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Sample records for dysprosium perchlorates

  1. PERCHLORATE FACTS

    Science.gov (United States)

    Perchlorate is an anion (negative ion) with the formula C1O 4-. Perchlorate salts are famous in inorganic chemistry on account of their high solubilities. As a result, they are very difficult to remove. Although hot and concentrated perchloric acid is a strong oxidizing agent,...

  2. PERCHLORATE FACTS

    Science.gov (United States)

    Perchlorate is an anion (negative ion) with the formula C1O 4-. Perchlorate salts are famous in inorganic chemistry on account of their high solubilities. As a result, they are very difficult to remove. Although hot and concentrated perchloric acid is a strong oxidizing agent,...

  3. Metronidazolium perchlorate

    Directory of Open Access Journals (Sweden)

    Gui-Mei Tang

    2010-10-01

    Full Text Available In the crystal structure of the title compound [systematic name: 1-(2-hydroxyethyl-2-methyl-5-nitro-1H-imidazol-3-ium perchlorate], C6H10N3O3+·ClO4−, the cations are linked by intermolecular N—H...O hydrogen bonds into zigzag chains along the c axis. The cations and anions are connected by O—H...O and C—H...O hydrogen bonds. A weak intramolecular C—H...O hydrogen bond is also observed.

  4. Dysprosium magneto-optical traps

    CERN Document Server

    Youn, Seo Ho; Ray, Ushnish; Lev, Benjamin L

    2010-01-01

    Magneto-optical traps (MOTs) of highly magnetic lanthanides open the door to explorations of novel phases of strongly correlated matter such as lattice supersolids and quantum liquid crystals. We recently reported the first MOTs of the five high abundance isotopes of the most magnetic atom, dysprosium. Described here are details of the experimental technique employed for repumper-free Dy MOTs containing up to half a billion atoms. Extensive characterization of the MOTs' properties---population, temperature, loading, metastable decay dynamics, trap dynamics---is provided.

  5. Perchlorate isotope forensics

    Science.gov (United States)

    Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Horita, J.; Brown, G.M.; Jackson, W.A.; Batista, J.; Hatzinger, P.B.

    2005-01-01

    Perchlorate has been detected recently in a variety of soils, waters, plants, and food products at levels that may be detrimental to human health. These discoveries have generated considerable interest in perchlorate source identification. In this study, comprehensive stable isotope analyses ( 37Cl/35Cl and 18O/17O/ 16O) of perchlorate from known synthetic and natural sources reveal systematic differences in isotopic characteristics that are related to the formation mechanisms. In addition, isotopic analyses of perchlorate extracted from groundwater and surface water demonstrate the feasibility of identifying perchlorate sources in contaminated environments on the basis of this technique. Both natural and synthetic sources of perchlorate have been identified in water samples from some perchlorate occurrences in the United States by the isotopic method. ?? 2005 American Chemical Society.

  6. Modified Activated Carbon Perchlorate Sorbents

    Science.gov (United States)

    2007-01-25

    Although alternative technologies for perchlorate remediation include membrane filtration (reverse osmosis ) and phytoremediation, they are either...materials and the perchlorate absorption capacity is the inverse correlation between % O and the perchlorate absorption capacity. Table 5. Comparison of

  7. On polymorphism of dysprosium trichloride

    Energy Technology Data Exchange (ETDEWEB)

    Zakiryanova, Irina D.; Khokhlov, Vladimir A.; Salyulev, Alexander B.; Korzun, Iraida V. [RAS Ural Branch, Ekaterinburg (Russian Federation). Institute of High-Temperature Electrochemistry

    2015-07-01

    For the first time, the structure of crystalline DyCl{sub 3} over a wide temperature range from room temperature to melting point was studied by Raman spectroscopy. The phonon modes (cm{sup -1}) of dysprosium trichloride (monoclinic crystal lattice of AlCl{sub 3} type, Z = 4, CN = 6) at room temperature are 257 (A{sub 1g}), 201 (E{sub g}), 112 (E{sub g}), 88 (A{sub 1g}), and 63 (E{sub g}). The monoclinic structure of the crystalline DyCl{sub 3} C{sub 2h}{sup 3} symmetry was found to remain constant over the studied temperature range. No polymorphic transformation in the solid state was detