskaran; Hareesh, Padinhattayil; Nair, Balagopal N.; Warrier, Krishna Gopakumar; Hareesh, Unnikrishnan Nair Saraswathy

    2014-01-01

    Graphical abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign thermal gelation process, performed the role of dual functional sorbent facilitating perchlorate adsorption and bioremediation through the growth of perchlorate reducing microbial colonies. - Highlights: • Lanthanum phosphate monoliths as efficient perchlorate adsorbents. • And also as substrates for biofilm (perchlorate reducing bacteria) growth. • Environmentally benign thermal gelation process for substrate fabrication. • 98% adsorption efficiency for perchlorate concentrations up to 100 μg/L. • The regenerated monoliths show nearly 100% reusability. - Abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign colloidal forming process employing methyl cellulose, are reported here as excellent adsorbents of perchlorate with >98% efficiency and with 100% reusability. Additionally, the effectiveness of such substrates as biocatalyst supports that facilitate biofilm formation of perchlorate reducing microbes (Serratia marcescens NIIST 5) is also demonstrated for the first time. The adsorption of perchlorate ions is attributed to the pore structure of lanthanum phosphate substrate and the microbial attachment is primarily ascribed to its intrinsic hydrophobic property. Lanthanum phosphate thus emerges as a dual functional material that possesses an integrated adsorption/bioremediation property for the effective removal of ClO 4 − which is an increasingly important environmental contaminant

  7. Natural Attenuation of Perchlorate in Groundwater: Processes, Tools and Monitoring Techniques

    2008-04-01

    environmental health concerns are associated with the uptake of perchlorate in food crops such as lettuce and milk (Kirk et al., 2003; USEPA, 2005b...that high concentrations of ammonium would remain in the soil and provide forensic clues regarding the source of perchlorate and plume history (Motzer

  8. COMMENT ON "PERCHLORATE IDENTIFICATION IN FERTILIZERS" AND THE SUBSEQUENT ADDITION/CORRECTION [LETTER TO EDITOR

    Perchlorate contamination has been reported in several fertilizer materials and not just in mined Chile saltpeter, where it is a welo-known natural impurity. To survey fertilizers for perchlorate, two analytical techniques have been applied to 45 products that span agricultural, ...

  9. Influence of the ammonium salt anion on the synergistic solvent extraction of lanthanides with mixtures of thenoyltrifluoroacetone and tridecylamine

    Dukov, I.L.; Jordanov, V.M.

    1998-01-01

    The synergistic solvent extraction of Pr, Gd and Yb with mixtures of thenoyltrifluoroacetone (HTTA) and primary ammonium salt (tridecylammonium chloride or perchlorate, TDAH(Cl, ClO 4 )) in C 6 H 6 has been studied. The composition of the extracted species have been determined as Ln(TTA) 3 TDAHA(A - = Cl - or ClO 4 - ). The values of the equilibrium constant K T,S have been calculated. The influence of the ammonium salt anion on the extraction process has been discussed. The separation factors of the pairs Gd/Pr and Yb/Gd have been determined

  10. Isolation and characterization of autotrophic, hydrogen-utilizing, perchlorate-reducing bacteria.

    Shrout, Joshua D; Scheetz, Todd E; Casavant, Thomas L; Parkin, Gene F

    2005-04-01

    Recent studies have shown that perchlorate (ClO(4) (-)) can be degraded by some pure-culture and mixed-culture bacteria with the addition of hydrogen. This paper describes the isolation of two hydrogen-utilizing perchlorate-degrading bacteria capable of using inorganic carbon for growth. These autotrophic bacteria are within the genus Dechloromonas and are the first Dechloromonas species that are microaerophilic and incapable of growth at atmospheric oxygen concentrations. Dechloromonas sp. JDS5 and Dechloromonas sp. JDS6 are the first perchlorate-degrading autotrophs isolated from a perchlorate-contaminated site. Measured hydrogen thresholds were higher than for other environmentally significant, hydrogen-utilizing, anaerobic bacteria (e.g., halorespirers). The chlorite dismutase activity of these bacteria was greater for autotrophically grown cells than for cells grown heterotrophically on lactate. These bacteria used fumarate as an alternate electron acceptor, which is the first report of growth on an organic electron acceptor by perchlorate-reducing bacteria.

  11. CRYSTALLIZATION KINETICS OF AMMONIUM PERCHLORATE IN AN AGITATED VESSEL

    Nahidh Kaseer

    2013-05-01

    Full Text Available 31Overall crystal growth kinetics for ammonium perchlorate in laboratory scale batch  agitated vessel crystallizer have been determined from batch experiments performed in an integral mode. The effects of temperature between 30-60ºC, seed size 0.07, 0.120 and 0.275 mm and stirrer speed 160, 340, and 480 rpm, on the kinetics of crystal growth were investigated. Two different methods, viz. polynomial fitting and initial derivative were used to predict the kinetics expression. In general both methods gave comparable results for growth kinetics estimation. The order of growth process is not more than two. The activation energy for crystal growth of ammonium perchlorate was determined and found  to be equal to 5.8 kJ/ mole.            Finally, the influence of the affecting parameters on the crystal growth rate gives general expression that had an obvious dependence of the growth rate on each variables of concern (temperature, seed size, and stirrer speed .The general overall growth rate expression had shown that super saturation is the most significant variable. While the positive dependence of the stirrer speed demonstrates the importance of the diffusional step in the growth rate model. Moreover, the positive dependence of the seed size demonstrate the importance of the surface integration  step in the growth rate model. All the studied variables tend to suggest that the growth rate characteristics  of ammonium perchlorate from aqueous solution commenced in a batch crystallizer are diffusion kinetic controlled process.

  12. Fusibility diagram of strontium perchlorate-water system

    Dobrynina, T.A.; Akhapkina, N.A.; Rosolovskij, V.Ya.

    1986-01-01

    Investigation into fusibility in Sr(ClO 4 ) 2 -H 2 O binary system using visual-polythermal method and DTA is conducted. Existence of the following solid phases in the system: ice, Sr(ClO 4 ) 2 x8H 2 O, Sr(ClO 4 ) 2 x3H 2 O, Sr(ClO 4 )xH 2 O and Sr(ClO 4 ) 2 is displayed. Anhydrous strontium perchlorate is crystallized as an equilibrium solid phase in the range of high Sr(ClO 4 ) 2 concentrations in the 155-295 deg C temperature range. Transitions between ice and Sr(ClO 4 ) 2 x8H 2 O and Sr(ClO 4 ) 2 x8H 2 O and Sr(ClO 4 ) 2 x3H 2 O belong to eutectic type. Transformations of Sr(ClO 4 ) 2 x3H 2 O into Sr(ClO 4 ) 2 x2H 2 O and Sr(ClO 4 ) 2 xH 2 O into Sr(ClO 4 ) 2 take place at the boundary of congruence. Metastable states characterized by formation of metastable eutectics between ice and Sr(ClO 4 ) 2 x3H 2 O, Sr(ClO 4 ) 2 x8H 2 O and Sr(ClO 4 ) 2 xh 2 O, Sr(ClO 4 ) 2 x3H 2 O and Sr(ClO 4 ) 2 are found for all hydrates of strontium perchlorate and for anhydrous perchlorate

  13. Phosphazene-promoted anionic polymerization

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  14. Simultaneous anionic and cationic redox

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  15. Schlenk Techniques for Anionic Polymerization

    Ratkanthwar, Kedar; Zhao, Junpeng; Zhang, Hefeng; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands

  16. The influence of D2O, perchlorate, and variation in temperature on the potential-dependent contractile function of frog skeletal muscle

    Foulks, J.G.; Morishita, L.

    1985-01-01

    D 2 O and perchlorate manifest opposing effects on the contractile function of skeletal muscle (amplitude of twitches and maximum K contractures, potential dependence of contraction and inactivation), and when combined the influence of one may effectively antagonize that of the other. The ratio of perchlorate concentrations required to produce effects of equal intensity, (e.g., twitch enhancement and restoration of maximum K contractures in media lacking divalent cations or containing a depressant concentration of a cationic amphipath) in H 2 O and D 2 O solutions was generally rather constant. These findings are compatible with the view that both agents can influence contractile function by virtue of their effects on solvent structure. In the absence of divalent cations, the effects of reduced temperature resemble those of D 2 O whereas the effects of increased temperature resemble those of the chaotropic anion. However, in other media, variation in temperature was found to result in additional nonsolvent effects so that low temperature could oppose rather than enhance the effects of D 2 O. These observations are discussed in terms of a model which postulates a role for solvent influences on the kinetics of two separate potential-dependent conformational transitions of membrane proteins which mediate the activation and inactivation of contraction in skeletal muscle

  17. Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent.

    Gündüz, T; Kiliç, E; Cakirer, O

    1996-05-01

    Thirteen aliphatic and four aromatic amines, namely diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-butylamine, isopropylamine, di-isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, aniline, N,N-dimethylaniline, 2-nitroaniline and 4-nitroaniline were titrated thermometrically with nitrosyl perchlorate in acetonitrile solvent. All the aliphatic amines gave very well-shaped thermometric titration curves. The calculated recovery values of the amines were very good. In comparison, the aromatic amines, aniline and N,N-dimethylaniline gave rather well-shaped titration curves, but the recovery values were fairly low. 2-Nitro- and 4-nitro anilines gave no thermometric response at all. The heats of reaction of the amines with nitrosyl perchlorate are rather high. However, the average heat of reaction of the aromatic amines is approximately two-thirds that of the average heat of the aliphatic amines. To support this method all the amines were also titrated potentiometrically and very similar results to those obtained with the thermometric method are seen. The nitrosyl ion is a Lewis acid, strong enough to titrate quantitatively aliphatic amines in acetonitrile solvent, but not strong enough to titrate aromatic amines at the required level in the same solvent.

  18. The photochemistry of neptunium in aqueous perchloric acid solutions

    Friedman, H.A.; Toth, L.M.; Osborne, M.M.

    1979-01-01

    The photochemistry of neptunium ions in aqueous perchloric acid has been investigated using 254 and 300 nm UV radiation. In the absence of other reagents, Np(IV) and (V) oxidized to Np(VI), in a stepwise fashion, with individual quantum efficiencies for each step that vary from 0.02 to 0.004. Decreasing acid concentration favors the Np(IV) → Np(V) reaction whereas it hinders the Np(V) → Np(VI) photo-oxidation. When ethanol, acetaldehyde and other mild reducing agents are added to neptunium-perchloric acid solutions which are then photolyzed, the Np species are reduced to Np(III) in a stepwise fashion with individual quantum efficiencies that vary from 0.07 to 0.006. The overall photoredox reactions of neptunium are subject to competing secondary product reactions that become significant as the photolysis products accumulate. Absorption spectrophotometry was used to monitor the changes in Np oxidation states and reference spectra of the various Np oxidation states are given for 1.0 N HClO 4 . The Np species have absorption bands in the 300 to 1320 nm region that obey Beer's law only when they were properly resolved. (author)

  19. A review of perchlorate (ClO4-) occurrence in fruits and vegetables.

    Calderón, R; Godoy, F; Escudey, M; Palma, P

    2017-02-01

    Since the 1990s, a large number of studies around the world have reported the presence of perchlorate in different types of environmental matrices. In view of their inherent characteristics, such as high solubility, mobility, persistence, and low affinity for the surface of soil, perchlorates are mobilized through the water-soil system and accumulate in edible plant species of high human consumption. However, the ingestion of food products containing perchlorate represents a potential health risk to people due to their adverse effects on thyroid, hormone, and neuronal development, mainly in infants and fetuses. At present, research has been centered on determining sources, fates, and remediation methods and not on its real extension in vegetables under farming conditions. This review presents a comprehensive overview and update of the frequent detection of perchlorate in fruits and vegetables produced and marketed around the world. Additionally, the impact of fertilizer on the potential addition of perchlorate to soil and its mobility in the water-soil-plant system is discussed. This review is organized into the following sections: sources of perchlorate, mobility in the water-soil system, presence in fruits and vegetables in different countries, international regulations, and toxicological studies. Finally, recommendations for future studies concerning perchlorate in fruits and vegetables are presented.

  20. Microbial community analysis of perchlorate-reducing cultures growing on zero-valent iron

    Son, Ahjeong; Schmidt, Carl J.; Shin, Hyejin; Cha, Daniel K.

    2011-01-01

    Anaerobic microbial mixed cultures demonstrated its ability to completely remove perchlorate in the presence of zero-valent iron. In order to understand the major microbial reaction in the iron-supported culture, community analysis comprising of microbial fatty acids and polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) techniques was performed for perchlorate reducing cultures. Analysis of fatty acid methyl esters (FAMEs) and subsequent principal component analysis (PCA) showed clear distinctions not only between iron-supported perchlorate reducing culture and seed bacteria, but also among perchlorate-reducing cultures receiving different electron donors. The DGGE pattern targeting the chlorite dismutase (cld) gene showed that iron-supported perchlorate reducing culture is similar to hydrogen-fed cultures as compared to acetate-fed culture. The phylogenetic tree suggested that the dominant microbial reaction may be a combination of the autotrophic and heterotrophic reduction of perchlorate. Both molecular and chemotaxonomic experimental results support further understanding in the function of zero-valent iron as an adequate electron source for enhancing the microbial perchlorate reduction in natural and engineered systems.

  1. Microbial community analysis of perchlorate-reducing cultures growing on zero-valent iron

    Son, Ahjeong, E-mail: ason@auburn.edu [Department of Civil Engineering, Auburn University, Auburn, AL 36849 (United States); Schmidt, Carl J. [Department of Animal and Food Sciences, University of Delaware, Newark, DE 19716 (United States); Shin, Hyejin [Department of Mathematics and Statistics, Auburn University, Auburn, AL 36849 (United States); Cha, Daniel K. [Department of Civil and Environmental Engineering, University of Delaware, Newark, DE 19716 (United States)

    2011-01-30

    Anaerobic microbial mixed cultures demonstrated its ability to completely remove perchlorate in the presence of zero-valent iron. In order to understand the major microbial reaction in the iron-supported culture, community analysis comprising of microbial fatty acids and polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) techniques was performed for perchlorate reducing cultures. Analysis of fatty acid methyl esters (FAMEs) and subsequent principal component analysis (PCA) showed clear distinctions not only between iron-supported perchlorate reducing culture and seed bacteria, but also among perchlorate-reducing cultures receiving different electron donors. The DGGE pattern targeting the chlorite dismutase (cld) gene showed that iron-supported perchlorate reducing culture is similar to hydrogen-fed cultures as compared to acetate-fed culture. The phylogenetic tree suggested that the dominant microbial reaction may be a combination of the autotrophic and heterotrophic reduction of perchlorate. Both molecular and chemotaxonomic experimental results support further understanding in the function of zero-valent iron as an adequate electron source for enhancing the microbial perchlorate reduction in natural and engineered systems.

  2. Gestational exposure to high perchlorate concentrations in drinking water and neonatal thyroxine levels.

    Amitai, Yona; Winston, Gary; Sack, Joseph; Wasser, Janice; Lewis, Matthew; Blount, Benjamin C; Valentin-Blasini, Liza; Fisher, Nirah; Israeli, Avi; Leventhal, Alex

    2007-09-01

    To assess the effect of gestational perchlorate exposure through drinking water on neonatal thyroxine (T(4)). T(4) values were compared among newborns in Ramat Hasharon, Israel, whose mothers resided in suburbs where drinking water contained perchlorate water exclusively (as determined by a telephone interview) were analyzed as a subset. Serum perchlorate levels in blood from donors residing in the area were used as proxy indicators of exposure. Neonatal T(4) values (mean +/- SD) in the very high, high, and low exposure groups were 13.9 +/- 3.8, 13.9 +/- 3.4, and 14.0 +/- 3.5 microg/dL, respectively (p = NS). Serum perchlorate concentrations in blood from donors residing in areas corresponding to these groups were 5.99 +/- 3.89, 1.19 +/- 1.37, and 0.44 +/- 0.55 microg/L, respectively. T(4) levels of neonates with putative gestational exposure to perchlorate in drinking water were not statistically different from controls. This study finds no change in neonatal T(4) levels despite maternal consumption of drinking water that contains perchlorate at levels in excess of the Environmental Protection Agency (EPA) drinking water equivalent level (24.5 microg/L) based on the National Research Council reference dose (RfD) [0.7 microg/(kg.day)]. Therefore the perchlorate RfD is likely to be protective of thyroid function in neonates of mothers with adequate iodide intake.

  3. Exposure to perchlorate induces the formation of macrophage aggregates in the trunk kidney of zebrafish and mosquitofish

    Capps, T.; Mukhi, S.; Rinchard, J.J.; Theodorakis, C.W.; Blazer, V.S.; Patino, R.

    2004-01-01

    Environmental contamination of ground and surface waters by perchlorate, derived from ammonium perchlorate (AP) and other perchlorate salts, is of increasing concern. Exposure to perchlorate can impair the thyroid endocrine system, which is thought to modulate renal and immune function in vertebrates. This study with zebrafish Danio rerio and eastern mosquitofish Gambusia holbrooki examined the histological effects of perchlorate on the trunk kidney, which in teleosts serves excretory and hemopoietic functions and therefore may be a target of perchlorate effects. Adult zebrafish of both sexes were exposed in the laboratory to waterborne, AP-derived perchlorate at measured concentrations of 18 mg/L for 8 weeks. Adult male mosquitofish were exposed to waterborne sodium perchlorate at measured perchlorate concentrations of 1-92 mg/L for 8 weeks. Control fish were kept in untreated water. The region of the body cavity containing the trunk kidney was processed from each fish for histological analysis. Macrophage aggregates (MAs), possible markers of contaminant exposure or immunotoxic effect, were present in the hemopoietic region of the kidney in both species exposed to perchlorate. The estimated percent area of kidney sections occupied by MAs was greater in zebrafish exposed to perchlorate at 18 mg/L (P < 0.05) than in controls. In male mosquitofish, the incidence of renal MAs increased proportionally with sodium perchlorate concentration and was significantly different from that of controls at 92 mg/L (P < 0.05). These observations confirm that in fish the kidney is affected by exposure to perchlorate. The concentrations of perchlorate at which the effects were noted are relatively high but within the range reported in some contaminated habitats.

  4. Solubility and Standard Gibb's energies of transfer of alkali metal perchlorates, tetramethyl- and tetraethylammonium from water to aqua-acetone solvents

    Kireev, A.A.; Pak, T.G.; Bezuglyj, V.D.

    1996-01-01

    Solubilities of KClO 4 , RbClO 4 , CsClO 4 , (CH 3 ) 4 NClO 4 , (C 2 M 5 ) 4 NClO 4 in water and water-acetone mixtures are determined by the method of isothermal saturation at 298.15 K. Dissociation constants of alkali metal perchlorates are found by conductometric method. Solubility products and standard Gibbs energies of transfer of corresponding electrolytes from water into water-acetone solvents are calculated. The character of transfer Gibbs energy dependence on solvent composition is explained by preferred solvation of cations by acetone molecules and anions-by water molecules. Features of tetraalkyl ammonium ions are explained by large changes in energy of cavity formation for these ions

  5. Transport and degradation of perchlorate in deep vadose zone: implications from direct observations during bioremediation treatment

    Dahan, Ofer; Katz, Idan; Avishai, Lior; Ronen, Zeev

    2017-08-01

    An in situ bioremediation experiment of a deep vadose zone ( ˜ 40 m) contaminated with a high concentration of perchlorate (> 25 000 mg L-1) was conducted through a full-scale field operation. Favourable environmental conditions for microbiological reduction of perchlorate were sought by infiltrating an electron donor-enriched water solution using drip irrigation underlying an airtight sealing liner. A vadose zone monitoring system (VMS) was used for real-time tracking of the percolation process, the penetration depth of dissolved organic carbon (DOC), and the variation in perchlorate concentration across the entire soil depth. The experimental conditions for each infiltration event were adjusted according to insight gained from data obtained by the VMS in previous stages. Continuous monitoring of the vadose zone indicated that in the top 13 m of the cross section, perchlorate concentration is dramatically reduced from thousands of milligrams per litre to near-detection limits with a concurrent increase in chloride concentration. Nevertheless, in the deeper parts of the vadose zone (< 17 m), perchlorate concentration increased, suggesting its mobilization down through the cross section. Breakthrough of DOC and bromide at different depths across the unsaturated zone showed limited migration capacity of biologically consumable carbon and energy sources due to their enhanced biodegradation in the upper soil layers. Nevertheless, the increased DOC concentration with concurrent reduction in perchlorate and increase in the chloride-to-perchlorate ratio in the top 13 m indicate partial degradation of perchlorate in this zone. There was no evidence of improved degradation conditions in the deeper parts where the initial concentrations of perchlorate were significantly higher.

  6. Perchlorate Exposure Reduces Primordial Germ Cell Number in Female Threespine Stickleback.

    Ann M Petersen

    Full Text Available Perchlorate is a common aquatic contaminant that has long been known to affect thyroid function in vertebrates, including humans. More recently perchlorate has been shown to affect primordial sexual differentiation in the aquatic model fishes zebrafish and threespine stickleback, but the mechanism has been unclear. Stickleback exposed to perchlorate from fertilization have increased androgen levels in the embryo and disrupted reproductive morphologies as adults, suggesting that perchlorate could disrupt the earliest stages of primordial sexual differentiation when primordial germ cells (PGCs begin to form the gonad. Female stickleback have three to four times the number of PGCs as males during the first weeks of development. We hypothesized that perchlorate exposure affects primordial sexual differentiation by reducing the number of germ cells in the gonad during an important window of stickleback sex determination at 14-18 days post fertilization (dpf. We tested this hypothesis by quantifying the number of PGCs at 16 dpf in control and 100 mg/L perchlorate-treated male and female stickleback. Perchlorate exposure from the time of fertilization resulted in significantly reduced PGC number only in genotypic females, suggesting that the masculinizing effects of perchlorate observed in adult stickleback may result from early changes to the number of PGCs at a time critical for sex determination. To our knowledge, this is the first evidence of a connection between an endocrine disruptor and reduction in PGC number prior to the first meiosis during sex determination. These findings suggest that a mode of action of perchlorate on adult reproductive phenotypes in vertebrates, including humans, such as altered fecundity and sex reversal or intersex gonads, may stem from early changes to germ cell development.

  7. Effects of ammonium perchlorate on the reproductive performance and thyroid follicle histology of zebrafish

    Patino, R.; Wainscott, M.R.; Cruz-Li, E. I.; Balakrishnan, S.; McMurry, C.; Blazer, V.S.; Anderson, T.A.

    2003-01-01

    Adult zebrafish were reared up to eight weeks in control water or in water containing ammonium perchlorate (AP) at measured perchlorate concentrations of 18 (environmentally relevant, high) and 677 ppm. Groups of eight females were paired with four males on a weekly basis to assess AP effects on spawned egg volume, an index of reproductive performance. All treatments were applied to four to five spawning replicates. At 677 ppm, spawn volume was reduced within one week and became negligible after four weeks. At 18 ppm, spawn volume was unaffected even after eight weeks. Also, perchlorate at 18 ppm did not affect percentage egg fertilization. Fish were collected at the end of the exposures (677 ppm, four weeks; control and 18 ppm, eight weeks) for whole-body perchlorate content and thyroid histopathological analysis. Fish perchlorate levels were about one-hundredth of those of treatment water levels, indicating that waterborne perchlorate does not accumulate in whole fish. At 677 ppm for four weeks, perchlorate caused thyroid follicle cell (nuclear) hypertrophy and angiogenesis, whereas at 18 ppm for eight weeks, its effects were more pronounced and included hypertrophy, angiogenesis, hyperplasia, and colloid depletion. In conclusion, an eight-week exposure of adult zebrafish to 18 ppm perchlorate (high environmentally relevant concentrations) affected the histological condition of their thyroid follicles but not their reproductive performance. The effect of 677 ppm perchlorate on reproduction may be due to extrathyroidal toxicity. Further research is needed to determine if AP at lower environmentally relevant concentrations also affects the thyroid follicles of zebrafish.

  8. Transport and degradation of perchlorate in deep vadose zone: implications from direct observations during bioremediation treatment

    O. Dahan

    2017-08-01

    Full Text Available An in situ bioremediation experiment of a deep vadose zone ( ∼  40 m contaminated with a high concentration of perchlorate (> 25 000 mg L−1 was conducted through a full-scale field operation. Favourable environmental conditions for microbiological reduction of perchlorate were sought by infiltrating an electron donor-enriched water solution using drip irrigation underlying an airtight sealing liner. A vadose zone monitoring system (VMS was used for real-time tracking of the percolation process, the penetration depth of dissolved organic carbon (DOC, and the variation in perchlorate concentration across the entire soil depth. The experimental conditions for each infiltration event were adjusted according to insight gained from data obtained by the VMS in previous stages. Continuous monitoring of the vadose zone indicated that in the top 13 m of the cross section, perchlorate concentration is dramatically reduced from thousands of milligrams per litre to near-detection limits with a concurrent increase in chloride concentration. Nevertheless, in the deeper parts of the vadose zone (< 17 m, perchlorate concentration increased, suggesting its mobilization down through the cross section. Breakthrough of DOC and bromide at different depths across the unsaturated zone showed limited migration capacity of biologically consumable carbon and energy sources due to their enhanced biodegradation in the upper soil layers. Nevertheless, the increased DOC concentration with concurrent reduction in perchlorate and increase in the chloride-to-perchlorate ratio in the top 13 m indicate partial degradation of perchlorate in this zone. There was no evidence of improved degradation conditions in the deeper parts where the initial concentrations of perchlorate were significantly higher.

  9. Spectroelectrochemical study of the adsorption of acetate anions at gold single crystal and thin-film electrodes

    Berna, Antonio; Delgado, Jose Manuel; Orts, Jose Manuel; Rodes, Antonio; Feliu, Juan Miguel

    2008-01-01

    Acetate adsorption at gold electrodes is studied in perchloric acid solutions by cyclic voltammetry and in-situ infrared spectroscopy. External reflection measurements, performed with gold single crystal electrodes, are combined with Surface Enhanced Infrared Reflection Absorption Spectroscopy experiments under attenuated total reflection conditions (ATR-SEIRAS) carried out with sputtered gold thin-film electrodes. Theoretical harmonic IR frequencies of acetate species adsorbed with different geometries on Au clusters with (1 1 1), (1 0 0) and (1 1 0) orientations have been obtained from B3LYP/LANL2DZ, 6-31 + G* calculations. The theoretical and experimental results confirm that, irrespective of the surface crystallographic orientation, bonding of acetate to the surface involves the two oxygen atoms of the carboxylate group, with the OCO plane perpendicular to the metal surface. DFT calculations reveal also that the total charge of the metal cluster-acetate supermolecule has small effect on the vibrational frequencies of adsorbed acetate species. Both the external and the internal reflection measurements show the co-adsorption of acetate and perchlorate anions. Step-scan measurements carried out with the gold thin-film electrodes have allowed the monitoring of the time-dependent behaviour of perchlorate, acetate and water bands in potential step experiments. Acetate adsorption under those conditions is shown to involve perchlorate desorption and to follow a Langmuir-type kinetics. The step-scan spectra also show the rise and decay of transient water structures with parallel time-dependent shifts of the background intensity in the infrared spectra

  10. Behavior of cationic, anionic and colloidal species of titanium, zirconium and thorium in presence of ion exchange resins

    Souza Filho, G. de; Abrao, A.

    1976-01-01

    The distribution of titanium, zirconium and thorium is aqueous and resin phases has been studied using strong cationic resin in the R-NH 4 form. Solutions of the above elements in perchloric, nitric, hydrochloric and suphuric media were used. Each set of experiments was made by separately varying one of the five parameters - type of anion present, acidity of solution, temperature of percolation, age of solution and concentration of the element. It was found that, depending on the particular balance of these parameters, the elements investigated may be found in acidic solutions either as cationic, anionic or colloidal species. It is emphasized that the colloidal species of titanium, zirconium or thorium are not retained by the ion exchangers, and from this property a method for the separation and purification of the above elements has been outlined [pt

  11. Reactions of atomic oxygen with the chlorate ion and the perchlorate ion

    Anan'ev, Vladimir; Miklin, Mikhail; Kriger, Ludmila

    2014-06-01

    The reactions of the chlorate ion with atomic oxygen formed under photolysis of the nitrate ion introduced to potassium chlorate crystal by co-crystallization were studied by optical and infrared absorption spectroscopy. The perchlorate ion was found to form in solids as product of addition reaction of singlet atomic oxygen, formed under dissociation of the peroxynitrite ion - the product of isomerization of the excited nitrate ion. Triplet atomic oxygen does not react with the chlorate ion. The atomic oxygen formed under photolysis of the nitrate ion introduced to potassium perchlorate crystal by co-crystallization does not react with the perchlorate ion.

  12. Detoxification of PAX-21 ammunitions wastewater by zero-valent iron for microbial reduction of perchlorate

    Ahn, Se Chang; Cha, Daniel K. [Department of Civil and Environmental Engineering, University of Delaware, Newark, DE 19716 (United States); Kim, Byung J. [U.S. Army Engineer Research and Development Center, Champaign, IL 61826-9005 (United States); Oh, Seok-Young, E-mail: quartzoh@ulsan.ac.kr [Department of Civil and Environmental Engineering, University of Ulsan, Ulsan 680-749 (Korea, Republic of)

    2011-08-30

    Highlights: {yields} Ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. {yields} DNAN is identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. {yields} Iron treatment not only removes energetic compounds but also eliminates the toxic constituents that inhibit the subsequent microbial process. - Abstract: US Army and the Department of Defense (DoD) facilities generate perchlorate (ClO{sub 4}{sup -}) from munitions manufacturing and demilitarization processes. Ammonium perchlorate is one of the main constituents in Army's new main charge melt-pour energetic, PAX-21. In addition to ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. In order to evaluate microbial perchlorate reduction as a practical option for the treatment of perchlorate in PAX-21 wastewater, we conducted biodegradation experiments using glucose as the primary sources of electrons and carbon. Batch experiments showed that negligible perchlorate was removed in microbial reactors containing PAX-21 wastewater while control bottles containing seed bacteria and glucose rapidly and completely removed perchlorate. These results suggested that the constituents in PAX-21 wastewater may be toxic to perchlorate reducing bacteria. A series of batch toxicity test was conducted to identify the toxic constituents in PAX-21 and DNAN was identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. It was hypothesized that pretreatment of PAX-21 by zero-valent iron granules will transform toxic constituents in PAX-21 wastewater to non-toxic products. We observed complete reduction of DNAN to 2,4-diaminoanisole (DAAN) and RDX to formaldehyde in abiotic iron reduction study. After a 3-day acclimation period, perchlorate in iron-treated PAX-21

  13. (Acetato-κO(aqua-κO(2-{bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN2methyl]amino-κN}ethanol-κOnickel(II perchlorate monohydrate

    Jia Zhou

    2012-04-01

    Full Text Available In the structure of the title complex, [Ni(CH3CO2(C14H23N5O(H2O]ClO4·H2O, the NiII centre has a distorted octahedral environment defined by one O and three N atoms derived from the tetradentate ligand, and two O atoms, one from a water molecule and the other from an acetate anion. The molecules are connected into a three-dimensional architecture by O—H...O hydrogen bonds. The perchlorate anion is disordered over two positions; the major component has a site-occupancy factor of 0.525 (19.

  14. Large-Scale Demonstration of Perchlorate Removal Using Weak Base Anion Resin at Well No. 3 in Rialto, California

    2012-12-01

    Nitrosodiethylamine NDMA N-Nitrosodimethylamine NDPA N-Nitrosodi-n-propylamine ng/L nanogram/liter NMEA N-Nitrosomethylethylamine NMOR N...using USEPA Method 521. N-nitrosodimethylamine ( NDMA ) was 2.6 parts per trillion (ppt) with a detection limit of 2 ppt. All other nitrosamines...was returned to service. All samples were analyzed by Weck Laboratories using USEPA Method 521. Analytes included NDEA, NDMA , NDBA, NDPA, NMEA

  15. Simultaneous Determination of Different Anions in Milk Samples Using Ion Chromatography with Conductivity Detection

    Gülçin Gümüş Yılmaz

    2016-12-01

    Full Text Available The description of a simple method for simultaneous determination of chloride, nitrate, sulfate, iodide, phosphate, thiocyanate, perchlorate, and orotic acid in milk samples was outlined. The method involves the use of dialysis cassettes for matrix elimination, followed by ion chromatography on a high capacity anion exchange column with suppressed conductivity detection. The novelty of dialysis process was that it did not need any chemical and organic solvent for elimination of macromolecules such as fat, carbohydrates and proteins from milk samples. External standard calibration curves for these analytes were linear with great correlation coefficients. The relative standard deviations of analyte concentrations were acceptable both inter-day and intra-day evaluations. Under optimized conditions, the limit of detection (Signal-to-Noise ratio = 3 for chloride, phosphate, thiocyanate, perchlorate, iodide, nitrate, sulfate, and orotate was found to be 0.012, 0.112, 0.140, 0.280, 0.312, 0.516, 0.520, and 0.840 mg L−1, respectively. Significant results were obtained for various spiked milk samples with % recovery in the range of 93.88 - 109.75 %. The proposed method was successfully applied to milk samples collected from Istanbul markets. The advantages of the method described herein are reagent-free, simple, and reliable.

  16. Effect of nitrate, acetate and hydrogen on native perchlorate-reducing microbial communities and their activity in vadose soil

    Nozawa-Inoue, Mamie; Jien, Mercy; Yang, Kun; Rolston, Dennis E.; Hristova, Krassimira R.; Scow, Kate M.

    2011-01-01

    Effect of nitrate, acetate and hydrogen on native perchlorate-reducing bacteria (PRB) was examined by conducting microcosm tests using vadose soil collected from a perchlorate-contaminated site. The rate of perchlorate reduction was enhanced by hydrogen amendment and inhibited by acetate amendment, compared to unamendment. Nitrate was reduced before perchlorate in all amendments. In hydrogen-amended and unamended soils, nitrate delayed perchlorate reduction, suggesting the PRB preferentially use nitrate as an electron acceptor. In contrast, nitrate eliminated the inhibitory effect of acetate amendment on perchlorate reduction and increased the rate and the extent, possibly because the preceding nitrate reduction/denitrification decreased the acetate concentration which was inhibitory to the native PRB. In hydrogen-amended and unamended soils, perchlorate reductase gene (pcrA) copies, representing PRB densities, increased with either perchlorate or nitrate reduction, suggesting either perchlorate or nitrate stimulates growth of the PRB. In contrast, in acetate-amended soil pcrA increased only when perchlorate was depleted: a large portion of the PRB may have not utilized nitrate in this amendment. Nitrate addition did not alter the distribution of the dominant pcrA clones in hydrogen-amended soil, likely because of the functional redundancy of PRB as nitrate-reducers/denitrifiers, whereas acetate selected different pcrA clones from those with hydrogen amendment. PMID:21284679

  17. Anion-Controlled Architecture and Photochromism of Naphthalene Diimide-Based Coordination Polymers

    Jian-Jun Liu

    2018-02-01

    Full Text Available Three new cadmium coordination polymers, namely [Cd(NO32(DPNDI(CH3OH]·CH3OH (1, [Cd(SCN2(DPNDI] (2, and [Cd(DPNDI2(DMF2]·2ClO4 (3 (DPNDI = N,N-di(4-pyridyl-1,4,5,8-naphthalene diimide, DMF = N,N-dimethylformamide have been synthesized by reactions of DPNDI with Cd(NO32, Cd(SCN2, and Cd(ClO42, respectively. Compound 1 is a one-dimensional coordination polymer with strong lone pair-π interactions between the coordinated NO3− anions and the imide ring of DPNDI; while 2 is a two-dimensional network with a (4, 4 net topology. In the case of 3, due to the presence of uncoordinated perchlorate counter ions, it exhibits a non-interpenetrated square-grid coordination polymer containing one-dimensional rhomboid channels. The structural diversity in these compounds is attributed to different coordination abilities and geometries of counter anions. Due to the presence of electron-deficient NDI moiety, the photochromic behavior of these compounds was studied. Interestingly, only compounds 1 and 3 exhibit color changes under light irradiation. The influence of the anions on the photochromism process of the NDI-based materials has been discussed.

  18. Integrated Ion Exchange Regeneration Process for Perchlorate in Drinking Water

    2010-08-01

    chloride NDEA N-Nitrosodiethylamine NDMA N-Nitrosodimethylamine NDPA N-Nitrosodipropylamine NAVFAC ESC Naval Facilities Engineering Command...NO3 37 mg/L as NO3 Uranium 1.6 μg/L 2.6 μg/L 2.2 mg/L NDMA ɚ.0 ng/L 32 ng/L ɚ.0 ng/L NDEA ɚ.0 ng/L ɚ.0 ng/L ɚ.0 ng/L NDPA ɚ.0 ng/L ɚ.0 ng...L ɚ.0 ng/L NDMA – N-Nitrosodimethylamine NDEA – N-Nitrosodiethylamine NDPA – N-Nitrosodipropylamine 15 Figure 5. Influent perchlorate

  19. Radiation-chemical oxidation of neptunium in perchloric acid solutions

    Shilov, V.P.; Gusev, Yu.K.; Pikaev, A.K.; Stepanova, E.S.; Krot, N.N.

    1979-01-01

    The γ-radiation effect (at a dose rate of 5x10 16 eV/mlxs) on 1x10 -3 Np(6) and Np(5) perchloric acid solutions is studied. The output of Np(6) loss in aerated 0.001-0.005M HClO 4 solutions was 2.4 ions/100 eV. The output of Np(5) loss in solutions saturated with nitrous oxide was 2.1 ions/100 eV at pH-4. In aerated 0.1-1.0 M HClO 4 solutions in presence of XeO 4 the output of Np(5) loss grows from 6.6 to 13.5 ions/100 eV as (XeO 3 ) 0 increases from 1x10 -3 to 2x10 -2 M. Possible process mechanisms have been proposed

  20. Ferroelectric Polarization Switching Dynamics and Domain Growth of Triglycine Sulfate and Imidazolium Perchlorate

    Ma, He; Gao, Wenxiu; Wang, Junling; Wu, Tao; Yuan, Guoliang; Liu, Junming; Liu, Zhiguo

    2016-01-01

    The weak bond energy and large anisotropic domain wall energy induce many special characteristics of the domain nucleation, growth, and polarization switch in triglycine sulfate (TGS) and imidazolium perchlorate (IM), two typical molecular

  1. 77 FR 64335 - Notification of a Public Teleconference of the Science Advisory Board; Perchlorate Advisory Panel

    2012-10-19

    ... ENVIRONMENTAL PROTECTION AGENCY [FRL--9743-2] Notification of a Public Teleconference of the Science Advisory Board; Perchlorate Advisory Panel AGENCY: Environmental Protection Agency (EPA). ACTION: Notice. SUMMARY: The Environmental Protection Agency (EPA) Science Advisory Board (SAB) Staff Office...

  2. Investigation of REE perchlorates complexing with benzimidazole in aqua-dioxane media

    Akhrimenko, Z.M.; Panyushkin, V.T.; Ishbulatova, S.K.

    1992-01-01

    Stability constant (K 1 ) of complexes of rare earth perchlorates with benzimidazole were determined by the method of pH-metric titration. Nonmonotonous change in lgK 1 with rare earth ordinal number increase was revealed

  3. Multi-Objective Optimization of an In situ Bioremediation Technology to Treat Perchlorate-Contaminated Groundwater

    The presentation shows how a multi-objective optimization method is integrated into a transport simulator (MT3D) for estimating parameters and cost of in-situ bioremediation technology to treat perchlorate-contaminated groundwater.

  4. Extraction of thorium(IV) as perchlorate and chloroacetate complexes with 1-phenyl-2,3-dimethyl-5-pyrazolone (antipyrine)

    Roopa Bose; Murty, D.S.R.; Chakrapani, G.

    2005-01-01

    Thorium was extracted quantitatively with the neutral ligand 1-phenyl-2,3-dimethyl-5-pyrazolone (Apy) in the presence of perchlorate (ClO 4 - )and di/trichloroacetates (DCA/TCA) at pH 2.5 into an organic solvent. Optimization of experimental parameters like pH, equilibration time, solvents, reactant concentrations, best suited conditions for back extraction, interference due to the presence of different anions and cations and effect of metal ion concentration were studied. The composition of the complexes has been established using log-log plots and are represented as [Th(Apy) 2 (ClO 4 ) 4 ], [Th(Apy) 2 (TCA) 4 ], [Th(Apy)(H 2 O)(DCA) 4 ]. The respective conditional stability constants of the effectively extracted complexes have also been calculated as 9.4 ± 0.03 and 10.4 ± 0.04, respectively . The method has been extended for the separation of thorium from a number of cations in binary and multicomponent mixtures. The method is simple, rapid, selective and has a good reproducibility (±0.5%). (author)

  5. Thyroid Hormones and Moderate Exposure to Perchlorate during Pregnancy in Women in Southern California.

    Steinmaus, Craig; Pearl, Michelle; Kharrazi, Martin; Blount, Benjamin C; Miller, Mark D; Pearce, Elizabeth N; Valentin-Blasini, Liza; DeLorenze, Gerald; Hoofnagle, Andrew N; Liaw, Jane

    2016-06-01

    Findings from national surveys suggest that everyone in the United States is exposed to perchlorate. At high doses, perchlorate, thiocyanate, and nitrate inhibit iodide uptake into the thyroid and decrease thyroid hormone production. Small changes in thyroid hormones during pregnancy, including changes within normal reference ranges, have been linked to cognitive function declines in the offspring. We evaluated the potential effects of low environmental exposures to perchlorate on thyroid function. Serum thyroid hormones and anti-thyroid antibodies and urinary perchlorate, thiocyanate, nitrate, and iodide concentrations were measured in 1,880 pregnant women from San Diego County, California, during 2000-2003, a period when much of the area's water supply was contaminated from an industrial plant with perchlorate at levels near the 2007 California regulatory standard of 6 μg/L. Linear regression was used to evaluate associations between urinary perchlorate and serum thyroid hormone concentrations in models adjusted for urinary creatinine and thiocyanate, maternal age and education, ethnicity, and gestational age at serum collection. The median urinary perchlorate concentration was 6.5 μg/L, about two times higher than in the general U.S. Adjusted associations were identified between increasing log10 perchlorate and decreasing total thyroxine (T4) [regression coefficient (β) = -0.70; 95% CI: -1.06, -0.34], decreasing free thyroxine (fT4) (β = -0.053; 95% CI: -0.092, -0.013), and increasing log10 thyroid-stimulating hormone (β = 0.071; 95% CI: 0.008, 0.133). These results suggest that environmental perchlorate exposures may affect thyroid hormone production during pregnancy. This could have implications for public health given widespread perchlorate exposure and the importance of thyroid hormone in fetal neurodevelopment. Steinmaus C, Pearl M, Kharrazi M, Blount BC, Miller MD, Pearce EN, Valentin-Blasini L, DeLorenze G, Hoofnagle AN, Liaw J. 2016. Thyroid

  6. Role of phosphate and other proton-donating anions in respiration-coupled transport of Ca2+ by mitochondria.

    Lehninger, A L

    1974-04-01

    Measurements of extra oxygen consumption, (45)Ca(2+) uptake, and the osmotic expansion of the matrix compartment show that not all permeant anions are capable of supporting and accompanying the energy-dependent transport of Ca(2+) from the medium into the matrix in respiring rat-liver mitochondria. Phosphate, arsenate, acetate, butyrate, beta-hydroxybutyrate, lactate, and bicarbonate + CO(2) supported Ca(2+) uptake, whereas the permeant anions, nitrate, thiocyanate, chlorate, and perchlorate, did not. The active anions share a common denominator, the potential ability to donate a proton to the mitochondrial matrix; the inactive anions lack this capacity. Phosphate and the other active permeant anions move into the matrix in response to the alkaline-inside electrochemical gradient of protons generated across the mitochondrial membrane by electron transport, thus forming a negative-inside anion gradient. It is postulated that the latter gradient is the immediate "pulling" force for the influx of Ca(2+) on the electrogenic Ca(2+) carrier in respiring mitochondria under intracellular conditions. Since mitochondria in the cell are normally exposed to an excess of phosphate (and the bicarbonate-CO(2) system), particularly in state 4, inward transport of these proton-yielding anions probably precedes and is necessary for inward transport of Ca(2+) and other cations under biological conditions. These observations indicate that a negative-inside gradient of phosphate generated by electron transport is a common step and provides the immediate motive power not only for (a) the inward transport of dicarboxylates and tricarboxylates and (b) the energy-dependent exchange of external ADP(3-) for internal ATP(4-) during oxidative phosphorylation, as has already been established, but also for (c) the inward transport of Ca(2+), K(+), and other cations.

  7. Passive Biobarrier for Treating Co-Mingled Perchlorate and RDX in Groundwater at an Active Range

    2016-12-31

    monitoring K hydraulic conductivity; sorption coefficient MCL Maximum Contaminant Level mg/kg milligram(s) per kilogram mg/L milligram(s) per liter...low concentrations. The effectiveness of the barrier for reducing migration of perchlorate and explosives in groundwater at the EEA of NSWCDD was...at NSWCDD suggests that an emulsified oil biobarrier is a viable alternative to reduce the migration of co-mingled perchlorate and explosives in

  8. Synthesis and characterisation of some lanthanide perchlorate complexes of 4-nitrosoantipyrine

    Jayasankar, H.; Indrasenan, P.

    1988-01-01

    Seven lanthanide perchlorate complexes of 4-nitrosoantipyrine (NAP) of the general formula [Ln(NAP) 4 ClO 4 ](ClO 4 ) 2 (where Ln=La, Pr, Nd, Sm, Gd, Dy and Y), have been synthesised and characterised by elemental analyses, molecular weights, conductances, magnetic moments and infrared and electronic spectral data. In these nine-coordinated complexes, all the four NAP molecules are coordinated bidentately and one of the perchlorate groups is coordinated monodentately. (author). 12 refs

  9. The vapour pressures over saturated aqueous solutions of sodium and potassium acetates, chlorates, and perchlorates

    Apelblat, Alexander [Department of Chemical Engineering, Ben Gurion University of the Negev, Beer Sheva 84105 (Israel)]. E-mail: apelblat@bgu.ac.il; Manzurola, Emanuel [Department of Chemical Engineering, Ben Gurion University of the Negev, Beer Sheva 84105 (Israel)

    2007-08-15

    Vapour pressures of water over saturated solutions of sodium acetate, potassium acetate, sodium perchlorate, and potassium perchlorate were determined over the (278 to 318) K temperature range and compared with available in the literature data. The cases of saturated solutions of sodium chlorate and potassium chlorate are also considered. The determined vapour pressures were used to obtain the water activities, the osmotic coefficients, and the molar enthalpies of vaporization in considered systems.

  10. Perchlorate reduction by hydrogen autotrophic bacteria and microbial community analysis using high-throughput sequencing.

    Wan, Dongjin; Liu, Yongde; Niu, Zhenhua; Xiao, Shuhu; Li, Daorong

    2016-02-01

    Hydrogen autotrophic reduction of perchlorate have advantages of high removal efficiency and harmless to drinking water. But so far the reported information about the microbial community structure was comparatively limited, changes in the biodiversity and the dominant bacteria during acclimation process required detailed study. In this study, perchlorate-reducing hydrogen autotrophic bacteria were acclimated by hydrogen aeration from activated sludge. For the first time, high-throughput sequencing was applied to analyze changes in biodiversity and the dominant bacteria during acclimation process. The Michaelis-Menten model described the perchlorate reduction kinetics well. Model parameters q(max) and K(s) were 2.521-3.245 (mg ClO4(-)/gVSS h) and 5.44-8.23 (mg/l), respectively. Microbial perchlorate reduction occurred across at pH range 5.0-11.0; removal was highest at pH 9.0. The enriched mixed bacteria could use perchlorate, nitrate and sulfate as electron accepter, and the sequence of preference was: NO3(-) > ClO4(-) > SO4(2-). Compared to the feed culture, biodiversity decreased greatly during acclimation process, the microbial community structure gradually stabilized after 9 acclimation cycles. The Thauera genus related to Rhodocyclales was the dominated perchlorate reducing bacteria (PRB) in the mixed culture.

  11. Microbial redox processes in deep subsurface environments and the potential application of (perchlorate in oil reservoirs

    Martin G Liebensteiner

    2014-09-01

    Full Text Available The ability of microorganisms to thrive under oxygen-free conditions in subsurface environments relies on the enzymatic reduction of oxidized elements, such as sulfate, ferric iron or CO2, coupled to the oxidation of inorganic or organic compounds. A broad phylogenetic and functional diversity of microorganisms from subsurface environments has been described using isolation-based and advanced molecular ecological techniques. The physiological groups reviewed here comprise iron-, manganese- and nitrate-reducing microorganisms. In the context of recent findings also the potential of chlorate and perchlorate [jointly termed (perchlorate] reduction in oil reservoirs will be discussed. Special attention is given to elevated temperatures that are predominant in the deep subsurface. Microbial reduction of (perchlorate is a thermodynamically favorable redox process, also at high temperature. However, knowledge about (perchlorate reduction at elevated temperatures is still scarce and restricted to members of the Firmicutes and the archaeon Archaeoglobus fulgidus. By analyzing the diversity and phylogenetic distribution of functional genes in (metagenome databases and combining this knowledge with extrapolations to earlier-made physiological observations we speculate on the potential of (perchlorate reduction in the subsurface and more precisely oil fields. In addition, the application of (perchlorate for bioremediation, souring control and microbial enhanced oil recovery are addressed.

  12. Fabrication of ammonium perchlorate/copper-chromium oxides core-shell nanocomposites for catalytic thermal decomposition of ammonium perchlorate

    Eslami, Abbas, E-mail: eslami@umz.ac.ir [Department of Inorganic Chemistry, Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-95447, Babolsar (Iran, Islamic Republic of); Juibari, Nafise Modanlou [Department of Inorganic Chemistry, Faculty of Chemistry, University of Mazandaran, P.O.Box 47416-95447, Babolsar (Iran, Islamic Republic of); Hosseini, Seyed Ghorban [Department of Chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3454, Tehran (Iran, Islamic Republic of)

    2016-09-15

    The ammonium perchlorate/Cu(II)-Cr(III)-oxides(AP/Cu-Cr-O) core-shell nanocomposites were in-situ prepared by deposition of copper and chromium oxides on suspended ammonium perchlorate particles in ethyl acetate as solvent. The results of differential scanning calorimetery (DSC) and thermal gravimetric analysis (TGA) experiments showed that the nanocomposites have excellent catalytic effect on the thermal decomposition of AP, so that the released heat increases up to about 3-fold over initial values, changing from 450 J/g for pure AP to 1510 J/g for most appropriate mixture. For better comparison, single metal oxide/AP core-shell nanocomposite have also been prepared and the results showed that they have less catalytic effect respect to mixed metal oxides system. Scanning electron microscopy (SEM) results revealed homogenous deposition of nanoparticles on the surface of AP and fabrication of core-shell structures. The kinetic parameters of thermal decomposition of both pure AP and AP/Cu-Cr-O samples have been calculated by Kissinger method and the results showed that the values of pre-exponential factor and activation energy are higher for AP/Cu-Cr-O nanocomposite. The better catalytic effect of Cu-Cr-O nanocomposites is probably attributed to the synergistic effect between Cu{sup 2+} and Cr{sup 3+} in the nanocomposites, smaller particle size and more crystal defect. - Highlights: • The Cu-Cr-O nanoparticles were synthesized by chemical liquid deposition method. • Then, the AP/Cu-Cr-O core-shell nanocomposites were prepared. • The core-shell samples showed high catalytic activity for AP decomposition. • Thermal decomposition of samples occurs at lower temperature range.

  13. Pu Anion Exchange Process Intensification

    Taylor-Pashow, Kathryn M. L.

    2017-01-01

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  14. Ionic liquids comprising heteraromatic anions

    Schneider, William F.; Brennecke, Joan F.; Maginn, Edward J.; Mindrup, Elaine; Gurkan, Burcu; Price, Erica; Goodrich, Brett

    2018-04-24

    Some embodiments described herein relate to ionic liquids comprising an anion of a heteraromatic compound such as optionally substituted pyrrolide, optionally substituted pyrazolide, optionally substituted indolide, optionally substituted phospholide, or optionally substituted imidazolide. Methods and devices for gas separation or gas absorption related to these ionic liquids are also described herein.

  15. Pu Anion Exchange Process Intensification

    Taylor-Pashow, Kathryn M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-10-06

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  16. IMPROVING OF ANION EXCHANGERES REGENERATION

    Muzher M. Ibrahim

    2013-05-01

    Full Text Available Inthis study, Different basis [NaOH and KOH] of variable concentration are usedto reactivate Anion exchangers employing different schemes .The Laboratoryresults showed large improvement in efficiency of these exchangers ( i.eoperating time was increased from 12 to 42 hours .The results of this work showed that the environmentalload (waste water can be reduced greatly when using the proposed regenerationscheme .

  17. Quantum mechanics of toroidal anions

    Afanas'ev, G.N.

    1990-01-01

    We consider a toroidal solenoid with an electric charge attached to it. It turns out that statistical properties of the wave function describing interacting toroidal anions depend on both their relative position and orientation. The influence of the particular gauge choice on the exchange properties of the wave function is studied. 30 refs.; 6 figs

  18. Anion binding in biological systems

    Feiters, Martin C [Department of Organic Chemistry, Institute for Molecules and Materials, Faculty of Science, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands); Meyer-Klaucke, Wolfram [EMBL Hamburg Outstation at DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Kostenko, Alexander V; Soldatov, Alexander V [Faculty of Physics, Southern Federal University, Sorge 5, Rostov-na-Donu, 344090 (Russian Federation); Leblanc, Catherine; Michel, Gurvan; Potin, Philippe [Centre National de la Recherche Scientifique and Universite Pierre et Marie Curie Paris-VI, Station Biologique de Roscoff, Place Georges Teissier, BP 74, F-29682 Roscoff cedex, Bretagne (France); Kuepper, Frithjof C [Scottish Association for Marine Science, Dunstaffnage Marine Laboratory, Oban, Argyll PA37 1QA, Scotland (United Kingdom); Hollenstein, Kaspar; Locher, Kaspar P [Institute of Molecular Biology and Biophysics, ETH Zuerich, Schafmattstrasse 20, Zuerich, 8093 (Switzerland); Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R, E-mail: m.feiters@science.ru.n [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)

    2009-11-15

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L{sub 3} (2p{sub 3/2}) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  19. Anion binding in biological systems

    Feiters, Martin C; Meyer-Klaucke, Wolfram; Kostenko, Alexander V; Soldatov, Alexander V; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Kuepper, Frithjof C; Hollenstein, Kaspar; Locher, Kaspar P; Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R

    2009-01-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L 3 (2p 3/2 ) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  20. Anion binding in biological systems

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  1. [μ-N,N′-Bis(2-aminoethylethane-1,2-diamine-κ4N1,N1′:N2,N2′]bis{[N,N′-bis(2-aminoethylethane-1,2-diamine-κ4N,N′,N′′,N′′′]cadmium} tetrakis(perchlorate

    Hamid Goudarziafshar

    2012-09-01

    Full Text Available The centrosymmetric dinuclear cadmium title complex, [Cd2(C6H18N43](ClO44, was obtained by the reaction of N,N′-bis(2-aminoethylethane-1,2-diamine (trien with Cd(NO32·4H2O and sodium perchlorate in methanol. The CdII cation is coordinated by four N atoms of a non-bridging trien ligand and by two N atoms of a bridging trien ligand in a slightly distorted octahedral coordination geometry. The bridging ligand shares another two N atoms with a neighboring symmetry-equivalent CdII cation. The structure displays C—H...O and N—H...O hydrogen bonding. The perchlorate anion is disordered over two sets of sites in a 0.854 (7: 0.146 (7 ratio.

  2. High-Nitrogen-Based Pyrotechnics: Development of Perchlorate-Free Green-Light Illuminants for Military and Civilian Applications

    2012-01-01

    Table 1. Magnesium served as the main fuel in the formulation, barium nitrate and potassium per- chlorate served as the oxidizers, and dechlorane plus...course of the investigation needed to be changed. Although the initial investigation set out to remove potassium per- chlorate oxidizer from the M195 HHS...become a concern of the US Department of Defense is the “perchlorate issue.” Potassium perchlorate and ammonium perchlorate oxidizers, once believed to be

  3. Tripodal receptors for cation and anion sensors

    Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  4. Electrochemical solid-phase microextraction of anions and cations using polypyrrole coatings and an integrated three-electrode device.

    Liljegren, Gustav; Pettersson, Jean; Markides, Karin E; Nyholm, Leif

    2002-05-01

    A method for the extraction, transfer and desorption of anions and cations under controlled potential conditions employing a new integrated three-electrode device is described. The device, containing working, reference and counter electrodes, was prepared from tubes that could be moved vertically with respect to each other. In this way, a small amount of solvent, held by capillary force, remained between the electrodes when the device was lifted out of a solution after an extraction. This design allowed the potential control to be maintained at all times. With the new integrated device, it was possible to perform potential controlled desorption into vials containing as little as 200 microl of solution. The required ion exchange capacity was obtained by electrodeposition of a polypyrrole coating on the surface of the glassy carbon working electrode. Solid-phase microextractions of several cations or anions were performed simultaneously under potentiostatic control by doping the polypyrrole coating with different anions such as perchlorate and p-toluenesulfonate. The efficiency of the extractions, which could be altered by varying the potential of the working electrode, could be increased by 150 to 200% compared to extractions using normal solid-phase microextraction conditions under open circuit conditions. A constant potential of +1.0 V and -0.5 V with respect to the silver pseudo reference electrode, was found to be well-suited for the extraction of samples containing ppm concentrations of anions (chloride, nitrite, bromide, nitrate, sulfate and phosphate) and cations (cadmium, cobalt and zinc), respectively.

  5. Study of microbial perchlorate reduction: Considering of multiple pH, electron acceptors and donors

    Xu, Xing [Key Laboratory of Water Pollution Control and Recycling (Shandong), School of Environmental Science and Engineering, Shandong University, Jinan 250100 (China); Gao, Baoyu, E-mail: bygao@sdu.edu.cn [Key Laboratory of Water Pollution Control and Recycling (Shandong), School of Environmental Science and Engineering, Shandong University, Jinan 250100 (China); Jin, Bo [School of Chemical Engineering, The University of Adelaide, Adelaide SA 5005,Australia (Australia); Zhen, Hu [Key Laboratory of Water Pollution Control and Recycling (Shandong), School of Environmental Science and Engineering, Shandong University, Jinan 250100 (China); Wang, Xiaoyi [CSIRO Land and Water, Gate 5, Waite Road, Urrbrae, SA 5064 (Australia); Dai, Ming [School of Chemical Engineering, The University of Adelaide, Adelaide SA 5005,Australia (Australia)

    2015-03-21

    Graphical abstract: Schemes of perchlorate reduction in ClO{sub 4}{sup −}/ClO{sub 3}{sup −}–NO{sub 3}{sup −} e{sup −}acceptor systems. - Highlights: • We created a multiple electron acceptor/donor system for ClO{sub 4}{sup −} reduction. • Nitrate reduction was inhibited when using perchlorate-grown Azospira sp. KJ. • Reduction proceeded as an order of ClO{sub 3}{sup −}, ClO{sub 4}{sup −}and NO{sub 3}{sup −}. • Oxidation of acetate was inhibited by succinate in acetate–succinate series. - Abstract: Bioremediation of perchlorate-cotaminated water by a heterotrophic perchlorate reducing bacterium creates a multiple electron acceptor-donor system. We experimentally determined the perchlorate reduction by Azospira sp. KJ at multiple pH, electron acceptors and donors systems; this was the aim of this study. Perchlorate reduction was drastically inhibited at the pH 6.0, and the maximum reduction of perchlorate by Azospira sp. KJ was observed at pH value of 8.0. Perchlorate reduction was retarded in ClO{sub 4}{sup −}–ClO{sub 3}{sup −}, ClO{sub 4}{sup −}–ClO{sub 3}{sup −}–NO{sub 3}{sup −},and ClO{sub 4}{sup −}–NO{sub 3}{sup −} acceptor systems, while being completely inhibited by the additional O{sub 2} in the ClO{sub 4}{sup −}–O{sub 2} acceptor system. The reduction proceeded as an order of ClO{sub 3}{sup −}, ClO{sub 4}{sup −}, and NO{sub 3}{sup −} in the ClO{sub 4}{sup −}–ClO{sub 3}{sup −}–NO{sub 3}{sup −} system. K{sub S,}v{sub max}, and q{sub max} obtained at different e{sup −} acceptor and donor conditions are calculated as 140.5–190.6 mg/L, 8.7–13.2 mg-perchlorate/L-h, and 0.094–0.16 mg-perchlorate/mg-DW-h, respectively.

  6. Pediatric neurobehavioral diseases in Nevada counties with respect to perchlorate in drinking water: an ecological inquiry.

    Chang, Soju; Crothers, Carol; Lai, Shenghan; Lamm, Steven

    2003-10-01

    Contamination of drinking water with perchlorate, a known thyrotropic agent, has been demonstrated in areas in the western United States. The health consequences of that exposure have been studied, particularly in the State of Nevada. Previous studies in Nevada, comparing the area with perchlorate in the drinking water and the areas without perchlorate in the drinking water, have found no difference in neonatal thyroxine (T(4)) or thyrotropin (TSH) levels, or in the prevalences of thyroid diseases and thyroid cancer. This same study design has now been applied to the major neurobehavioral diseases of childhood (i.e., attention deficit-hyperactivity disorder (ADHD) and autism) and to school performance in order to determine whether those conditions are more frequent in the area with perchlorate-contaminated water. Medical services data on ADHD and autism were obtained from the Nevada Medicaid system for the period of January 1, 1996, to December 31, 2000, with county of residence used as the basis for residential information. Analyses of fourth-grade school performance results for two recent time periods came from the state government. Perchlorate concentrations in drinking water had been determined by local water authorities. ADHD and autism rates for the area with perchlorate in the drinking water (Clark County) were calculated and compared with the rates for the other areas in the state, as were fourth-grade school performances. Analysis of the data from the Nevada Medicaid program shows that the rates for ADHD and for autism in the area where perchlorate was in the drinking water did not exceed the rates in those areas where there was no perchlorate contamination in the drinking water. Fourth-grade standardized test results for students in Clark County were not different from those of the remainder of the state. This ecological study of children in the exposure area did not find evidence of an increased risk of either ADHD or of autism caused by perchlorate

  7. The Effects of Perchlorate and its Precursors on Organic Molecules under Simulated Mars Conditions

    Carrier, B. L.; Beegle, L. W.; Bhartia, R.; Abbey, W. J.

    2016-12-01

    Perchlorate (ClO4-) was first detected on Mars by the Phoenix Lander in 2008 [1] and has subsequently been detected by Curiosity in Gale Crater [2], in Mars meteorite EETA79001 [3], and has been proposed as a possible explanation for results obtained by Viking [4]. Perchlorate has also been shown to be formed under current Mars conditions via the oxidation of mineral chlorides, further supporting the theory that perchlorate is present globally on Mars [5]. The discovery of perchlorate on Mars has raised important questions about its effects on the survival and detection of organic molecules. Although it has been shown that pyrolysis in the presence of perchlorate results in the alteration or destruction of organic molecules [2, 4], few studies have been conducted on the potential effects of perchlorate and its precursors on organic molecules prior to analysis. Perchlorate is typically inert under Mars temperatures and pressures, but it has been shown to decompose to form reactive oxychlorine species such as chlorite (ClO2-), hypochlorite (ClO-) and chlorine dioxide (ClO2) when exposed to Mars conditions including ionizing radiation [6]. The oxidation of chloride to perchlorate also results in the formation of reactive oxychlorine species such as chlorate (ClO3-) [5]. Here we investigate the effects of perchlorate and its oxychlorine precursors on organic molecules. Experiments are performed in a Mars Simulation Chamber (MSC) capable of reproducing the temperature, pressure, atmospheric composition and UV flux found on Mars. Soil simulants are prepared consisting of Mojave Mars Simulant (MMS) [7] and each organic, as well as varying concentrations of perchlorate and/or chloride salts, and exposed in the MSC. Subsequent to exposure in the MSC samples are leached and the leachate analyzed by HPLC and LC-MS to determine the degree of degradation of the original organic and the identity of any potential decomposition products formed by oxidation or chlorination

  8. The geochemical associations of nitrate and naturally formed perchlorate in the Mojave Desert, California, USA

    Lybrand, Rebecca A.; Michalski, Greg; Graham, Robert C.; Parker, David R.

    2013-03-01

    Perchlorate is a widely studied environmental contaminant that may adversely affect human health, and whose natural occurrence has emerged as a subject of great interest. Naturally formed perchlorate has been found to co-occur with nitrate in arid environments worldwide, but the relationship is not fully understood in the desert soils of the southwestern United States. The main objective of this research was to explore the origin, pedogenic distribution, and possible preservation of perchlorate and nitrate in the Mojave Desert mud hill deposits of California and to determine if the co-occurrence of putatively natural perchlorate was significantly correlated with nitrate in these soils. We identified 39 soil horizons in the Mojave Desert, California that contained reportable levels of perchlorate (MRL >165 μg kg-1) with a maximum concentration of 23 mg kg-1. A weak yet significant correlation was observed between perchlorate and nitrate (r2 = 0.321∗∗∗), which could be indicative of similar mechanisms of accumulation. When compared to published data for the Atacama Desert, the Mojave Desert perchlorate concentrations were remarkably lower for a given nitrate concentration. Oxygen isotopes in the nitrate were examined to identify variation within the Mojave Desert field sites, and to compare with the available literature for the Atacama Desert. The Mojave Desert Δ17O values ranged from 7‰ to 13‰, indicating a mixture of biologically and atmospherically-derived nitrate. An investigation of the distribution of perchlorate among soil horizons revealed that over sixty percent of the samples containing perchlorate were from C horizons while only twenty percent of the samples were from B horizons and even fewer in the overlying A horizons. Soil chemical, morphologic, and geologic characteristics of the soils suggest that the perchlorate, nitrate and/or other soluble salts have moved in a "bottom-up" manner wherein the salts were deposited in strata through

  9. On solubility of perchloric (periodic) acid and α-cyanacetanmide in aqueous solutions at 25 deg C

    Omarova, R.A.; Balysbekov, S.M.; Erkasov, R.Sh.; Nikolenko, O.N.

    1996-01-01

    Acid-base interaction within perchloric (periodic) acid-α-cyanacetamide-water systems in studied by method of solubility under isothermal conditions at 25 deg C. Solubility regularities of crystalline α-cyanacetamide in perchloric and periodic acid solutions are determined, the concentration limits of formation of a new solid phase-tris(α-cyanacetamide) perchlorate within perchloric acid-α-cyanacetamide-water system are determined. The compound is identified by means of chemical and X-ray phase analyses, its density and melting temperature are determined. Iodic acid and α-cyanacetamide water solution base system is shown to belong to a simple eutonic type. 2 refs., 3 figs., 2 tabs

  10. Evidence of Influence of Human Activities and Volcanic Eruptions on Environmental Perchlorate from a 300-Year Greenland Ice Core Record.

    Cole-Dai, Jihong; Peterson, Kari Marie; Kennedy, Joshua Andrew; Cox, Thomas S; Ferris, David G

    2018-06-26

    A 300-year (1700-2007) chronological record of environmental perchlorate, reconstructed from high-resolution analysis of a central Greenland ice core, shows that perchlorate levels in the post-1980 atmosphere were two-to-three times those of the pre-1980 environment. While this confirms recent reports of increased perchlorate in Arctic snow since 1980 compared with the levels for the prior decades (1930-1980), the longer Greenland record demonstrates that the Industrial Revolution and other human activities, which emitted large quantities of pollutants and contaminants, did not significantly impact environmental perchlorate, as perchlorate levels remained stable throughout the eighteenth, nineteenth, and much of the twentieth centuries. The increased levels since 1980 likely result from enhanced atmospheric perchlorate production, rather than from direct release from perchlorate manufacturing and applications. The enhancement is probably influenced by the emission of organic chlorine compounds in the last several decades. Prior to 1980, no significant long-term temporal trends in perchlorate concentration are observed. Brief (a few years) high concentration episodes appear frequently over an apparently stable and low background (~1 ng kg‒1). Several such episodes coincide in time with large explosive volcanic eruptions including the 1912 Novarupta/Katmai eruption in Alaska. It appears that atmospheric perchlorate production is impacted by large eruptions in both high and low latitudes, but not by small eruptions and non-explosive degassing.

  11. Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

    Estrada, Nubia Luz; Böhlke, J K; Sturchio, Neil C; Gu, Baohua; Harvey, Greg; Burkey, Kent O; Grantz, David A; McGrath, Margaret T; Anderson, Todd A; Rao, Balaji; Sevanthi, Ritesh; Hatzinger, Paul B; Jackson, W Andrew

    2017-10-01

    Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth

  12. Methods and systems for measuring anions

    Masih, Dilshad; Mohammed, Omar F.; Aly, Shawkat M.; Alarousu, Erkki

    2016-01-01

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  13. Methods and systems for measuring anions

    Masih, Dilshad

    2016-08-18

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  14. Extractive separation of uranium(VI) as perchlorate/chloroacetate complexes with 1-phenyl-2,3 dimethyl-5-pyrazolone and its applications

    Bose, R.; Murty, D.S.R.

    2003-01-01

    The extraction of U(VI) with 1-phenyl 2,3 dimethyl-5-pyrazolone, at a pH of 2.5, in the presence of common anions, like perchlorate and tri-, di-, and monochloroacetates has been investigated. The optimum experimental conditions have been evaluated by studying various parameters such as pH, equilibration period, reagent concentration, metal concentration, and solvents. Effect of diverse anions and cations on the extraction has also been studied. The extracted species, determined by log D - log R plots are represented as, [UO 2 (Apy) 4 (ClO 4 ) 2 ], [UO 2 (Apy) 2 (TCA) 2 ], [UO 2 (Apy) 2 (DCA) 2 ], [UO 2 (Apy)(H 2 O)(MCA) 2 ]. The conditional stability constants of the quantitatively extracted complexes are calculated. The proposed method allows the selective separation of uranium(VI) from multicomponent mixtures and geological matrices and is also applied for the separation and chemical characterization of impurities at trace and ultratrace levels. (author)

  15. CO-occurring exposure to perchlorate, nitrate and thiocyanate alters thyroid function in healthy pregnant women

    Horton, Megan K., E-mail: megan.horton@mssm.edu [Department of Preventive Medicine, Icahn School of Medicine, New York, New York (United States); Blount, Benjamin C.; Valentin-Blasini, Liza [National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, Georgia (United States); Wapner, Ronald [Department of Obstetrics and Gynecology, Columbia University, New York, New York (United States); Whyatt, Robin [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, New York, New York (United States); Gennings, Chris [Department of Preventive Medicine, Icahn School of Medicine, New York, New York (United States); Factor-Litvak, Pam [Department of Epidemiology, Mailman School of Public Health, Columbia University, New York, New York (United States)

    2015-11-15

    Background: Adequate maternal thyroid function during pregnancy is necessary for normal fetal brain development, making pregnancy a critical window of vulnerability to thyroid disrupting insults. Sodium/iodide symporter (NIS) inhibitors, namely perchlorate, nitrate, and thiocyanate, have been shown individually to competitively inhibit uptake of iodine by the thyroid. Several epidemiologic studies examined the association between these individual exposures and thyroid function. Few studies have examined the effect of this chemical mixture on thyroid function during pregnancy Objectives: We examined the cross sectional association between urinary perchlorate, thiocyanate and nitrate concentrations and thyroid function among healthy pregnant women living in New York City using weighted quantile sum (WQS) regression. Methods: We measured thyroid stimulating hormone (TSH) and free thyroxine (FreeT4) in blood samples; perchlorate, thiocyanate, nitrate and iodide in urine samples collected from 284 pregnant women at 12 (±2.8) weeks gestation. We examined associations between urinary analyte concentrations and TSH or FreeT4 using linear regression or WQS adjusting for gestational age, urinary iodide and creatinine. Results: Individual analyte concentrations in urine were significantly correlated (Spearman's r 0.4–0.5, p<0.001). Linear regression analyses did not suggest associations between individual concentrations and thyroid function. The WQS revealed a significant positive association between the weighted sum of urinary concentrations of the three analytes and increased TSH. Perchlorate had the largest weight in the index, indicating the largest contribution to the WQS. Conclusions: Co-exposure to perchlorate, nitrate and thiocyanate may alter maternal thyroid function, specifically TSH, during pregnancy. - Highlights: • Perchlorate, nitrate, thiocyanate and iodide measured in maternal urine. • Thyroid function (TSH and Free T4) measured in maternal blood

  16. CO-occurring exposure to perchlorate, nitrate and thiocyanate alters thyroid function in healthy pregnant women

    Horton, Megan K.; Blount, Benjamin C.; Valentin-Blasini, Liza; Wapner, Ronald; Whyatt, Robin; Gennings, Chris; Factor-Litvak, Pam

    2015-01-01

    Background: Adequate maternal thyroid function during pregnancy is necessary for normal fetal brain development, making pregnancy a critical window of vulnerability to thyroid disrupting insults. Sodium/iodide symporter (NIS) inhibitors, namely perchlorate, nitrate, and thiocyanate, have been shown individually to competitively inhibit uptake of iodine by the thyroid. Several epidemiologic studies examined the association between these individual exposures and thyroid function. Few studies have examined the effect of this chemical mixture on thyroid function during pregnancy Objectives: We examined the cross sectional association between urinary perchlorate, thiocyanate and nitrate concentrations and thyroid function among healthy pregnant women living in New York City using weighted quantile sum (WQS) regression. Methods: We measured thyroid stimulating hormone (TSH) and free thyroxine (FreeT4) in blood samples; perchlorate, thiocyanate, nitrate and iodide in urine samples collected from 284 pregnant women at 12 (±2.8) weeks gestation. We examined associations between urinary analyte concentrations and TSH or FreeT4 using linear regression or WQS adjusting for gestational age, urinary iodide and creatinine. Results: Individual analyte concentrations in urine were significantly correlated (Spearman's r 0.4–0.5, p<0.001). Linear regression analyses did not suggest associations between individual concentrations and thyroid function. The WQS revealed a significant positive association between the weighted sum of urinary concentrations of the three analytes and increased TSH. Perchlorate had the largest weight in the index, indicating the largest contribution to the WQS. Conclusions: Co-exposure to perchlorate, nitrate and thiocyanate may alter maternal thyroid function, specifically TSH, during pregnancy. - Highlights: • Perchlorate, nitrate, thiocyanate and iodide measured in maternal urine. • Thyroid function (TSH and Free T4) measured in maternal blood

  17. Simultaneous anion and cation mobility in polypyrrole

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

    2003-01-01

    and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  18. Hydrogen oxidation on gold electrode in perchloric acid solution

    Sustersic, M.G.; Almeida, N.V.; Von Mengershausen, A.E. [Facultad de Ingenieria y Ciencias Economico Sociales, Universidad Nacional de San Luis, 25 de Mayo N 384, 5730 Villa Mercedes, San Luis (Argentina)

    2010-06-15

    The aim of this research is to study the interface gold/perchloric acid solution in presence of hydrogen. The reactive is generated by H{sup +} ion reduction and by saturating the electrolyte with the gaseous H{sub 2}. No evidence of H{sub 2} dissociative adsorption is found. In special conditions, a strongly adsorbed layer is formed from the atoms diffusing from inside of the metal. The mass transport occurs in three ways: the diffusion of H atoms inwards, the diffusion of H atoms back to the surface and the dissolved H{sub 2} diffusion from the bulk electrolyte to the surface. When dissolved H{sub 2} reacts, the reaction is kinetically controlled when the H{sub 2} partial pressure is high, and it is diffusionally controlled when the reactive partial pressure is low. Above 0.7 V, (measured vs. RHE), the (100) plane surface reconstruction lifts, and the rate determining step is the H diffusion towards inside of the metal, and the current suddenly falls. The Hydrogen redox reaction on gold shows reversibility with respect to the potential when the reactives are the H diffusing outwards of the metal and the H{sup +} ion present in the electrolyte. However, the absolute current values of oxidation and reduction are different because the reactive sources are different. (author)

  19. Chlorine-36 abundance in natural and synthetic perchlorate

    Heikoop, Jeffrey M [Los Alamos National Laboratory; Dale, M [NON LANL; Sturchio, Neil C [UNIV OF ILLIONOIS; Caffee, M [PURDUE UNIV; Belosa, A D [UNIV OF ILLINOIS; Heraty, Jr., L J [UNIV OF ILLINOIS; Bohike, J K [RESTON, VA; Hatzinger, P B [SHAW ENIVIORNMENTAL C0.; Jackson, W A [TEXAS TECH; Gu, B [ORNL

    2009-01-01

    Perchlorate (ClO{sub 4}{sup -}) is ubiquitous in the environment. It occurs naturally as a product of atmospheric photochemical reactions, and is synthesized for military, aerospace, and industrial applications. Nitrate-enriched soils of the Atacama Desert (Chile) contain high concentrations of natural ClO{sub 4}{sup -}; nitrate produced from these soils has been exported worldwide since the mid-1800's for use in agriculture. The widespread introduction of synthetic and agricultural ClO{sub 4}{sup -} into the environment has complicated attempts to understand the geochemical cycle of ClO{sub 4}{sup -}. Natural ClO{sub 4}{sup -} samples from the southwestern United States have relatively high {sup 36}Cl abundances ({sup 36}Cl/Cl = 3,100 x 10{sup -15} to 28,800 x 10{sup -15}), compared with samples of synthetic ({sup 36}Cl/Cl = 0.0 x 10{sup -15} to 40 x 10{sup -15}) and Atacama Desert ({sup 36}Cl/Cl = 0.9 x 10{sup -15} to 590 x 10{sup -15}) ClO{sub 4}{sup -}. These data give a lower limit for the initial {sup 36}Cl abundance of natural ClO{sub 4}{sup -} and provide temporal and other constraints on its geochemical cycle.

  20. Widespread occurrence of (per)chlorate in the Solar System

    Jackson, W. Andrew; Davila, Alfonso F; Sears, Derek W. G.; Coates, John D.; McKay, Christopher P.; Brundrett, Meaghan; Estrada, Nubia; Böhlke, John Karl

    2015-01-01

    Perchlorate (ClO− 4 ) and chlorate (ClO− 3 ) are ubiquitous on Earth and ClO− 4 has also been found on Mars. These species can play important roles in geochemical processes such as oxidation of organic matter and as biological electron acceptors, and are also indicators of important photochemical reactions involving oxyanions; on Mars they could be relevant for human habitability both in terms of in situ resource utilization and potential human health effects. For the first time, we extracted, detected and quantified ClO− 4 and ClO− 3 in extraterrestrial, non-planetary samples: regolith and rock samples from the Moon, and two chondrite meteorites (Murchison and Fayetteville). Lunar samples were collected by astronauts during the Apollo program, and meteorite samples were recovered immediately after their fall. This fact, together with the heterogeneous distribution of ClO− 4 and ClO− 3 within some of the samples, and their relative abundance with respect to other soluble species (e.g., NO− 3 ) are consistent with an extraterrestrial origin of the oxychlorine species. Our results, combined with the previously reported widespread occurrence on Earth and Mars, indicate that ClO− 4 and ClO− 3 could be present throughout the Solar System.

  1. Radiative Ignition of fine-ammonium perchlorate composite propellants

    Cain, Jeremy; Brewster, M. Quinn [Department of Mechanical Science and Industrial Engineering, University of Illinois, Urbana, IL 61801 (United States)

    2006-08-15

    Radiative ignition of quasi-homogeneous mixtures of ammonium perchlorate (AP) and hydroxyterminated polybutadiene (HTPB) binder has been investigated experimentally. Solid propellants consisting of fine AP (2 {mu}m) and HTPB binder ({proportional_to}76/24% by mass) were ignited by CO{sub 2} laser radiation. The lower boundary of a go/no-go ignition map (minimum ignition time vs. heat flux) was obtained. Opacity was varied by adding carbon black up to 1% by mass. Ignition times ranged from 0.78 s to 0.076 s for incident fluxes ranging from 60 W/cm{sup 2} to 400 W/cm{sup 2}. It was found that AP and HTPB are sufficiently strongly absorbing of 10.6 {mu}m CO{sub 2} laser radiation (absorption coefficient {approx}250 cm{sup -1}) so that the addition of carbon black in amounts typical of catalysts or opacitymodifying agents (up to 1%) would have only a small influence on radiative ignition times at 10.6 {mu}m. A simple theoretical analysis indicated that the ignition time-flux data are consistent with in-depth absorption effects. Furthermore, this analysis showed that the assumption of surface absorption is not appropriate, even for this relatively opaque system. For broadband visible/near-infrared radiation, such as from burning metal/oxide particle systems, the effects of in-depth absorption would probably be even stronger. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  2. Biological perchlorate reduction in packed bed reactors using elemental sulfur.

    Sahu, Ashish K; Conneely, Teresa; Nüsslein, Klaus R; Ergas, Sarina J

    2009-06-15

    Sulfur-utilizing perchlorate (ClO4-)-reducing bacteria were enriched from a denitrifying wastewater seed with elemental sulfur (S0) as an electron donor. The enrichment was composed of a diverse microbial community, with the majority identified as members of the phylum Proteobacteria. Cultures were inoculated into bench-scale packed bed reactors (PBR) with S0 and crushed oyster shell packing media. High ClO4-concentrations (5-8 mg/L) were reduced to PBR performance decreased when effluent recirculation was applied or when smaller S0 particle sizes were used, indicating that mass transfer of ClO4- to the attached biofilm was not the limiting mechanism in this process, and that biofilm acclimation and growth were key factors in overall reactor performance. The presence of nitrate (6.5 mg N/L) inhibited ClO4- reduction. The microbial community composition was found to change with ClO4- availability from a majority of Beta-Proteobacteria near the influent end of the reactor to primarily sulfur-oxidizing bacteria near the effluent end of the reactor.

  3. SFG study of platinum electrodes in perchloric acid solutions

    Zheng, W. Q.; Pluchery, O.; Tadjeddine, A.

    2002-04-01

    Infrared-visible sum-frequency generation (SFG) spectroscopy has been used to study the structure of water molecules (and/or its derivatives OH -, H 3O + etc.) at aqueous electrolyte/electrode interfaces. For Pt(1 1 0) and Pt(1 0 0) electrodes in 0.1 M perchloric acid solution, we did not observe any significant O-H stretching resonance. In striking contrast to the resonant SFG signal, the nonresonant SFG (NRSFG) signal varies sensitively with the applied electrochemical potential, indicating that the interaction of water molecules with platinum electrodes is relatively weak as compared to that of H + and ClO 4- ions. From changes in the NRSFG signal and on the basis of an ionic adsorption model, we can also deduce that the potential of zero charge of Pt(1 1 0) in 0.1 M HClO 4 should be located at about 0.22 V (vs. NHE). This value is in good agreement with that measured recently by electrochemical method.

  4. Supramolecular Chemistry of Environmentally Relevant Anions

    Bowman-James, Kristin; Moyer, B.A.; Sessler, Jonathan L.

    2003-01-01

    The goal of this project is the development of highly selective extractants for anions targeting important and timely problems of critical interest to the EMSP mission. In particular, sulfate poses a special problem in cleaning up the Hanford waste tanks in that it interferes with vitrification, but available technologies for sulfate removal are limited. The basic chemical aspects of anion receptor design of functional pH independent systems as well as design of separations strategies for selective and efficient removal of targeted anions have been probed. Key findings include: (1) some of the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate from acidic, nitrate-containing aqueous media. Receptor design, structural influences on anion binding affinities, and findings from liquid-liquid extraction studies will be discussed

  5. (μ-Acetato-κ2 O:O′)[μ-2,6-bis­({bis­[(pyri­din-2-yl-κN)meth­yl]amino-κN}meth­yl)-4-methyl­phenolato-κ2 O:O](metha­nol-κO)dizinc bis­(perchlorate)

    Das, Biswanath; Haukka, Matti; Nordlander, Ebbe

    2014-01-01

    The binuclear title complex, [Zn2(C33H33N6O)(CH3COO2)(CH3OH)](ClO4)2, was synthesized by the reaction between 2,6-bis­({[bis­(pyridin-2-yl)meth­yl]amino}­meth­yl)-4-methyl­phenol (H-BPMP), Zn(OAc)2 and NaClO4. The two ZnII ions are bridged by the phenolate O atom of the octadentate ligand and the acetate group. An additional methanol ligand is terminally coordinated to one of the ZnII ions, rendering the whole structure unsymmetric. Other symmetric dizinc complexes of BPMP have been reported. However, to the best of our knowledge, the present structure, in which the two ZnII ions are distinguishable by the number of coordinating ligands and the coordination geometries (octahedral and square-pyramidal), is unique. The dizinc complex is a dication, and two perchlorate anions balance the charge. The –OH group of the coordinating methanol solvent mol­ecule forms a hydrogen bond with a perchlorate counter-anion. One of the anions is disordered over two sets of sites with an occupancy ratio of 0.734 (2):0.266 (2). PMID:24826088

  6. Effect of perchlorate in fertilisers on lettuce and fruit vegetables : Uptake and distribution of perchlorate in greenhouse soil-grown butterhead lettuce and solless-grown cucumber, sweet pepper, round and cherry tomate

    Voogt, W.; Eveleens, B.A.; Steenhuizen, J.W.; Vandevelde, I.; Vis, de R.; Lommel, van J.

    2014-01-01

    In 2013 traces of perchlorate were detected in fruits and vegetable samples. Because perchlorate (ClO4 -) is part of a group of substances (goitrogens) that may inhibit the uptake of iodine by the thyroid, these findings caused commotion in the markets. Fertilizers were named as one of the sources

  7. Possible Calcite and Magnesium Perchlorate Interaction in the Mars Phoenix Thermal and Evolved Gas Analyzer (TEGA)

    Cannon, K. M.; Sutter, B.; Ming, D. W.; Boynton, W. V.; Quinn, R. C.

    2012-01-01

    The Mars Phoenix Lander's TEGA instrument detected a calcium carbonate phase decomposing at high temperatures (approx.700 C) from the Wicked Witch soil sample [1]. TEGA also detected a lower temperature CO2 release between 400 C and 680 C [1]. Possible explanations given for this lower temperature CO2 release include thermal decomposition of Mg or Fe carbonates, a zeolitictype desorption reaction, or combustion of organic compounds in the soil [2]. The detection of 0.6 wt % soluble perchlorate by the Wet Chemistry Laboratory (WCL) on Phoenix [3] has implications for the possibility of organic molecules in the soil. Ming et al. [4] demonstrated that perchlorates could have oxidized organic compounds to CO2 in TEGA, preventing detection of their characteristic mass fragments. Here, we propose that a perchlorate salt and calcium carbonate present in martian soil reacted to produce the 400 C - 680 C TEGA CO2 release. The parent salts of the perchlorate on Mars are unknown, but geochemical models using WCL data support the possible dominance of Mg-perchlorate salts [5]. Mg(ClO4)2 6H2O is the stable phase at ambient martian conditions [6], and breaks down at lower temperatures than carbonates giving off Cl2 and HCl gas [7,8]. Devlin and Herley [7] report two exotherms at 410-478 C and 473-533 C which correspond to the decomposition of Mg(ClO4)2.

  8. The occurrence of perchlorate during drinking water electrolysis using BDD anodes

    Bergmann, M.E. Henry; Rollin, Johanna; Iourtchouk, Tatiana

    2009-01-01

    Electrochemical studies were carried out to estimate the risks of perchlorate formation in drinking water disinfected by direct electrolysis. Boron Doped Diamond (BDD) anodes were used in laboratory and commercially available cells at 20 deg. C. The current density was changed between 50 and 500 A m -2 . For comparison, other anode materials such as platinum and mixed oxide were also tested. It was found that BDD anodes have a thousandfold higher perchlorate formation potential compared with the other electrode materials that were tested. In long-term discontinuous experiments all the chloride finally reacted to form perchlorate. The same result was obtained when probable oxychlorine intermediates (OCl - , ClO 2 - , ClO 3 - ) were electrolysed in synthetic waters in the ppm range of concentrations. The tendency to form perchlorate was confirmed when the flow rate of drinking water was varied between 100 and 300 L h -1 and the temperature increased to 30 deg. C. In a continuous flow mode of operation a higher chloride concentration in the water resulted in a lower perchlorate formation. This can be explained by reaction competition of species near and on the anode surface for experiments both with synthetic and local drinking waters. It is concluded that the use of electrodes producing highly reactive species must be more carefully controlled in hygienically and environmentally oriented applications

  9. Occurrence of perchlorate in drinking water and seawater in South Korea.

    Her, Namguk; Jeong, Hyunchan; Kim, Jongsung; Yoon, Yeomin

    2011-08-01

    Concentrations of perchlorate were determined by both liquid-chromatography-mass spectrometry (LC-MS) and ion chromatography tandem mass spectrometry (IC-MS/MS) in 520 tap-water, 48 bottled-water, and 9 seawater samples obtained or purchased from >100 different locations in South Korea. The method detection limits were 0.013 μg/L for LC-MS and 0.005 μg/L for IC-MS/MS, and the limits of quantification (LOQs) were 0.10 μg/L for LC-MS and 0.032 μg/L for IC-MS/MS. Perchlorate was detected in most (80%) of the tap-water samples, with concentrations higher than the LOQ; the concentrations ranged from water samples, with concentrations higher then the LOQ, ranging from 0.04 to 0.29 μg/L (mean 0.07 ± 0.01). The concentrations of perchlorate in all seawater samples collected from the various locations were higher than the LOQ, with a mean concentration of 1.15 ± 0.01 μg/L (maximum 6.11 and minimum 0.11). This study provides further evidence that drinking-water sources have been contaminated by perchlorate. To the best of our knowledge, this is the first comprehensive study on perchlorate assessment in drinking water and seawater in South Korea.

  10. Anion

    A. Vadivel Murugan

    2003-01-01

    . Its characterization is investigated by Fourier Transform Infrared Spectroscopy (FT-IR and Scanning Electron Microscopy (SEM. The hybrid material presents predominantly high electronic conductivities of around 2.0 and 7.0 S cm-1 at 300 and 400K respectively.

  11. Effective adsorption/electrocatalytic degradation of perchlorate using Pd/Pt supported on N-doped activated carbon fiber cathode

    Yao, Fubing; Zhong, Yu [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Yang, Qi, E-mail: yangqi@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Wang, Dongbo, E-mail: dongbowang@hnu.edu.cn [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China); Chen, Fei; Zhao, Jianwei; Xie, Ting; Jiang, Chen; An, Hongxue; Zeng, Guangming; Li, Xiaoming [College of Environmental Science and Engineering, Hunan University, Changsha 410082 (China); Key Laboratory of Environmental Biology and Pollution Control, Hunan University, Ministry of Education, Changsha 410082 (China)

    2017-02-05

    Highlights: • Pd/Pt-NACF served as an adsorption/electrocatalysis electrode to reduce perchlorate. • The possible mechanisms involved in the reaction process were explained. • The reusability and stability of Pd/Pt-NACF bifunctional material was evaluated. - Abstract: In this work, Pd/Pt supported on N-doped activated carbon fiber (Pd/Pt-NACF) was employed as the electrode for electrocatalytic degradation of perchlorate through adsorption/electroreduction process. Perchlorate in solution was firstly adsorbed on Pd/Pt-NACF and then reduced to non-toxic chloride by the catalytic function of Pd/Pt at a constant current (20 mA). Compared with Pd/Pt-ACF, the adsorption capacity and electrocatalytic degradation efficiency of Pd/Pt-NACF for perchlorate increased 161% and 28%, respectively. Obviously, positively charged N-functional groups on NACF surface enhanced the adsorption capacity of Pd/Pt-NACF, and the dissociation of hydrogen to atomic H* by the Pd/Pt nanostructures on the cathode might drastically promote the electrocatalytic reduction of perchlorate. The role of atomic H* in the electroreduction process was identified by tertiary butanol inhibition test. Meanwhile, the perchlorate degradation performance was not substantially lower after three successive adsorption/electrocatalytic degradation experiments, demonstrating the electrochemical reusability and stability of the as-prepared electrode. These results showed that Pd/Pt-NACF was effective for electrocatalytic degradation of perchlorate and had great potential in perchlorate removal from water.

  12. Perchlorate exposure and association with iron homeostasis and other biological functions among NHANES 2005-2008 subjects

    Perchlorate exposure and association with iron homeostasis and other biological functions among NHANES 2005-2008 subjects Schreinemachers DM, Ghio AJ, Cascio WE, Sobus JR. U.S. EPA, RTP, NC, USA Perchlorate (ClO4-), an environmental pollutant, is a known thyroid toxicant and...

  13. Isolation of perchlorate-reducing Azospira suillum strain JB524 from tidal flats of the Yellow Sea

    Nirmala Bardiya

    2016-11-01

    Full Text Available Objective: To isolate and identify perchlorate-reducing bacterium from an enriched consortium from tidal flats of the Yellow Sea. Methods: A perchlorate-enriched consortium from tidal flats of the Yellow Sea was used to isolate Azospira suillum (A. suillum strain JB524. The strain was identified based on partial 16S rDNA sequencing. Perchlorate reduction by the strain was tested with acetate as the e - donor in the presence of NaCl, nitrate and at different growth temperatures using standard anaerobic techniques. The complete enzymatic destruction of perchlorate was confirmed as evolution of O2 by chlorite dismutase in the absence of acetate. Results: Strain JB524 shared 100% 16S rDNA sequence similarity with the type strain A. suillum PST isolated from a swine waste treatment lagoon. Perchlorate reduction coincided with concomitant increase in cell density. Although, acclimatization of the strain PST at suboptimal temperature for perchlorate reduction is not reported, the newly isolated strain could rapidly reduce perchlorate at 22 °C after brief acclimatization. Conclusions: Reduction of perchlorate by A. suillum strain JB524 was negatively affected in the presence of NaCl, suboptimal temperature, presence of nitrate, and limiting amount of acetate as the e-donor.

  14. Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation

    Paul B. Hatzinger,; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua

    2013-01-01

    Increased health concerns about perchlorate (ClO4-) during the past decade and subsequent regulatory considerations have generated appreciable interest in source identification. The key objective of the isotopic techniques described in this guidance manual is to provide evidence concerning the origin of ClO4- in soils and groundwater and, more specifically, whether that ClO4- is synthetic or natural. Chlorine and oxygen isotopic analyses of ClO4- provide the primary direct approach whereby different sources of ClO4- can be distinguished from each other. These techniques measure the relative abundances of the stable isotopes of chlorine (37Cl and 35Cl) and oxygen (18O, 17O, and 16O) in ClO4- using isotope-ratio mass spectrometry (IRMS). In addition, the relative abundance of the radioactive chlorine isotope 36Cl is measured using accelerator mass spectrometry (AMS). Taken together, these measurements provide four independent quantities that can be used to distinguish natural and synthetic ClO4- sources, to discriminate different types of natural ClO4-, and to detect ClO4- biodegradation in the environment. Other isotopic, chemical, and geochemical techniques that can be applied in conjunction with isotopic analyses of ClO4- to provide supporting data in forensic studies are also described.

  15. A simplified method for obtaining high-purity perchlorate from groundwater for isotope analyses.

    vonKiparski, G; Hillegonds, D

    2011-04-04

    Investigations into the occurrence and origin of perchlorate (ClO{sub 4}{sup -}) found in groundwater from across North America have been sparse until recent years, and there is mounting evidence that natural formation mechanisms are important. New opportunities for identifying groundwater perchlorate and its origin have arisen with the utilization of improved detection methods and sampling techniques. Additionally, application of the forensic potential of isotopic measurements has begun to elucidate sources, potential formation mechanisms and natural attenuation processes. Procedures developed appear to be amenable to enable high precision stable isotopic analyses, as well as lower precision AMS analyses of {sup 36}Cl. Immediate work is in analyzing perchlorate isotope standards and developing full analytical accuracy and uncertainty expectations. Field samples have also been collected, and will be analyzed when final qa/qc samples are deemed acceptable.

  16. Environmental behavior of inorganic anions

    Garland, T.R.; Cataldo, D.A.; Fellows, R.J.; Wildung, R.E.

    1987-01-01

    Recent efforts have addressed two aspects of anion behavior in the soil/plant system. The first involves evaluation of the gaseous component of the terrestrial iodine cycle in soils and plants. Field analyses of 129 I in soils and vegetation adjacent to a fuels reprocessing facility, which was idle for 10 years prior to the study, indicated that there may be a significant gaseous component to the terrestrial iodine cycle. Soil substrates, including a silt-sand, organic forest soil, quartz sand, and a sterilized soil, were amended with radioiodide, and the rates and quality of the volatile components evaluated

  17. Effects of prolonged exposure to perchlorate on thyroid and reproductive function in zebrafish

    Mukhi, S.; Patino, R.

    2007-01-01

    The objectives of this study were to determine the effects of prolonged exposure to perchlorate on (1) thyroid status and reproductive performance of adult zebrafish (Danio rerio) and (2) F1 embryo survival and early larval development. Using a static-renewal procedure, mixed sex populations of adult zebrafish were exposed to 0, 10, and 100 mg/l nominal concentrations of waterborne perchlorate for 10 weeks. Thyroid histology was qualitatively assessed, and females and males were separated and further exposed to their respective treatments for six additional weeks. Eight females in each tank replicate (n = 3) were paired weekly with four males from the same respective treatment, and packed-egg (spawn) volume (PEV) was measured each of the last five weeks. At least once during weeks 14-16 of exposure, other end points measured included fertilization rate, fertilized egg diameter, hatching rate, standard length, and craniofacial development of 4-day-postfertilization larvae and thyroid hormone content of 3.5-h embryos and of exposed mothers. At 10 weeks of exposure, perchlorate at both concentrations caused thyroidal hypertrophy and colloid depletion. A marked reduction in PEV was observed toward the end of the 6-week spawning period, but fertilization and embryo hatching rates were unaffected. Fertilized egg diameter and larval length were increased by parental exposure to perchlorate. Larval head depth was unaffected but the forward protrusion of the lower jaw-associated cartilage complexes, Meckel's and ceratohyal, was decreased. Exposure to both concentrations of perchlorate inhibited whole-body thyroxine content in mothers and embryos, but triiodothyronine content was unchanged. In conclusion, prolonged exposure of adult zebrafish to perchlorate not only disrupts their thyroid endocrine system but also impairs reproduction and influences early F1 development. ?? 2007 Oxford University Press.

  18. Effects of larval-juvenile treatment with perchlorate and co-treatment with thyroxine on zebrafish sex ratios

    Mukhi, S.; Torres, L.; Patino, R.

    2007-01-01

    The objective of this study was to determine the effect of larval-juvenile exposure to perchlorate, a thyroid hormone synthesis inhibitor, on the establishment of gonadal sex ratios in zebrafish. Zebrafish were exposed to untreated water or water containing perchlorate at 100 or 250 ppm for a period of 30 days starting at 3 days postfertilization (dpf). Recovery treatments consisted of a combination of perchlorate and exogenous thyroxine (T4; 10 nM). Thyroid histology was assessed at the end of the treatment period (33 dpf), and gonadal histology and sex ratios were determined in fish that were allowed an additional 10-day period of growth in untreated water. As expected, exposure to perchlorate caused changes in thyroid histology consistent with hypothyroidism and these effects were reversed by co-treatment with exogenous T4. Perchlorate did not affect fish survival but co-treatment with T4 induced higher mortality. However, relative to the corresponding perchlorate concentration, co-treatment with T4 caused increased mortality only at a perchlorate concentration of 100 ppm. Perchlorate alone or in the presence of T4 suppressed body length at 43 dpf relative to control values. Perchlorate exposure skewed the sex ratio toward female in a concentration-dependent manner, and co-treatment with T4 not only blocked the feminizing effect of perchlorate but also overcompensated by skewing the sex ratio towards male. Moreover, co-treatment with T4 advanced the onset of spermatogenesis in males. There was no clear association between sex ratios and larval survival or growth. We conclude that endogenous thyroid hormone plays a role in the establishment of gonadal sex phenotype during early development in zebrafish. ?? 2006 Elsevier Inc. All rights reserved.

  19. Perchlorate in Lake Water from an Operating Diamond Mine.

    Smith, Lianna J D; Ptacek, Carol J; Blowes, David W; Groza, Laura G; Moncur, Michael C

    2015-07-07

    Mining-related perchlorate [ClO4(-)] in the receiving environment was investigated at the operating open-pit and underground Diavik diamond mine, Northwest Territories, Canada. Samples were collected over four years and ClO4(-) was measured in various mine waters, the 560 km(2) ultraoligotrophic receiving lake, background lake water and snow distal from the mine. Groundwaters from the underground mine had variable ClO4(-) concentrations, up to 157 μg L(-1), and were typically an order of magnitude higher than concentrations in combined mine waters prior to treatment and discharge to the lake. Snow core samples had a mean ClO4(-) concentration of 0.021 μg L(-1) (n=16). Snow and lake water Cl(-)/ClO4(-) ratios suggest evapoconcentration was not an important process affecting lake ClO4(-) concentrations. The multiyear mean ClO4(-) concentrations in the lake were 0.30 μg L(-1) (n = 114) in open water and 0.24 μg L(-1) (n = 107) under ice, much below the Canadian drinking water guideline of 6 μg L(-1). Receiving lake concentrations of ClO4(-) generally decreased year over year and ClO4(-) was not likely [biogeo]chemically attenuated within the receiving lake. The discharge of treated mine water was shown to contribute mining-related ClO4(-) to the lake and the low concentrations after 12 years of mining were attributed to the large volume of the receiving lake.

  20. Growth and optical characterizations on 3-aminophenol perchlorate (3-AMPP) crystal

    Boopathi, K., E-mail: ramasamyp@ssn.edu.in; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in [Centre for Crystal Growth, SSN College of Engineering, Kalavakkam-603110 (India)

    2014-04-24

    A single crystal of organic nonlinear optical material 3-aminophenol perchlorate (3-AMP) was successfully grown by the slow evaporation solution method. Single-crystal X-ray diffractrometer was utilized to measure unit cell parameters and to confirm lattice parameter. 3-aminophenol perchlorate belongs to monoclinic space group P2{sub 1}. The optical transparency window in the UV-vis-NIR region is found to be good for nonlinear optical applications second harmonic studies were carried out. The second harmonic output intensity was tested using the Kurtz and Perry powder method and was found to be 1.1 times that of potassium dihydrogen phosphate (KDP)

  1. Environmental Health Assessment for Pyrotechnic Perchlorate Elimination/Mitigation Program for M118/M119 Simulators

    2009-09-11

    17% Potassium Chlorate 3811-04-9 67% 80% Potassium Nitrate 7757-79-1 81% 13% 70% 70% Red Gum 9000-20-8 3% 3% Silicon 7440-21-3 6% Sulfur 7704-34-9 8... potassium perchlorate from the flash composition of the formulations for the Ml18 and Ml19 simulators. These simulators are used in training to produce...simulators that are more efficient, are life-cycle cost effective, and more conducive to human health and environmental quality. b. Potassium perchlorate

  2. Possible Detection of Perchlorates by the Sample Analysis at Mars (SAM) Instrument: Comparison with Previous Missions

    Navarro-Gonzalex, Rafael; Sutter, Brad; Archer, Doug; Ming, Doug; Eigenbrode, Jennifer; Franz, Heather; Glavin, Daniel; McAdam, Amy; Stern, Jennifer; McKay, Christopher; hide

    2013-01-01

    The first chemical analysis of soluble salts in the soil was carried out by the Phoenix Lander in the Martian Arctic [1]. Surprisingly, chlorine was present as magnesium or calcium perchlorate at 0.4 to 0.6 percent. Additional support for the identification of perchlorate came from the evolved gas analysis which detected the release of molecular oxygen at 350-550C [1]. When Mars-like soils from the Atacama Desert were spiked with magnesium perchlorate (1 percent) and heated using the Viking GC-MS protocol, nearly all the organics were combusted but a small amount was chlorinated, forming chloromethane and dichloromethane [2]. These chlorohydrocarbons were detected by the Viking GC-MS experiments when the Martian soil was analyzed but they were considered to be terrestrial contaminants [3]. Reinterpretation of the Viking results suggests Analysis at Mars (SAM) instrument on board the Mars Science Laboratory (MSL) ran four samples from an aeolian bedform named Rocknest. The samples analyzed were portioned from the fifth scoop at this location. The samples were heated to 835C at 35C/min with a He flow. The SAM QMS detected a major oxygen release (300-500C) [5], coupled with the release of chlorinated hydrocarbons (chloromethane, dichloromethane, trichloromethane, and chloromethylpropene) detected both by SAM QMS and GC-MS derived from known Earth organic contaminants in the instrument [6]. Calcium perchlorate appears to be the best candidate for evolved O2 in the Rocknest samples at this time but other Cl species (e.g., chlorates) are possible and must be evaluated. The potential detection of perchlorates in Rocknest material adds weight to the argument that both Viking Landers measured signatures of perchlorates. Even if the source of the organic carbon detected is still unknown, the chlorine source was likely Martian. Two mechanisms have been hypothesized for the formation of soil perchlorate: (1) Atmospheric oxidation of chlorine; and (2) UV photooxidation of

  3. Solid polymer electrolyte on the basis of polyethylene carbonate-lithium perchlorate system

    Dukhanin, G.P.; Dumler, S.A.; Sablin, A.N.; Novakov, I.A.

    2009-01-01

    Reaction in the system polyethylene carbonate-lithium perchlorate was investigated by IR spectroscopy, differential thermal and X-ray structural analyses. Specific electric conductivity of the prepared composition has been measured. Solid polymer electrolytes on the basis of polyethylene carbonate have conducting properties as electrolytes on the basis of unmodified polyethylene oxide. Compositions of polyethylene carbonate : LiClO 4 =10 : 1Al 2 O 3 -ZrO 2 possess maximum value of electrical conductivity. Activation energies of the process is calculated for all investigated compositions, and dependence of these values from concentration of lithium perchlorate is established

  4. Structure, spectra and phase transition in p-nitroanilinium perchlorate crystal

    Marchewka, M.K.; Drozd, M.; Pietraszko, A

    2003-07-25

    The first X-ray diffraction and vibrational spectroscopic analysis of a novel complex between p-nitroaniline and perchloric acid is reported. The structure was solved in 295 K. Room temperature powder infrared and Raman measurements for the p-nitroanilinium perchlorate (1:1) crystals were carried out. The vibrational spectra in the region of internal vibrations of ions corroborates the X-ray data which show that p-nitroaniline molecule is monoprotonated. DSC measurements on powder sample indicate the phase transition point at about 213 and 208 K for heating and cooling, respectively. No detectable signal was observed during powder test for second harmonic generation.

  5. Schlenk Techniques for Anionic Polymerization

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  6. Crystal structure of 4-tert-butyl-2-{2-[N-(3,3-dimethyl-2-oxobutyl-N-isopropylcarbamoyl]phenyl}-1-isopropyl-1H-imidazol-3-ium perchlorate

    Olga V. Hordiyenko

    2015-02-01

    Full Text Available In the title salt, C26H40N3O2+·ClO4−, the positive charge of the organic cation is delocalized between the two N atoms of the imidazole ring. The C...;N bond distances are 1.338 (2 and 1.327 (3 Å. The substituents on the benzene ring are rotated almost orthogonal with respect to this ring due to the presence of the bulky isopropyl substituents. The dihedral angle between the benzene and imidazole rings is 75.15 (12°. Three of the O atoms of the anion are disordered over two sets of sites due to rotation around one of the O—Cl bonds. The ratio of the refined occupancies is 0.591 (14:0.409 (14. In the crystal, the cation and perchlorate anion are bound by an N—H...O hydrogen bond. In addition, the cation–anion pairs are linked into layers parallel to (001 by multiple weak C—H...O hydrogen bonds.

  7. Influence of the ammonium salt anion on the synergistic solvent extraction of lanthanides with mixtures of thenoyltrifluoroacetone and tridecylamine

    Dukov, I.L.; Jordanov, V.M. [Univ. of Chemical Technology and Metallurgy, Sofia (Bulgaria). Dept. of Inorganic Chemistry

    1998-08-01

    The synergistic solvent extraction of Pr, Gd and Yb with mixtures of thenoyltrifluoroacetone (HTTA) and primary ammonium salt (tridecylammonium chloride or perchlorate, TDAH(Cl, ClO{sub 4})) in C{sub 6}H{sub 6} has been studied. The composition of the extracted species have been determined as Ln(TTA){sub 3}TDAHA(A{sup {minus}} = Cl{sup {minus}} or ClO{sub 4}{sup {minus}}). The values of the equilibrium constant K{sub T,S} have been calculated. The influence of the ammonium salt anion on the extraction process has been discussed. The separation factors of the pairs Gd/Pr and Yb/Gd have been determined.

  8. The colloidal thyroxine (T4) ring as a novel biomarker of perchlorate exposure in the African clawed frog Xenopus laevis

    Hu, F.; Sharma, Bibek; Mukhi, S.; Patino, R.; Carr, J.A.

    2006-01-01

    The purpose of this study was to determine if changes in colloidal thyroxine (T4) immunoreactivity can be used as a biomarker of perchlorate exposure in amphibian thyroid tissue. Larval African clawed frogs (Xenopus laevis) were exposed to 0, 1, 8, 93, and 1131 ??g perchlorate/l for 38 and 69 days to cover the normal period of larval development and metamorphosis. The results of this study confirmed the presence of an immunoreactive colloidal T4 ring in thyroid follicles of X. laevis and demonstrated that the intensity of this ring is reduced in a concentration-dependent manner by perchlorate exposure. The smallest effective concentration of perchlorate capable of significantly reducing colloidal T4 ring intensity was 8 ??g perchlorate/l. The intensity of the immunoreactive colloidal T4 ring is a more sensitive biomarker of perchlorate exposure than changes in hind limb length, forelimb emergence, tail resorption, thyrocyte hypertrophy, or colloid depletion. We conclude that the colloidal T4 ring can be used as a sensitive biomarker of perchlorate-induced thyroid disruption in amphibians. ?? Copyright 2006 Oxford University Press.

  9. Probability of detecting perchlorate under natural conditions in deep groundwater in California and the Southwestern United States

    Fram, Miranda S.; Belitz, Kenneth

    2011-01-01

    We use data from 1626 groundwater samples collected in California, primarily from public drinking water supply wells, to investigate the distribution of perchlorate in deep groundwater under natural conditions. The wells were sampled for the California Groundwater Ambient Monitoring and Assessment Priority Basin Project. We develop a logistic regression model for predicting probabilities of detecting perchlorate at concentrations greater than multiple threshold concentrations as a function of climate (represented by an aridity index) and potential anthropogenic contributions of perchlorate (quantified as an anthropogenic score, AS). AS is a composite categorical variable including terms for nitrate, pesticides, and volatile organic compounds. Incorporating water-quality parameters in AS permits identification of perturbation of natural occurrence patterns by flushing of natural perchlorate salts from unsaturated zones by irrigation recharge as well as addition of perchlorate from industrial and agricultural sources. The data and model results indicate low concentrations (0.1-0.5 μg/L) of perchlorate occur under natural conditions in groundwater across a wide range of climates, beyond the arid to semiarid climates in which they mostly have been previously reported. The probability of detecting perchlorate at concentrations greater than 0.1 μg/L under natural conditions ranges from 50-70% in semiarid to arid regions of California and the Southwestern United States to 5-15% in the wettest regions sampled (the Northern California coast). The probability of concentrations above 1 μg/L under natural conditions is low (generally <3%).

  10. Perchlorate-Coupled Carbon Monoxide (CO Oxidation: Evidence for a Plausible Microbe-Mediated Reaction in Martian Brines

    Marisa R. Myers

    2017-12-01

    Full Text Available The presence of hydrated salts on Mars indicates that some regions of its surface might be habitable if suitable metabolizable substrates are available. However, several lines of evidence have shown that Mars’ regolith contains only trace levels of the organic matter needed to support heterotrophic microbes. Due to the scarcity of organic carbon, carbon monoxide (CO at a concentration of about 700 parts per million (about 0.4 Pa might be the single most abundant readily available substrate that could support near-surface bacterial activity. Although a variety of electron acceptors can be coupled to CO oxidation, perchlorate is likely the most abundant potential oxidant in Mars’ brines. Whether perchlorate, a potent chaotrope, can support microbial CO oxidation has not been previously documented. We report here the first evidence for perchlorate-coupled CO oxidation based on assays with two distinct euryarchaeal extreme halophiles. CO oxidation occurred readily in 3.8 M NaCl brines with perchlorate concentrations from 0.01 to 1 M. Both isolates were able to couple CO with perchlorate or chlorate under anaerobic conditions with or without nitrate as an inducer for nitrate reductase, which serves as a perchlorate reductase in extreme halophiles. In the presence of perchlorate, CO concentrations were reduced to levels well below those found in Mars’ atmosphere. This indicates that CO could contribute to the survival of microbial populations in hydrated salt formations or brines if water activities are suitably permissive.

  11. (Per)chlorate reduction by an acetogenic bacterium, Sporomusa sp., isolated from an underground gas storage.

    Balk, Melike; Mehboob, Farrakh; van Gelder, Antonie H; Rijpstra, W Irene C; Damsté , Jaap S Sinninghe; Stams, Alfons J M

    2010-01-01

    A mesophilic bacterium, strain An4, was isolated from an underground gas storage reservoir with methanol as substrate and perchlorate as electron acceptor. Cells were Gram-negative, spore-forming, straight to curved rods, 0.5-0.8 microm in diameter, and 2-8 microm in length, growing as single cells or in pairs. The cells grew optimally at 37 degrees C, and the pH optimum was around 7. Strain An4 converted various alcohols, organic acids, fructose, acetoin, and H(2)/CO(2) to acetate, usually as the only product. Succinate was decarboxylated to propionate. The isolate was able to respire with (per)chlorate, nitrate, and CO(2). The G+C content of the DNA was 42.6 mol%. Based on the 16S rRNA gene sequence analysis, strain An4 was most closely related to Sporomusa ovata (98% similarity). The bacterium reduced perchlorate and chlorate completely to chloride. Key enzymes, perchlorate reductase and chlorite dismutase, were detected in cell-free extracts.

  12. (Per)chlorate reduction by an acetogenic bacterium, Sporomusa sp., isolated from an underground gas storage.

    Balk, Melike

    2010-08-03

    A mesophilic bacterium, strain An4, was isolated from an underground gas storage reservoir with methanol as substrate and perchlorate as electron acceptor. Cells were Gram-negative, spore-forming, straight to curved rods, 0.5-0.8 microm in diameter, and 2-8 microm in length, growing as single cells or in pairs. The cells grew optimally at 37 degrees C, and the pH optimum was around 7. Strain An4 converted various alcohols, organic acids, fructose, acetoin, and H(2)/CO(2) to acetate, usually as the only product. Succinate was decarboxylated to propionate. The isolate was able to respire with (per)chlorate, nitrate, and CO(2). The G+C content of the DNA was 42.6 mol%. Based on the 16S rRNA gene sequence analysis, strain An4 was most closely related to Sporomusa ovata (98% similarity). The bacterium reduced perchlorate and chlorate completely to chloride. Key enzymes, perchlorate reductase and chlorite dismutase, were detected in cell-free extracts.

  13. Removal of Perchlorate from Water and Wastewater by Catalytic Hydrogen Gas Membrane Systems

    2007-01-01

    Quimica, Serie A: Quimica Fisica e Ingenieria Quimica, 1984. 80(2): p. 219-25. Logan, B.E. and D. LaPoint, Treatment of Perchlorate- and Nitrate...ion at iridium electrodes. Ion concentration and solution pH effects. Anales de Quimica, Serie A: Quimica Fisica e Ingenieria Quimica (1985), 81(3

  14. Zero-Pressure Organic Superconductor: Di-(Tetramethyltetraselenafulvalenium)-Perchlorate [(TMTSF)2ClO4

    Bechgaard, Klaus; da Costa Carneiro, Kim; Olsen, Malte

    1981-01-01

    Evidence for superconductivity in the organic conductor di-(tetramethyltetraselenafulvalenium)-perchlorate [(TMTSF)2ClO4] has been found by resistance measurements in the absence of applied pressure. For different crystals the transitions are approximately 0.3 K wide and are centered around...

  15. DETERMINATION OF PERCHLORATE IN SOME FERTILIZERS AND PLANT TISSUE BY RAMAN SPECTROSCOPY

    We have successfully used Raman spectroscopy for the direct qualitative and quantitative analysis of perchlorate in fertilizer extracts without the need for chromatographic separation. This approach is attractive because Raman is not hindered by the presence of water or of high ...

  16. RAMAN ANALYSIS OF FERTILIZER AND PLANT TISSUE EXTRACTS FOR PERCHLORATE CONTAMINATION

    Recently, we and others found perchlorate at high levels (approximately 500 - 8000 mg/kg) in ~ 90% of 25+ fertilizers products (primarily lawn-and-garden type) with no known link to mined nitrate-bearing Chilean ore. This ore is used, albeit in small scale, in fertilizer product...

  17. A STUDY ON THE ACCUMULATION OF PERCHLORATE IN YOUNG HEAD LETTUCE

    The overall objective of this study was to demonstrate in a greenhouse study the potential for incorporation of perchlorate from aqueous solutions of 10, 50, 100, 500, 1,000, 5,000, and 10,000 ppb into an agricultural food crop (lettuce; Lactuca sativa), which is typically grown ...

  18. Groundwater movement, recharge, and perchlorate occurrence in a faulted alluvial aquifer in California (USA)

    Izbicki, John A.; Teague, Nicholas F.; Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.

    2015-01-01

    Perchlorate from military, industrial, and legacy agricultural sources is present within an alluvial aquifer in the Rialto-Colton groundwater subbasin, 80 km east of Los Angeles, California (USA). The area is extensively faulted, with water-level differences exceeding 60 m across parts of the Rialto-Colton Fault separating the Rialto-Colton and Chino groundwater subbasins. Coupled well-bore flow and depth-dependent water-quality data show decreases in well yield and changes in water chemistry and isotopic composition, reflecting changing aquifer properties and groundwater recharge sources with depth. Perchlorate movement through some wells under unpumped conditions from shallower to deeper layers underlying mapped plumes was as high as 13 kg/year. Water-level maps suggest potential groundwater movement across the Rialto-Colton Fault through an overlying perched aquifer. Upward flow through a well in the Chino subbasin near the Rialto-Colton Fault suggests potential groundwater movement across the fault through permeable layers within partly consolidated deposits at depth. Although potentially important locally, movement of groundwater from the Rialto-Colton subbasin has not resulted in widespread occurrence of perchlorate within the Chino subbasin. Nitrate and perchlorate concentrations at the water table, associated with legacy agricultural fertilizer use, may be underestimated by data from long-screened wells that mix water from different depths within the aquifer.

  19. Evaluation of an Innovative Technology for Treatment of Water Contaminated with Perchlorate and Organic Compounds

    2009-03-26

    2004). Exposure to perchlorate can result in negative health effects including hypothyroidism and various other thyroid disorders (NRC, 2005). Ion...level (DWEL) of 24.5 µg/L (U. S. EPA, 2006a). This dose is based on a 154-pound adult consuming 2 liters of water per day that contains 24.5 µg/L of

  20. Different Supramolecular Coordination Polymers of [N,N'-di(pyrazin-2-yl-pyridine-2,6-diamine]Ni(II with Anions and Solvent Molecules as a Result of Hydrogen Bonding

    Hsin-Ta Wang

    2007-04-01

    Full Text Available Ni(II complexes of N,N'–di(pyrazin–2–ylpyridine–2,6–diamine (H2dpzpda with different anions were synthesized and their structures were determined by X-ray diffraction. Hydrogen bonds between the amino groups and anions assembled the mononuclear molecules into different architectures. The perchlorate complex had a 1-D chain structure, whereas switching the anion from perchlorate to nitrate resulted in a corresponding change of the supramolecular structure from 1-D to 3-D. When the nitrate complex packed with the co-crystallized water, a double chain structure was formed through hydrogen bonding. The magnetic studies revealed values of g = 2.14 and D = 3.11 cm-1 for [Ni(H2dpzpda2](ClO42 (1 and g = 2.18 and D = 2.19 cm-1 for [Ni(H2dpzpda2](NO32 (2, respectively.

  1. Mechanisms of direct inhibition of the respiratory sulfate-reduction pathway by (per)chlorate and nitrate.

    Carlson, Hans K; Kuehl, Jennifer V; Hazra, Amrita B; Justice, Nicholas B; Stoeva, Magdalena K; Sczesnak, Andrew; Mullan, Mark R; Iavarone, Anthony T; Engelbrektson, Anna; Price, Morgan N; Deutschbauer, Adam M; Arkin, Adam P; Coates, John D

    2015-06-01

    We investigated perchlorate (ClO(4)(-)) and chlorate (ClO(3)(-)) (collectively (per)chlorate) in comparison with nitrate as potential inhibitors of sulfide (H(2)S) production by mesophilic sulfate-reducing microorganisms (SRMs). We demonstrate the specificity and potency of (per)chlorate as direct SRM inhibitors in both pure cultures and undefined sulfidogenic communities. We demonstrate that (per)chlorate and nitrate are antagonistic inhibitors and resistance is cross-inducible implying that these compounds share at least one common mechanism of resistance. Using tagged-transposon pools we identified genes responsible for sensitivity and resistance in Desulfovibrio alaskensis G20. We found that mutants in Dde_2702 (Rex), a repressor of the central sulfate-reduction pathway were resistant to both (per)chlorate and nitrate. In general, Rex derepresses its regulon in response to increasing intracellular NADH:NAD(+) ratios. In cells in which respiratory sulfate reduction is inhibited, NADH:NAD(+) ratios should increase leading to derepression of the sulfate-reduction pathway. In support of this, in (per)chlorate or nitrate-stressed wild-type G20 we observed higher NADH:NAD(+) ratios, increased transcripts and increased peptide counts for genes in the core Rex regulon. We conclude that one mode of (per)chlorate and nitrate toxicity is as direct inhibitors of the central sulfate-reduction pathway. Our results demonstrate that (per)chlorate are more potent inhibitors than nitrate in both pure cultures and communities, implying that they represent an attractive alternative for controlling sulfidogenesis in industrial ecosystems. Of these, perchlorate offers better application logistics because of its inhibitory potency, solubility, relative chemical stability, low affinity for mineral cations and high mobility in environmental systems.

  2. Interaction and dynamics of (alkylamide + electrolyte) deep eutectics: Dependence on alkyl chain-length, temperature, and anion identity

    Guchhait, Biswajit; Das, Suman; Daschakraborty, Snehasis; Biswas, Ranjit

    2014-01-01

    Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH 2 + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH 2 ) considered are acetamide (CH 3 CONH 2 ), propionamide (CH 3 CH 2 CONH 2 ), and butyramide (CH 3 CH 2 CH 2 CONH 2 ); the electrolytes (LiX) are lithium perchlorate (LiClO 4 ), lithium bromide (LiBr), and lithium nitrate (LiNO 3 ). Differential scanning calorimetric measurements reveal glass transition temperatures (T g ) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady state fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual T g s. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH 3 CONH 2 + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in terms of temporal heterogeneity and amide clustering in these multi

  3. Test procedure for anion exchange chromatography

    Cooper, T.D.

    1994-01-01

    Plutonium from stored nitrate solutions will be sorbed onto anion exchange resins and converted to storable plutonium dioxide. Useful information will be simultaneously gained on the thermal stability and ion exchange capacity of four commercially available anion exchange resins over several years and under severe degradative conditions. This information will prove useful in predicting the safe and efficient lifetimes of these resins

  4. Tripodal Receptors for Cation and Anion Sensors

    David N. Reinhoudt

    2006-08-01

    Full Text Available This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  5. Neutral anion receptors: design and application

    Antonisse, M.M.G.; Reinhoudt, David

    1998-01-01

    After the development of synthetic cation receptors in the late 1960s, only in the past decade has work started on the development of synthetic neutral anion receptors. Combination and preorganization of different anion binding groups, like amides, urea moieties, or Lewis acidic metal centers lead

  6. Creating molecular macrocycles for anion recognition

    Amar H. Flood

    2016-03-01

    Full Text Available The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures.

  7. Anion channels: master switches of stress responses.

    Roelfsema, M Rob G; Hedrich, Rainer; Geiger, Dietmar

    2012-04-01

    During stress, plant cells activate anion channels and trigger the release of anions across the plasma membrane. Recently, two new gene families have been identified that encode major groups of anion channels. The SLAC/SLAH channels are characterized by slow voltage-dependent activation (S-type), whereas ALMT genes encode rapid-activating channels (R-type). Both S- and R-type channels are stimulated in guard cells by the stress hormone ABA, which leads to stomatal closure. Besides their role in ABA-dependent stomatal movement, anion channels are also activated by biotic stress factors such as microbe-associated molecular patterns (MAMPs). Given that anion channels occur throughout the plant kingdom, they are likely to serve a general function as master switches of stress responses. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Anion Gap Blood Test: MedlinePlus Lab Test Information

    ... https://medlineplus.gov/labtests/aniongapbloodtest.html Anion Gap Blood Test To use the sharing features on this page, please enable JavaScript. What is an Anion Gap Blood Test? An anion gap blood test is a way ...

  9. Energetic co-ordination compounds: synthesis, characterization and thermolysis studies on bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(III) perchlorate (BNCP) and its new transition metal (Ni/Cu/Zn) perchlorate analogues

    Talawar, M.B.; Agrawal, A.P.; Asthana, S.N.

    2005-01-01

    Bis-(5-nitro-2H-tetrazolato-N 2 )tetraammine[cobalt(III)/nickel(III)] perchlorates (BNCP/BNNP) and mono-(5-nitro-H-tetrazolato-N)triammine [copper(II)/zinc(II)] perchlorates (MNCuP/MNZnP) have been synthesized during this work. The synthesis was carried out by addition of carbonato tetraammine metal [Co/Ni/Cu/Zn] nitrate [CTCN/CTNN/CTCuN/CTZnN] to the aqueous solution of sodium salt of 5-nitrotetrazole followed by reaction with perchloric acid. The precursors were synthesized by the reaction of aqueous solution of their respective nitrates with ammonium carbonate at 70 deg. C. The complexes and their precursors were characterized by determining metal and perchlorate content as well as infrared (IR), electron spectra for chemical analysis (ESCA) and X-ray diffraction (XRD) techniques. The TG profiles indicated that BNCP, BNNP and MNCuP are thermally stable up to the temperature of 260-278 deg. C unlike MNZnP (150 deg. C). Sudden exothermic decomposition was observed in case of bis-(5-nitro-2H-tetrazolato-N 2 )tetraammine cobalt(III) perchlorate, bis-(5-nitro-2H-tetrazolato-N 2 )tetraammine nickel(III) perchlorate and mono-(5-nitro-H-tetrazolato-N)triammine zinc(II) perchlorate resulting in the severe damage of the sample cup. Sensitivity data indicated that the Co/Ni/Cu complexes are more friction sensitive (3-4.8 kg) than mono-(5-nitro-H-tetrazolato-N)triammine zinc(II) perchlorate (14 kg). The impact sensitivity results of the complexes corresponded to h 50% of 30-36 cm

  10. Anion-π Catalysts with Axial Chirality.

    Wang, Chao; Matile, Stefan

    2017-09-04

    The idea of anion-π catalysis is to stabilize anionic transition states by anion-π interactions on aromatic surfaces. For asymmetric anion-π catalysis, π-acidic surfaces have been surrounded with stereogenic centers. This manuscript introduces the first anion-π catalysts that operate with axial chirality. Bifunctional catalysts with tertiary amine bases next to π-acidic naphthalenediimide planes are equipped with a bulky aromatic substituent in the imide position to produce separable atropisomers. The addition of malonic acid half thioesters to enolate acceptors is used for evaluation. In the presence of a chiral axis, the selective acceleration of the disfavored but relevant enolate addition was much better than with point chirality, and enantioselectivity could be observed for the first time for this reaction with small-molecule anion-π catalysts. Enantioselectivity increased with the π acidity of the π surface, whereas the addition of stereogenic centers around the aromatic plane did not cause further improvements. These results identify axial chirality of the active aromatic plane generated by atropisomerism as an attractive strategy for asymmetric anion-π catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Development of a Screening Tool to Facilitate Technology Transfer of an Innovative Technology to Treat Perchlorate-Contaminated Water

    Craig, Daniel A

    2008-01-01

    Perchlorate contamination of drinking water is a significant problem nationwide. The purpose of this study was to develop a tool to predict the cost and performance of tailored granular activated carbon (T-GAC...

  12. Perchlorate exposure is associated with oxidative stress and indicators of serum iron homeostasis among NHANES 2005-2008 subjects

    ABSTRACT Perchlorate (ClO4-), an oxidizing agent, is a ubiquitous environmental pollutant. Several studies have investigated its thyroid hormone disrupting properties. Its associations with other biological measures are largely unknown. This study, combining 2005-2008 National H...

  13. Global patterns and environmental controls of perchlorate and nitrate co-occurrence in arid and semi-arid environments

    Jackson, W Andrew; Böhlke, John Karl; Andraski, Brian J.; Fahlquist, Lynne S.; Bexfield, Laura M.; Eckardt, Frank D.; Gates, John B.; Davila, Alfonso F.; McKay, Christopher P.; Rao, Balaji; Sevanthi, Ritesh; Rajagopalan, Srinath; Estrada, Nubia; Sturchio, Neil C.; Hatzinger, Paul B.; Anderson, Todd A.; Orris, Greta J.; Betancourt, Julio L.; Stonestrom, David A.; Latorre, Claudio; Li, Yanhe; Harvey, Gregory J.

    2015-01-01

    Natural perchlorate (ClO4−) is of increasing interest due to its wide-spread occurrence on Earth and Mars, yet little information exists on the relative abundance of ClO4− compared to other major anions, its stability, or long-term variations in production that may impact the observed distributions. Our objectives were to evaluate the occurrence and fate of ClO4− in groundwater and soils/caliche in arid and semi-arid environments (southwestern United States, southern Africa, United Arab Emirates, China, Antarctica, and Chile) and the relationship of ClO4− to the more well-studied atmospherically deposited anions NO3−and Cl− as a means to understand the prevalent processes that affect the accumulation of these species over various time scales. ClO4− is globally distributed in soil and groundwater in arid and semi-arid regions on Earth at concentrations ranging from 10−1to 106 μg/kg. Generally, the ClO4− concentration in these regions increases with aridity index, but also depends on the duration of arid conditions. In many arid and semi-arid areas, NO3− and ClO4− co-occur at molar ratios (NO3−/ClO4−) that vary between ∼104and 105. We hypothesize that atmospheric deposition ratios are largely preserved in hyper-arid areas that support little or no biological activity (e.g. plants or bacteria), but can be altered in areas with more active biological processes including N2 fixation, N mineralization, nitrification, denitrification, and microbial ClO4− reduction, as indicated in part by NO3− isotope data. In contrast, much larger ranges of Cl−/ClO4− and Cl−/NO3−ratios indicate Cl− varies independently from both ClO4− and NO3−. The general lack of correlation between Cl− and ClO4− or NO3− implies that Cl− is not a good indicator of co-deposition and should be used with care when interpreting oxyanion cycling in arid systems. The Atacama Desert appears to be unique compared to all other terrestrial locations having a

  14. Global patterns and environmental controls of perchlorate and nitrate co-occurrence in arid and semi-arid environments

    Jackson, W. Andrew; Böhlke, J. K.; Andraski, Brian J.; Fahlquist, Lynne; Bexfield, Laura; Eckardt, Frank D.; Gates, John B.; Davila, Alfonso F.; McKay, Christopher P.; Rao, Balaji; Sevanthi, Ritesh; Rajagopalan, Srinath; Estrada, Nubia; Sturchio, Neil; Hatzinger, Paul B.; Anderson, Todd A.; Orris, Greta; Betancourt, Julio; Stonestrom, David; Latorre, Claudio; Li, Yanhe; Harvey, Gregory J.

    2015-09-01

    Natural perchlorate (ClO4-) is of increasing interest due to its wide-spread occurrence on Earth and Mars, yet little information exists on the relative abundance of ClO4- compared to other major anions, its stability, or long-term variations in production that may impact the observed distributions. Our objectives were to evaluate the occurrence and fate of ClO4- in groundwater and soils/caliche in arid and semi-arid environments (southwestern United States, southern Africa, United Arab Emirates, China, Antarctica, and Chile) and the relationship of ClO4- to the more well-studied atmospherically deposited anions NO3- and Cl- as a means to understand the prevalent processes that affect the accumulation of these species over various time scales. ClO4- is globally distributed in soil and groundwater in arid and semi-arid regions on Earth at concentrations ranging from 10-1 to 106 μg/kg. Generally, the ClO4- concentration in these regions increases with aridity index, but also depends on the duration of arid conditions. In many arid and semi-arid areas, NO3- and ClO4- co-occur at molar ratios (NO3-/ClO4-) that vary between ∼104 and 105. We hypothesize that atmospheric deposition ratios are largely preserved in hyper-arid areas that support little or no biological activity (e.g. plants or bacteria), but can be altered in areas with more active biological processes including N2 fixation, N mineralization, nitrification, denitrification, and microbial ClO4- reduction, as indicated in part by NO3- isotope data. In contrast, much larger ranges of Cl-/ClO4- and Cl-/NO3- ratios indicate Cl- varies independently from both ClO4- and NO3-. The general lack of correlation between Cl- and ClO4- or NO3- implies that Cl- is not a good indicator of co-deposition and should be used with care when interpreting oxyanion cycling in arid systems. The Atacama Desert appears to be unique compared to all other terrestrial locations having a NO3-/ClO4- molar ratio ∼103. The relative

  15. Assessment of the feasibility of anaerobic composting for treatment of perchlorate - contaminated soils in a war zone

    Mohammad Mehdi Amin

    2015-01-01

    Full Text Available Aims: The objectives of this study were to determine the perchlorate concentrations in surface soils and assess feasibility of anaerobic bioremediation in full-scale for perchlorate-contaminated soils in a war zone. Materials and Methods: Fifteen samples of surface soil were collected using a composite sampling method in the study area. The soil samples, after extraction and preparation, were analyzed by ion chromatography. Anaerobic composting technique (soil excavation, mixing with manure, transfer into treatment cell and cover with a 6-mil high-density polyethylene liner considered to cleanup perchlorate-contaminated soil in a war zone. Results: The concentration of perchlorate in the soil surface samples ranged from 3 to 107.9 mg/kg, which is more than State advisory levels for residential and protection of domestic groundwater use pathway. This study indicates that technologies, skills, experience, raw materials (manure, lands, and machinery needed for implementation of full-scale composting, are available in the study area. Conclusions: Based on the results, anaerobic composting technique could be considered as a feasible, viable and cost-effective alternative for perchlorate bioremediation in the study area. According to the available of techniques and skills, successful experiences of anaerobic composting in other countries, and potential of study area, The application of anaerobic composting is technically feasible and can be use for perchlorate contaminated soil cleanup in a zone war.

  16. High Vacuum Techniques for Anionic Polymerization

    Ratkanthwar, Kedar; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization

  17. The Investigation of Perchlorate/Iron Phase Mixtures as A Possible Source of Oxygen Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

    Sutter, B.; Heil, E.; Morris, R. V.; Archer, P. D.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Freissinet C.; Glavin, D. P.; hide

    2015-01-01

    The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detected O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumberland (CB) drill hole materials in Gale Crater. Chlorinated hydrocarbons have also been detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS). These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) suggesting perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander's Wet Chemistry Laboratory suggested perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of pure perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Analog laboratory analysis of iron mineralogy detected in Gale materials that was physically mixed with Ca- and Mg-perchlorate has been shown to catalyze lower O2 release temperatures and approach some SAM O2 release data. Instead of physical mixtures used in previous work, the work presented here utilized perchlorate solutions added to Fe phases. This technique allowed for perchlorate to come in closer contact with the Fe-phase and may more closely mimic Mars conditions where humidity can increase enough to cause deliquescence of the highly hygroscopic perchlorate phases. The objective of this work is to: 1) Utilize a laboratory SAM analog instrument to evaluate the O2 release temperatures from Mg- and Ca-perchlorates solutions applied to Fephases detetected in Gale Crate; and 2) Determine if perchlorate solutions can provide improved matches with the SAM O2 temperature release profiles.

  18. Photoelectron spectroscopy of the 6-azauracil anion.

    Chen, Jing; Buonaugurio, Angela; Dolgounitcheva, Olga; Zakrzewski, V G; Bowen, Kit H; Ortiz, J V

    2013-02-14

    We report the photoelectron spectrum of the 6-azauracil anion. The spectrum is dominated by a broad band exhibiting a maximum at an electron binding energy (EBE) of 1.2 eV. This spectral pattern is indicative of a valence anion. Our calculations were carried out using ab initio electron propagator and other many-body methods. Comparison of the anion and corresponding neutral of 6-azauracil with those of uracil shows that substituting a nitrogen atom for C-H at the C6 position of uracil gives rise to significant changes in the electronic structure of 6-azauracil versus that of uracil. The adiabatic electron affinity (AEA) of the canonical 6-azauracil tautomer is substantially larger than that of canonical uracil. Among the five tautomeric, 6-azauracil anions studied computationally, the canonical structure was found to be the most stable. The vertical detachment energies (VDE) of the canonical, valence-bound anion of 6-azauracil and its closest "very-rare" tautomer have been calculated. Electron propagator calculations on the canonical anion yield a VDE value that is in close agreement with the experimentally determined VDE value of 1.2 eV. The AEA value of 6-azauracil, assessed at the CCSD(T) level of theory to be 0.5 eV, corresponds with the EBE value of the onset of the experimental spectrum.

  19. Bis[(E-N-(pyridin-3-ylmethylidenehydroxylamine-κN1]silver(I perchlorate

    Jing Xu

    2012-06-01

    Full Text Available Each of the ions in the title salt, [Ag(C6H6N2O2]ClO4, is completed by the application of crystallographic twofold symmetry. The AgI atom is coordinated by two pyridine N atoms in an almost linear fashion [N—Ag—N = 170.0 (2°], with the T-shaped coordination geometry being completed by a weakly associated perchlorate-O atom. Supramolecular zigzag chains along [100] mediated by O—H...N hydrogen bonds [as parts of R22(6 loops] feature in the crystal packing. The perchlorate O atoms are disordered over two sets of sites in a statistical ratio.

  20. Reaction Kinetics of Monomethylhydrazine With Nitrous Acid in Perchloric Acid Solution

    Wei Yan; Wang Hui; Pan Yongjun; Cong Haifeng; Jiao Haiyang; Jia Yongfen; Zheng Weifang

    2009-01-01

    The oxidation of monomethylhydrazine (MMH) by nitrous acid was researched in perchloric acid solution with spectrophotometry. The rate equation has been determined as follows: -dc (HNO 2 ) /dt= kc (H + ) 0.9 c (MMH) 1.1 c (HNO 2 ), k is (46.0 ± 2.7) L 2 / (mol 2 · s) with the initial perchlorate concentration of 0.50 mol/L at the temperature of 4.5 degree C. The corresponding activation energy of the reaction is (42.4 ± 0.1) kJ/mol. The results indicate that oxidation of mono-methylhydrazine (MMH) by nitrous acid is fast. The higher concentration of MMH can accelerate the reduction process of nitrous acid. Higher acidity can also speed up the reduction of nitrous acid. (authors)

  1. [(6-Methyl-2-pyridylmethyl(2-pyridylmethylamine][(2-pyridylmethylamine]copper(II bis(perchlorate

    Ray J. Butcher

    2008-01-01

    Full Text Available The title compound, [Cu(C6H8N2(C13H15N3](ClO42, is a mixed ligand complex with the CuII atom coordinated by (6-methyl-2-pyridylmethyl(2-pyridylmethylamine, acting as a tridentate ligand, and 2-(2-aminomethylpyridine, as a bidentate ligand, leading to an N5 square-pyramidal geometry. The amine H atoms are involved in hydrogen bonding to the perchlorate O atoms and there are extensive but weak intermolecular C—H...O interactions in the crystal structure. The perchlorate ions are each disordered over two positions, with site occupancies of 0.601 (8:0.399 (8 and 0.659 (11:0.341 (11.

  2. Radiation-chemical behaviour of Rh(4) in perchlorate and nitrate solutions

    Vladimirova, M.V.; Khalkina, E.V.

    1994-01-01

    Kinetic of rhodium(4) reduction in the process of radiolysis in solutions of perchloric (0.6-3.2 mol/l) and nitric (2-9 mol/l) acids with rhodium (4) concentration (0.4-5)x10 -3 mol/l has been studied. Irradiation of the solutions was carried out using a 60 Co source with dose rate of 3.5 Gy/s in the absorbed dose range up to 10 4 Gy. A mechanism of radiation-chemical reduction of rhodium(4) in perchloric and nitric acid solutions in suggested, the reason for high radiation-chemical yields of reduction is discussed. 7 refs.; 9 figs.; 2 tabs

  3. Removal of an acid fume system contaminated with perchlorates located within hot cell

    Rosenberg, K.E.; Henslee, S.P.; Vroman, W.R.; Krsul, J.R.; Michelbacher, J.A.; Knighton, G.C.

    1992-09-01

    An add scrubbing system located within the confines of a highly radioactive hot cell at Argonne National Laboratory-West (ANL-W) was remotely removed. The acid scrubbing system was routinely used for the dissolution of irradiated reactor fuel samples and structural materials. Perchloric acid was one of the acids used in the dissolution process and remained in the system with its inherent risks. Personnel could not enter the hot cell to perform the dismantling of the acid scabbing system due to the high radiation field and the explosion potential associated with the perchlorates. A robot was designed and built at ANL-W and used to dismantle the system without the need for personnel entry into the hot cell. The robot was also used for size reduction of removed components and loading of the removed components into waste containers

  4. Experimental investigation on the heterogeneous kinetic process of the low thermal decomposition of ammonium perchlorate particles

    Longuet, Baptiste [Laboratoire Energetique Explosions et Structures Universite d' Orleans (Germany); Gillard, Philippe [Laboratoire Energetic Explosions et Structures, Universite d' Orleans, Bourges (France)

    2009-02-15

    The thermal decomposition of ammonium perchlorate has been extensively studied in the past. Nevertheless, the various results published illustrate, on the one hand, significant differences regarding the influence of different parameters on the decomposition and on the other hand, a lack of useful quantitative laws to predict the thermal behaviour of this crystal under a range of conditions (temperature, duration of exposure, presence of confinement). (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  5. Uptake and Transformation of the Propellants 2,4-DNT, Perchlorate and Nitroglycerin by Grasses

    2006-07-31

    they stabilize and prevent contamination from spreading. Grasses native to a region tend to grow rapidly and can be easily cultivated without digging...to the live soil. The alternative of cultivating strictly sterile plants was deemed too difficult. In addition problems often result from experiments...Lu Yu, Jaclyn E.Cafias, Cobb G.P., Jackson W.A. Anderson T.A. "Uptake of perchlorate in terrestrial plants." Ecotoxicology and Environmental Safety 58

  6. Perchlorate Detection at Nanomolar Concentrations by Surface-Enhanced Raman Scattering

    2009-01-01

    grooves/mm grating light path controlled by Renishaw WiRE software and analyzed by Galactic GRAMS software. RESULTS AND DISCUSSION Quantitative... Federal Rights License 14. ABSTRACT Perchlorate (ClO4 ) has emerged as a widespread environmental contaminant and has been detected in various food...by means of dynamic light scattering using a ZetaPlus particle size analyzer (Brookhaven Instruments, Holtsville, NY). Data were collected for every

  7. Study of the Deposition of Ammonium Perchlorate Following the Static Firing of MK-58 Rocket Motors

    2008-10-01

    hyperthyroidism , gas generators, electrolytes for lithium cells, and as chemical reagents. The occurrence of perchlorate in the environment is...and prevent their movement by the rocket motor plume (Fig. 5). The water in the traps was collected using 1-l amber glass containers and the exact...them. On day one, after the firing of the second motor, heavy rain and lightning prevented the collection of samples from the witness plates. Only

  8. Perchlorate Destruction and Potable Water Production Using Membrane Biofilm Reduction and Membrane Filtration

    2013-11-18

    drainages , and infiltration (rainfall and irrigation water) provide the majority of recharge to the system (Wooldenden and Kadhim 2005). 4.3 CONTAMINANT...restarted the system at 15:44. To mitigate accumulation of rainwater into secondary containment, the southern secondary containment wall was temporarily...phase to assess system robustness and resiliency. Using indigenous organisms, the MBfR was colonized with perchlorate- and nitrate-reducing bacteria

  9. Evaluation of Potential for Monitored Natural Attenuation of Perchlorate in Groundwater

    2010-09-01

    by agricultural areas. The facility has been used for industrial purposes, such as fireworks manufacturing, munitions production, pesticide ... microorganisms and enzyme functions involved with bioremediation . These methods can be applied selectively to detect and/or enumerate the proportion...particular functional gene based upon the abundance of messenger RNA (mRNA). The perchlorate reducing microorganisms use the mRNA to assemble the CD enzyme

  10. Electrochemical reduction of CO2 to CO over Zn in propylene carbonate/tetrabutylammonium perchlorate

    Shen, Feng-xia; Shi, Jin; Chen, Tian-you; Shi, Feng; Li, Qing-yuan; Zhen, Jian-zheng; Li, Yun-fei; Dai, Yong-nian; Yang, Bin; Qu, Tao

    2018-02-01

    Developing low cost and high efficient electrode for carbon dioxide (CO2) reduction in organic media is essential for practical application. Zn is a cheap metal and has high catalytic effects on CO2 reduction to carbon monoxide (CO) in aqueous solution. However, little attention has been given to investigate the performance of Zn in organic media for CO2 reduction. In present work, we have conducted CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate on Zn due to that propylene carbonate is a widely used industrial absorber, and tetrabutylammonium perchlorate is a commonly used organic supporting electrolyte. In addition, because electrochemical reduction of CO2 to CO naturally produces H2O, we have discussed water effects on CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate+6.8 wt % H2O. Our experiment results reveal that the faradaic efficiency for CO formation reaches to 83%, and the current density remains stable at 6.72 mA/cm2 at voltage -2.3 V for 4 h. Interestingly, Zn presents higher catalytic activity than Ag, and slightly lower than Au. X-ray photoelectron spectroscopy results confirm that no poisonous species is formed and absorbed on the cathode, which is an important advantage in practical application.

  11. Investigation of radiation-chemical behaviour of divalent palladium in perchloric acid solutions

    Vladimirova, M.V.; Kalinina, S.V.

    1988-01-01

    Gamma-radiolysis of divalent palladium in perchloric acid solutions is studied. Absorption spectra of intermediate palladium compounds formed in the irradiated solution are taken. The analysis of literature data as well as comparative analysis of the absorption spectra obtained under irradiation of palladium (2) perchloric acid solutions with absorption spectra of palladium chlorocomplexes allows to suppose that the mentioned compounds are chlorocomplexes of palladium (2) of different composition depending on HClO 4 concentration in the initial solution and absorbed radiation dose. Radiation-chemical reduction of palladium (2) up to metal is stated to take place in the whole studied range of initial concentrations of components of the system and dose rates. Kinetic dependences of metallic palladium formation are obtained. Values of radiation-chemical yields of metallic palladium formation depending on the initial concentrations of palladium (2) and perchloric acid are given. A mechanism of radiolytic reduction of palladium (2) in the investigated system is suggested based on the experimental data, and a theoretical value of the radiation-chemical yield of palladium (2) reduction being in a good agreement with experimentally found values is calculated

  12. Tris(2,2′-bipyridine-κ2 N,N′)cobalt(III) bis­[bis­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)cobaltate(III)] perchlorate dimethyl­formamide hemisolvate 1.3-hydrate

    Golenya, Irina A.; Boyko, Alexander N.; Kotova, Natalia V.; Haukka, Matti; Iskenderov, Turganbay S.

    2012-01-01

    In the title compound, [Co(C10H8N2)3][Co(C7H3NO4)2]2(ClO4)·0.5C3H7NO·1.3H2O, the CoIII atom in the complex cation is pseudoocta­hedrally coordinated by six N atoms of three chelating bipyridine ligands. The CoIII atom in the complex anion is coordinated by two pyridine N atoms and four carboxyl­ate O atoms of two doubly deprotonated pyridine-2,6-dicarboxyl­ate ligands in a distorted octa­hedral geometry. One dimethyl­formamide solvent mol­ecule and two water mol­ecules are half-occupied and one water mol­ecule is 0.3-occupied. O—H⋯O hydrogen bonds link the water mol­ecules, the perchlorate anions and the complex anions. π–π inter­actions between the pyridine rings of the complex anions are also observed [centroid–centroid distance = 3.804 (3) Å]. PMID:23125573

  13. Tris(2,2′-bipyridine-κ2N,N′cobalt(III bis[bis(pyridine-2,6-dicarboxylato-κ3O2,N,O6cobaltate(III] perchlorate dimethylformamide hemisolvate 1.3-hydrate

    Irina A. Golenya

    2012-10-01

    Full Text Available In the title compound, [Co(C10H8N23][Co(C7H3NO42]2(ClO4·0.5C3H7NO·1.3H2O, the CoIII atom in the complex cation is pseudooctahedrally coordinated by six N atoms of three chelating bipyridine ligands. The CoIII atom in the complex anion is coordinated by two pyridine N atoms and four carboxylate O atoms of two doubly deprotonated pyridine-2,6-dicarboxylate ligands in a distorted octahedral geometry. One dimethylformamide solvent molecule and two water molecules are half-occupied and one water molecule is 0.3-occupied. O—H...O hydrogen bonds link the water molecules, the perchlorate anions and the complex anions. π–π interactions between the pyridine rings of the complex anions are also observed [centroid–centroid distance = 3.804 (3 Å].

  14. The properties of anion-exchange resines in mixtures of organic solvents and water

    Naveh, J.

    1978-02-01

    The behaviour of anion-exchange resins in water and mixtures of organic solvents and water was studied with special reference to the swelling of the polymer and to the density and enthalpy changes accompanying the swelling. A linear dependence was found between the swelling of dry resin and 1/X (X being the nominal cross-linking percent of the polymer). This dependence is interpreted theoretically. The nominal cross-linking percent,defined by the quantity ratio of the components, is corrected for real cross-linking percent. For the swelling of the resin in dilute aqueous alcohols, a preference for the alcohol was found which is enhanced as the molecular weight of the alcohol increases. Moreover, for certain mole fractions, the preference of the perchlorate form of the resin is greater than that of the chloride form. The temperature dependence of the swelling was measured and the invasion of an electrolyte (LiCl), dissolved in the aqueous-organic phase, into the resine phase was determined. Contrary to what usually happens in pure aqueous phase, where the electrolyte is rejected in accordance with the Donnan law, an almost total invasion of the electrolyte into the resin phase occurs. (author)

  15. Thermal Aging of Anions in Ionic Liquids containing Lithium Salts by IC/ESI-MS

    Pyschik, Marcelina; Kraft, Vadim; Passerini, Stefano; Winter, Martin; Nowak, Sascha

    2014-01-01

    Highlights: • Thermal aging investigation of TFSI- and FSI- based ionic liquids and their mixtures with Li salts. • PYR 13 FSI shows thermal decomposition when mixed with LiPF 6 and LiClO 4 . • PYR 13 TFSI does not show any decomposition products with the electrolyte salts. • LiPF 6 dissolved in ionic liquids suffers of thermal aging as in conventional Li-ion battery electrolytes. - Abstract: The stability of 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 13 TFSI) and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (PYR 13 FSI) ionic liquids at elevated temperatures (60 °C) is investigated by ion chromatography. Additionally, the influence of the electrolyte salts, lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium perchlorate (LiClO 4 ), on the decomposition of both the ionic liquids was analysed over a long term stability study. It has been found out that TFSI has a much higher thermal stability than FSI. The addition of LiTFSI did not show any effect on the aging of both ionic liquid anions. However, PYR 13 FSI degraded when mixed with the electrolyte salts LiPF 6 and LiClO 4 , while PYR 13 TFSI did not. Finally, LiPF 6 forms the same hydrolysis products in the investigated ionic liquids as in the commonly used electrolytes based on organic solvents in lithium-ion batteries

  16. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-01-01

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  17. Infrared spectroscopy of anionic hydrated fluorobenzenes

    Schneider, Holger; Vogelhuber, Kristen M.; Weber, J. Mathias

    2007-01-01

    We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C 6 F 6 - ·H 2 O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules

  18. Cytotoxic mechanisms of hydrosulfide anion and cyanide anion in primary rat hepatocyte cultures

    Thompson, Rodney W.; Valentine, Holly L.; Valentine, William M.

    2003-01-01

    Hydrogen sulfide and hydrogen cyanide are known to compromise mitochondrial respiration through inhibition of cytochrome c oxidase and this is generally considered to be their primary mechanism of toxicity. Experimental studies and the efficiency of current treatment protocols suggest that H 2 S may exert adverse physiological effects through additional mechanisms. To evaluate the role of alternative mechanisms in H 2 S toxicity, the relative contributions of electron transport inhibition, uncoupling of mitochondrial respiration, and opening of the mitochondrial permeability transition pore (MPTP) to hydrosulfide and cyanide anion cytotoxicity in primary hepatocyte cultures were examined. Supplementation of hepatocytes with the glycolytic substrate, fructose, rescued hepatocytes from cyanide anion induced toxicity, whereas fructose supplementation increased hydrosulfide anion toxicity suggesting that hydrosulfide anion may compromise glycolysis in hepatocytes. Although inhibitors of the MPTP opening were protective for hydrosulfide anion, they had no effect on cyanide anion toxicity, consistent with an involvement of the permeability transition pore in hydrosulfide anion toxicity but not cyanide anion toxicity. Exposure of isolated rat liver mitochondria to hydrosulfide did not result in large amplitude swelling suggesting that if H 2 S induces the permeability transition it does so indirectly through a mechanism requiring other cellular components. Hydrosulfide anion did not appear to be an uncoupler of mitochondrial respiration in hepatocytes based upon the inability of oligomycin and fructose to protect hepatocytes from hydrosulfide anion toxicity. These findings support mechanisms additional to inhibition of cytochrome c oxidase in hydrogen sulfide toxicity. Further investigations are required to assess the role of the permeability transition in H 2 S toxicity, determine whether similar affects occur in other cell types or in vivo and evaluate whether this may

  19. Gas-Phase Reactivity of Microsolvated Anions

    Thomsen, Ditte Linde

    the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared......Gas-phase studies of ion-molecule reactions shed light on the intrinsic factors that govern reactivity; and even solvent effects can be examined in the gasphase environment by employing microsolvated ions. An area that has received considerable attention with regard to the interplay between...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  20. Patchy proteins, anions and the Hofmeister series

    Lund, Mikael; Jungwirth, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo namesti 2, 16610 Prague 6 (Czech Republic); Center for Complex Molecular Systems and Biomolecules, Flemingovo namesti 2, 16610 Prague 6 (Czech Republic)], E-mail: mikael.lund@uochb.cas.cz

    2008-12-10

    We investigate specific anion binding to a range of patchy protein models and use our results to probe protein-protein interactions for aqueous lysozyme solutions. Our molecular simulation studies show that the ion-protein interaction mechanism and strength largely depend on the nature of the interfacial amino acid residues. Via direct ion pairing, small anions interact with charged side-chains while larger anions are attracted to non-polar residues due to several solvent assisted mechanisms. Incorporating ion and surface specificity into a mesoscopic model for protein-protein interactions we calculate the free energy of interaction between lysozyme molecules in aqueous solutions of sodium chloride and sodium iodide. In agreement with experiment, our finding is that 'salting out' follows the reverse Hofmeister series for pH below the iso-electric point and the direct series for pH above pI.

  1. New borohydride anion B6H7-

    Kuznetsov, I.Yu.; Vinitskij, D.M.; Solntsev, K.A.

    1985-01-01

    The [Ni(Bipy) 3 ] (B 6 H 7 ) 2 , (Ph 4 P)B 6 H 7 , [Ni(Phen) 3 ](B 6 H 7 ) 2 crystals (where Bipy = bipyridine, Phen = phenathroline, Ph = phenyl) are obtained via the exchange reaction with a subsequent recrystallization from aqua-acetonic and acetonic solutions. The structure is studied of a new borohydride anion B 6 H 7 - possessing a four-valence bond unique for polyhedral borohydride anions. A triangular face of boride skeleton coordinating a hydrogen atom is considerably larger than other faces, and the electron density on this hydrogen atom is evidently much higher than at the end hydride hydrogen atoms. The trend of B 6 H 7 - anion to form statistically disordered structurs testifies to a rather slight effect of the seventh hydrogen atom position on the structure pattern of the ionic crystal lattice

  2. The absorption of plutonium by anion resins

    Durham, R. W.; Mills, R.

    1961-10-15

    Equilibrium experiments have shown Pu{sup +4} to be absorbed from nitric acid onto an anion resin as a complex anion Pu(NO{sub 3}){sub 6}{sup -2}. The amount of absorption is dependent on the plutonium and nitric acid concentrations in the equilibrium solution with a maximum at 7N to 8N HNO{sub 3}. A low cross-linked resin has a higher capacity and reaches equilibrium more rapidly than the normally supplied resin. Saturation capacity of one per cent cross-linked Nalcite SBR (Dowex 1), 50 -- 100 mesh, is 385 mg Pu/gram dry resin. (author)

  3. High Vacuum Techniques for Anionic Polymerization

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  4. Dibromine radical anion reactions with heme enzymes

    Gebicka, L.; Gebicki, J.L.

    1996-01-01

    Reactions of Br 2 radical anion with heme enzymes, catalase horseradish peroxidase, have been studied by pulse radiolysis. It has been found that Br 2 - does not react with the heme centre of investigated enzymes. Dibromine radical anion reacts with tryptophan residues of catalase without any influence on the activity of catalase. It is suggested that in pulse radiolysis studies, where horseradish peroxidase is at about tenfold excess toward Br 2 - , the enzyme is modified rather by Br 2 , than by Br 2 - . (author). 26 refs., 3 figs

  5. The assessment of pellicular anion-exchange resins for the determination of anions by ion chromatography

    Pohlandt, C.

    1981-01-01

    Because pellicular anion-exchange resins suitable for the determination, by ion chromatography, of anions with alkaline eluents were unavailable in South Africa at the inception of this work, an attempt was made to prepare such resins. In this study it is shown that the pellicular resins produced are more efficient than the surface-aminated resins used previously. The simultaneous separation and determination of five common anions is demonstrated. The method was applied to the analysis of uranium leach liquors, effluent samples, and a solid sample of ferric oxide (goethite)

  6. 37Cl/35Cl isotope ratio analysis in perchlorate by ion chromatography/multi collector -ICPMS: Analytical performance and implication for biodegradation studies.

    Zakon, Yevgeni; Ronen, Zeev; Halicz, Ludwik; Gelman, Faina

    2017-10-01

    In the present study we propose a new analytical method for 37 Cl/ 35 Cl analysis in perchlorate by Ion Chromatography(IC) coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). The accuracy of the analytical method was validated by analysis of international perchlorate standard materials USGS-37 and USGS -38; analytical precision better than ±0.4‰ was achieved. 37 Cl/ 35 Cl isotope ratio analysis in perchlorate during laboratory biodegradation experiment with microbial cultures enriched from the contaminated soil in Israel resulted in isotope enrichment factor ε 37 Cl = -13.3 ± 1‰, which falls in the range reported previously for perchlorate biodegradation by pure microbial cultures. The proposed analytical method may significantly simplify the procedure for isotope analysis of perchlorate which is currently applied in environmental studies. Copyright © 2017. Published by Elsevier Ltd.

  7. Interstellar dehydrogenated PAH anions: vibrational spectra

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  8. Anion-conducting polymer, composition, and membrane

    Pivovar, Bryan S [Los Alamos, NM; Thorn, David L [Los Alamos, NM

    2009-09-01

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  9. Synthesis of azaphenanthridines via anionic ring closure

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.

    2005-01-01

    A new and convergent synthesis of azaphenanthridines via an anionic ring closure is reported. Ortho-lithiation/in situ borylation of cyanopyridines produces the corresponding cyanopyridylboronic esters, which undergo a Suzuki-Miyaura cross-coupling to give the key intermediates. Addition of lithium...

  10. Combined effects of perchlorate, thiocyanate, and iodine on thyroid function in the National Health and Nutrition Examination Survey 2007–08

    Steinmaus, Craig; Miller, Mark D.; Cushing, Lara; Blount, Benjamin C.; Smith, Allan H.

    2013-01-01

    Perchlorate, thiocyanate, and low iodine intake can all decrease iodide intake into the thyroid gland. This can reduce thyroid hormone production since iodide is a key component of thyroid hormone. Previous research has suggested that each of these factors alone may decrease thyroid hormone levels, but effect sizes are small. We hypothesized that people who have all three factors at the same time have substantially lower thyroid hormone levels than people who do not, and the effect of this combined exposure is substantially larger than the effects seen in analyses focused on only one factor at a time. Using data from the 2007–2008 National Health and Nutrition Examination Survey, subjects were categorized into exposure groups based on their urinary perchlorate, iodine, and thiocyanate concentrations, and mean serum thyroxine concentrations were compared between groups. Subjects with high perchlorate (n=1939) had thyroxine concentrations that were 5.0% lower (mean difference=0.40 μg/dl, 95% confidence interval=0.14–0.65) than subjects with low perchlorate (n=2084). The individual effects of iodine and thiocyanate were even smaller. Subjects with high perchlorate, high thiocyanate, and low iodine combined (n=62) had thyroxine concentrations 12.9% lower (mean difference=1.07 μg/dl, 95% confidence interval=0.55–1.59) than subjects with low perchlorate, low thiocyanate, and adequate iodine (n=376). Potential confounders had little impact on results. Overall, these results suggest that concomitant exposure to perchlorate, thiocyanate, and low iodine markedly reduces thyroxine production. This highlights the potential importance of examining the combined effects of multiple agents when evaluating the toxicity of thyroid-disrupting agents. -- Highlights: ► Recent data suggest that essentially everyone in the US is exposed to perchlorate. ► Perchlorate exposure may be associated with lower thyroid hormone levels. ► Some groups may be more susceptible to

  11. Combined effects of perchlorate, thiocyanate, and iodine on thyroid function in the National Health and Nutrition Examination Survey 2007–08

    Steinmaus, Craig, E-mail: craigs@berkeley.edu [Office of Environmental Health Hazard Assessment, California Environmental Protection Agency, 1515 Clay St. 16th Floor, Oakland, CA 94612 (United States); Miller, Mark D., E-mail: ucsfpehsumiller@gmail.com [Office of Environmental Health Hazard Assessment, California Environmental Protection Agency, 1515 Clay St. 16th Floor, Oakland, CA 94612 (United States); Cushing, Lara, E-mail: lara.cushing@berkeley.edu [Energy and Resources Group, 310 Barrows Hall, University of California, Berkeley, CA 93720-3050 (United States); Blount, Benjamin C., E-mail: bkb3@cdc.gov [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, 4770 Buford Highway, NE, Mail Stop F47, Atlanta, GA (United States); Smith, Allan H., E-mail: ahsmith@berkeley.edu [Arsenic Health Effects Research Group, 1950 Addison St., Suite 204, University of California, Berkeley, CA 94704 (United States)

    2013-05-15

    Perchlorate, thiocyanate, and low iodine intake can all decrease iodide intake into the thyroid gland. This can reduce thyroid hormone production since iodide is a key component of thyroid hormone. Previous research has suggested that each of these factors alone may decrease thyroid hormone levels, but effect sizes are small. We hypothesized that people who have all three factors at the same time have substantially lower thyroid hormone levels than people who do not, and the effect of this combined exposure is substantially larger than the effects seen in analyses focused on only one factor at a time. Using data from the 2007–2008 National Health and Nutrition Examination Survey, subjects were categorized into exposure groups based on their urinary perchlorate, iodine, and thiocyanate concentrations, and mean serum thyroxine concentrations were compared between groups. Subjects with high perchlorate (n=1939) had thyroxine concentrations that were 5.0% lower (mean difference=0.40 μg/dl, 95% confidence interval=0.14–0.65) than subjects with low perchlorate (n=2084). The individual effects of iodine and thiocyanate were even smaller. Subjects with high perchlorate, high thiocyanate, and low iodine combined (n=62) had thyroxine concentrations 12.9% lower (mean difference=1.07 μg/dl, 95% confidence interval=0.55–1.59) than subjects with low perchlorate, low thiocyanate, and adequate iodine (n=376). Potential confounders had little impact on results. Overall, these results suggest that concomitant exposure to perchlorate, thiocyanate, and low iodine markedly reduces thyroxine production. This highlights the potential importance of examining the combined effects of multiple agents when evaluating the toxicity of thyroid-disrupting agents. -- Highlights: ► Recent data suggest that essentially everyone in the US is exposed to perchlorate. ► Perchlorate exposure may be associated with lower thyroid hormone levels. ► Some groups may be more susceptible to

  12. Δ17O Isotopic Investigation of Nitrate Salts Found in Co-Occurrence with Naturally Formed Perchlorate in the Mojave Desert, California, USA and the Atacama Desert, Chile

    Lybrand, R. A.; Parker, D.; Rech, J.; Prellwitz, J.; Michalski, G.

    2009-12-01

    Perchlorate is both a naturally occurring and manmade contaminant that has been identified in soil, groundwater and surface water. Perchlorate directly affects human health by interfering with iodide uptake in the thyroid gland, which may in turn lower the production of key hormones that are needed for proper growth and development. Until recently, the Atacama Desert, Chile was thought to be the only location where perchlorate salts formed naturally. Recent work has documented the occurrence of these salts in several semi-arid regions of the United States. This study identified putatively natural sources of perchlorate in the Mojave Desert of California. Soil samples were collected from six field sites varying in geologic age. The co-occurrence of perchlorate and nitrate in caliches from the Atacama Desert and soils from the Mojave Desert was also investigated. Although the former are richer in NO3-, near-ore-grade (~5%) deposits occur in the vicinity of Death Valley National Park. Weak but significant correlations exist between ClO4- and NO3- at both locations, but the perchlorate levels are much higher (up to 800 mg/kg) in the Chilean samples than in California (atmospheric origin for the Atacama nitrate salts, and a mixture between biological nitrate and atmospherically-derived nitrate for the Mojave samples. When corrected for the percentage of atmospheric nitrate measured in the Atacama samples, the Mojave samples still contain much lower perchlorate concentrations than would be expected if the occurrence of perchlorate correlated strictly with atmospherically derived nitrate. These results indicate that the variation in the origins of the nitrate salts is not the only factor influencing perchlorate distribution in these environments. These findings suggest that there are other geologic differences in landform age and stability that are crucial to understanding the co-occurrence of nitrate and perchlorate between the two locations.

  13. Magneto and spectral behaviour of lanthanide(III) perchlorate complexes of n-isonicotinamidoanisalaldimine

    Agarwal, R.K.; Agarwal, Himanshu; Sarin, R.K.

    1996-01-01

    A new series of lanthanide(III) perchlorate complexes of N-isonicotinamidoanisalaldimine (INH-SAL) with the general composition (Ln(INH-SAL) 4 )(ClO) 4 ) 3 (Ln=La, Pr, Nd, Sm, Gd, Tb or Dy) were synthesized and characterized by elemental analyses, conductance, molecular weight, infrared and electronic spectral data. INH-SAL acts as a bidentate (N, O) chelating agents. The tentative coordination number eight has been assigned. Thermal behaviour of some representative chelates has also been investigated. (author). 14 refs., 2 tabs

  14. Field and Laboratory Evaluation of the Potential for Monitored Natural Attenuation of Perchlorate in Groundwater

    2007-07-01

    Petroleum hydrocarbons mg/L 1.03 50.3 0.19 PHC as Gasoline µg/L 10,700 224,000 2160 PHC as Diesel Fuel mg/L 0.25 16 ɘ.095 Water Quality Total Organic...Intrinsic Bioremediation . Ground Water 33(2):180-189. Borden, R. C., M. J. Hunt, M. B. Shafer, M. A. Barlaz, 1997a. Environmental Research Brief...and J. Pollock, 2003. Potential for In Situ Bioremediation of Perchlorate in Contaminated Environments. Presented at: In Situ and On- Site

  15. Ecological Risk Assessment of Perchlorate in Avian Species, Rodents, Amphibians and Fish

    2003-04-01

    http://www .indiana.edu/- axolotl ). 10.0 JUSTIFICATION OF TEST SYSTEM Perchlorate occurs in ground and surface waters in 44 states in the USA... axolotl ). * Sequentially numbered in order of the date that the change is effective Dept. of Biological Sciences (DBS) Box 43131 Lubbock, TX 79409...KCl, 0.025 giL; CaCh2 H20, 0.65 g/L; MgS04·7H20, 0.1 giL (http://www.indiana.edu/~ axolotl ). *Sequentially numbered in order of the date that the

  16. A vacuum ultraviolet photoionization study on the thermal decomposition of ammonium perchlorate

    Góbi, Sándor; Zhao, Long; Xu, Bo; Ablikim, Utuq; Ahmed, Musahid; Kaiser, Ralf I.

    2018-01-01

    Pyrolysis products of ammonium perchlorate (NH4ClO4) at 483 K were monitored on line and in situ via single photon photoionization reflectron time-of-flight spectrometry (PI-ReTOF-MS) in the photon energy range of 9.00-17.50 eV. The photoionization efficiency curves (PIE) of the subliming product molecules were collected and allowed for detection of three class of products containing chlorine, nitrogen, and oxygen including atoms and free radicals. These results suggest a new insight into possible low-temperature decomposition pathways of NH4ClO4.

  17. Magnetic moment oscillation in ammonium perchlorate in a DC SQUID-based magnetic resonance experiment

    Montero, V.; Cernicchiaro, G.

    2008-01-01

    In this work we describe experimental results in which a DC SQUID (superconducting quantum interference device) is used as free induction decay detector. Measurements of a solid ammonium perchlorate (NH 4 ClO 4 ) sample were performed, in zero field, at 4.2 K. Unexpected magnetic moment oscillations were detected at 1.5 kHz. The computation of the magnetic fields suggests that the proton nuclear magnetic resonance may explain the measured resonance, considering reorientation of the ammonium group by quantum tunneling of protons and a magnetic proton dipole-dipole intermolecular interaction model

  18. Kinetics and Mechanism of Oxidation of Isoleucine by N-Bromophthalimide in Aqueous Perchloric Acid Medium

    N. M. I. Alhaji

    2011-01-01

    Full Text Available The kinetics of oxidation of isoleucine with N-bromophthalimide has been studied in perchloric acid medium potentiometrically. The reaction is of first order each in [NBP] and [amino acid] and negative fractional order in [H+]. The rate is decreased by the addition of phthalimide. A decrease in the dielectric constant of the medium increases the rate. Addition of halide ions or acrylonitrile has no effect on the kinetics. Similarly, variation of ionic strength of the medium does not affect the reaction rate. The reaction rate has been determined at different temperatures and activation parameters have been calculated. A suitable mechanism involving hypobromous acid as reactive species has been proposed.

  19. Investigation of uranyl-ion hydrolysis in uranyl pertechnetate and uranyl perchlorates solutions by two-phases potentiometric titration method

    Volk, V.I.; Belikov, A.D.

    1977-01-01

    The applicability of the method of two-phase potentiometric titration for studying hydrolysis of multi-charge ions has been shown. Hydrolysis of uranyl-ion has been investigated and hydrolysis constants in the solutions of uranyl pertechnetate and perchlorate have been calculated equal to (6.2+-0.15)x10 -5 and (9.25+-0.5)10 -5 , respectively. Infrared spectra of the initial crystallohydrates of uranyl pertechnetate and perchlorate has been analyzed. The data on hydrolysis of an uranyl-ion and IR spectra of crystallohydrates of the investigated salts have revealed the ability of pertechnetate ion to complexing with an uranyl group

  20. Modelling the transport of carbonic acid anions through anion-exchange membranes

    Nikonenko, V.; Lebedev, K.; Manzanares, J.A.; Pourcelly, G.

    2003-01-01

    Electrodiffusion of carbonate and bicarbonate anions through anion-exchange membranes (AEM) is described on the basis of the Nernst-Planck equations taking into account coupled hydrolysis reactions in the external diffusion boundary layers (DBLs) and internal pore solution. The model supposes local electroneutrality as well as chemical and thermodynamic equilibrium. The transport is considered in three layers being an anion exchange membrane and two adjoining diffusion layers. A mechanism of competitive transport of HCO 3 - and CO 3 2- anions through the membrane which takes into account Donnan exclusion of H + ions is proposed. It is predicted that the pH of the depleting solution decreases and that of the concentrating solution increases during electrodialysis (ED). Eventual deviations from local electroneutrality and local chemical equilibrium are discussed

  1. Regulation of organic anion transport in the liver

    Roelofsen, H; Jansen, PLM

    1997-01-01

    In several liver diseases the biliary transport is disturbed, resulting in, for example, jaundice and cholestasis. Many of these symptoms can be attributed to altered regulation of hepatic transporters. Organic anion transport, mediated by the canalicular multispecific organic anion transporter

  2. Changes in plasma osmolality and anion gap: potential predictors of ...

    Changes in plasma osmolality and anion gap: potential predictors of ... PROMOTING ACCESS TO AFRICAN RESEARCH ... Objective: To determine the relationship of mortality to plasma osmolality and anion gap inpatients on haemodialysis.

  3. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    Sessler, Jonathan L.

    2007-01-01

    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  4. Interaction and dynamics of (alkylamide + electrolyte) deep eutectics: Dependence on alkyl chain-length, temperature, and anion identity

    Guchhait, Biswajit; Das, Suman; Daschakraborty, Snehasis; Biswas, Ranjit, E-mail: ranjit@bose.res.in [Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India)

    2014-03-14

    Here we investigate the solute-medium interaction and solute-centered dynamics in (RCONH{sub 2} + LiX) deep eutectics (DEs) via carrying out time-resolved fluorescence measurements and all-atom molecular dynamics simulations at various temperatures. Alkylamides (RCONH{sub 2}) considered are acetamide (CH{sub 3}CONH{sub 2}), propionamide (CH{sub 3}CH{sub 2}CONH{sub 2}), and butyramide (CH{sub 3}CH{sub 2}CH{sub 2}CONH{sub 2}); the electrolytes (LiX) are lithium perchlorate (LiClO{sub 4}), lithium bromide (LiBr), and lithium nitrate (LiNO{sub 3}). Differential scanning calorimetric measurements reveal glass transition temperatures (T{sub g}) of these DEs are ∼195 K and show a very weak dependence on alkyl chain-length and electrolyte identity. Time-resolved and steady state fluorescence measurements with these DEs have been carried out at six-to-nine different temperatures that are ∼100–150 K above their individual T{sub g}s. Four different solute probes providing a good spread of fluorescence lifetimes have been employed in steady state measurements, revealing strong excitation wavelength dependence of probe fluorescence emission peak frequencies. Extent of this dependence, which shows sensitivity to anion identity, has been found to increase with increase of amide chain-length and decrease of probe lifetime. Time-resolved measurements reveal strong fractional power dependence of average rates for solute solvation and rotation with fraction power being relatively smaller (stronger viscosity decoupling) for DEs containing longer amide and larger (weaker decoupling) for DEs containing perchlorate anion. Representative all-atom molecular dynamics simulations of (CH{sub 3}CONH{sub 2} + LiX) DEs at different temperatures reveal strongly stretched exponential relaxation of wavevector dependent acetamide self dynamic structure factor with time constants dependent both on ion identity and temperature, providing justification for explaining the fluorescence results in

  5. ZnO twin-cones: synthesis, photoluminescence, and catalytic decomposition of ammonium perchlorate.

    Sun, Xuefei; Qiu, Xiaoqing; Li, Liping; Li, Guangshe

    2008-05-19

    ZnO twin-cones, a new member to the ZnO family, were prepared directly by a solvothermal method using a mixed solution of zinc nitrate and ethanol. The reaction and growth mechanisms of ZnO twin-cones were investigated by X-ray diffraction, UV-visible spectra, infrared and ion trap mass spectra, and transmission electron microscopy. All as-prepared ZnO cones consisted of tiny single crystals with lengths of several micrometers. With prolonging of the reaction time from 1.5 h to 7 days, the twin-cone shape did not change at all, while the lattice parameters increased slightly and the emission peak of photoluminescence shifted from the green region to the near orange region. ZnO twin-cones are also explored as an additive to promote the thermal decomposition of ammonium perchlorate. The variations of photoluminescence spectra and catalytic roles in ammonium perchlorate decomposition were discussed in terms of the defect structure of ZnO twin-cones.

  6. Development of a Health-Protective Drinking Water Level for Perchlorate

    Ting, David; Howd, Robert A.; Fan, Anna M.; Alexeeff, George V.

    2006-01-01

    We evaluated animal and human toxicity data for perchlorate and identified reduction of thyroidal iodide uptake as the critical end point in the development of a health-protective drinking water level [also known as the public health goal (PHG)] for the chemical. This work was performed under the drinking water program of the Office of Environmental Health Hazard Assessment of the California Environmental Protection Agency. For dose–response characterization, we applied benchmark-dose modeling to human data and determined a point of departure (the 95% lower confidence limit for 5% inhibition of iodide uptake) of 0.0037 mg/kg/day. A PHG of 6 ppb was calculated by using an uncertainty factor of 10, a relative source contribution of 60%, and exposure assumptions specific to pregnant women. The California Department of Health Services will use the PHG, together with other considerations such as economic impact and engineering feasibility, to develop a California maximum contaminant level for perchlorate. We consider the PHG to be adequately protective of sensitive subpopulations, including pregnant women, their fetuses, infants, and people with hypothyroidism. PMID:16759989

  7. The discrimination of 72 nitrate, chlorate and perchlorate salts using IR and Raman spectroscopy

    Zapata, Félix; García-Ruiz, Carmen

    2018-01-01

    Inorganic oxidizing energetic salts including nitrates, chlorates and perchlorates are widely used in the manufacture of not only licit pyrotechnic compositions, but also illicit homemade explosive mixtures. Their identification in forensic laboratories is usually accomplished by either capillary electrophoresis or ion chromatography, with the disadvantage of dissociating the salt into its ions. On the contrary, vibrational spectroscopy, including IR and Raman, enables the non-invasive identification of the salt, i.e. avoiding its dissociation. This study focuses on the discrimination of all nitrate, chlorate and perchlorate salts that are commercially available, using both Raman and IR spectroscopy, with the aim of testing whether every salt can be unequivocally identified. Besides the visual spectra comparison by assigning every band with the corresponding molecular vibrational mode, a statistical analysis based on Pearson correlation was performed to ensure an objective identification, either using Raman, IR or both. Positively, 25 salts (out of 72) were unequivocally identified using Raman, 30 salts when using IR and 44 when combining both techniques. Negatively, some salts were undistinguishable even using both techniques demonstrating there are some salts that provide very similar Raman and IR spectra.

  8. Anion-sensitive regions of L-type CaV1.2 calcium channels expressed in HEK293 cells.

    Norbert Babai

    2010-01-01

    Full Text Available L-type calcium currents (I(Ca are influenced by changes in extracellular chloride, but sites of anion effects have not been identified. Our experiments showed that CaV1.2 currents expressed in HEK293 cells are strongly inhibited by replacing extracellular chloride with gluconate or perchlorate. Variance-mean analysis of I(Ca and cell-attached patch single channel recordings indicate that gluconate-induced inhibition is due to intracellular anion effects on Ca(2+ channel open probability, not conductance. Inhibition of CaV1.2 currents produced by replacing chloride with gluconate was reduced from approximately 75%-80% to approximately 50% by omitting beta subunits but unaffected by omitting alpha(2delta subunits. Similarly, gluconate inhibition was reduced to approximately 50% by deleting an alpha1 subunit N-terminal region of 15 residues critical for beta subunit interactions regulating open probability. Omitting beta subunits with this mutant alpha1 subunit did not further diminish inhibition. Gluconate inhibition was unchanged with expression of different beta subunits. Truncating the C terminus at AA1665 reduced gluconate inhibition from approximately 75%-80% to approximately 50% whereas truncating it at AA1700 had no effect. Neutralizing arginines at AA1696 and 1697 by replacement with glutamines reduced gluconate inhibition to approximately 60% indicating these residues are particularly important for anion effects. Expressing CaV1.2 channels that lacked both N and C termini reduced gluconate inhibition to approximately 25% consistent with additive interactions between the two tail regions. Our results suggest that modest changes in intracellular anion concentration can produce significant effects on CaV1.2 currents mediated by changes in channel open probability involving beta subunit interactions with the N terminus and a short C terminal region.

  9. Silver nanoplate-decorated copper wire for the on-site microextraction and detection of perchlorate using a portable Raman spectrometer.

    Zhu, Sha; Zhang, Xiaoli; Cui, Jingcheng; Shi, Yu-E; Jiang, Xiaohong; Liu, Zhen; Zhan, Jinhua

    2015-04-21

    Perchlorate, which causes health concerns because of its effects on the thyroid function, is highly soluble and mobile in the environment. In this study, diethyldithiocarbamate (DDTC)-modified silver nanoplates were fabricated on a copper wire to perform the on-site microextraction and detection of perchlorate. This fiber could be inserted into water or soil to extract perchlorate through electrostatic interaction and then can be detected by a portable Raman spectrometer, owing to its surface-enhanced Raman (SERS) activity. A relatively stable vibrational mode (δ(HCH)(CH3), (CH2)) of DDTC at 1273 cm(-1) was used as an internal standard, which was negligibly influenced by the absorption of ClO4(-). The DDTC-modified Ag/Cu fiber showed high uniformity, good reusability and temporal stability under continuous laser radiation each with an RSD lower than 10%. The qualitative and quantitative detection of perchlorate were also realized. A log-log plot of the normalized SERS intensity against perchlorate concentration showed a good linear relationship. The fiber could be also directly inserted into the perchlorate-polluted soil, and the perchlorate could thereby be detected on site. The detection limit in soil reached 0.081 ppm, which was much lower than the EPA-published safety standard. The recovery of the detection was 105% and comparable with the ion chromatography. This hyphenated method of microextraction with direct SERS detection may find potential application for direct pollutant detection free from complex sample pretreatment.

  10. Thermal Decomposition of Calcium Perchlorate/Iron-Mineral Mixtures: Implications of the Evolved Oxygen from the Rocknest Eolian Deposit in Gale Crater, Mars

    Bruck, A. M.; Sutter, B.; Ming, D. W.; Mahaffy, P.

    2014-01-01

    A major oxygen release between 300 and 500 C was detected by the Mars Curiosity Rover Sample Analysis at Mars (SAM) instrument at the Rocknest eolian deposit. Thermal decomposition of perchlorate (ClO4-) salts in the Rocknest samples are a possible explanation for this evolved oxygen release. Releative to Na-, K-, Mg-, and Fe-perchlorate, the thermal decomposition of Ca-perchlorate in laboratory experiments released O2 in the temperature range (400-500degC) closest to the O2 release temperatures observed for the Rocknest material. Furthermore, calcium perchlorate could have been the source of Cl in the chlorinated-hydrocarbons species that were detected by SAM. Different components in the Martian soil could affect the decomposition temperature of calcium per-chlorate or another oxychlorine species. This interaction of the two components in the soil could result in O2 release temperatures consistent with those detected by SAM in the Rocknest materials. The decomposition temperatures of various alkali metal perchlorates are known to decrease in the presence of a catalyst. The objective of this work is to investigate catalytic interactions on calcium perchlorate from various iron-bearing minerals known to be present in the Rocknest material

  11. Medium effects on a C-H bond fission reaction. Solvent and salt effects on the solvolysis of arylsulfonylmethyl perchlorates.

    Menninga, Lubbertus

    1976-01-01

    In this thesis, medium effects on the general basecatelyzed solvolysis of two arylsulfonylmethyl perchlorates are described and analyzed in some detail. For the aqueous media, special attention is given to possible effects due to changes in diffusionally averaged water structure. ... Zie: Summary

  12. Enhancement of perchlorate removal from groundwater by cationic granular activated carbon: Effect of preparation protocol and surface properties.

    Hou, Pin; Yan, Zhe; Cannon, Fred S; Yue, Ye; Byrne, Timothy; Nieto-Delgado, Cesar

    2018-06-01

    In order to obtain a high adsorption capacity for perchlorate, the epoxide-forming quaternary ammonium (EQA) compounds were chemically bonded onto granular activated carbon (GAC) surface by cationic reaction. The optimum preparation condition of the cationic GAC was achieved while applying softwood-based Gran C as the parent GAC, dosing EQA first at a pH of 12, preparation time of 48 h, preparation temperature of 50 °C, and mole ratio of EQA/oxygen groups of 2.5. The most favorable cationic GAC that had the QUAB360 pre-anchored exhibited the highest perchlorate adsorption capacity of 24.7 mg/g, and presented the longest bed volumes (3000 BV) to 2 ppb breakthrough during rapid small scale column tests (RSSCTs), which was 150 times higher than that for the pristine Gran C. This was attributed to its higher nitrogen amount (1.53 At%) and higher positive surface charge (0.036 mmol/g) at pH 7.5. Also, there was no leaching of the quaternary ammonium detected in the effluent of the RSSCTs, indicating there was no secondary pollution occurring during the perchlorate removal process. Overall, this study provides an effective and environmental-friendly technology for improving GAC perchlorate adsorption capacity for groundwater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Phase behaviour and molecular dynamics in the binary system of sodium perchlorate and 1,2-propanediamine

    Terashima, Yukio; Takeda, Kiyoshi; Honda, Makoto

    2011-01-01

    The phase and glass transition behaviour in a binary mixture of sodium perchlorate and 1,2-propanediamine {(NaClO 4 ) x (12PDA) 1-x , x 4 ) 1 (12PDA) 4 and (NaClO 4 ) 2 (12PDA) 5 . The concentration dependence of the glass transition point shows a sigmoid curve implying an underlying anomaly.

  14. DETERMINATION OF PERCHLORATE BY ION CHROMATOGRAPHY, SUPPRESSED CONDUCTIVITY AND MASS SPECTROMETRIC DETECTION USING AN OXYGEN-18 ENRICHED ISOTROPIC INTERNAL STANDARD

    Perchlorate (ClO4 -) is a drinking water contaminant originating from the dissolution of the salts of ammonium, potassium, magnesium, or sodium in water. It is used primarily as an oxidant in solid propellant for rockets, missiles, pyrotechnics, as a component in air bag infla...

  15. MEASUREMENT OF PERCHLORATE IN WATER USING AN OXYGEN-18 ENRICHED ISOTOPE STANDARD AND ION CHROMATOGRAPHY MASS SPECTROMETRIC DETECTION

    Perchlorate (ClO4 -) is a drinking water contaminant originating from the dissolution of the salts of ammonium, potassium, magnesium, or sodium in water. It is used primarily as an oxidant in solid propellant for rockets, missiles, pyrotechnics, as a component in air bag infla...

  16. EFFECTS OF AMMONIUM PERCHLORATE ON LIVER ENZYMES AND THE THYROID AXIS OF RATS PRETREATED WITH PCB126.

    Ammonium perchlorate and 3,3,4,4,5-pentachlorobiphenyl (PCB126) are environmental contaminants that are known to disturb thyroid hormone (TH) homeostasis by well defined modes of action that lead to hypothyroidism in the rat. PCB126 increases phase II conjugation of T4 by induc...

  17. Analysis of perchlorate, thiocyanate, nitrate and iodide in human amniotic fluid using ion chromatography and electrospray tandem mass spectrometry

    Blount, Benjamin C.; Valentin-Blasini, Liza

    2006-01-01

    Because of health concerns surrounding in utero exposure to perchlorate, we developed a sensitive and selective method for quantifying iodide, as well as perchlorate and other sodium-iodide symporter (NIS) inhibitors in human amniotic fluid using ion chromatography coupled with electrospray ionization tandem mass spectrometry. Iodide and NIS inhibitors were quantified using a stable isotope-labeled internal standards (Cl 18 O 4 - , S 13 CN - and 15 NO 3 - with excellent assay accuracy of 100%, 98%, 99%, 95% for perchlorate, thiocyanate, nitrate and iodide, respectively, in triplicate analysis of spiked amniotic fluid sample). Excellent analytical precision (<5.2% RSD for all analytes) was found when amniotic fluid quality control pools were repetitively analyzed for iodide and NIS-inhibitors. Selective chromatography and tandem mass spectrometry reduced the need for sample cleanup, resulting in a rugged and rapid method capable of routinely analyzing 75 samples/day. Analytical response was linear across the physiologically relevant concentration range for the analytes. Analysis of a set of 48 amniotic fluid samples identified the range and median levels for perchlorate (0.057-0.71, 0.18 μg/L), thiocyanate (<10-5860, 89 μg/L), nitrate (650-8900, 1620 μg/L) and iodide (1.7-170, 8.1 μg/L). This selective, sensitive, and rapid method will help assess exposure of the developing fetus to low levels of NIS-inhibitors and their potential to inhibit thyroid function

  18. Water permeation through anion exchange membranes

    Luo, Xiaoyan; Wright, Andrew; Weissbach, Thomas; Holdcroft, Steven

    2018-01-01

    An understanding of water permeation through solid polymer electrolyte (SPE) membranes is crucial to offset the unbalanced water activity within SPE fuel cells. We examine water permeation through an emerging class of anion exchange membranes, hexamethyl-p-terphenyl poly (dimethylbenzimidazolium) (HMT-PMBI), and compare it against series of membrane thickness for a commercial anion exchange membrane (AEM), Fumapem® FAA-3, and a series of proton exchange membranes, Nafion®. The HMT-PMBI membrane is found to possess higher water permeabilities than Fumapem® FAA-3 and comparable permeability than Nafion (H+). By measuring water permeation through membranes of different thicknesses, we are able to decouple, for the first time, internal and interfacial water permeation resistances through anion exchange membranes. Permeation resistances on liquid/membrane interface is found to be negligible compared to that for vapor/membrane for both series of AEMs. Correspondingly, the resistance of liquid water permeation is found to be one order of magnitude smaller compared to that of vapor water permeation. HMT-PMBI possesses larger effective internal water permeation coefficient than both Fumapem® FAA-3 and Nafion® membranes (60 and 18% larger, respectively). In contrast, the effective interfacial permeation coefficient of HMT-PMBI is found to be similar to Fumapem® (±5%) but smaller than Nafion®(H+) (by 14%).

  19. Evidence of martian perchlorate, chlorate, and nitrate in Mars meteorite EETA79001: Implications for oxidants and organics

    Kounaves, Samuel P.; Carrier, Brandi L.; O'Neil, Glen D.; Stroble, Shannon T.; Claire, Mark W.

    2014-02-01

    The results from the Viking mission in the mid 1970s provided evidence that the martian surface contained oxidants responsible for destroying organic compounds. In 2008 the Phoenix Wet Chemistry Lab (WCL) found perchlorate (ClO4-) in three soil samples at concentrations from 0.5 to 0.7 wt%. The detection of chloromethane (CH3Cl) and dichloromethane (CH2Cl2) by the Viking pyrolysis gas chromatograph-mass spectrometer (GC-MS) may have been a result of ClO4- at that site oxidizing either terrestrial organic contaminates or, if present, indigenous organics. Recently, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) Curiosity directly measured the presence of CH3Cl, CH2Cl2 and, along with measurements of HCl and oxygen, indirectly indicate the presence of ClO4-. However, except for Phoenix, no other direct measurement of the ClO4- anion in martian soil or rock has been made. We report here ion chromatographic (IC) and isotopic analyses of a unique sawdust portion of the martian meteorite EETA79001 that show the presence by mass of 0.6 ± 0.1 ppm ClO4-, 1.4 ± 0.1 ppm ClO3-, and 16 ± 0.2 ppm NO3- at a quantity and location within the meteorite that is difficult to reconcile with terrestrial contamination. The sawdust sample consists of basaltic material with a minor salt-rich inclusion in a mass ratio of ∼300:1, thus the salts may be 300 times more concentrated within the inclusion than the whole sample. The molar ratios of NO3-:ClO4- and Cl:ClO4-, are very different for EETA79001 at ∼40:1 and 15:1, respectively, than the Antarctic soils and ice near where the meteorite was recovered at ∼10,000:1 and 5000:1, respectively. In addition, the isotope ratios for EETA79001 with δ15N = -10.48 ± 0.32‰ and δ18O = +51.61 ± 0.74‰ are significantly different from that of the nearby Miller Range blue ice with δ15N = +102.80 ± 0.14‰ and δ18O = +43.11 ± 0.64‰. This difference is notable, because if the meteorite had been

  20. Hydration of a Large Anionic Charge Distribution - Naphthalene-Water Cluster Anions

    Weber, J. Mathias; Adams, Christopher L.

    2010-06-01

    We report the infrared spectra of anionic clusters of naphthalene with up to three water molecules. Comparison of the experimental infrared spectra with theoretically predicted spectra from quantum chemistry calculations allow conclusions regarding the structures of the clusters under study. The first water molecule forms two hydrogen bonds with the π electron system of the naphthalene moiety. Subsequent water ligands interact with both the naphthalene and the other water ligands to form hydrogen bonded networks, similar to other hydrated anion clusters. Naphthalene-water anion clusters illustrate how water interacts with negative charge delocalized over a large π electron system. The clusters are interesting model systems that are discussed in the context of wetting of graphene surfaces and polyaromatic hydrocarbons.

  1. Concurrent bioremediation of perchlorate and 1,1,1-trichloroethane in an emulsified oil barrier

    Borden, Robert C.

    2007-10-01

    A detailed field pilot test was conducted to evaluate the use of edible oil emulsions for enhanced in situ biodegradation of perchlorate and chlorinated solvents in groundwater. Edible oil substrate (EOS®) was injected into a line of ten direct push injection wells over a 2-day period to form a 15-m-long biologically active permeable reactive barrier (bio-barrier). Field monitoring results over a 2.5-year period indicate the oil injection generated strongly reducing conditions in the oil-treated zone with depletion of dissolved oxygen, nitrate, and sulfate, and increases in dissolved iron, manganese and methane. Perchlorate was degraded from 3100 to 20,000 μg/L to below detection (oil and adaptation of the in situ microbial community. Approximately 4 months after emulsion injection, concentrations of 1,1,1-trichloroethane (TCA), perchloroethene (PCE), trichloroethene (TCE) and their degradation products appeared to reach a quasi steady-state condition. During the period from 4 to 18 months, TCA was reduced from 30-70 μM to 0.2-4 μM during passage through the bio-barrier. However, 1-9 μM 1,1-dichloroethane (DCA) and 8-14 μM of chloroethane (CA) remained indicating significant amounts of incompletely degraded TCA were discharging from the oil-treated zone. During this same period, PCE and TCE were reduced with concurrent production of 1,2- cis-dichloroethene ( cis-DCE). However, very little VC or ethene was produced indicating reductive dechlorination slowed or stopped at cis-DCE. The incomplete removal of TCA, PCE and TCE is likely associated with the short (5-20 days) hydraulic retention time of contaminants in the oil-treated zone. The permeability of the injection wells declined by 39-91% (average = 68%) presumably due to biomass growth and/or gas production. However, non-reactive tracer tests and detailed monitoring of the perchlorate plume demonstrated that the permeability loss did not result in excessive flow bypassing around the bio

  2. Crystal structure of bis{μ2-2,2′-[(4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diylbis(methylene]bis(4-oxo-4H-pyran-3-olato}dicobaltcalcium bis(perchlorate 1.36-hydrate

    Patrizia Rossi

    2017-12-01

    Full Text Available The title compound, [CaCo2(C22H30N4O62](ClO42·1.36H2O or {Ca[Co(H–2L1]2}·2ClO4·1.36H2O {where L1 is 4,10-bis[(3-hydroxy-4-pyron-2-ylmethyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane}, is a trinuclear complex whose asymmetric unit comprises a quarter of the {Ca[Co(H–2L1]2}2+ trinuclear complex, half of a perchlorate ion and 0.34-water molecules. In the neutral [Co(H–2L1] moiety, the cobalt ion is hexacoordinated in a trigonal–prismatic fashion by the surrounding N4O2 donor set. A Ca2+ cation holds together two neutral [Co(H–2L1] moieties and is octacoordinated in a distorted trigonal–dodecahedral fashion by the surrounding O atoms belonging to the deprotonated oxide and carbonyl groups of two [Co(H–2L1] units. The coordination of the CoII cation preorganizes L1 and an electron-rich area forms, which is able to host hard metal ions. The comparison between the present structure and the previously published ones suggests a high versatility of this ligand; indeed, hard metal ions with different nature and dimensions lead to complexes having different stoichiometry (mono- and dinuclear monomers and trinuclear dimers or even a polymeric structure. The heterotrinuclear CoII–CaII–CoII complexes are connected in three dimensions via weak C—H...O hydrogen bonds, which are also responsible for the interactions with the perchlorate anions and the lattice water molecules. The perchlorate anion is disordered about a twofold rotation axis and was refined giving the two positions a fixed occupancy factor of 0.5. The crystal studied was refined as a two-component inversion twin [BASF parameter = 0.14 (4].

  3. Graphene-coated polymeric anion exchangers for ion chromatography

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Wu, Shuchao, E-mail: wushch2002@163.com [Zhejiang Institute of Geology and Mineral Resources, Hangzhou 310007 (China); Zhang, Peimin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Zhi, Mingyu [Hangzhou Vocational & Technical College, Hangzhou, 310018 (China); Zhu, Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China)

    2017-06-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  4. Inhibiting effects of some oxadiazole derivatives on the corrosion of mild steel in perchloric acid solution

    Lebrini, Mounim; Bentiss, Fouad; Vezin, Herve; Lagrenee, Michel

    2005-01-01

    The efficiency of 3,5-bis(n-pyridyl)-1,3,4-oxadiazole (n-POX, n = 1, 2, 3), as corrosion inhibitors for mild steel in 1 M perchloric acid (HClO 4 ) have been determined by weight loss measurements and electrochemical studies. The results show that these inhibitors revealed a good corrosion inhibition even at very low concentrations. Comparison of results among those obtained by the studied oxadiazoles shows that 3-POX was the best inhibitor. Polarisation curves indicate that n-pyridyl substituted-1,3,4-oxadiazoles are mixed type inhibitors in 1 M HClO 4 . The adsorption of these inhibitors follows a Langmuir isotherm model. The electronic properties of n-POX, obtained using the AM1 semi-empirical quantum chemical approach, were correlated with their experimental efficiencies using the linear resistance model (LR)

  5. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China); Zhou, Yong [Eco-materials and Renewable Energy Research Center (ERERC), School of Physics, National Lab of Solid State Microstructure, ERERC, Nanjing University, Nanjing 210093 (China); Pei, Chonghua, E-mail: peichonghua@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010 (China)

    2014-02-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS {sup 13}C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g.

  6. The Nitrate/Perchlorate Ratio on Mars as an Indicator for Habitability

    Stern, J. C.; Sutter, B.; McKay, C. P.; Navarro-Gonzalex, R.; Freissinet, C.; Conrad, P. G.; Mahaffy, P. R.; Archer, P. D., Jr.; Ming, D. W.; Niles, P. B.; hide

    2015-01-01

    Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and the potential development of a nitrogen cycle at some point in martian history. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected evolved nitric oxide (NO) gas during pyrolysis of scooped aeolian sediments and drilled mudstone acquired in Gale Crater. The detection of NO suggests an indigenous source of fixed N, and may indicate a mineralogical sink for atmospheric N2 in the form of nitrate. The ratio of nitrate to oxychlorine species (e.g. perchlorate) may provide insight into the extent of development of a nitrogen cycle on Mars.

  7. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui; Zhou, Yong; Pei, Chonghua

    2014-01-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS 13 C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g

  8. {Tris[2-(imidazol-2-ylmethyliminoethyl]methylammonium}iron(II tris(perchlorate dihydrate

    Greg A. Brewer

    2008-01-01

    Full Text Available The title complex, [Fe(C19H27N10](ClO43·2H2O, is a new polymorph of an iron(II Schiff base complex of tris(2-aminoethylmethylammonium with imidazole-2-carboxaldehyde. The octahedral FeII atom is bound to three facial imidazole N atoms with average Fe—Nimidazole and Fe—Nimine bond distances of 1.963 (5 and 1.951 (5 Å, respectively. The central N atom of the tripodal ligand is outside the bonding distance at 3.92 Å. The crystal packing is stabilized by the hydrogen-bonding interactions between the two water molecules (acceptor and two of the three imidazole NH groups (donor. The third imidazole NH group (donor forms a hydrogen bond to one of the three perchlorate counter-ions (acceptor.

  9. Nanocrystalline transition metal oxides as catalysts in the thermal decomposition of ammonium perchlorate

    Kapoor, Inder Pal Singh; Srivastava, Pratibha; Singh, Gurdip [Department of Chemistry, DDU Gorakhpur University, Gorakhpur (India)

    2009-08-15

    Nanocrystalline transition metal oxides (NTMOs) have been successfully prepared by three different methods: novel quick precipitation method (Cr{sub 2}O{sub 3} and Fe{sub 2}O{sub 3}); surfactant mediated method (CuO), and reduction of metal complexes with hydrazine as reducing agent (Mn{sub 2}O{sub 3}). The nano particles have been characterized by X-ray diffraction (XRD) which shows an average particle diameter of 35-54 nm. Their catalytic activity was measured in the thermal decomposition of ammonium perchlorate (AP). AP decomposition undergoes a two step process where the addition of metal oxide nanocrystals led to a shifting of the high temperature decomposition peak toward lower temperature. The kinetics of the thermal decomposition of AP and catalyzed AP has also been evaluated using model fitting and isoconversional method. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  10. Degradation study of trichloroethylene and perchloric ethylene using high energy electron beam generated in industrial accelerator

    Silva, B.L.R.; Sampa, M.H.O.; Avolio, R.M.; Somessari, E.S.R.; Vieira, J.M.; Rela, P.R.

    1995-01-01

    The pollution of potable water with chlorinated hydrocarbons, mainly trichloroethylene (TCE) and perchloric ethylene (PCE), is seriously increasing the problem of contamination of water, specially in highly industrialized areas. Recent studies show that depuration by ionizing radiation has been considered a possible alternative to the control of water pollution, wherein the process by ionizing radiation converts TCE and PCE into approximately 100% carbon dioxide ions. Water samples containing TCE e PCE were submitted to radiation in the pilot plant installed in the industrial electron accelerator at IPEN from Radiation Dynamics, Dynamitron II, of 1,5 MeV - 25 m A, with doses varying from 2 kGy to 8 kGy, being its parameters analyzed before and after irradiation TCE and PCE concentrations were determined by the gas chromatography method by liquid-liquid extraction using a gas chromatograph, model CG 90, with an electron capture detector. (author). 5 refs, 4 figs

  11. Theoretical Investigation of Oxazine 170 Perchlorate Doped Polymeric Optical Fiber Amplifier

    Piotr Miluski

    2017-01-01

    Full Text Available Optical signal amplification in the waveguiding structure of optical fibers can be used for optical telecommunication systems and new light sources constructions. Organic dyes doped materials are interesting for new applications in polymeric optical fibers technology due to their benefits (efficient fluorescence, high absorption cross section, and easy processing. This article presents a numerical simulation of gain in poly(methyl methacrylate optical fiber doped by Oxazine 170 Perchlorate. The calculated gain characteristic for the used dye molar concentration (0.2·10-6–1.4·10-6 and pump power (1–10 kW is presented. The fabricated fluorescent polymeric optical fiber is also shown. The presented analysis can be used for optical amplifier construction based on dye-doped polymeric optical fiber (POF.

  12. Complexes of Th(IV) perchlorates, nitrates and thiocyanates with some heterocyclic bases

    Agarwal, R.K.; Srivastava, A.K.; Srivastava, M.; Bhakru, N.; Srivastava, T.N.

    1980-01-01

    Some Th(IV) perchlorate complexes of heterocyclic bases have been reported previously. Adducts of Th(IV) nitrates and thiocyanates with some heterocyclic N-oxides have been prepared and physico-chemical properties investigated. Comparatively little is known about the complexes of Th(IV) ion with the ligands containing nitrogen atom acting as electron donating centres. In view of this, the adducts of Th(IV) ion with certain nitrogen heterocyclic bases such as pyridine (Py), α-picoline (Pic), 2-amino pyridine (NH 2 Py), 2:4-lutidine (2,4LN), 2:6-lutidine, (2,6LN), quinoline (Q), isoquinoline (Isoq), 2,2'-bipyridine (Bipy) and 1,10-phenanthroline (Phen) were synthesised and characterised by analysis and IR absorption spectra. The results are presented and discussed. (author)

  13. Solubility and solvation of alkali metal perchlorates, tetramethyl and tetraethylammonium in aqua-ketone solvents

    Kireev, A.A.; Pak, T.G.; Bezuglyj, V.D.

    1998-01-01

    The KClO 4 , RbClO 4 , CsClO 4 , (CH 3 ) 4 NClO 4 , (C 2 H 5 ) 4 NClO 4 solubility in water and water-acetone, water-methylethylketone mixtures is determined through the method of isothermal saturation at 298.15 K. Dissociation constants of alkali metals perchlorates in acetone and its 90% mixtures (by volume) are determined conductometrically. Solubility products and standard energies of the Gibbs transfer of the studied electrolytes from water into water-acetone and water-methylethylketone solvents. It is established that the Gibbs standard energies of Na + , K + , Rb + and Cs + cations transfer from water to water-ketone solvents are close to each other. It is shown that the effect of acetone and methylethylketone on solvation of the studied electrolytes is practically similar

  14. Ligand isotopic exchange of tris(acetylacetonato)germanium(IV) perchlorate in organic solvents

    Nagasawa, Akira; Saito, Kazuo

    1978-01-01

    The ligand isotopic exchange between tris(acetylacetonato)germanium(IV) perchlorate and acetylacetone[ 14 C] has been studied in 1,1,2,2-tetrachloroethane (TCE), nitromethane (NM), and acetonitrile (AN), at 100 - 120 0 C. In these solvents, the rate formula was R = k[H 2 O][complex]; the concentrations of the complex, free ligand, and water in solution were in the ranges from 0.01 to 0.1 mol dm -3 . The activation enthalpies and entropies for the k's are 105, 98, and 90 kJ mol -1 ; and -25, -53, and -69 JK -1 mol -1 , in TCE, NM, and AN, respectively. Influence of acid and base concentrations, and deuterium isotope effect on the rate in AN suggest that the rate controlling step of the exchange is governed by the ease of the proton transfer between the leaving and the incoming acac - in an intermediate. (auth.)

  15. A summary of recent developments in transportation hazard classification activities for ammonium perchlorate

    Koller, A. M., Jr.; Hannum, J. A. E.

    1983-01-01

    The transportation hazard classification of Ammonium Perchlorate is discussed. A test program was completed and data were forwarded to retain a Class 5.1 designation (oxidizer) for AP which is shipped internationally. As a follow-on to the initial team effort to conduct AP tests existing data were examined and a matrix which catalogs test parameters and findings was compiled. A collection of test protocols is developed to standardize test methods for energetic materials of all types. The actions to date are summarized; the participating organizations and their roles as presently understood; specific findings on AP (matrix); and issues, lessons learned, and potential actions of particular interest to the propulsion community which may evolve as a result of future U.N. propellant transportation classification activities.

  16. Infrared Spectroscopy of Discrete Uranyl Anion Complexes

    Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

    2008-01-01

    The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity

  17. METHOD 332.0: DETERMINATION OF PERCHLORATE IN DRINKING WATER BY ION CHROMATOGRAPHY WITH SUPPRESSED CONDUCTIVITY AND ELECTROSPRAY IONIZATION MASS SPECTROMETRY

    This method is applicable to the identification and quantitation of perchlorate in raw and finished drinking waters. The approach used is ion chromatography with suppressed conductivity and electrospray ionization mass spectrometry (IC-ESI/MS)

  18. Probes for anionic cell surface detection

    Smith, Bradley D.

    2013-03-05

    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  19. [Health survey of plant workers for an occupational exposure to ammonium perchlorate].

    Chen, Hong-xia; Shao, Yuan-peng; Wu, Feng-hong; Li, Yang-ping; Peng, Kai-liang

    2013-01-01

    To understand the occupational hazards of ammonium perchlorate dust on operating workers and to provide the basis preventive measures for protecting the workers' health. 36 workers exposed to ammonium perchlorate dust and 48 unexposed workers from one factory were selected as the exposure and control groups. Investigations on the general condition, sampling of dust in the workplaces and a special medical examination were conducted for two groups, including occupational history, clinical manifestations, blood routine test, hepatic and renal functions, indexes of thyroid hormone, spirometric test and chest X-ray. The total dust concentration of AP in the batch plant reached to 51.63 ± 43.27 mg/m(3), exceeding the U.S. Occupational Safety and Health Administration (OSHA) permission exposure limits. The systolic blood pressure in the exposure group was higher than that of the control group (146.14 ± 21.03 VS 134.67 ± 18.58), and the difference was statistically significant (P detection rates of the cumulative total symptoms, short of breath and skin itch symptoms in the exposure group were significantly higher than those in the control group (86.11% VS 66.67%; 30.56% VS 12.50%) (P detected on the left of lung door area in the control group. The systolic blood pressure of workers in the exposure group was significantly higher, which could not exclude related to the exposure to AP dust; The T(3) levels in the exposure workers were lower than those in the control group, which may due to AP exposure, suggesting that long-term chronic exposure to AP dust may affect thyroid function.

  20. Synthesis, crystal structure and magnetic properties of (acetato-κ²O,O')bis(5,5'-dimethyl-2,2'-bipyridine-κ²N,N')nickel(II) perchlorate monohydrate.

    Farkašová, Nela; Černák, Juraj; Falvello, Larry R; Orendáč, Martin; Boča, Roman

    2015-04-01

    The title hydrated ionic complex, [Ni(CH3COO)(C12H12N2)2]ClO4·H2O or [Ni(ac)(5,5'-dmbpy)2]ClO4·H2O (where 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine and ac is acetate), (1), was isolated as violet crystals from the aqueous ethanolic nickel acetate-5,5'-dmbpy-KClO4 system. Within the complex cation, the Ni(II) atom is hexacoordinated by two chelating 5,5'-dmbpy ligands and one chelating ac ligand. The mean Ni-N and Ni-O bond lengths are 2.0628 (17) and 2.1341 (15) Å, respectively. The water solvent molecule is disordered over two partially occupied positions and links two complex cations and two perchlorate anions into hydrogen-bonded centrosymmetric dimers, which are further connected by π-π interactions. The magnetic properties of (1) at low temperatures are governed by the action of single-ion anisotropy, D, which arises from the reduced local symmetry of the cis-NiO2N4 chromophore. The fitting of the variable-temperature magnetic data (2-300 K) gives g(iso) = 2.134 and D/hc = 3.13 cm(-1).

  1. Comparative Demonstration of Active and Semi-Passive In Situ Bioremediation Approaches for Perchlorate Impacted Groundwater: Active In Situ Bioremediation Demonstration

    2013-04-01

    http://www.itrcweb.org/Documents/PERC-1.pdf • ITRC Perchlorate Team. 2008. Remediation Technologies for Perchlorate Contamination in Water and Soil ...pdf • Solutions EIS. 2006. Protocol for Enhanced In Situ Bioremediation Using Emulsified Vegetable Oil . Prepared for ESTCP. May 2006. • http...Air Force. 2007. Protocol for In Situ Bioremediation of Chlorinated Solvents Using Edible Oil . Prepared for AFCEC - Environmental Science Division

  2. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    Wang, Lai-Sheng

    2015-01-01

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES

  3. Perchlorate and Volatiles in the Brine of Lake Vida (antarctica): Implication for the Analysis of Mars Sediments

    Kenig, F. P. H.; Chou, L.; McKay, C.; Jackson, W. A.; Doran, P. T.; Murray, A. E.; Fritsen, C. H.

    2015-12-01

    A cold (-13.4 °C), saline (188 psu) evaporative brine is encapsulated in the thick (> 27 m) ice of Lake Vida (McMurdo Dry Valleys, Antarctica). The Lake Vida brine (LVBr), which contains abundant dissolved organic carbon (48.2 mmol/L), support an active but slow microbial community. LVBr contains oxychlorines with 50 μg/L of perchlorate and 11 μg/L of chlorate. The McMurdo Dry Valleys have often been considered as a good Mars analog. The oxychlorine-rich brine of Lake Vida constitutes a potential equivalent to perchlorate-rich preserved saline liquid water on Mars. We report here on the artifacts created by oxychlorines upon analysis of volatiles and volatile organic compounds (VOCs) of LVBr by direct immersion (DI) and head space (HS) solid phase micro extraction (SPME) gas chromatography-mass spectrometry (GCMS). We compare analytical blanks to a standard containing 40 μg/L of perchlorate and to actual LVBr sample runs. All blanks, perchlorate blanks and samples were analyzed using two types of SPME fibers, CarboxenTM/polydimethylsiloxane (PDMS) and divinylbenzene (DVB)/ PDMS. The similarities and differences between our results and those obtained by the Sample Analysis at Mars instruments of the rover Curiosity are discussed. The volatiles evolved from LVBr upon analysis with DI- and HS-SPME GCMS are dominated by CO2, dichloromethane, HCl, and volatile organic sulfur compounds (VOSCs, such as DMS, DMDS). The volatiles also include oxygenated compounds such as acids and ketones, aromatic compounds, hydrocarbons, chlorinated compounds (dominated by dichloromethane). Apart from the VOSCs, short chain hydrocarbons and some functionalized compounds derived from the brine itself, all compounds observed are artifacts formed upon oxychlorine breakdown in the injector of the GCMS. The distribution of aromatic compounds seems to be directly dependant on the type of SPME fiber used. The perchlorate blanks show a clear pattern of carbon limitation, likely affecting the

  4. Zero-point energy effects in anion solvation shells.

    Habershon, Scott

    2014-05-21

    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  5. Process for removing sulfate anions from waste water

    Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.

    1997-01-01

    A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.

  6. The chemistry of molecular anions in circumstellar sources

    Agúndez, Marcelino [LUTH, Observatoire de Paris-Meudon, 5 Place Jules Janssen, 92190 Meudon (France); Cernicharo, José [Departamento de Astrofísica, CAB, CSIC-INTA, Ctra. de Torrejón a Ajalvir km 4, 28850 Madrid (Spain); Guélin, Michel [Institut de Radioastronomie Millimétrique, 300 rue de la Piscine, 38406 Saint Martin d' Héres (France)

    2015-01-22

    The detection of negatively charged molecules in the interstellar and circumstellar medium in the past four years has been one of the most impacting surprises in the area of molecular astrophysics. It has motivated the interest of astronomers, physicists, and chemists on the study of the spectroscopy, chemical kinetics, and prevalence of molecular anions in the different astronomical regions. Up to six different molecular anions have been discovered in space to date, the last one being the small ion CN{sup −}, which has been observed in the envelope of the carbon star IRC +10216 and which contrary to the other larger anions is not formed by electron attachment to CN, but through reactions of large carbon anions with nitrogen atoms. Here we briefly review the current status of our knowledge of the chemistry of molecular anions in space, with particular emphasis on the circumstellar source IRC +10216, which to date is the astronomical source harboring the largest variety of anions.

  7. Anion photoelectron spectroscopy of radicals and clusters

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  8. Acute and chronic activity of perchlorate and hexavalent chromium contamination on the survival and development of Culex quinquefasciatus Say (Diptera: Culicidae)

    Sorensen, Mary A.; Jensen, Peter D.; Walton, William E.; Trumble, John T.

    2006-01-01

    Effects of water contamination with perchlorate and hexavalent chromium [Cr (VI)] on the mosquito Culex quinquefasciatus were assessed. The chronic (10-day) LC 5 s values for perchlorate and chromium were 74 ± 8.0 mg/L and 0.41 ± 0.15 mg/L, respectively. Relative Growth Index, a measure of growth and mortality rates in a population, was significantly reduced within 5 days for levels of perchlorate as low as 25 mg/L and for levels of chromium as low as 0.16 mg/L. Neither compound altered wing length of surviving adults. In combination, contaminants were synergistic, causing 14% more mortality than predicted. Acute (24-h) LC 5 values for perchlorate and Cr (VI) were 17,000 ± 3200 and 38 ± 1.3 mg/L, respectively. Effects on mosquito larvae in contaminated environments are likely to be observed for Cr (VI) but not for perchlorate, which generally does not occur at levels as high as those shown here to affect larval mosquitoes. - While pollution with hexavalent chromium may adversely affect Culex quinquefasciatus larvae, levels of perchlorate currently in the environment will not impact these insects

  9. Acute and chronic activity of perchlorate and hexavalent chromium contamination on the survival and development of Culex quinquefasciatus Say (Diptera: Culicidae)

    Sorensen, Mary A. [Department of Entomology, University of California, Riverside, CA 92521 (United States)]. E-mail: mary.sorensen@email.ucr.edu; Jensen, Peter D. [Department of Entomology, University of California, Riverside, CA 92521 (United States); Walton, William E. [Department of Entomology, University of California, Riverside, CA 92521 (United States); Trumble, John T. [Department of Entomology, University of California, Riverside, CA 92521 (United States)

    2006-12-15

    Effects of water contamination with perchlorate and hexavalent chromium [Cr (VI)] on the mosquito Culex quinquefasciatus were assessed. The chronic (10-day) LC{sub 5}s values for perchlorate and chromium were 74 {+-} 8.0 mg/L and 0.41 {+-} 0.15 mg/L, respectively. Relative Growth Index, a measure of growth and mortality rates in a population, was significantly reduced within 5 days for levels of perchlorate as low as 25 mg/L and for levels of chromium as low as 0.16 mg/L. Neither compound altered wing length of surviving adults. In combination, contaminants were synergistic, causing 14% more mortality than predicted. Acute (24-h) LC{sub 5} values for perchlorate and Cr (VI) were 17,000 {+-} 3200 and 38 {+-} 1.3 mg/L, respectively. Effects on mosquito larvae in contaminated environments are likely to be observed for Cr (VI) but not for perchlorate, which generally does not occur at levels as high as those shown here to affect larval mosquitoes. - While pollution with hexavalent chromium may adversely affect Culex quinquefasciatus larvae, levels of perchlorate currently in the environment will not impact these insects.

  10. Tetraammine(carbonato-κ2 O,O′)cobalt(III) perchlorate

    Mohan, Singaravelu Chandra; Jenniefer, Samson Jegan; Muthiah, Packianathan Thomas; Jothivenkatachalam, Kandasamy

    2013-01-01

    In the title complex, [Co(CO3)(NH3)4]ClO4, both the cation and anion lie on a mirror plane. The CoIII ion is coordinated by two NH3 ligands and a chelating carbonato ligand in the equatorial sites and by two NH3 groups in the axial sites, forming a distorted octa­hedral geometry. In the crystal, N—H⋯O hydrogen bonds connect the anions and cations, forming a three-dimensional network. PMID:24109252

  11. Tetraammine(carbonato-κ(2) O,O')cobalt(III) perchlorate.

    Mohan, Singaravelu Chandra; Jenniefer, Samson Jegan; Muthiah, Packianathan Thomas; Jothivenkatachalam, Kandasamy

    2013-01-01

    In the title complex, [Co(CO3)(NH3)4]ClO4, both the cation and anion lie on a mirror plane. The Co(III) ion is coordinated by two NH3 ligands and a chelating carbonato ligand in the equatorial sites and by two NH3 groups in the axial sites, forming a distorted octa-hedral geometry. In the crystal, N-H⋯O hydrogen bonds connect the anions and cations, forming a three-dimensional network.

  12. Anion concurrence and anion selectivity in the sorption of radionuclides by organotones

    Behnsen, Julia G.

    2007-01-01

    Some long-lived and radiologically important nuclear fission products, such as I-129 (half-life t 1/2 = 1,6 . 10 7 a), Tc-99 (t 1/2 = 2,1 . 10 5 a), and Se-79 (t 1/2 = 6,5 . 10 4 a) are anionic in aqueous environments. This study focuses on the adsorption of such anions to organoclays and the understanding of the selectivity of the process. The organoclays used in this study were prepared from a bentonite (MX-80) and a vermiculite clay, and the cationic surfactants hexadcylpyridium, hexadecyltrimethylammonium, and benzethonium. Surfactant adsorption to the bentonite exceeds the cation exchange capacity of the clay, with the surplus positive charge being balanced by the co-adsorption of chloride. The interlayer distance of the bentonites is increased sufficiently to contain bi- and pseudotrimolecular structures of the surfactants. Adsorption experiments were carried out using the batch technique. Anion adsorption of iodide, perrhenate, selenite, nitrate, and sulphate is mainly due to ion exchange with chloride. As an additional adsorption mechanism, the incorporation of inorganic ion pairs into the interlayer space of the clay is proposed as a result of experiments showing differences in the adsorption levels of sodium and potassium iodide. Anion adsorption results show a clear selectivity of the organoclays, with the affinity sequence being: ReO - 4 > I - > NO - 3 > Cl - > SO 2- 4 > SeO 2- 3 . This sequence corresponds to the sequence of increasing hydration energies of the anions, thus selectivity could be due to the process of minimization of free energy of the system. (orig.)

  13. Inhibition of nuclear waste solutions containing multiple aggressive anions

    Congdon, J.W.

    1987-01-01

    The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans, supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions, however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion. 10 refs., 5 figs., 2 tabs

  14. A Porous Perchlorate-Doped Polypyrrole Nanocoating on Nickel Nanotube Arrays for Stable Wide-Potential-Window Supercapacitors.

    Chen, Gao-Feng; Li, Xian-Xia; Zhang, Li-Yi; Li, Nan; Ma, Tian Yi; Liu, Zhao-Qing

    2016-09-01

    A bottom-up synthetic strategy is developed to fabricate a highly porous wave-superposed perchlorate-doped polypyrrole nanocoating on nickel nanotube arrays. The delicate nanostructure and the unique surface chemistry synergistically endow the obtained electrode with revealable pseudocapacitance, large operating potential window, and excellent cycling stability, which are highly promising for both asymmetric and symmetric supercapacitors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. PERCHLORATE: Occurrence is Widespread but at Varying Levels; Federal Agencies Have Taken Some Actions to Respond to and Lessen Releases

    2010-08-01

    presents a meaningful opportunity for reducing health risks for persons served by public water systems. History of EPA’s Investigation and Study...Colorado River region reported perchlorate in milk and various fruits and vegetables, including lettuce , but researchers concluded that few...installations. Of the 361 installations that reported not sampling, the primary reason cited for not sampling was that there was no history , record, or

  16. Fluorescence anisotropy of tyrosinate anion using one-, two- and three-photon excitation: tyrosinate anion fluorescence.

    Kierdaszuk, Borys

    2013-03-01

    We examined the emission spectra and steady-state anisotropy of tyrosinate anion fluorescence with one-photon (250-310 nm), two-photon (570-620 nm) and three-photon (750-930 nm) excitation. Similar emission spectra of the neutral (pH 7.2) and anionic (pH 13) forms of N-acetyl-L-tyrosinamide (NATyrA) (pKa 10.6) were observed for all modes of excitation, with the maxima at 302 and 352 nm, respectively. Two-photon excitation (2PE) and three-photon excitation (3PE) spectra of the anionic form were the same as that for one-photon excitation (1PE). In contrast, 2PE spectrum from the neutral form showed ~30-nm shift to shorter wavelengths relative to 1PE spectrum (λmax 275 nm) at two-photon energy (550 nm), the latter being overlapped with 3PE spectrum, both at two-photon energy (550 nm). Two-photon cross-sections for NATyrA anion at 565-580 nm were 10 % of that for N-acetyl-L-tryptophanamide (NATrpA), and increased to 90 % at 610 nm, while for the neutral form of NATyrA decreased from 2 % of that for NATrpA at 570 nm to near zero at 585 nm. Surprisingly, the fundamental anisotropy of NATyrA anion in vitrified solution at -60 °C was ~0.05 for 2PE at 610 nm as compared to near 0.3 for 1PE at 305 nm, and wavelength-dependence appears to be a basic feature of its anisotropy. In contrast, the 3PE anisotropy at 900 nm was about 0.5, and 3PE and 1PE anisotropy values appear to be related by the cos(6) θ to cos(2) θ photoselection factor (approx. 10/6) independently of excitation wavelength. Attention is drawn to the possible effect of tyrosinate anions in proteins on their multi-photon induced fluorescence emission and excitation spectra as well as excitation anisotropy spectra.

  17. Column adsorption of perchlorate by amine-crosslinked biopolymer based resin and its biological, chemical regeneration properties.

    Song, Wen; Xu, Xing; Tan, Xin; Wang, Yan; Ling, Jianya; Gao, Baoyu; Yue, Qinyan

    2015-01-22

    Column adsorption of perchlorate by amine-crosslinked biopolymer based resin was investigated by considering the bed depth, stream flow rate and influent pH. The empty bed contact time (EBCT) increased with the growth of bed depths, meanwhile rising flow rate at constant bed depth (3.4 cm) decreased the breakthrough time. It was observed that perchlorate adsorption capacity was optimum at neutral condition (pH: 6.0, 170.4 mg/g), and decreased at acidic (pH: 3.0, 96.4 mg/g) or alkalic (pH: 12.0, 72.8 mg/g) influents. The predominant strains of the acclimated sludge for resin biological regeneration were the β-subclass of Proteobacteria. Biological regeneration of the saturated amine-crosslinked biopolymer based resin with mixed bacteria have shown its merit with regeneration and biological perchlorate destruction simultaneously, although its regeneration efficiency was only 61.2-84.1% by contrast to chemical regeneration with efficiency more than 95%. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

    Li, Xiang; Danell, Ryan M; Brinckerhoff, William B; Pinnick, Veronica T; van Amerom, Friso; Arevalo, Ricardo D; Getty, Stephanie A; Mahaffy, Paul R; Steininger, Harald; Goesmann, Fred

    2015-02-01

    Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.

  19. Once upon Anion: A Tale of Photodetachment

    Lineberger, W. Carl

    2013-04-01

    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, “with a little help from my friends.” Actually, it was so much more than a little help!

  20. Adsorption of an anionic dispersant on lignite

    Yavuz, R.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey). Dept. of Chemical Engineering, Chemical & Metallurgical Engineering Faculty

    2001-12-01

    Since coal is not a homogeneous substance but a mixture of carbonaceous materials and mineral matter, it has a variety of surface properties. Therefore, it is not easy to control the properties of coal suspensions by simply adjusting variables, such as pH and/or electrolyte. A chemical agent needs to be added to control the properties of the coal suspensions. The adsorption behavior of an anionic dispersant in the presence of a wetting agent using some Turkish lignite samples was investigated. The effects of dispersant concentration, temperature and pH on the dispersant adsorption were studied systematically, and the experimental results are presented. Pellupur B69 as a dispersant, commercial mixture of formaldehyde condensate sodium salt of naphthalene sulphonic acid, and Texapon N{sub 2}5 as a wetting agent, a sodium lauryl ether sulfate, have been used.

  1. Structures and properties of anionic clay minerals

    Koch, Chr. Bender

    1998-01-01

    The Moessbauer spectra of pyroaurite-sjoegrenite-type compounds (PTC) (layered anion exchangers) are discussed with reference to the crystal structure, cation order, and crystallite morphology. It is shown that cation-ordered layers are produced in the synthesis of carbonate and sulphate types of green rust. In contrast, synthetic and natural pyroaurite only occurs as disordered types. The redox chemistry of Fe(III) within the metal hydroxide layer is illustrated with examples of electrochemical oxidation and reversible reduction by boiling glycerol. The chemistry of iron in the interlayer is exemplified by the intercalation of Fe-cyanide complexes in hydrotalcite. This reaction may be used as a probe for the charge distribution in the interlayer

  2. Advanced polymer chemistry of organometallic anions

    Chamberlin, R.M.; Abney, K.D.; Balaich, G.J.; Fino, S.A.

    1997-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes

  3. Perchlorate remediation using packed-bed bioreactors and electricity generation in microbial fuel cells (MFCs)

    Min, Booki

    Two pilot-scale fixed bed bioreactors were operated in continuous mode in order to treat groundwater contaminated by perchlorate. The bioreactors were constructed and operated side-by-side at the Texas Street Well Facility in Redlands, California. Each reactor was packed with either sand or plastic media. A perchlorate-reducing bacterium, Dechlorosoma sp. KJ, was used to inoculate the bioreactors. Perchlorate was successfully removed down to a non-detectable level (microbial fuel cells (MFCs), which were run either in batch or continuous mode. In batch experiments, both a pure culture (Geobactor metallireducens) and a mixed culture (wastewater inoculum) were used as the biocatalyst, and acetate was added as substrate in the anode chamber of the MFC. Power output in a membrane MFC with either inoculum was essentially the same, with 40 +/- 1 mW/m2 for G. metallireducens and 38 +/- 1 mW/m2 for mixed culture. A different type of the MFC containing a salt bridge instead of a membrane system was examined to generate power using the same substrate and pure culture as used in the membrane MFC. Power output in the salt bridge MFC was 2.2 mW/m 2. It was found that the lower power output was directly attributed to the higher internal resistance of the salt bridge system (19920 +/- 50 O) in comparison with that of the membrane system (1286 +/- 1 O). Continuous electricity generation was examined in a flat plate microbial fuel cell (FPMFC) using domestic wastewater and specific organic substrates. The FPMFC, containing a combined electrode/proton exchange membrane (PEM), was initially acclimated for one month to domestic wastewater, and then was operated as a plug flow reactor system. Power density using domestic wastewater as a substrate was 72 +/- 1 mW/m2 at a liquid flow rate of 0.39 mL/min (1.1 hr hydraulic retention time, HRT), and COD removal was 42%. At a longer HRT of 4.0 hr, the COD removal increased to 79%, and power density was 43 mW/m2. Several organic compounds

  4. Anion binding by biotin[6]uril in water

    Lisbjerg, Micke; Nielsen, Bjarne Enrico; Milhøj, Birgitte Olai

    2015-01-01

    In this contribution we show that the newly discovered 6 + 6 biotin-formaldehyde macrocycle Biotin[6]uril binds a variety of anionic guest molecules in water. We discuss how and why the anions are bound based on data obtained using NMR spectroscopy, mass spectrometry, isothermal titration...

  5. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    Nielsen, K. A.

    2012-01-01

    The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  6. Diffuse neutron scattering from anion-excess strontium chloride

    Goff, J.P.; Clausen, K.N.; Fåk, B.

    1992-01-01

    The defect structure and diffusional processes have been studied in the anion-excess fluorite (Sr, Y)Cl2.03 by diffuse neutron scattering techniques. Static cuboctahedral clusters found at ambient temperature break up at temperatures below 1050 K, where the anion disorder is highly dynamic. The a...

  7. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

  8. Thermodynamics of the complexation of ciprofloxacin with calcium and magnesium perchlorate

    Al-Mustafa, Jamil, E-mail: malkawi@just.edu.jo [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid (Jordan); Taha, Ziyad A. [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid (Jordan)

    2011-07-10

    Highlights: {yields} The thermodynamics of the reactions of ciprofloxacin (CIP) with Ca(ClO{sub 4}){sub 2} and Mg(ClO{sub 4}){sub 2} were investigated by conductometric titration. {yields} The reactions of CIP with each ion produce two ionic complexes with the formulas M(CIP){sup 2+} and M(CIP){sub 2}{sup 2+}. {yields} The change in enthalpy and entropy were negative which indicate that the complexation is driven by the enthalpy change. - Abstract: The thermodynamics of the reactions of ciprofloxacin (CIP) with calcium perchlorate (Ca(ClO{sub 4}){sub 2}) and magnesium perchlorate (Mg(ClO{sub 4}){sub 2}) have been investigated in water-methanol solvent using conductometric titration. The reactions of CIP with each ion produce two ionic complexes with the general formulas M(CIP){sup 2+} and M(CIP){sub 2}{sup 2+}. The stability constants K{sub 1} and K{sub 2} at 25 {sup o}C for the complexes formed from the reaction with Ca(ClO{sub 4}){sub 2} were 8.84 x 10{sup 4} and 3.62 x 10{sup 4}, respectively. For the reaction with Mg(ClO{sub 4}){sub 2}K{sub 1} and K{sub 2} were 1.72 x 10{sup 5} and 2.50 x 10{sup 3}, respectively. The enthalpy ({Delta}H{sub 1}, {Delta}H{sub 2}, {Delta}H{sub 12}) and entropy ({Delta}S{sub 1}, {Delta}S{sub 2}, {Delta}S{sub 12}) of complexation reactions were determined from the temperature dependence of the complexation constants. The reactions of CIP with both ions are accompanied by a decrease in entropy ({Delta}S{sub 12} = -468.12 and -478.89 J/K mol for complexation with Ca(ClO{sub 4}){sub 2} and Mg(ClO{sub 4}){sub 2}, respectively) and enthalpy ({Delta}H{sub 12} = -193.09 and -192.01 kJ/mol for complexation with Ca(ClO{sub 4}){sub 2} and Mg(ClO{sub 4}){sub 2}, respectively), which indicate that the reactions are driven by the enthalpy change.

  9. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    Moyer, Bruce a.; Bostick, Debra A.; Fowler, Christopher J.; Kang, Hyun-Ah; Ruas, Alexandre; Delmau, Laetitia H.; Haverlock, Tamara J.; Llinares, Jose M.; Hossain, Alamgir; Kang, S. O.; Bowman-James, Kristin; Shriver, James A.; Marquez, Manuel; Sessler, Jonathan L.

    2005-01-01

    The major thrust of this project led by the University of Kansas (Prof. Kristin Bowman-Jones) entails the exploration of the principles of recognition and separation of sulfate by the design, synthesis, and testing of novel sulfate extractants. A key science need for the cleanup of tank wastes at Hanford has been identified in developing methods to separate those bulk waste components that have low solubilities in borosilicate glass. Sulfate has been identified as a particularly difficult and expensive problem in that its concentration in the waste is relatively high, its solubility in glass is especially low, and it interferes with the performance of both vitrification equipment and the glass waste form. The new extractants will be synthesized by the University of Kansas and the University of Texas, Austin. Oak Ridge National Laboratory (ORNL) is subjecting the new extractants to experiments that will determine their properties and effectiveness in separating sulfate from the major competing anions in the waste, especially nitrate. Such experiments will entail primarily liquid-liquid extraction. Current efforts focus on exciting new systems in which the anion receptors act as synergists for anion exchange

  10. AT Base Pair Anions vs. (9-methyl-A)(1-methyl-T) Base Pair Anions

    Radisic, Dunja; Bowen, Kit H.; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej S.

    2005-01-01

    The anionic base pairs of adenine and thymine, (AT)-, and 9-methyladenine and 1-methylthymine, (MAMT)-, have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)- found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration that was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)- was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)- and a resulting (MAMT)- configuration that wa s either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)- occurred at a completely different electron binding energy than had (AT)-. Moreover, the VDE value of (MAMT)- was in agreement with that predicted by theory. The configuration of (MAMT)- and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced damage, BFPT in the WC/HS configurations of (AT)- is not feasible

  11. AT base pair anions versus (9-methyl-A)(1-methyl-T) base pair anions.

    Radisic, Dunja; Bowen, Kit H; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej

    2005-05-04

    The anionic base pairs of adenine and thymine, (AT)(-), and 9-methyladenine and 1-methylthymine, (MAMT)(-), have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)(-) found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)(-) was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)(-) and a resulting (MAMT)(-) configuration that was either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)(-) occurred at a completely different electron binding energy than had (AT)(-). Moreover, the VDE value of (MAMT)(-) was in agreement with that predicted by theory. The configuration of (MAMT)(-) and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced DNA alterations, BFPT in the WC/HS configurations of (AT)(-) is not feasible.

  12. Superoxide anion production by human neutrophils activated by Trichomonas vaginalis.

    Song, Hyun-Ouk; Ryu, Jae-Sook

    2013-08-01

    Neutrophils are the predominant inflammatory cells found in vaginal discharges of patients infected with Trichomonas vaginalis. In this study, we examined superoxide anion (O2 (.-)) production by neutrophils activated by T. vaginalis. Human neutrophils produced superoxide anions when stimulated with either a lysate of T. vaginalis, its membrane component (MC), or excretory-secretory product (ESP). To assess the role of trichomonad protease in production of superoxide anions by neutrophils, T. vaginalis lysate, ESP, and MC were each pretreated with a protease inhibitor cocktail before incubation with neutrophils. Superoxide anion production was significantly decreased by this treatment. Trichomonad growth was inhibited by preincubation with supernatants of neutrophils incubated for 3 hr with T. vaginalis lysate. Furthermore, myeloperoxidase (MPO) production by neutrophils was stimulated by live trichomonads. These results indicate that the production of superoxide anions and MPO by neutrophils stimulated with T. vaginalis may be a part of defense mechanisms of neutrophils in trichomoniasis.

  13. Coumarin amide derivatives as fluorescence chemosensors for cyanide anions

    Wu, Qianqian [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Liu, Zhiqiang [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong (China); Cao, Duxia, E-mail: duxiacao@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Guan, Ruifang, E-mail: mse_guanrf@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Wang, Kangnan; Shan, Yanyan; Xu, Yongxiao; Ma, Lin [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China)

    2015-07-01

    Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions have been examined. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change, at the same time, obvious color and fluorescence change can be observed by naked eye. The in situ hydrogen nuclear magnetic resonance spectra and photophysical properties change confirm that Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin. - Highlights: • Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group were synthesized. • The compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change. • Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin.

  14. The Thermodynamics of Anion Complexation to Nonpolar Pockets.

    Sullivan, Matthew R; Yao, Wei; Tang, Du; Ashbaugh, Henry S; Gibb, Bruce C

    2018-02-08

    The interactions between nonpolar surfaces and polarizable anions lie in a gray area between the hydrophobic and Hofmeister effects. To assess the affinity of these interactions, NMR and ITC were used to probe the thermodynamics of eight anions binding to four different hosts whose pockets each consist primarily of hydrocarbon. Two classes of host were examined: cavitands and cyclodextrins. For all hosts, anion affinity was found to follow the Hofmeister series, with associations ranging from 1.6-5.7 kcal mol -1 . Despite the fact that cavitand hosts 1 and 2 possess intrinsic negative electrostatic fields, it was determined that these more enveloping hosts generally bound anions more strongly. The observation that the four hosts each possess specific anion affinities that cannot be readily explained by their structures, points to the importance of counter cations and the solvation of the "empty" hosts, free guests, and host-guest complexes, in defining the affinity.

  15. Crystal structure, quantum mechanical investigation, IR and NMR spectroscopy of two new organic perchlorates: (C6H18N3)·(ClO4)3H2O (I) and (C9H11N2)·ClO4(II)

    Bayar, I.; Khedhiri, L.; Soudani, S.; Lefebvre, F.; Ferretti, V.; Ben Nasr, C.

    2018-06-01

    The reaction of perchloric acid with 1-(2-aminoethyl)piperazine or 5,6-dimethyl-benzimidazole results in the formation of 1-(2-amonioethyl)piperazine-1,4-dium triperchlorate hydrate (C6H18N3)·(ClO4)3·H2O (I) or 5,6-dimethyl-benzylimidazolium perchlorate (C9H11N2)·ClO4(II). Both compounds were fully structurally characterized including single crystal X-ray diffraction analysis. Compound (I) crystallizes in the centrosymmetric triclinic space group P 1 bar with the lattice parameters a = 7.455 (2), b = 10.462 (2), c = 10.824 (2) Å, α = 80.832 (2), β = 88.243 (2), γ = 88.160 (2) °, Z = 2 and V = 832.77 (3) Å3. Compound (II) has been found to belong to the P21/c space group of the monoclinic system, with a = 7.590 (3), b = 9.266 (3), c = 16.503 (6) Å, β = 107.38 (2) °, V = 1107.69 (7) Å3 and Z = 4. The structures of (I) and (II) consist of slightly distorted [ClO4]- tetrahedra anions and 1-(2-amonioethyl)piperazine-1,4-dium trication (I) or 5,6-dimethyl-benzylimidazolium cations (II) and additionally a lattice water in (I). The crystal structures of (I) and (II) exhibit complex three-dimensional networks of H-bonds connecting all their components. In the atomic arrangement of (I), the ClO4- anions form corrugated chains, while in (II) the atomic arrangement exhibits wide pseudo-hexagonal channels of ClO4 tetrahedra including the organic entities. The lattice water serves as a link between pairs of cations and pairs of anions via several Osbnd H⋯O and N-H⋯O interactions in compound (I). The vibrational absorption bands were identified by infrared spectroscopy. These compounds were also investigated by solid-state 13C, 35Cl and 15N NMR spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. Intermolecular interactions were investigated by Hirshfeld surfaces. Electronic properties such as HOMO and LUMO energies were derived.

  16. Immunological detection of small organic molecules in the presence of perchlorates: relevance to the life marker chip and life detection on Mars.

    Rix, Catherine S; Sims, Mark R; Cullen, David C

    2011-11-01

    The proposed ExoMars mission, due to launch in 2018, aims to look for evidence of extant and extinct life in martian rocks and regolith. Previous attempts to detect organic molecules of biological or abiotic origin on Mars have been unsuccessful, which may be attributable to destruction of these molecules by perchlorate salts during pyrolysis sample extraction techniques. Organic molecules can also be extracted and measured with solvent-based systems. The ExoMars payload includes the Life Marker Chip (LMC) instrument, capable of detecting biomarker molecules of extant and extinct Earth-like life in liquid extracts of martian samples with an antibody microarray assay. The aim of the work reported here was to investigate whether the presence of perchlorate salts, at levels similar to those at the NASA Phoenix landing site, would compromise the LMC extraction and detection method. To test this, we implemented an LMC-representative sample extraction process with an LMC-representative antibody assay and used these to extract and analyze a model sample that consisted of a Mars analog sample matrix (JSC Mars-1) spiked with a representative organic molecular target (pyrene, an example of abiotic meteoritic infall targets) in the presence of perchlorate salts. We found no significant change in immunoassay function when using pyrene standards with added perchlorate salts. When model samples spiked with perchlorate salts were subjected to an LMC-representative liquid extraction, immunoassays functioned in a liquid extract and detected extracted pyrene. For the same model sample matrix without perchlorate salts, we observed anomalous assay signals that coincided with yellow coloration of the extracts. This unexpected observation is being studied further. This initial study indicates that the presence of perchlorate salts, at levels similar to those detected at the NASA Phoenix landing site, is unlikely to prevent the LMC from extracting and detecting organic molecules from

  17. Carbon-coated copper nanoparticles prepared by detonation method and their thermocatalysis on ammonium perchlorate

    An, Chongwei; Ding, Penghui; Ye, Baoyun; Geng, Xiaoheng; Wang, Jingyu

    2017-03-01

    Carbon-coated copper nanoparticles (CCNPs) were prepared by initiating a high-density charge pressed with a mixture of microcrystalline wax, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and copper nitrate hydrate (Cu(NO3)2.3H2O) in an explosion vessel filled with nitrogen gas. The detonation products were characterized by transmission electron microcopy (TEM), high resolution transmission electron microcopy (HRTEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Raman spectroscopy. The effects of CCNPs on thermal decomposition of ammonium perchlorate (AP) were also investigated by differential scanning calorimeter (DSC). Results indicated that the detonation products were spherical, 25-40 nm in size, and had an apparent core-shell structure. In this structure, the carbon shell was 3-5 nm thick and mainly composed of graphite, C8 (a kind of carbyne), and amorphous carbon. When 5 wt.% CCNPs was mixed with 95 wt.% AP, the high-temperature decomposition peak of AP decreased by 95.97, 96.99, and 96.69 °Cat heating rates of 5, 10, and 20 °C/min, respectively. Moreover, CCNPs decreased the activation energy of AP as calculated through Kissinger's method by 25%, which indicated outstanding catalysis for the thermal decomposition of AP.

  18. Carbon-coated copper nanoparticles prepared by detonation method and their thermocatalysis on ammonium perchlorate

    Chongwei An

    2017-03-01

    Full Text Available Carbon-coated copper nanoparticles (CCNPs were prepared by initiating a high-density charge pressed with a mixture of microcrystalline wax, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, and copper nitrate hydrate (Cu(NO32·3H2O in an explosion vessel filled with nitrogen gas. The detonation products were characterized by transmission electron microcopy (TEM, high resolution transmission electron microcopy (HRTEM, energy dispersive X-ray spectroscopy (EDX, X-ray diffraction (XRD, and Raman spectroscopy. The effects of CCNPs on thermal decomposition of ammonium perchlorate (AP were also investigated by differential scanning calorimeter (DSC. Results indicated that the detonation products were spherical, 25-40 nm in size, and had an apparent core-shell structure. In this structure, the carbon shell was 3-5 nm thick and mainly composed of graphite, C8 (a kind of carbyne, and amorphous carbon. When 5 wt.% CCNPs was mixed with 95 wt.% AP, the high-temperature decomposition peak of AP decreased by 95.97, 96.99, and 96.69 °Cat heating rates of 5, 10, and 20 °C/min, respectively. Moreover, CCNPs decreased the activation energy of AP as calculated through Kissinger’s method by 25%, which indicated outstanding catalysis for the thermal decomposition of AP.

  19. Preparation and characterization of superfine ammonium perchlorate (AP) crystals through ceramic membrane anti-solvent crystallization

    Ma, Zhenye; Li, Cheng; Wu, Rujun; Chen, Rizhi; Gu, Zhenggui

    2009-10-01

    In this paper, a novel ceramic membrane anti-solvent crystallization (CMASC) method was proposed for the safe and rapid preparation ammonium perchlorate (AP) crystals, in which the acetone and ethyl acetate were chosen as solvent and anti-solvent, respectively. Comparing with the conventional liquid anti-solvent crystallization (LASC), CMASC which successfully introduces ceramic membrane with regular pore structure to the LASC as feeding medium, is favorable to control the rate of feeding rate and, therefore, to obtain size and morphology controllable AP. Several kinds of micro-sized AP particles with different morphology were obtained including polyhedral-like, quadrate-like to rod-like. The effect of processing parameters on the crystal size and shape of AP crystals such as volume ratio of anti-solvent to solvent, feeding pressure and crystallization temperature were investigated. It is found that higher volume ratio of anti-solvent to solvent, higher feeding pressure and higher temperature result in smaller particle size. Scaning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the resulting AP crystals. The nucleation and growth kinetic of the resulting AP crystals were also discussed.

  20. The influence of VO2(B nanobelts on thermal decomposition of ammonium perchlorate

    Zhang Yifu

    2015-09-01

    Full Text Available The influence of vanadium dioxide VO2(B on thermal decomposition of ammonium perchlorate (AP has not been reported before. In this contribution, the effect of VO2(B nanobelts on the thermal decomposition of AP was investigated by the Thermo- Gravimetric Analysis and Differential Thermal Analysis (TG/DTA. VO2(B nanobelts were hydrothermally prepared using peroxovanadium (V complexes, ethanol and water as starting materials. The thermal decomposition temperatures of AP in the presence of I wt.%, 3 wt.% and 6 wt.% of as-obtained VO2

  1. Kinetics of thermal decomposition of ammonium perchlorate with nanocrystals of binary transition metal ferrites

    Singh, Gurdip; Kapoor, Inder Pal Singh; Dubey, Shalini [Department of Chemistry, D. D. U. Gorakhpur University, Gorakhpur (India); Siril, Prem Felix [Laboratoire de Chimie Physique (LCP), Universite de Paris Sud, Orsay (France)

    2009-02-15

    Binary transition metal ferrite (BTMF) nanocrystals of formula MFe{sub 2}O{sub 4}(M=Cu,Co,Ni) were prepared by the coprecipitation method and characterized by X-ray diffraction (XRD). XRD patterns gave average particle size by using Scherrer's equation for CuFe{sub 2}O{sub 4}(CuF), CoFe{sub 2}O{sub 4}(CoF), and NiFe{sub 2}O{sub 4} (NiF) as 39.9, 27.3, and 43.8 nm, respectively. The catalytic activity measurements on the thermal decomposition of ammonium perchlorate (AP) were carried out by using thermogravimetry (TG), differential thermal analysis (DTA), and ignition delay studies. Isothermal TG data up to a mass loss of 45% have been used to evaluate kinetic parameters by using model fitting as well as isoconversional method. The order of catalytic activity was found to be: CoFe{sub 2}O{sub 4}>NiFe{sub 2}O{sub 4}. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  2. Ferroelectric Polarization Switching Dynamics and Domain Growth of Triglycine Sulfate and Imidazolium Perchlorate

    Ma, He

    2016-04-10

    The weak bond energy and large anisotropic domain wall energy induce many special characteristics of the domain nucleation, growth, and polarization switch in triglycine sulfate (TGS) and imidazolium perchlorate (IM), two typical molecular ferroelectrics. Their domain nucleation and polarization switch are rather slower than those of conventional oxide ferroelectrics, which may be due to the weaker bond energy of hydrogen bond or van der Waals bond than that of ionic bond. These chemical bonds dominate the elastic energy, with the latter being an important component of domain wall energy and playing an important role in domain nucleation and domain growth. The ratio of anisotropic domain wall energy to Gibbs free energy is large in TGS and IM, which allows a favorable domain shape and a special domain evolution under a certain electric field. Therefore, this study not only sheds light on the physical nature but also indicates the application direction for molecular ferroelectrics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  3. Shock wave response of ammonium perchlorate single crystals to 6 GPa

    Yuan, G.; Feng, R.; Gupta, Y. M.; Zimmerman, K.

    2000-01-01

    Plane shock wave experiments were carried out on ammonium perchlorate single crystals compressed along [210] and [001] orientations to peak stresses ranging from 1.2 to 6.2 GPa. Quartz gauge and velocity interferometer techniques were used to measure the elastic and plastic shock wave velocities, and stress and particle velocity histories in the shocked samples. The measured Hugoniot elastic limit (HEL) was 0.48±0.09 GPa. Above the HEL and up to about 6 GPa, the data show a clear two-wave structure, indicating an elastic-plastic response. Time-dependent elastic precursor decay and plastic wave ramping are discernable and orientation dependent in the low stress data. However, the orientation dependence of the peak state response is small. Hence, data for both orientations were summarized into a single isotropic, elastic-plastic-stress relaxation model. Reasonable agreement was obtained between the numerical simulations using this model and the measured wave profiles. At a shock stress of about 6 GPa and for the time duration and crystal orientations examined, we did not observe any features that may be identified as a sustained chemical reaction or a phase transformation. (c) 2000 American Institute of Physics

  4. Simultaneous determination of inorganic and organic anions by ion chromatography

    Park, Yang Soon; Joe, Ki Soo; Han, Sun Ho; Park, Soon Dal; Choi, Kwang Soon

    1999-06-01

    Four methods were investigated for the simultaneous determination of several inorganic and organic anions in aqueous solution by ion chromatography. The first is two columns coupled system. The second is the gradient elution system with an anion exchange column. The third is the system with a mixed-mode stationary phase. The fourth is the system with an anion exchange column and the eluant of low conductivity without ion suppressor. The advantages and disadvantages of individual systems were discussed. The suitable methods were proposed for the application to the samples of the nuclear power industry and the environment. (author)

  5. Unusual structures of MgF5- superhalogen anion

    Anusiewicz, Iwona; Skurski, Piotr

    2007-05-01

    The vertical electron detachment energies (VDE) of three MgF5- anions were calculated at the outer valence Green function level with the 6-311 + G(3df) basis sets. This species was found to form unusual geometrical structures each of which corresponds to an anionic state exhibiting superhalogen nature. The global minimum structure was described as a system in which two central magnesium atoms are linked via symmetrical triangle formed by three fluorine atoms. Extremely large electron binding energies of these anions (exceeding 8.5 eV in all cases) were predicted and discussed.

  6. Nitrate Anion Exchange in Pu-238 Aqueous Scrap Recovery Operations

    Pansoy-Hjelvik, M.E.; Silver, G.L.; Reimus, M.A.H.; Ramsey, K.B.

    1999-01-01

    Strong base, nitrate anion exchange (IX) is crucial to the purification of 238 Pu solution feedstocks with gross levels of impurities. This paper discusses the work involved in bench scale experiments to optimize the nitrate anion exchange process. In particular, results are presented of experiments conducted to (a) demonstrate that high levels of impurities can be separated from 238 Pu solutions via nitrate anion exchange and, (b) work out chemical pretreatment methodology to adjust and maintain 238 Pu in the IV oxidation state to optimize the Pu(IV)-hexanitrato anionic complex sorption to Reillex-HPQ resin. Additional experiments performed to determine the best chemical treatment methodology to enhance recovery of sorbed Pu from the resin, and VIS-NIR absorption studies to determine the steady state equilibrium of Pu(IV), Pu(III), and Pu(VI) in nitric acid are discussed

  7. Dehydroabiethylamine acetate as metal-containing anion precipitant

    Skrylev, L.D.; Borisov, V.A.

    1979-01-01

    The precipitation is studied of vanadate, tungstate-, molybdate- and chromate-ions by dehydroabiethylamine acetate. The degree of precipitation of metal-bearing anions is a function of the anion and of pH of the treated solutions. There exists a predetermined value of pH for each anion, at which the content of metal-bearing anion in the ultra-filtrate is at a minimum. For vanadate-ions, this pH is 5.0; for tungstate-ions, 3.0; for molybdate-ions, 4.0; for chrommate-ions, 8.0. The heats of solution of methavanadate, paratungstate, paramolybdate and dehydroabiethylamine chromate, calculated in accordance with the Vant-Hoff equation, range between 3.5 and 8.3 kJ/mole; free energy varies between 45.8 and 137.5 kJ/mole; and entropy varies between 110 and 371 J/degree mole

  8. Detection of cyanide anion by zinc porphyrin-spiropyran dyad

    Kho, Young Min; Hur, Dae Young; Shin, Eun Ju

    2016-01-01

    Versatile methods of the sensitive and selective detection for cyanide anion to monitor toxic cyanide have been developed. These include colorimetric, colorimetric, chromatographic, and electrochemical analyses. Among those methods for cyanide detection, optical methods based on absorption and fluorescence spectroscopy are relatively simple, inexpensive, and sensitive. A number of organic sensors for cyanide anion have been designed and synthesized. Absorption and/or fluorescence spectra of these sensors are changed by forming coordination complex or bonding covalently with cyanide. Compared with other anions, cyanide anion has some characteristic properties, such as its strong nucleophilicity and high binding affinity toward metal ions, and is superior and useful for the development of the sensors. Both covalent bond-based sensors and coordination complex-based sensors have been developed for cyanide detection. The results indicate that ZnP-SP plays a role as a CN"- selective, colorimetric sensor either without or with UV irradiation

  9. Electronic spectra of anions intercalated in layered double hydroxides

    groups of the layers and interlayer water through the termi- nal atom symmetry ... results in a reaction with the metal hydroxide layers lead- ing to the ..... List of band positions observed for potassium salts of anion and LDH samples. Salts.

  10. Detection of cyanide anion by zinc porphyrin-spiropyran dyad

    Kho, Young Min; Hur, Dae Young; Shin, Eun Ju [Dept. of Chemistry, Sunchon National University, Suncheon (Korea, Republic of)

    2016-10-15

    Versatile methods of the sensitive and selective detection for cyanide anion to monitor toxic cyanide have been developed. These include colorimetric, colorimetric, chromatographic, and electrochemical analyses. Among those methods for cyanide detection, optical methods based on absorption and fluorescence spectroscopy are relatively simple, inexpensive, and sensitive. A number of organic sensors for cyanide anion have been designed and synthesized. Absorption and/or fluorescence spectra of these sensors are changed by forming coordination complex or bonding covalently with cyanide. Compared with other anions, cyanide anion has some characteristic properties, such as its strong nucleophilicity and high binding affinity toward metal ions, and is superior and useful for the development of the sensors. Both covalent bond-based sensors and coordination complex-based sensors have been developed for cyanide detection. The results indicate that ZnP-SP plays a role as a CN{sup -} selective, colorimetric sensor either without or with UV irradiation.

  11. Two independent anion transport systems in rabbit mandibular salivary glands

    Novak, I; Young, J A

    1986-01-01

    Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion in the foll......Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion...... stimulated secretion by about 30%, but when infused in addition to furosemide (0.1 mmol/l), it inhibited by about 20%. Amiloride (1.0 mmol/l) caused no inhibition. The results suggest that there are at least three distinct carriers in the rabbit mandibular gland. One is a furosemide-sensitive Na-coupled Cl...

  12. Mechanism of protection of adenosine from sulphate radical anion ...

    Unknown

    Keywords. Repair by caffeic acid; repair of adenosine radicals; oxidation by sulphate radical anions. ... known that hydroxycinnamic acids are natural anti- oxidants ... acid. 2. Experimental ..... ously and independently under kinetic conditions at.

  13. New anion-exchange polymers for improved separations

    Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.

    1997-01-01

    Objective is to improve the understanding of how the structure of a new class of anion-exchange polymers controls the binding of anionic actinide complexes from solution. This is needed to develop practical separation systems that will reduce the cost of actinide processing operations within the DOE complex. In addition anion exchange is widely used in industry. Several new series of bifunctional anion- exchange polymers have been designed, synthesized, and tested for removing Pu(IV), Am(III), and U(VI) from nitric acid. The polymers contain a pyridinium site derived from the host poly(4-vinylpyridine) and a second cationic site attached through a chain of 2 to 6 methylene groups. The new polymers removed Pu four to ten times more efficiently than the best commercial materials

  14. Intestinal transporters for endogenic and pharmaceutical organic anions

    Grandvuinet, Anne Sophie; Vestergaard, Henrik Tang; Rapin, Nicolas

    2012-01-01

    This review provides an overview of intestinal human transporters for organic anions and stresses the need for standardization of the various in-vitro methods presently employed in drug-drug interaction (DDI) investigations....

  15. Expanding frontiers in materials chemistry and physics with multiple anions.

    Kageyama, Hiroshi; Hayashi, Katsuro; Maeda, Kazuhiko; Attfield, J Paul; Hiroi, Zenji; Rondinelli, James M; Poeppelmeier, Kenneth R

    2018-02-22

    During the last century, inorganic oxide compounds laid foundations for materials synthesis, characterization, and technology translation by adding new functions into devices previously dominated by main-group element semiconductor compounds. Today, compounds with multiple anions beyond the single-oxide ion, such as oxyhalides and oxyhydrides, offer a new materials platform from which superior functionality may arise. Here we review the recent progress, status, and future prospects and challenges facing the development and deployment of mixed-anion compounds, focusing mainly on oxide-derived materials. We devote attention to the crucial roles that multiple anions play during synthesis, characterization, and in the physical properties of these materials. We discuss the opportunities enabled by recent advances in synthetic approaches for design of both local and overall structure, state-of-the-art characterization techniques to distinguish unique structural and chemical states, and chemical/physical properties emerging from the synergy of multiple anions for catalysis, energy conversion, and electronic materials.

  16. Adsorption and desorption dynamics of citric acid anions in soil

    Oburger, E.; Leitner, D.; Jones, D. L.; Zygalakis, K. C.; Schnepf, A.; Roose, T.

    2011-01-01

    The functional role of organic acid anions in soil has been intensively investigated, with special focus on (i) microbial respiration and soil carbon dynamics, (ii) nutrient solubilization or (iii) metal detoxification and reduction of plant metal

  17. Synthesis and anion binding properties of porphyrins and related compounds

    Figueira, Flá vio; Rodrigues, Joã o M M; Farinha, Andreia; Cavaleiro, José A S; Tomé , Joã o P C

    2016-01-01

    promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  18. Changing certain dietary cationic and anionic minerals: Impact on ...

    Changing certain dietary cationic and anionic minerals: Impact on blood chemistry, milk ... Increased blood pH and serum HCO3 were noticed in buffaloes fed with LC ... Serum calcium and chloride increased with decreased DCAD level while ...

  19. Effects of the anti-thyroidal compound potassium-perchlorate on the thyroid system of the zebrafish

    Schmidt, Florian, E-mail: florian.schmidt@zoo.uni-heidelberg.de [Aquatic Ecology and Toxicology Group, Centre for Organismal Studies, University of Heidelberg, Im Neuenheimer Feld 230, D-69120 Heidelberg (Germany); Schnurr, Sarah; Wolf, Raoul; Braunbeck, Thomas [Aquatic Ecology and Toxicology Group, Centre for Organismal Studies, University of Heidelberg, Im Neuenheimer Feld 230, D-69120 Heidelberg (Germany)

    2012-03-15

    The increasing pollution of aquatic habitats with anthropogenic compounds has led to various test strategies to detect hazardous chemicals. However, information on effects of pollutants in the thyroid system in fish, which is essential for growth, development and parts of reproduction, is still scarce. Other vertebrate groups such as amphibians or mammals are well-studied; so the need for further knowledge especially in fish as a favored vertebrate model test organism is evident. Modified early life-stage tests were carried out with zebrafish exposed to the known thyroid inhibitor potassium perchlorate (0, 62.5, 125, 250, 500 and 5000 {mu}g/L) to identify adverse effects on the hypothalamic-pituitary-thyroid axis. Especially higher perchlorate concentrations led to conspicuous alterations in thyroidal tissue architecture and to effects in the pituitary. In the thyroid, severe hyperplasia at concentrations {>=}500 {mu}g/L together with an increase in follicle number could be detected. The most sensitive endpoint was the colloid, which showed alterations at {>=}250 {mu}g/L. The tinctorial properties and the texture of the colloid changed dramatically. Interestingly, effects on epithelial cell height were minor. The pituitary revealed significant proliferations of TSH-producing cells resulting in alterations in the ratio of adeno- to neurohypophysis. The liver as the main site of T4 deiodination showed severe glycogen depletion at concentrations {>=}250 {mu}g/L. In summary, the thyroid system in zebrafish showed effects by perchlorate from concentrations {>=}250 {mu}g/L, thus documenting a high sensitivity of the zebrafish thyroid gland for goitrogens. In the future, such distinct alterations could lead to a better understanding and identification of potential thyroid-disrupting chemicals.

  20. Ion-exchange concentration of inorganic anions from aqueous solution

    L. P. Bondareva

    2016-01-01

    Full Text Available Monitoring of natural waters in the present time - consuming process, the accuracy of which is influenced by many factors: the composition of water, the presence of impurities and "interfering" components. The water sample preparation process includes the step of concentration and separation of ions determined. The most versatile, efficient, and frequently used method is the concentration of inorganic anions from aqueous solutions by ion exchanger, which can optimize the composition of water to the optimal for identification and quantitative determination of anions. The characteristics of sorption chloride, nitrate and sulfate ions of basic anion exchange resin AВ-17 and Purolite A430 were compared in the article. The constants of protolysis of ion exchangers both AB 17 and Purolite A430 are the same and equal 0.037 ± 0,002. The value of total capacity (POE Purolite A430 was 4.3 mmol/g, AB 17 – 3.4 mmol/g. The studied ion exchangers have the same type of ionic groups – quaternary ammonium, but their number and denotes differ. The number of quaternary ammonium groups is higher in Purolite A430, respectively the number of absorbed anions of these ion exchanger is higher. The values of dynamic exchange capacity (DOE of ion exchanger Purolite A430 is higher than these values of AB-17 and equal to 1.48 ± 0.03 mmol / dm3 for chloride ion, 1.50 ± 0.03 mmol / dm3 for nitrate ion, 1.62 ± 0.03 mmol / dm3 for sulfate ion. The values of the POE and DOE of anion-exchange resins Purolite A430 and AV-17 and the characteristics of the individual sorption of chloride, nitrate, sulfate ions showed an advantage of the Purolite for the concentrationing of anions. It is found that times of anions sorption from triple-anion solutions by Purolite A430 are significantly different for different anions, and these times are close for anion-exchanger AV-17. It proves the possibility of quantitative separation and concentration by anion-exchanger Purolite A430.

  1. Uptake of N-nitrosodimethylamine (NDMA) from water by phreatophytes in the absence and presence of perchlorate as a co-contaminant.

    Yifru, Dawit D; Nzengung, Valentine A

    2006-12-01

    The uptake and fate of the emerging contaminants N-nitrosodimethylamine (NDMA) and perchlorate in phreatophytes was studied in a hydroponics system under greenhouse conditions. NDMA is a potent carcinogen, and perchlorate disrupts the functioning ofthe human thyroid gland. The rate of removal of NDMA from solution by rooted cuttings of black willow (Salix nigra) and hybrid poplar (Populus deltoides x nigra, DN34) trees varied seasonally, with faster removal in summer months when transpiration rates were highest. A linear correlation between the volume of water transpired and mass of NDMA removed from the root zone was observed, especially at higher NDMA concentrations. In bioreactors dosed with both NDMA (0.7-1.0 mg L(-1)) and perchlorate (27 mg L(-1)), no competitive uptake of NDMA and perchlorate was observed. While NDMA was primarily removed from solution by plant uptake, perchlorate was predominantly removed by rhizodegradation. In the presence of NDMA, a slower rate of rhizodegradation of perchlorate was observed, but still significantly faster than the rate of NDMA uptake. For experiments conducted with radiolabeled NDMA, 46.4 +/- 1.1% of the total 14C-activity was recovered in the plant tissues and 47.5% was phytovolatilized. The 46.4 +/- 1.1% recovered in the plants was distributed as follows: 18.8 +/- 1.4% in leaves, 15.9 +/- 5.9% in stems, 7.6 +/- 3.2% in branches, and 3.5 +/- 3.3% in roots. The poor extractability of NDMA with methanol-water (1:1 v/v) from stem and leaf tissues suggested that some fraction of NDMA was assimilated. The calculated transpiration stream concentration factor (TSCF) of 0.28 +/- 0.06 suggests that NDMA is passively taken up by phreatophytes, and mainly phytovolatilized.

  2. Stripping analysis of nanomolar perchlorate in drinking water with a voltammetric ion-selective electrode based on thin-layer liquid membrane.

    Kim, Yushin; Amemiya, Shigeru

    2008-08-01

    A highly sensitive analytical method is required for the assessment of nanomolar perchlorate contamination in drinking water as an emerging environmental problem. We developed the novel approach based on a voltammetric ion-selective electrode to enable the electrochemical detection of "redox-inactive" perchlorate at a nanomolar level without its electrolysis. The perchlorate-selective electrode is based on the submicrometer-thick plasticized poly(vinyl chloride) membrane spin-coated on the poly(3-octylthiophene)-modified gold electrode. The liquid membrane serves as the first thin-layer cell for ion-transfer stripping voltammetry to give low detection limits of 0.2-0.5 nM perchlorate in deionized water, commercial bottled water, and tap water under a rotating electrode configuration. The detection limits are not only much lower than the action limit (approximately 246 nM) set by the U.S. Environmental Protection Agency but also are comparable to the detection limits of the most sensitive analytical methods for detecting perchlorate, that is, ion chromatography coupled with a suppressed conductivity detector (0.55 nM) or electrospray ionization mass spectrometry (0.20-0.25 nM). The mass transfer of perchlorate in the thin-layer liquid membrane and aqueous sample as well as its transfer at the interface between the two phases were studied experimentally and theoretically to achieve the low detection limits. The advantages of ion-transfer stripping voltammetry with a thin-layer liquid membrane against traditional ion-selective potentiometry are demonstrated in terms of a detection limit, a response time, and selectivity.

  3. Evaluation of perturbations in serum thyroid hormones during human pregnancy due to dietary iodide and perchlorate exposure using a biologically based dose-response model.

    Lumen, Annie; Mattie, David R; Fisher, Jeffrey W

    2013-06-01

    A biologically based dose-response model (BBDR) for the hypothalamic pituitary thyroid (HPT) axis was developed in the near-term pregnant mother and fetus. This model was calibrated to predict serum levels of iodide, total thyroxine (T4), free thyroxine (fT4), and total triiodothyronine (T3) in the mother and fetus for a range of dietary iodide intake. The model was extended to describe perchlorate, an environmental and food contaminant, that competes with the sodium iodide symporter protein for thyroidal uptake of iodide. Using this mode-of-action framework, simulations were performed to determine the daily ingestion rates of perchlorate that would be associated with hypothyroxinemia or onset of hypothyroidism for varying iodide intake. Model simulations suggested that a maternal iodide intake of 75 to 250 µg/day and an environmentally relevant exposure of perchlorate (~0.1 µg/kg/day) did not result in hypothyroxinemia or hypothyroidism. For a daily iodide-sufficient intake of 200 µg/day, the dose of perchlorate required to reduce maternal fT4 levels to a hypothyroxinemic state was estimated at 32.2 µg/kg/day. As iodide intake was lowered to 75 µg/day, the model simulated daily perchlorate dose required to cause hypothyroxinemia was reduced by eightfold. Similarly, the perchlorate intake rates associated with the onset of subclinical hypothyroidism ranged from 54.8 to 21.5 µg/kg/day for daily iodide intake of 250-75 µg/day. This BBDR-HPT axis model for pregnancy provides an example of a novel public health assessment tool that may be expanded to address other endocrine-active chemicals found in food and the environment.

  4. (100) faceted anion voids in electron irradiated fluorite

    Johnson, E.

    1979-01-01

    High fluence electron irradiation of fluorite crystals in the temperature range 150 to 320 K results in formation of a simple cubic anion void superlattice. Above 320 K the damage structure changes to a random distribution of large [001] faceted anion voids. This voidage behaviour, similar to that observed in a range of irradiated metals, is discussed in terms points defect rather than conventional colour centre terminology. (Auth.)

  5. Determination of nitrate by anion exchange with ultraviolet detection

    McComas, J.G.

    1976-01-01

    A weak base anion exchange resin is synthesized by surface bonding 3-aminopropyltriethoxysilane to silica gel. This silylated silica gel is used to separate nitrate from interferences. The nitrate is then determined by measuring its absorbance at 220 nm. An interference study was performed and no anions commonly found in potable water interferes. A comparison of this method was made with the brucine method on real samples and satisfactory agreement was obtained between the two methods.

  6. Gas-Grain Models for Interstellar Anion Chemistry

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  7. The crystal structures of some alkyldiaminium perchlorates, permanganates and hexachlouranates (IV)

    Marais, M.A.

    1984-12-01

    The diquaternary nitrogen cations N,N,N,N 1 ,N 1 ,N 1 -hexaalkyl-1,2-ethane-diaminium and N,N,N,N 1 ,N 1 ,N 1 -hexaalkyl-1,6-hexanediaminium (alkyl = n-octyl for example) are important potential solvent extractants for the extraction of transition metals (Co, Cu) and uranium from HCl medium. Since the alkyldiaminium skeleton constitutes the active centre in solution, the conformations of the cations in association with typical metallate counter-ions were of interest. The crystal structures of the hexachloro-uranate (IV) and permanganate salts of the hexamethyl ethanediaminium ion, as well as the hexachlorouranate (IV) and perchlorate salts of the hexamethyl hexanediaminium ion were therefore determined by X-ray crystallography. No evidence of any deformation of the cation skeleton from their previously well-established conformations were, however, found. The structures can all be understood as typical ionic salts in which the packing and structural features are dominated by the relatively large cations. In the permanganate salt of the N,N,N,N 1 ,N 1 ,N 1 -1,2-ethanediaminium cation the bridging methylene groups display an unusual type of positional disorder, for which there is only one precedent (also discovered in this laboratory). The values of the Mn-O and U-Cl bond lengths in the permanganate and hexachlorouranate ions were determined with a precision comparable to that of the most accurate values obtained so far in other salts. These distances are also in excellent agreement with previous values, and provide further confirmation for two bond lengths for which very few estimates were previously available

  8. Anodic dissolution of UO2 in slightly alkaline sodium perchlorate solutions

    Sunder, S.; Strandlund, L.K.; Shoesmith, D.W.

    1996-04-01

    The anodic dissolution of UO 2 has been studied in aqueous sodium perchlorate solutions at pH ∼ 9.5. Under potentiostatic conditions two distinct regions of oxidation/dissolution behaviour were observed. In the potential (E) range 0.100 V A , Q C respectively) obtained by integration of the anodic current-time plots (Q A ) and cathodic potential scans to reduce accumulated oxidized surface films (Q C ), it was shown that > ∼ 90% of the anodic oxidation current went to produce these films. For E > ∼ 0.350 V, steady-state currents were obtained and measurements of Q A and Q C showed the majority of the current went to produce soluble species. The film blocking anodic dissolution appeared to be either UO 2.27 or, more probably, UO 3 .2H 2 O located primarily at grain boundaries. It is proposed that, at the higher potentials, rapid oxidation and dissolution followed by the hydrolysis of dissolved uranyl species leads to the development of acidic conditions in the grain boundaries. At these lower pH values the UO 3 .2H 2 O is soluble and therefore does not accumulate. Alternatively, if this oxide has been formed by prior oxidation at a lower potential, the formation of protons on oxidizing at E > ∼ 0.350V causes its redissolution, allowing the current to rise to a steady-state value. On the basis of Tafel slopes, an attempt was made to demonstrate that the observed behaviour was consistent with dissolution under acidic conditions. This analysis was only partially successful. (author) 34 refs. 11 figs

  9. Fluorination of Boron-Doped Diamond Film Electrodes for Minimization of Perchlorate Formation.

    Gayen, Pralay; Chaplin, Brian P

    2017-08-23

    This research investigated the effects of surface fluorination on both rates of organic compound oxidation (phenol and terephthalic acid (TA)) and ClO 4 - formation at boron-doped diamond (BDD) film anodes at 22 °C. Different fluorination methods (i.e., electrochemical oxidation with perfluorooctanoic acid (PFOA), radio frequency plasma, and silanization) were used to incorporate fluorinated moieties on the BDD surface, which was confirmed by X-ray photoelectron spectroscopy (XPS). The silanization method was found to be the most effective fluorination method using a 1H,1H,2H,2H-perfluorodecyltrichlorosilane precursor to form a self-assembled monolayer (SAM) on the oxygenated BDD surface. The ClO 4 - formation decreased from rates of 0.45 ± 0.03 mmol m -2 min -1 during 1 mM NaClO 3 oxidation and 0.28 ± 0.01 mmol m -2 min -1 during 10 mM NaCl oxidation on the BDD electrode to below detectable levels (layer on the BDD surface that inhibited charge transfer via steric hindrance and hydrophobic effects. The surface coverages and thicknesses of the fluorinated films controlled the charge transfer rates, which was confirmed by estimates of film thicknesses using XPS and density functional theory simulations. The aliphatic silanized electrode also showed very high stability during OH • production. Perchlorate formation rates were below the detection limit (<0.12 μmoles m -2 min -1 ) for up to 10 consecutive NaClO 3 oxidation experiments.

  10. Evaluation of Perchlorate Sources in the Rialto-Colton and Chino California Subbasins using Chlorine and Oxygen Isotope Ratio Analysis

    2015-03-01

    matches, air bags , chlorine bleach, safety flares, perchloric acid, and chlorate herbicides (Trumpholt et al., 2005; Aziz et al., 2006, 2008). Based...L, assuming no losses to biodegradation or other removal processes. Additional information on Atacama NO3- fertilizers as a source of ClO4- can be...in each well), the IX columns were removed from the each well, sealed in Zip-Loc type bags , placed at 4oC (or on ice), and shipped to the UIC EIGL

  11. Picosecond laser fabricated Ag, Au and Ag-Au nanoparticles for detecting ammonium perchlorate using a portable Raman spectrometer

    Byram, Chandu; Moram, Sree Sathya Bharathi; Soma, Venugopal Rao

    2018-04-01

    In this paper, we present the results from fabrication studies of Ag, Au, and Ag-Au alloy nanoparticles (NPs) using picosecond laser ablation technique in the presence of liquid media. The alloy formation in the NPs was confirmed from UV-Visible measurements. The shape and crystallinity of NPs were investigated by using high resolution transmission electron microscopy (HRTEM), selected area diffraction pattern (SAED) and energy dispersive spectroscopy (EDS). The SERS effect of fabricated NPs was tested with methylene blue and an explosive molecule (ammonium perchlorate) using a portable Raman spectrometer and achieved EFs of ˜106.

  12. The gecko visual pigment: the anion hypsochromic effect.

    Crescitelli, F; Karvaly, B

    1991-01-01

    The 521-pigment in the retina of the Tokay gecko (Gekko gekko) readily responds to particular physical and chemical changes in its environment. When solubilized in chloride deficient state the addition of Class I anions (Cl-, Br-) induces a bathochromic shift of the absorption spectrum. Class II anions (NO3-, IO3-, N3-, OCN-, SCN-, SeCN-, N(CN)2-), which exhibit ambidental properties, cause an hypsochromic shift. Class III anions (F-, I-, NO2-, CN-, AsO3-, SO2(4-), S2O2(3-) have no spectral effect on the 521-pigment. Cations appear to have no influence on the pigment absorption and Class I anions prevent or reverse the hypsochromic shift caused by Class II anions. It is suggested that the spectral displacements reflect specific changes in the opsin conformation, which alter the immediate (dipolar) environment of the retinal chromophore. The protein conformation seems to promote excited-state processes most in the native 521-pigment state and least in the presence of Class II anions. This in turn suggests that the photosensitivity of the 521-pigment is controlled by the excited rather than by the ground-state properties of the pigment.

  13. Vibrational Spectroscopy of Cation and Anion Channelrhodopsins

    Yi, Adrian S.

    Optogenetics is a technique to control and monitor cell activity with light by expression of specific microbial rhodopsins. Cation channelrhodopsins (CCRs) and anion channelrhodopsins (ACRs) have been demonstrated to activate and silence cell activity, respectively. In this dissertation, the molecular mechanisms of two channelrhodopsins are studied: a CCR from Chlamydomonas augustae (CaChR1) and an ACR from Guillardia theta (GtACR1). The recently discovered GtACR1is especially interesting, as it achieves neural silencing with 1/1000th of the light intensity compared to previous microbial rhodopsin silencing ion pumps. Static and time-resolved resonance Raman, FTIR difference, and UV-visible spectroscopies were utilized in addition to various biochemical and genetic techniques to explore the molecular mechanisms of these channelrhodopsins. In CaChR1, Glu169 and Asp299 residues are located nearby the Schiff base (SB) similar to the homologous residues Asp85 and Asp212, which exist in an ionized state in unphotolyzed bacteriorhodopsin (BR) and play a key role in proton pumping. We observe significant changes in the protonation states of the SB, Glu169, and Asp299 of CaChR1 leading up to the open-channel P2 state, where all three groups exist in a charge neutral state. This unusual charge neutrality along with the position of these groups in the CaChR1 ion channel suggests that charge neutrality plays an important role in cation gating and selectivity in these low efficiency CCRs. Significant differences exist in the photocycle and protonation/hydrogen bonding states of key residues inGtACR1compared to BR and CaChR1. Resonance Raman studies reveal that in the unphotolyzed state of GtACR1, residues Glu68, Ser97 (BR Asp85 homolog), and Asp234 (BR Asp212 homolog) located near the SB exist in charge neutral states. Furthermore, upon K formation, these residues do not change their protonation states. At room temperature, a slow decay of the red-shifted K intermediate is

  14. Ab initio theoretical study of dipole-bound anions of molecular complexes: (HF)3- and (HF)4- anions

    Ramaekers, Riet; Smith, Dayle M. A.; Smets, Johan; Adamowicz, Ludwik

    1997-12-01

    Ab initio calculations have been performed to determine structures and vertical electron detachment energy (VDE) of the hydrogen fluoride trimer and tetramer anions, (HF)3- and (HF)4-. In these systems the excess electron is bound by the dipole field of the complex. It was determined that, unlike the neutral complexes which prefer the cyclic structures, the equilibrium geometries of the anions have "zig-zag" shapes. For both complexes the predicted VDEs are positive [210 meV and 363 meV for (HF)3- and (HF)4-, respectively], indicating that the anions are stable systems with respect to the vertical electron detachment. These results were obtained at the coupled-cluster level of theory with single, double and triple excitations [CCSD(T) method; the triple-excitation contribution in this method is calculated approximately using the perturbation approach] with the anion geometries obtained using the second-order Møller-Plesset perturbation theory (MP2) method. The same approach was also used to determine the adiabatic electron affinities (AEA) of (HF)3 and (HF)4. In addition to the electronic contribution, we also calculated the contributions (using the harmonic approximation) resulting from different zero-point vibration energies of the neutral and anionic clusters. The calculations predicted that while the AEA of (HF)3 is positive (44 meV), the AEA for (HF)4 is marginally negative (-16 meV). This suggests that the (HF)3- anion should be a stable system, while the (HF)4- is probably metastable.

  15. Evaluation of the risk of perchlorate exposure in a population of late-gestation pregnant women in the United States: Application of probabilistic biologically-based dose response modeling

    Lumen, A; George, N I

    2017-01-01

    The risk of ubiquitous perchlorate exposure and the dose-response on thyroid hormone levels in pregnant women in the United States (U.S.) have yet to be characterized. In the current work, we integrated a previously developed perchlorate submodel into a recently developed population-based pregnancy model to predict reductions in maternal serum free thyroxine (fT4) levels for late-gestation pregnant women in the U.S. Our findings indicated no significant difference in geometric mean estimates of fT4 when perchlorate exposure from food only was compared to no perchlorate exposure. The reduction in maternal fT4 levels reached statistical significance when an added contribution from drinking water (i.e., 15 μg/L, 20 μg/L, or 24.5 μg/L) was assumed in addition to the 90th percentile of food intake for pregnant women (0.198 μg/kg/day). We determined that a daily intake of 0.45 to 0.50 μg/kg/day of perchlorate was necessary to produce results that were significantly different than those obtained from no perchlorate exposure. Adjusting for this food intake dose, the relative source contribution of perchlorate from drinking water (or other non-dietary sources) was estimated to range from 0.25–0.3 μg/kg/day. Assuming a drinking water intake rate of 0.033 L/kg/day, the drinking water concentration allowance for perchlorate equates to 7.6–9.2 μg/L. In summary, we have demonstrated the utility of a probabilistic biologically-based dose-response model for perchlorate risk assessment in a sensitive life-stage at a population level; however, there is a need for continued monitoring in regions of the U.S. where perchlorate exposure may be higher. - Highlights: • Probabilistic risk assessment for perchlorate in U.S. pregnant women was conducted. • No significant change in maternal fT4 predicted due to perchlorate from food alone. • Drinking water concentration allowance for perchlorate estimated as 7.6–9.2 μg/L

  16. Evaluation of the risk of perchlorate exposure in a population of late-gestation pregnant women in the United States: Application of probabilistic biologically-based dose response modeling

    Lumen, A, E-mail: Annie.Lumen@fda.hhs.gov [Division of Biochemical Toxicology, National Center for Toxicological Research, U.S. Food and Drug Administration, 3900 NCTR Rd, HFT-110, Jefferson, AR 72079 (United States); George, N I, E-mail: Nysia.George@fda.hhs.gov [Division of Bioinformatics and Biostatistics, National Center for Toxicological Research, U.S. Food and Drug Administration, 3900 NCTR Rd, HFT-20, Jefferson, AR 72079 (United States)

    2017-05-01

    The risk of ubiquitous perchlorate exposure and the dose-response on thyroid hormone levels in pregnant women in the United States (U.S.) have yet to be characterized. In the current work, we integrated a previously developed perchlorate submodel into a recently developed population-based pregnancy model to predict reductions in maternal serum free thyroxine (fT4) levels for late-gestation pregnant women in the U.S. Our findings indicated no significant difference in geometric mean estimates of fT4 when perchlorate exposure from food only was compared to no perchlorate exposure. The reduction in maternal fT4 levels reached statistical significance when an added contribution from drinking water (i.e., 15 μg/L, 20 μg/L, or 24.5 μg/L) was assumed in addition to the 90th percentile of food intake for pregnant women (0.198 μg/kg/day). We determined that a daily intake of 0.45 to 0.50 μg/kg/day of perchlorate was necessary to produce results that were significantly different than those obtained from no perchlorate exposure. Adjusting for this food intake dose, the relative source contribution of perchlorate from drinking water (or other non-dietary sources) was estimated to range from 0.25–0.3 μg/kg/day. Assuming a drinking water intake rate of 0.033 L/kg/day, the drinking water concentration allowance for perchlorate equates to 7.6–9.2 μg/L. In summary, we have demonstrated the utility of a probabilistic biologically-based dose-response model for perchlorate risk assessment in a sensitive life-stage at a population level; however, there is a need for continued monitoring in regions of the U.S. where perchlorate exposure may be higher. - Highlights: • Probabilistic risk assessment for perchlorate in U.S. pregnant women was conducted. • No significant change in maternal fT4 predicted due to perchlorate from food alone. • Drinking water concentration allowance for perchlorate estimated as 7.6–9.2 μg/L.

  17. Benzonitrile: Electron affinity, excited states, and anion solvation

    Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

    2015-10-01

    We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

  18. Synthesis of polycrystalline Co{sub 3}O{sub 4} nanowires with excellent ammonium perchlorate catalytic decomposition property

    Zhou, Hai [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Lv, Baoliang, E-mail: lbl604@sxicc.ac.cn [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 (China); Wu, Dong; Xu, Yao [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 (China)

    2014-12-15

    Graphical abstract: Co{sub 3}O{sub 4} nanowires with excellent ammonium perchlorate catalytic decomposition property were synthesized via a methanamide-assisted hydrolysis and subsequent dissolution–recrystallization process in the presence of methanamide. - Abstract: Co{sub 3}O{sub 4} nanowires, with the length of tens of micrometers and the width of several hundred nanometers, were produced by a hydrothermal treatment and a post-anneal process. X-ray diffraction (XRD) result showed that the Co{sub 3}O{sub 4} nanowires belong to cubic crystal system. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analysis indicated that the Co{sub 3}O{sub 4} nanowires, composed by single crystalline nanoparticles, were of polycrystalline nature. On the basis of time-dependent experiments, methanamide-assisted hydrolysis and subsequent dissolution–recrystallization process were used to explain the precursors' formation process of the polycrystalline Co{sub 3}O{sub 4} nanowires. The TGA experiments showed that the as-obtained Co{sub 3}O{sub 4} nanowires can catalyze the thermal decomposition of ammonium perchlorate (AP) effectively.

  19. A novel hydrolysis method to synthesize chromium hydroxide nanoparticles and its catalytic effect in the thermal decomposition of ammonium perchlorate

    Li, Ping; Zhou, Zhen; Xu, Hongbin; Zhang, Yi

    2012-01-01

    Highlights: ► Synthesis of Cr(OH) 3 nanoparticles in Cr 3+ –F − aqueous solution. ► The F − ion tailors coagulated materials, Cr(OH) 3 nanoparticles are obtained. ► Adding nanosized Cr(OH) 3 , AP thermal decomposition temperature decreases to 200 °C. ► The nanosized Cr(OH) 3 catalyzes NH 3 oxidation, accelerating AP thermal decomposition. - Abstract: A procedure for the preparation of spherical Cr(OH) 3 nanoparticles was developed based on the aging of chromium nitrate aqueous solutions in the presence of sodium fluoride, urea, and polyvinylpyrrolidone. Using scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy, the morphological characteristics of Cr(OH) 3 were controlled by altering the molar ratio of fluoride ion to chromium ion, as well as the initial pH and chromium ion concentration. The prepared nanosized Cr(OH) 3 decreased the temperature required to decompose ammonium perchlorate from 450 °C to about 250 °C as the catalyst. The possible catalytic mechanism of the thermal decomposition of ammonium perchlorate was also discussed.

  20. Morphological changes of porphine films on graphite by perchloric and phosphoric electrolytes. An electrochemical-AFM study

    Yivlialin, Rossella; Penconi, Marta; Bussetti, Gianlorenzo; Biroli, Alessio Orbelli; Finazzi, Marco; Duò, Lamberto; Bossi, Alberto

    2018-06-01

    Organic molecules have been proposed as promising candidates for electrode protection in acidic electrolytes. The use of tetraphenyl-porphines (H2TPP) as graphite surface-protecting agents in sulphuric acid (H2SO4) is one of the newest. With the aim of unveiling the mechanism of such a protective effect, in this paper we test the stability of a H2TPP thin film immersed in perchloric and phosphoric acid solutions that differently interact with porphyrins. The protective role of H2TPP is tested in the electrochemical potential range where the pristine graphite undergoes an oxidation process that erodes the surface and eventually exfoliate the stratified crystal. The electrochemical analysis is performed in a three-electrode cell, while the surface morphology is monitored ex-situ and in-situ by atomic force microscopy. Electrospray mass analysis is also employed to investigate the presence of H2TPP fragments in the solution. We find that the organic film is not stable in perchloric solution, while it is stable and avoids graphite surface corrosion in phosphoric acid solution. These results provide a rationale for the role played by free-base porphines in graphite protection.

  1. Kinetics and mechanism of the oxidation of uranium (IV) by hypochlorous acid in aqueous acidic perchlorate media

    Silverman, R.A.; Gordon, G.

    1976-01-01

    The oxidation of uranium(IV) by hypochlorous acid has been studied in aqueous sodium perchlorate--perchloric acid solutions. The reaction U 4 + + 2HOCl = UO 2 2 + + Cl 2 (aq) + 2H + proceeds appropriate to the rate law --d[U(IV)]/dt = k 0 . [U 4+ ][HOCl][H + ] -1 . At 25 0 and 3 M ionic strength, k 0 is 1.08 +- 0.07 sec -1 . Over the 1--25 0 temperature range, ΔH 2+ is 18.4 +- 0.1 kcal mole -1 , and ΔS 2+ is 3.1 +- 0.4 eu. The inverse hydrogen ion dependence of the rate law is explained by a rapid preequilibrium, in which a proton is lost from one of the reactants. A uranyl-like activated complex, [H 2 UO 2 Cl 3+ ] 2+ , is suggested, with one proton likely to be residing on each oxygen atom. Evidence is presented that the mechanism involves a two-electron transfer, with the intermediate chloride ion rapidly reacting with hypochlorous acid to form chlorine. The uranium(IV)-hypochlorous acid reaction plays an important role in the oxidation of uranium(IV) by aqueous chlorine solutions. The magnitude of this role was seriously underestimated by previous investigators

  2. Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate

    Burton, A. S.; Locke, D. R.; Lewis, E. K.

    2017-01-01

    Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that

  3. Titania nanotube powders obtained by rapid breakdown anodization in perchloric acid electrolytes

    Ali, Saima; Hannula, Simo-Pekka

    2017-01-01

    Titania nanotube (TNT) powders are prepared by rapid break down anodization (RBA) in a 0.1 M perchloric acid (HClO 4 ) solution (Process 1), and ethylene glycol (EG) mixture with HClO 4 and water (Process 2). A study of the as-prepared and calcined TNT powders obtained by both processes is implemented to evaluate and compare the morphology, crystal structure, specific surface area, and the composition of the nanotubes. Longer TNTs are formed in Process 1, while comparatively larger pore diameter and wall thickness are obtained for the nanotubes prepared by Process 2. The TNTs obtained by Process 1 are converted to nanorods at 350 °C, while nanotubes obtained by Process 2 preserve tubular morphology till 350 °C. In addition, the TNTs prepared by an aqueous electrolyte have a crystalline structure, whereas the TNTs obtained by Process 2 are amorphous. Samples calcined till 450 °C have XRD peaks from the anatase phase, while the rutile phase appears at 550 °C for the TNTs prepared by both processes. The Raman spectra also show clear anatase peaks for all samples except the as-prepared sample obtained by Process 2, thus supporting the XRD findings. FTIR spectra reveal the presence of O-H groups in the structure for the TNTs obtained by both processes. However, the presence is less prominent for annealed samples. Additionally, TNTs obtained by Process 2 have a carbonaceous impurity present in the structure attributed to the electrolyte used in that process. While a negligible weight loss is typical for TNTs prepared from aqueous electrolytes, a weight loss of 38.6% in the temperature range of 25–600 °C is found for TNTs prepared in EG electrolyte (Process 2). A large specific surface area of 179.2 m 2 g −1 is obtained for TNTs prepared by Process 1, whereas Process 2 produces nanotubes with a lower specific surface area. The difference appears to correspond to the dimensions of the nanotubes obtained by the two processes. - Graphical abstract: Titania nanotube

  4. Studies on composite solid propellant with tri-modal ammonium perchlorate containing an ultrafine fraction

    K.V. Suresh Babu

    2017-08-01

    Full Text Available Composite solid propellant is prepared using tri-modal Ammonium perchlorate (AP containing coarse, fine and ultrafine fractions of AP with average particle size (APS 340, 40 and 5 μm respectively, in various compositions and their rheological, mechanical and burn rate characteristics are evaluated. The optimum combination of AP coarse to fine to ultrafine weight fraction was obtained by testing of series of propellant samples by varying the AP fractions at fixed solid loading. The concentration of aluminium was maintained constant throughout the experiments for ballistics requirement. The propellant formulation prepared using AP with coarse to fine to ultrafine ratio of 67:24:9 has lowest viscosity for the propellant paste and highest tensile strength due to dense packing as supported by the literature. A minimum modulus value was also observed at 9 wt. % of ultrafine AP concentration indicates the maximum solids packing density at this ratio of AP fractions. The burn rate is evaluated at different pressures to obtain pressure exponent. Incorporation of ultrafine fraction of AP in propellant increased burn rate without adversely affecting the pressure exponent. Higher solid loading propellants are prepared by increased AP concentration from 67 to 71 wt. % using AP with coarse to fine to ultrafine ratio of 67:24:9. Higher solid content up to 89 wt. % was achieved and hence increased solid motor performance. The unloading viscosity showed a trend with increased AP content and the propellant couldn't able to cast beyond 71 wt. % of AP. Mechanical properties were also studied and from the experiments noticed that % elongation decreased with increased AP content from 67 to 71 wt.%, whereas tensile strength and modulus increased. Burn rate increased with increased AP content and observed that pressure exponent also increased and it is high for the propellant containing with 71 wt.% of AP due to increased oxidiser to fuel ratio. Catalysed

  5. Atomic absorption spectrophotometry of europium using an enhancing effect of ammonium perchlorate

    Oguro, Hiroshi

    1976-01-01

    In the atomic absorption spectrophotometry of europium in air-acetylene flame, ammonium perchlorate (NH 4 ClO 4 ) increases the absorption of europium. In the case of 0.5 M NH 4 ClO 4 , the increase is by about 1.5 times. In this paper, a method for eliminating the interferences of many coexisting compounds using an enhancing effect and a method for determining Eu 2 O 3 in La 2 O 3 were investigated. The working conditions using Nippon Jarrell-Ash model AA-1 atomic absorption/flame emission spectrophotometer were as follows; wavelength 4594 A, lamp current 15 mA, burner height 10 mm, air flow-rate 6.51/min, acetylene flow-rate 1.81/min. Though the enhancing or depressing effects of HCl, HNO 3 , HBr and HClO 4 in concentrations below 0.1 M were eliminated by 0.5 M NH 4 ClO 4 , the remarkable depressing effects of H 2 SO 4 and H 3 PO 4 on europium could not be eliminated. The interferences of Na + , K + , Cs + and Al 3+ in the concentration of 200 ppm were not eliminated, but those of other cations including rare earth elements were completely eliminated. Lanthanum in the range of (2000--10000) ppm increased the absorption of europium by about 1.4 times. But the effect of lanthanum in the range of (0--9000) ppm was also eliminated by NH 4 ClO 4 . The calibration curve for europium in the presence of NH 4 ClO 4 was linear in the range of (0--400) ppm with a sensitivity larger by about 1.5 times than that for europium alone. The analytical procedure is as follows. A sample is dissolved in HCl and NH 4 ClO 4 is added. Europium in the sample solution is determined by atomic absorption method using air-acetylene flame. For practical samples, the values obtained were in fair agreement with those by the flame emission method using a nitrous oxide-acetylene flame. The coefficients of variation by the present method were (3.7--2.4)% (Eu 2 O 3 content (1--3)%). (auth.)

  6. Titania nanotube powders obtained by rapid breakdown anodization in perchloric acid electrolytes

    Ali, Saima, E-mail: saima.ali@aalto.fi; Hannula, Simo-Pekka

    2017-05-15

    Titania nanotube (TNT) powders are prepared by rapid break down anodization (RBA) in a 0.1 M perchloric acid (HClO{sub 4}) solution (Process 1), and ethylene glycol (EG) mixture with HClO{sub 4} and water (Process 2). A study of the as-prepared and calcined TNT powders obtained by both processes is implemented to evaluate and compare the morphology, crystal structure, specific surface area, and the composition of the nanotubes. Longer TNTs are formed in Process 1, while comparatively larger pore diameter and wall thickness are obtained for the nanotubes prepared by Process 2. The TNTs obtained by Process 1 are converted to nanorods at 350 °C, while nanotubes obtained by Process 2 preserve tubular morphology till 350 °C. In addition, the TNTs prepared by an aqueous electrolyte have a crystalline structure, whereas the TNTs obtained by Process 2 are amorphous. Samples calcined till 450 °C have XRD peaks from the anatase phase, while the rutile phase appears at 550 °C for the TNTs prepared by both processes. The Raman spectra also show clear anatase peaks for all samples except the as-prepared sample obtained by Process 2, thus supporting the XRD findings. FTIR spectra reveal the presence of O-H groups in the structure for the TNTs obtained by both processes. However, the presence is less prominent for annealed samples. Additionally, TNTs obtained by Process 2 have a carbonaceous impurity present in the structure attributed to the electrolyte used in that process. While a negligible weight loss is typical for TNTs prepared from aqueous electrolytes, a weight loss of 38.6% in the temperature range of 25–600 °C is found for TNTs prepared in EG electrolyte (Process 2). A large specific surface area of 179.2 m{sup 2} g{sup −1} is obtained for TNTs prepared by Process 1, whereas Process 2 produces nanotubes with a lower specific surface area. The difference appears to correspond to the dimensions of the nanotubes obtained by the two processes. - Graphical abstract

  7. Effect of ammonium perchlorate grain sizes on the combustion of solid rocket propellant

    Hegab, A.; Balabel, A. [Menoufia Univ., Menoufia (Egypt). Faculty of Engineering

    2007-07-01

    The combustion of heterogeneous solid rocket propellant consisting of ammonium perchlorate (AP) particles was discussed with reference to the chemical and physical complexity of the propellant and the microscopic scale of the combustion zone. This study considered the primary flame between the decomposition products of the binder and the AP oxidizer; the primary diffusion flame from the oxidizer; density and conductivity of the AP and binder; temperature-dependent gas-phase transport properties; and, an unsteady non-planer regression surface. Three different random packing disc models for the AP particles imbedded in a matrix of a hydroxyl terminated polybutadience (HTPB) fuel-binder were used as a base of the combustion code. The models have different AP grain sizes and distribution with the fuel binder. A 2D calculation was developed for the combustion of heterogeneous solid propellant, accounting for the gas phase physics, the solid phase physics and an unsteady non-planar description of the regressing propellant surface. The mathematical model described the unsteady burning of a heterogeneous propellant by simultaneously solving the combustion fields in the gas phase and the thermal field in the solid phase with appropriate jump condition across the gas/solid interface. The gas-phase kinetics was represented by a two-step reaction mechanism for the primary premixed flame and the primary diffusion flame between the decomposition products of the HTPB and the oxidizer. The essentially-non-oscillatory (ENO) scheme was used to describe the propagation of the unsteady non-planer regression surface. The results showed that AP particle size has a significant effect on the combustion surface deformation as well as on the burning rate. This study also determined the effect of various parameters on the surface propagation speed, flame structure, and the burning surface geometry. The speed by which the combustion surface recedes was found to depend on the exposed pressure

  8. Metal-Oxide Film Conversions Involving Large Anions

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C.

    2008-01-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I - , Br - , S 2- ). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag 2 O to (1) AgI and (2) AgBr. (authors)

  9. Metal-Oxide Film Conversions Involving Large Anions

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C. [The University of Western Ontario, Chemistry Department, 1151 Richmond St., N6A 5B7, London, Ontario (Canada)

    2008-07-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I{sup -}, Br{sup -}, S{sup 2-}). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag{sub 2}O to (1) AgI and (2) AgBr. (authors)

  10. Anion analysis in uranium more concentrates by ion chromatography

    Badaut, V.

    2009-01-01

    In the present exploratory study, the applicability of anionic impurities or attributing nuclear material to a certain chemical process or origin has been investigated. Anions (e.g., nitrate, sulphate, fluoride, chloride) originate from acids or salt solutions that are used for processing of solutions containing uranium or plutonium. The study focuses on uranium ore concentrates ('yellow cakes') originating from different mines. Uranium is mined from different types of ore body and depending on the type of rock, different chemical processes for leaching, dissolving and precipitating the uranium need to be applied. Consequently, the anionic patterns observed in he products of these processes (the 'ore concentrates') are different. The concentrations of different anionic species were measured by ion chromatography using conductivity detection. The results show clear differences of anion concentrations and patterns between samples from different uranium mines. Besides this, differences between sampling campaigns n a same mine were also observed indicating that the uranium ore is not homogeneous in a mine. These within-mine variations, however, were smaller than the between-mine variations. (author)

  11. Vertical detachment energies of anionic thymidine: Microhydration effects.

    Kim, Sunghwan; Schaefer, Henry F

    2010-10-14

    Density functional theory has been employed to investigate microhydration effects on the vertical detachment energy (VDE) of the thymidine anion by considering the various structures of its monohydrates. Structures were located using a random searching procedure. Among 14 distinct structures of the anionic thymidine monohydrate, the low-energy structures, in general, have the water molecule bound to the thymine base unit. The negative charge developed on the thymine moiety increases the strength of the intermolecular hydrogen bonding between the water and base units. The computed VDE values of the thymidine monohydrate anions are predicted to range from 0.67 to 1.60 eV and the lowest-energy structure has a VDE of 1.32 eV. The VDEs of the monohydrates of the thymidine anion, where the N(1)[Single Bond]H hydrogen of thymine has been replaced by a 2(')-deoxyribose ring, are greater by ∼0.30 eV, compared to those of the monohydrates of the thymine anion. The results of the present study are in excellent agreement with the accompanying experimental results of Bowen and co-workers [J. Chem. Phys. 133, 144304 (2010)].

  12. Identification of inorganic anions by gas chromatography/mass spectrometry.

    Sakayanagi, Masataka; Yamada, Yaeko; Sakabe, Chikako; Watanabe, Kunio; Harigaya, Yoshihiro

    2006-03-10

    Inorganic anions were identified by using gas chromatography/mass spectrometry (GC/MS). Derivatization of the anions was achieved with pentafluorobenzyl p-toluenesulphonate (PFB-Tos) as the reaction reagent and a crown ether as a phase transfer catalyst. When PFB-Br was used as the reaction reagent, the retention time of it was close to those of the derivatized inorganic anions and interfered with the analysis. In contrast, the retention time of PFB-Tos differed greatly from the PFB derivatives of the inorganic anions and the compounds of interest could be detected without interference. Although the PFB derivatives of SO4, S2O3, CO3, ClO4, and ClO3 could not be detected, the derivatives of F, Cl, Br, I, CN, OCN, SCN, N3, NO3, and NO2 were detected using PFB-Tos as the derivatizing reagent. The inorganic anions were detectable within 30 ng approximately, which is of sufficient sensitivity for use in forensic chemistry. Accurate mass number was measured for each PFB derivative by high-resolution mass spectrometry (HRMS) within a measurement error of 2 millimass units (mmu), which allowed determination of the compositional formula from the mass number. In addition, actual analysis was performed successively by our method using trial samples of matrix.

  13. Separation of transfer ribonucleic acids on polystyrene anion exchangers

    Singhal, R.P.; Griffin, G.D.; Novelli, G.D.

    1976-11-16

    The transfer RNA separation by chromatography on strong-base-polystyrene exchange materials is examined and compared with the widely used reversed-phase chromatography. Results indicate important differences in some transfer RNA (tRNA) elution patterns by the anion-exchange chromatography, as compared with the reversed-phase chromatography. Transfer RNAs containing hydrophobic groups are adsorbed more strongly. The anion exchanger has twice the number of theoretical plates. Single peaks of tRNA/sub 2//sup Glu/ and tRNA/sub 1//sup Phe/ obtained from the reversed-phase column give multiple peaks on polystyrene anion-exchange chromatography. All six leucine tRNAs (Escherichia coli) and differences in tRNA populations synthesized during early and late stages of the dividing lymphocytes from normal human blood can be characterized by the anion-exchange chromatography. Different separation profiles are obtained by two separation systems for tyrosine tRNAs from mouse liver and mouse-plasma-cell tumor. The results indicate that, in contrast to the reversed-phase chromatography, strong-base-polystyrene anion-exchange chromatography is capable of separating tRNAs with minor structural differences.

  14. REACTIVITY OF ANIONS IN INTERSTELLAR MEDIA: DETECTABILITY AND APPLICATIONS

    Senent, M. L. [Departamento de Quimica y Fisica Teoricas, Instituto de Estructura de la Materia, IEM-C.S.I.C., Serrano 121, Madrid E-28006 (Spain); Hochlaf, M., E-mail: senent@iem.cfmac.csic.es, E-mail: hochlaf@univ-mlv.fr [Laboratoire de Modelisation et Simulation Multi Echelle, Universite Paris-Est, MSME UMR 8208 CNRS, 5 boulevard Descartes, F-77454 Marne-la-Vallee (France)

    2013-05-01

    We propose a general rule to distinguish between detectable and undetectable astronomical anions. We believe that only few anions live long enough in the interstellar medium and thus can be detected. Our method is based on quantum mechanical calculations capable of describing accurately the evolution of electronic states during chemical processes. The still not fully understood reactivity at low temperatures is discussed considering non-adiabatic effects. The role of excited states has usually been neglected in previous works which basically focused on the ground electronic state for interpretations of experimental observations. Here, we deal with unsaturated carbon chains (e.g., C{sub n} H{sup -}), which show a high density of electronic states close to their corresponding ground electronic states, complex molecular dynamics, and non-adiabatic phenomena. Our general rule shows that it is not sufficient that anions exist in the gas phase (in the laboratory) to be present in media such as astrophysical media, since formation and decomposition reactions of these anions may allow the population of anionic electronic states to autodetach, forming neutrals. For C{sub n} H, reactivity depends strongly on n, where long and short chains behave differently. Formation of linear chains is relevant.

  15. Addition compounds of perchlorates from yttrium and lanthanides elements with the N,N,N',N'tetramethyl amide of phthalic acid

    Silva, C.P.G. da.

    1974-01-01

    The reaction between lanthanide perchlorates and yttrium with tetra methyl phthalamide (TMPA) was studied, and compounds of the general formula Ln (C 10 4 ) 3 . TMPA have been isolated. The compounds were characterized by analysis of their components, infra-red spectra, molar conductances in nitromethane and nitrobenzene, X ray powder patterns and thermal analysis. (author)

  16. ANALYSIS OF THE KINETICS OF SOLVOLYSIS OF P-NITROPHENYLSULFONYLMETHYL PERCHLORATE IN BINARY ALCOHOLIC MIXTURES IN TERMS OF THE THERMODYNAMIC PROPERTIES OF THE SOLVENT MIXTURES

    Wijnen, J W; Engberts, J B F N; Blandamer, Michael J

    Rate constants are reported for the solvolysis of p-nitrophenylsulfonylmethyl perchlorate in binary ethanolic and methanolic mixtures at 298.2 K. Co-solvents include hydrocarbons, chlorinated hydrocarbons and 1,4-dioxane. The kinetic data are examined in terms of the effect of decreasing mole

  17. MEASUREMENT OF PERCHLORATE IN WATER BY USE OF AN 18O-ENRICHED ISOTOPIC STANDARD AND ION CHROMATOGRAPHY WITH MASS SPECTROMETRIC DETECTION

    Perchlorate (ClO4-) is a drinking water contaminant originating from the dissolution of the salts of ammonium, potassium, magnesium, or sodium in water. It is used primarily as an oxidant in solid propellant for rockets, missiles, pyrotechnics, as a compone...

  18. SUB-PPB QUANTITATION AND CONFIRMATION OF PERCHLORATE IN DRINKING WATERS CONTAINING HIGH TOTAL DISSOLVED SOLIDS USING ION CHROMATOGRAPHY WITH MASS SPECTROMETRIC DETECTION

    Perchlorate (ClO4 -) is a drinking water contaminant originating from the dissolution of the salts of ammonium, potassium, magnesium, or sodium in water. It is used primarily as an oxidant in solid propellant for rockets, missiles, pyrotechnics, as a component in air bag infla...

  19. Investigation of REE perchlorates complexing with benzimidazole in aqua-dioxane media. Issledovanie kompleksoobrazovaniya perkhloratov RZEh s benzimidazolom v vodno-dioksanovoj srede

    Akhrimenko, Z M; Panyushkin, V T; Ishbulatova, S K [Kubanskij Gosudarstvennyj Univ., Krasnodar (Russian Federation)

    1992-01-01

    Stability constant (K[sub 1]) of complexes of rare earth perchlorates with benzimidazole were determined by the method of pH-metric titration. Nonmonotonous change in lgK[sub 1] with rare earth ordinal number increase was revealed.

  20. An Anthracene-Based Tripodal Chemosensor for Anion Sensing

    Whitney A. Quinn

    2010-05-01

    Full Text Available An anthracene-based tripodal ligand was synthesized from the condensation of tren with 9-anthraldehyde, and the subsequent reduction with sodium borohydride. The neutral ligand was protonated from the reaction with p-toluenesulfonic acid to give a triply charged chemosensor that was examined for its anion binding ability toward fluoride, chloride, bromide, sulfate and nitrate by the fluorescence spectroscopy in DMSO. The addition of an anion to the ligand resulted in an enhancement in fluorescence intensity at the excitation of 310 nm. Analysis of the spectral changes suggested that the ligand formed a 1:1 complex with each of the anions, showing strong affinity for fluoride and sulfate in DMSO. The unsubstituted tren was reacted with sulfuric acid to form a sulfate complex and the structure was determined by the X-ray crystallography. Analysis of the complex revealed that three sulfates are held between two ligands by multiple hydrogen bonding interactions with protonated amines.

  1. Copper(I) coordination compounds with closododecaborate anion

    Malinina, E.A.; Drozdova, V.V.; Mustyatsa, V.N.; Goeva, L.V.; Polyakova, I.N.; Votinova, N.A.; Zhizhin, K.Yu.; Kuznetsov, N.T.

    2006-01-01

    Cu(I) Complexes with closo-dodecaborate anion Cat[CuB 12 H 12 ], where Cat= Cs + , Ph 4 P + , Ph 4 As + , R x NH 4-x + (R=Me, Et, Pr, Bu, X=3-4) are synthesized. Synthesis of complexes was conducted in the copper(II) salt-salt of dodecaborate anion-sulfur dioxide (sodium sulfite) system. Structure of the complex [Cu 2 (NCCH 3 ) 4 B 12 H 12 ] assigned by X-ray structural analysis discloses that B 12 H 12 2- anion enters into the inner sphere of metal-complexing agent, and connection of closo-borate ligand with the metal is caused by the formation of three-centric metal-hydrogen-boron bonds [ru

  2. Cell wall bound anionic peroxidases from asparagus byproducts.

    Jaramillo-Carmona, Sara; López, Sergio; Vazquez-Castilla, Sara; Jimenez-Araujo, Ana; Rodriguez-Arcos, Rocio; Guillen-Bejarano, Rafael

    2014-10-08

    Asparagus byproducts are a good source of cationic soluble peroxidases (CAP) useful for the bioremediation of phenol-contaminated wastewaters. In this study, cell wall bound peroxidases (POD) from the same byproducts have been purified and characterized. The covalent forms of POD represent >90% of the total cell wall bound POD. Isoelectric focusing showed that whereas the covalent fraction is constituted primarily by anionic isoenzymes, the ionic fraction is a mixture of anionic, neutral, and cationic isoenzymes. Covalently bound peroxidases were purified by means of ion exchange chromatography and affinity chromatography. In vitro detoxification studies showed that although CAP are more effective for the removal of 4-CP and 2,4-DCP, anionic asparagus peroxidase (AAP) is a better option for the removal of hydroxytyrosol (HT), the main phenol present in olive mill wastewaters.

  3. Reactivity of niobium cluster anions with nitrogen and carbon monoxide

    Mwakapumba, Joseph; Ervin, Kent M.

    1997-02-01

    Reactions of small niobium cluster anions, Nbn-(n = 2-7), with CO and N2 are investigated using a flow tube reactor (flowing afterglow) apparatus. Carbon monoxide chemisorption on niobium cluster anions occurs with faster reaction rates than nitrogen chemisorption on corresponding cluster sizes. N2 addition to niobium cluster anions is much more size-selective than is CO addition. These general trends follow those reported in the literature for reactions of neutral and cationic niobium clusters with CO and N2. Extensive fragmentation of the clusters is observed upon chemisorption. A small fraction of the larger clusters survive and sequentially add multiple CO or N2 units without fragmentation. However, chemisorption saturation is not reached at the experimentally accessible pressure and reagent concentration ranges. The thermochemistry of the adsorption processes and the nature of the adsorbed species, molecular or dissociated, are discussed.

  4. Synthesis and anion binding properties of porphyrins and related compounds

    Figueira, Flávio

    2016-12-02

    Over the last two decades the preparation of pyrrole-based receptors for anion recognition has attracted considerable attention. In this regard porphyrins, phthalocyanines and expanded porphyrins have been used as strong and selective receptors while the combination of those with different techniques and materials can boost their applicability in different applications as chemosensors and extracting systems. Improvements in the field, including the synthesis of this kind of compounds, can contribute to the development of efficient, cheap, and easy-to-prepare anion receptors. Extensive efforts have been made to improve the affinity and selectivity of these compounds and the continuous expansion of related research makes this chemistry even more promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  5. Determination of arsenate in water by anion selective membrane electrode using polyurethane–silica gel fibrous anion exchanger composite

    Khan, Asif Ali, E-mail: asifkhan42003@yahoo.com; Shaheen, Shakeeba, E-mail: shakeebashaheen@ymail.com

    2014-01-15

    Highlights: • PU–Si gel is new anion exchanger material synthesized and characterized. • This material used as anion exchange membrane is applied for electroanalytical studies. • The method for detection and determination of AsO{sub 4}{sup 3−} in traces amounts discussed. • The results are also verified from arsenic analyzer. -- Abstract: Polyurethane (PU)–silica (Si gel) based fibrous anion exchanger composites were prepared by solid–gel polymerization of polyurethane in the presence of different amounts of silica gel. The formation of PU–Si gel fibrous anion exchanger composite was characterized by Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA-DTA), scanning electron microscopy (SEM) and elemental analysis. The membrane having a composition of 5:3 (PU:Si gel) shows best results for water content, porosity, thickness and swelling. Our studies show that the present ion selective membrane electrode is selective for arsenic, having detection limit (1 × 10{sup −8} M to 1 × 10{sup −1} M), response time (45 s) and working pH range (5–8). The selectivity coefficient values for interfering ions indicate good selectivity for arsenate (AsO{sub 4}{sup 3−}) over interfering anions. The accuracy of the detection limit results was compared by PCA-Arsenomat.

  6. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    Ye Jiesheng; Liu Chunxi; Chen Zhijin; Zhang Na; Wang Aihua

    2008-01-01

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles (≤20 nm) onto the surface of the binary complexes. The small solid lipid nanoparticles (SLNs) were prepared by a modified film dispersion-ultrasonication method, and adsorption of the anionic SLNs onto the binary complexes was typically carried out in water via electrostatic interaction. The formulated ternary nanoparticles were found to be relatively uniform in size (257.7 ± 10.6 nm) with a 'bumpy' surface, and the surface charge inversion from 19.28 ± 1.14 mV to -17.16 ± 1.92 mV could be considered as evidence of the formation of the ternary nanoparticles. The fluorescence intensity measurements from three batches of the ternary nanoparticles gave a mean adsorption efficiency of 96.75 ± 1.13%. Circular dichroism spectra analysis showed that the protamine/DNA complexes had been coated by small SLNs, and that the anionic ternary nanoparticles formed did not disturb the construction of the binary complexes. SYBR Green I analysis suggested that the ternary nanoparticles could protect the DNA from nuclease degradation, and cell viability assay results showed that they exhibit lower cytotoxicity to A549 cells compared with the binary complexes and lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo

  7. Anion effect on the retention of recoil atom of coordination crystalline compounds

    Dimotakis, P.N.; Papadopoulos, B.P.

    1980-01-01

    The anion effect of various cobaltic crystalline compounds - having the same cation and differing in anion -on the retention of neutron activated central cobalt atom has been studied. The cation was trans-dichloro(bis)ethylenediamine cobalt(III) and the anions were simple spherical anions (Cl - , Br - , I - ), planar anions (NO 3 - ), trigonal pyramidal anions (ClO 3 - , BrO 3 - ), tetrahedral anions (SO 4 2- , CrO 4 2- , MnO 4 - ) and linear anions (SCN - ). The cobalt-60 activity after reactor irradiation either in simple Co 2+ cation or in cobaltic complex cation determined the retention values. In all irradiations at ordinary temperature and at liquid nitrogen temperature the results showed an effect of the different anions, depending on the geometry, volume and charge, on the recombination of the recoil cobalt with the ligands in the coordination sphere. (author)

  8. Electrokinetic remediation of anionic contaminants from unsaturated soils

    Lindgren, E.R.; Kozak, M.W.; Mattson, E.D.

    1992-01-01

    Heavy-metal contamination of soil and groundwater is a widespread problem in the DOE weapons complex, and for the nation as a whole. Electrokinetic remediation is one possible technique for in situ removal of such contaminants from unsaturated soils. In previous studies at Sandia National Laboratories, the electromigration of chromate ions and anionic dye ions have been demonstrated. This paper reports on a series of experiments that were conducted to study the effect of moisture content on the electromigration rate of anionic contaminants in unsaturated soil and determine the limiting moisture content for which electromigration occurs

  9. A study of model systems in anionic exchange

    Haegele, R.; Boeyens, J.C.A.

    1977-01-01

    Preliminary experiments are reported on the preparation and characterization of anionic sulphate and chloride complexes of UO 2+ 2 and iron(III), benzyl-trimethylammonium cation being used as a model substance for the simulation of positive sites in an anionic-exchange resin. The structure of (BTMA) 4 [UO 2 CL 3 -O 2 -CL 3 UO 2 ], a binuclear uranyl-peroxocomplex that has not been reported in the literature, was elucidated by single-crystal x-ray examination, and is described and discussed [af

  10. Procedure for reducing hydrogen ion concentration in acidic anion eluate

    Parobek, P.; Baloun, S.; Plevac, S.

    1992-01-01

    A procedure is suggested for reducing the concentration of hydrogen ions in the acidic anionic eluate formed during the separation of uranium. The procedure involves anex elution, precipitation, filtration, precipitate rinsing, and anex rinsing. The procedure is included in the uranium elution process and requires at least one ion exchanger column and at least one tank in the continuous or discontinuous mode. Sparing the neutralizing agent by reducing the hydrogen ion concentration in the acidic anionic eluate is a major asset of this procedure. (Z.S.). 1 fig

  11. Derivatives of Dodecahalo-Closo-Dodecaborate Di-Anion

    Avelar, Amy Cindy

    2009-01-01

    ABSTRACT OF THE DISSERTATIONDerivatives of the Dodecahalo-Closo-Dodecaborate Di-AnionbyAmy AvelarDoctor of Philosophy, Graduate Program in ChemistryUniversity of California, Riverside, December 2009Dr. Christopher A. Reed, ChairpersonThe di-anion, dodecahalo-closo-dodecaborate, B12X122-, where the X = Cl or Br, has been determined to be a useful weakly coordinating anion, WCA. Despite the di- negative charge, several elusive and reactive cationic species were stabilized with B12X122- as the c...

  12. Introducing various ligands into superhalogen anions reduces their electronic stabilities

    Smuczyńska, Sylwia; Skurski, Piotr

    2008-02-01

    The vertical electron detachment energies (VDE) of six NaX2- anions (where X = F, Cl, Br) were calculated at the OVGF level with the 6-311++G(3df) basis sets. In all the cases studied the VDE exceeds the electron affinity of chlorine atom and thus those species were classified as superhalogen anions. The largest vertical binding energy was found for the NaF2- system (6.644 eV). The strong VDE dependence on the ligand type, ligand-central atom distance, and the character of the highest occupied molecular orbital (HOMO) was observed and discussed.

  13. Uranium extraction from sulfuric acid solution using anion exchange resin

    Sheta, M. E.; Abdel Aal, M. M.; Kandil, A. T.

    2012-12-01

    Uranium is currently recovered from sulfuric acid leach liquor using anion exchange resin as Amberlite IRA 402 (CT). This technology is based on fact that, uranium exists as anionic complexes. This takes place by controlling the pH of the solution, agitation time, temperature and resin to solution ratio (R/S). In this work, batch stirrer tank used for uranium extraction from sulfate medium and after extraction, elution process was done using 1M NaCl solution. After extraction and elution process, the resin was separated from the system and uranium was determined in the solution. (Author)

  14. Uranium isotopic effect studies on cation and anion exchange resins

    Sarpal, S.K.; Gupta, A.R.

    1975-01-01

    Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

  15. Preparation of Cationic MOFs with Mobile Anions by Anion Stripping to Remove 2,4-D from Water

    Tao Chen

    2017-07-01

    Full Text Available A cationic porous framework with mobile anions (MIL-101(Cr-Cl was easily and successfully synthesized by utilizing the stronger affinity of F− to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr. The structure, morphology and porosity of MIL-101(Cr-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr. With the mobile Cl− anion, MIL-101(Cr-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs. At the same time, this material also shows high anti-interference performance with changing solution pH.

  16. Equilibrium and Thermodynamic Studies of Anionic Dyes Removal by an Anionic Clay-Layered Double Hydroxide

    Kantasamy, N.; Siti Mariam Sumari

    2016-01-01

    Adsorption isotherm describes the interaction of adsorbates with adsorbent in equilibrium. Equilibrium data was examined using Langmuir and Freundlich isotherm models. Thermodynamic studies were used to evaluate the thermodynamic parameters; heat of enthalpy change (ΔH degree), Gibbs free energy change (ΔG degree) and heat of entropy change (ΔSdegree) in order to gain information regarding the nature of adsorption (exothermic or endothermic). Four reactive dyes of anionic type, Acid Blue 29 (AB29), Reactive Black 5 (RB5), Reactive Orange 16 (RO16) and Reactive Red 120 (RR120) were used to obtain equilibrium isotherms at 25, 35, 45 and 55 degree Celsius. Based on Giles' classification, the isotherm produced were of L2-type, indicating strong dye affinity towards the adsorbent, and with weak competition with the solvent molecules for active adsorption sites. Equilibrium data fitted both Langmuir and Freundlich isotherm models with high correlation coefficient (R"2 > 0.91) indicating the possibility of both homogeneity and heterogeneous nature of adsorption. The negative values of ΔGdegree indicate the adsorption processes were spontaneous and feasible. The negative values of ΔHdegree lie between -20 to -75 kJ/ mol, suggesting these processes were exothermic and physical in nature. The negative values of ΔSdegree are indication of decreased disorder and randomness of spontaneous adsorption of reactive dyes on layered double hydroxide as adsorbent. (author)

  17. Bowl adamanzanes--bicyclic tetraamines: syntheses and crystal structures of complexes with cobalt(III) and chelating coordinated oxo-anions.

    Broge, Louise; Søtofte, Inger; Jensen, Kristian; Jensen, Nicolai; Pretzmann, Ulla; Springborg, Johan

    2007-09-14

    Seven cobalt(III) complexes of the macrobicyclic tetraamine ligand [2(4).3(1)]adamanzane ([2(4).3(1)]adz) are reported along with the crystal structure of six of these complexes. The solid state and solution structures are discussed, and a detailed assignment of the NMR spectra of the sulfato complex is provided. Four of the seven complexes contain a chelate coordinating oxo-anion (sulfate, formiate, nitrate, carbonate). Equilibration of these species with the corresponding diaqua complex is generally slow. The rates of equilibration in 5 mol dm(-3) perchloric acid at 25 degrees C have been measured, yielding half lives of 20 min, 10 min and 3 h for the sulfato, formiato and carbonato species respectively. The corresponding reaction for the nitrato complex occurs with a half life of less than 3 min. The concentration acid dissociation constant for the Co([2(4).3(1)]adz)(HCO(3))(2+) ion has been measured to K(a) = 0.33 mol dm(-3) [25 degrees C, I = 2 mol dm(-3)] and K(a) = 0.15 mol dm(-3) [25 degrees C, I = 5 mol dm(-3)]. The propensity for coordination of sulfate was found to be large enough for a quantitative conversion of the carbonato complex to the sulfato complex to occur in 3 mol dm(-3) triflic acid containing a small sulfate contamination. On this basis the decarboxylation in 5 mol dm(-3) triflic acid of the corresponding cobalt(III) carbonato complex of the larger macrobicyclic tetraamine ligand [3(5)]adz was reinvestigated and found to lead to the sulfato complex as well. The difference in exchange rate of the oxo-anion ligands for the cobalt(III) complexes of the two adamanzane ligands is discussed and attributed to fundamental differences in the molecular structure where an inverted configuration of the secondary non-bridged amine groups is seen for the complexes of the larger [3(5)]adz ligand. The high affinity for chelating coordination of oxo-anions for these two cobalt(iii)-adamanzane-moieties is rationalised on basis of the N-Co-N angles. N

  18. Freezing of perchlorate and chloride brines under Mars-relevant conditions

    Primm, K. M.; Gough, R. V.; Chevrier, V. F.; Tolbert, M. A.

    2017-09-01

    Perchlorate and chloride salts on Mars could readily absorb water vapor and deliquesce into aqueous solutions. The deliquescence relative humidity (RH) as well as the efflorescence (recrystallization) RH of several Mars-relevant salts are now well known; however, the conditions that could cause a brine to freeze are not well established. It is often assumed that ice formation will occur whenever the saturation with respect to ice, Sice, of the system is greater than or equal to unity; however, ice nucleation is often hindered due to a kinetic barrier. For ice to form, a critical cluster of the ice crystal must first be achieved, often requiring Sice > 1. Here we use a Raman microscope and an environmental cell to examine the RH and temperature conditions required for Mg(ClO4)2 and MgCl2 brines to freeze into ice. By examining the salt phase present both optically and spectrally under different low temperature conditions, it is found that both salts exhibit Sice values much greater than unity, meaning that supersaturation readily occurs and brines can persist under conditions previously thought to lead to freezing. The RH range of ice formation for Mg(ClO4)2 from 218 to 245 K is 83-95%, respectively, corresponding to Sice = 1.30-1.54. The RH of ice formation for MgCl2 ranges from 80 to 100% for temperatures between 221 and 252 K, corresponding to Sice = 1.30-1.35. In addition to ice nucleation, the deliquescence and efflorescence relative humidity values for MgCl2 were determined. Two hydrates for MgCl2 were observed, and exhibited different deliquescence relative humidity (DRH) values. The DRH for MgCl2·4H2O was found to be 12.8 ± 0.3% at 243 K with slightly increasing DRH as temperature decreased. The DRH for MgCl2·6H2O was found to be 31.3 ± 0.6% at 242 K with little temperature dependence. The DRH of MgCl2·6H2O was measured below the previously reported eutectic, 240 K, suggesting that the eutectic might be incorrect or that there is a different relevant

  19. Synthesis of CNTs/CuO and its catalytic performance on the thermal decomposition of ammonium perchlorate

    Ping Cui

    2016-05-01

    Full Text Available Copper oxide (CuO nanoparticles were successfully deposited on carbon nanotubes’ (CNTs surface via complex-precipitation method, the nanocomposite was characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray photoelectron spectroscopy (XPS, X-ray powder diffraction (XRD, Raman spectroscopy, Fourier transform infrared (FT-IR and Brunauer–Emmett–Teller (BET. The catalytic performance of CNTs/CuO on ammonium perchlorate (AP decomposition was analyzed by differential thermal analyzer (DTA, the DTA results showed its excellent catalytic effect on AP decomposition, as 8 wt.% CNTs/CuO was added in AP, the second exothermic peak temperature decreased by 158 °C. Such composite may be a promising candidate for catalyzing the AP thermal decomposition.

  20. Synthesis of Azanucleosides by Anodic Oxidation in a Lithium Perchlorate-Nitroalkane Medium and Diversification at the 4'-Nitrogen Position.

    Shoji, Takao; Kim, Shokaku; Chiba, Kazuhiro

    2017-03-27

    Azanucleosides, in which the 4'-oxygen atom has been replaced with a nitrogen atom, have drawn much attention owing to their anticancer and antivirus activity, and tolerance towards nucleases. However, the traditional synthetic strategy requires multiple steps and harsh conditions, thereby limiting the structural and functional diversity of the products. Herein we describe the synthesis of azanucleosides by an electrochemical reaction in a lithium perchlorate-nitroethane medium, followed by postmodification at the 4'-N position. N-Acryloyl prolinol derivatives were converted into azanucleosides by anodic activation of the N-α-C-H bond. Moreover, the use of nitroethane instead of nitromethane lowered the oxidation potential of the N-acryloyl prolinols and increased the Faradic yield. The prepared azanucleosides were efficiently functionalized at the 4'-N-acryloyl group with a lipophilic alkanethiol and a fluorescent dye by conjugate addition and olefin cross-metathesis, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Effects of addition of surfactants on viscosity of uncured ammonium perchlorate(A/P)/hydroxyl-terminated polybutadiene (HTPB) propellant

    Koga, M.; Hagihara, Y. [National Defense Academy, Kanagawa (Japan)

    1998-08-31

    In production of ammonium perchlorate (AP)/hydroxyl-terminated polybutadiene (HTPB) propellants, it is preferable that the uncured propellant has a low viscosity during the mixing and forming processes. In this study, effects of surfacant on viscosity of the uncured propellant are studied for a total of 11 types of surfacants. It is found that sodium lauryl sulfate decreases viscosity of the AP/HTPB mixture more efficiently than any other surfacants tested. Apparent viscosity decreases by 30%, and its optimum dosage will be 0.005wt% based on the mixture to sufficiently decrease viscosity of the mixture. Viscosity of the mixture can be also decreased by improving wettability between AP and HTPB prepolymer. Sodium lauryl sulfate also shows an effect of delaying the potlife, i.e., time extending from addition of a curing agent to a thermosetting resin until it is cured to be unserviceable. 6 refs., 4 figs., 2 tabs.

  2. Phase behaviour and molecular dynamics in the binary system of sodium perchlorate and 1,2-propanediamine

    Terashima, Yukio [Department of Natural Science Education, Joint Graduate School, Hyogo University of Teacher Education (Japan); Takeda, Kiyoshi, E-mail: takeda@naruto-u.ac.j [Department of Chemistry, Naruto University of Education, 748 Nakajima, Takashima Naruto-cho, Naruto, Tokushima 772-8502 (Japan); Honda, Makoto [Department of Physics, Naruto University of Education (Japan)

    2011-03-15

    The phase and glass transition behaviour in a binary mixture of sodium perchlorate and 1,2-propanediamine {l_brace}(NaClO{sub 4}){sub x}(12PDA){sub 1-x}, x < 0.40{r_brace} was investigated by differential scanning calorimetry and Raman scattering measurements. A eutectic point and a peritectic point were found at x = 0.17 and 0.19, respectively. The phase diagram indicates the existence of solvated compounds of (NaClO{sub 4}){sub 1}(12PDA){sub 4} and (NaClO{sub 4}){sub 2}(12PDA){sub 5}. The concentration dependence of the glass transition point shows a sigmoid curve implying an underlying anomaly.

  3. Analysis of tellurium-silicon alloys. Part 1. Determination of tellurium by the reduction from perchloric acid solution

    Teperek, J.

    1977-01-01

    When 100-150 mg of tellurium is dissolved in the solution containing 20 cm 3 72 wt.% of perchloric acid, the reduction of tellurium to elementary form is possible only after adding 60-100 milimoles of HCl. The reduction is performed by adding 1 cm 3 of saturated sodium pyrosulphite solution (Na 2 S 2 O 5 ) and 10 cm 3 of 10 wt.% hydrazine hydrochloride solution (N 2 H 4 .2HCl) to 80-90 cm 3 of cold solution of Te in HClO 4 -HCl mixture. The reduction is completed after 3-5 min. of boiling. When 150-200 mg sample of Te-Si alloy is dissolved in 20 cm 3 of hot 72% per chloric acid, the separation of components is reached. Tellurium can be determinated in filtrate by proposed procedure with high accuracy and precision. (author)

  4. Optimized geometry, vibration (IR and Raman spectra and nonlinear optical activity of p-nitroanilinium perchlorate molecule: A theoretical study

    Tamer Ömer

    2016-03-01

    Full Text Available The molecular modeling of p-nitroanilinium perchlorate molecule was carried out by using B3LYP and HSEH1PBE levels of density functional theory (DFT. The IR and Raman spectra were simulated and the assignments of vibrational modes were performed on the basis of relative contribution of various internal co-ordinates. NBO analysis was performed to demonstrate charge transfer, conjugative interactions and the formation of intramolecular hydrogen bonding interactions within PNAPC. Obtained large dipole moment values showed that PNAPC is a highly polarizable complex, and the charge transfer occurs within PNAPC. Hydrogen bonding and charge transfer interactions were also displayed by small HOMO-LUMO gap and molecular electrostatic potential (MEP surface. The strong evidences that the material can be used as an efficient nonlinear optical (NLO material of PNAPC were demonstrated by considerable polarizability and hyperpolarizability values obtained at DFT levels.

  5. Anion-based approaches to tunable functionality in oxide heterostructures

    May, Steven

    2014-03-01

    The ability to control the position and composition of the anion site is emerging as a promising route to tune properties in epitaxial perovskites. This talk will focus on recent and ongoing efforts aimed at developing anion-based approaches to tailor electronic and magnetic properties in oxide films. First, I will discuss how the position of the oxygen anions can be tailored to stabilize non-bulk-like bond angles and lengths, thereby altering electronic bandwidth. Recent work on La2/3Sr1/3MnO3 will be presented in which ultrathin films under the same strain state exhibit dramatically different electronic and magnetic properties when grown on substrates with different symmetries. In the second half of the talk, I will describe efforts focused on altering the composition of the anion site. In La1/3Sr2/3FeO3-δ films, a reversible change in oxygen content leads to dramatic changes in electrical, optical, and structural properties. Finally, the synthesis of oxyfluoride ferrite and nickelate perovskite films via topotactic reactions carried out following thin film deposition will be described. This work is supported by the Office of Naval Research (N00014-11-1-0664) and the U. S. Army Research Office (W911NF-12-1-0132).

  6. Anionic construction of the SLq,s(2) algebra

    Matheus-Valle, J.L.; Monteiro, M.R.

    1993-01-01

    Considering anionic oscillators in a two-dimensional lattice, the quantum semi-group sl (q,s ) (2) is realized by means of a generalized Schwinger construction. It is found that the parameter q of the algebra is connected to the statistical parameter, whereas the s parameter is related to a s-deformed oscillator introduced at each point of the lattice. (author)

  7. Effect of biocides and anionic homopolymeric inhibitors on the ...

    This paper describes the effect of biocides and of the anionic homopolymeric inhibitors on the precipitation behavior of calcium fluoride (CaF2).The efficiency of inhibitors in the presence and absence of biocides was calculated using the half-life (t1/2) approach, where 50% of the concentration has been precipitated.

  8. Adsorption and intercalation of anionic surfactants onto layered ...

    Unknown

    Department of Polymer Technology, Kamaraj College of Engineering and Technology, Virudhunagar 626 ... Layered double hydroxides (LDH) with brucite like structure was modified with various anionic ... Recently the application of layered double hydroxides ..... Yuan Q, Wei M, Wang Z and Duan X 2004 Clays Clay Miner.

  9. Contribution of attendant anions on cadmium toxicity to soil enzymes.

    Tian, Haixia; Kong, Long; Megharaj, Mallavarapu; He, Wenxiang

    2017-11-01

    Sorption and desorption are critical processes to control the mobility and biotoxicity of cadmium (Cd) in soils. It is known that attendant anion species of heavy metals could affect metal adsorption on soils and might further alter their biotoxicity. However, for Cd, the influence of attendant anions on its sorption in soils and subsequent toxicity on soil enzymes are still unknown. In this work, four Cd compounds with different salt anions (SO 4 2- , NO 3 - , Cl - , and Ac - ) were selected to investigate their impact of on the sorption, soil dehydrogenase activity (DHA) and alkaline phosphatase activity (ALP). Thus, a series of simulated Cd pollution batch experiments including measuring adsorption-desorption behavior of Cd on soils and soil enzyme activities were carried out. Results showed that CdSO 4 exhibited highest sorption capacity among the tested soils except in Hunan soil. The Cd sorption with NO 3 - displayed a similar behavior with Cl - on all tested soils. Compared with soil properties, all four kinds of anions on Cd sorption played a more significant role affecting Cd ecological toxicity to soil DHA and ALP. Cd in acetate or nitrate form appears more sensitive towards DHA than sulphate and chloride, while the later pair is more toxic towards ALP than the former. These results have important implications for evaluation of Cd contamination using soil enzyme as bioindicator. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Efficiency of superoxide anions in the inactivation of selected dehydrogenases

    Rodacka, Aleksandra; Serafin, Eligiusz; Puchala, Mieczyslaw

    2010-01-01

    The most ubiquitous of the primary reactive oxygen species, formed in all aerobes, is the superoxide free radical. It is believed that the superoxide anion radical shows low reactivity and in oxidative stress it is regarded mainly as an initiator of more reactive species such as · OH and ONOO - . In this paper, the effectiveness of inactivation of selected enzymes by radiation-generated superoxide radicals in comparison with the effectiveness of the other products of water radiolysis is examined. We investigate three enzymes: glyceraldehyde-3-phosphate dehydrogenase (GAPDH), alcohol dehydrogenase (ADH) and lactate dehydrogenase (LDH). We show that the direct contribution of the superoxide anion radical to GAPDH and ADH inactivation is significant. The effectiveness of the superoxide anion in the inactivation of GAPDH and ADG was only 2.4 and 2.8 times smaller, respectively, in comparison with hydroxyl radical. LDH was practically not inactivated by the superoxide anion. Despite the fact that the studied dehydrogenases belong to the same class of enzymes (oxidoreductases), all have a similar molecular weight and are tetramers, their susceptibility to free-radical damage varies. The differences in the radiosensitivity of the enzymes are not determined by the basic structural parameters analyzed. A significant role in inactivation susceptibility is played by the type of amino acid residues and their localization within enzyme molecules.

  11. Efficiency of superoxide anions in the inactivation of selected dehydrogenases

    Rodacka, Aleksandra, E-mail: olakow@biol.uni.lodz.p [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland); Serafin, Eligiusz, E-mail: serafin@biol.uni.lodz.p [Laboratory of Computer and Analytical Techniques, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland); Puchala, Mieczyslaw, E-mail: puchala@biol.uni.lodz.p [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland)

    2010-09-15

    The most ubiquitous of the primary reactive oxygen species, formed in all aerobes, is the superoxide free radical. It is believed that the superoxide anion radical shows low reactivity and in oxidative stress it is regarded mainly as an initiator of more reactive species such as {sup {center_dot}}OH and ONOO{sup -}. In this paper, the effectiveness of inactivation of selected enzymes by radiation-generated superoxide radicals in comparison with the effectiveness of the other products of water radiolysis is examined. We investigate three enzymes: glyceraldehyde-3-phosphate dehydrogenase (GAPDH), alcohol dehydrogenase (ADH) and lactate dehydrogenase (LDH). We show that the direct contribution of the superoxide anion radical to GAPDH and ADH inactivation is significant. The effectiveness of the superoxide anion in the inactivation of GAPDH and ADG was only 2.4 and 2.8 times smaller, respectively, in comparison with hydroxyl radical. LDH was practically not inactivated by the superoxide anion. Despite the fact that the studied dehydrogenases belong to the same class of enzymes (oxidoreductases), all have a similar molecular weight and are tetramers, their susceptibility to free-radical damage varies. The differences in the radiosensitivity of the enzymes are not determined by the basic structural parameters analyzed. A significant role in inactivation susceptibility is played by the type of amino acid residues and their localization within enzyme molecules.

  12. based anion exchange membrane for alkaline polymer electrolyte

    Administrator

    Abstract. Hydroxyl ion (OH–) conducting anion exchange membranes based on modified poly (phenylene oxide) are fabricated for their application in alkaline polymer electrolyte fuel cells (APEFCs). In the present study, chloromethylation of poly(phenylene oxide) (PPO) is performed by aryl substitution rather than benzyl.

  13. Anion-exchange membranes in electrochemical energy systems

    Varcoe, J.R.; Atanassov, P.; Dekel, D.R.; Herring, A.M.; Hickner, M.A.; Kohl, P.A.; Kucernak, A. R.; Mustain, W.E.; Nijmeijer, K.; Scott, Keith; Xu, Tongwen; Zhuang, Lin

    2014-01-01

    This article provides an up-to-date perspective on the use of anion-exchange membranes in fuel cells, electrolysers, redox flow batteries, reverse electrodialysis cells, and bioelectrochemical systems (e.g. microbial fuel cells). The aim is to highlight key concepts, misconceptions, the current

  14. Anion complexation by calix[4]arene–TTF conjugates

    Flídrová, K.; Tkadlecová, M.; Lang, Kamil; Lhoták, P.

    2012-01-01

    Roč. 92, č. 1 (2012), s. 668-673 ISSN 0143-7208 R&D Projects: GA ČR GA203/09/0691 Institutional research plan: CEZ:AV0Z40320502 Keywords : calix[4]arene * tetrathiafulvalene * anion recognition * receptor * NMR titration * UV/vis spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 3.532, year: 2012

  15. Novel Biscalix[4]arene-based Anion Receptors

    Šťastný, V.; Lhoták, P.; Michlová, V.; Stibor, I.; Sýkora, Jan

    2002-01-01

    Roč. 58, č. 36 (2002), s. 7207-7211 ISSN 0040-4020 R&D Projects: GA ČR GA104/00/1722; GA ČR GA203/00/1011 Keywords : calixarenes * anion receptors * NMR titration Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.420, year: 2002

  16. Physicochemical treatments of anionic surfactants wastewater: Effect on aerobic biodegradability.

    Aloui, Fathi; Kchaou, Sonia; Sayadi, Sami

    2009-05-15

    The effect of different physicochemical treatments on the aerobic biodegradability of an industrial wastewater resulting from a cosmetic industry has been investigated. This industrial wastewater contains 11423 and 3148mgL(-1) of chemical oxygen demand (COD) and anionic surfactants, respectively. The concentration of COD and anionic surfactants were followed throughout the diverse physicochemical treatments and biodegradation experiments. Different pretreatments of this industrial wastewater using chemical flocculation process with lime and aluminium sulphate (alum), and also advanced oxidation process (electro-coagulation (Fe and Al) and electro-Fenton) led to important COD and anionic surfactants removals. The best results were obtained using electro-Fenton process, exceeding 98 and 80% of anionic surfactants and COD removals, respectively. The biological treatment by an isolated strain Citrobacter braakii of the surfactant wastewater, as well as the pretreated wastewater by the various physicochemical processes used in this study showed that the best results were obtained with electro-Fenton pretreated wastewater. The characterization of the treated surfactant wastewater by the integrated process (electro-coagulation or electro-Fenton)-biological showed that it respects Tunisian discharge standards.

  17. The effect of membrane diffusion potential change on anionic drugs ...

    The effect of membrane potential change on anionic drugs Indomethacin and barbitone induced human erythrocyte shape change and red cell uptake of drug has been studied using microscopy and spectrophotometry techniques respectively. The membrane potential was changed by reducing the extracellular chloride ...

  18. The alkylation of imine anions formation of enamines

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The ambident anions derived from imines were alkylated using a variety of solvents and alkylating agents. Under reactive conditions enamines (N-alkylation) are formed as the main products instead of the usually obsd. homologous imines (C-alkylation). The influence of the type of imine, solvent, and

  19. Alkylation of enolate anions formation of enol ethers

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The alkylation of ambident enolate anions-obtained from aliphatic ketones (and one particular type of aldehyde)-was studied using various solvents, bases, alkylating agents and substrates. Alkylation with a reactive alkylating agent (dialkyl sulfates, triethyloxonium fluoroborate) in an aprotic

  20. Synthesis of Terpyridine-Terminated Polymers by Anionic Polymerization

    Guerrero-Sanchez, C.A.; Lohmeijer, B.G.G.; Meier, M.A.R.; Schubert, U.S.

    2005-01-01

    The synthesis of terpyridine-functionalized polystyrene was achieved by reacting 4‘-chloro-2,2‘:6‘,2‘ ‘-terpyridine (terminating agent) with "living" polymeric carbanions synthesized by anionic polymerization. The obtained polymers were characterized by gel permeation chromatography, nuclear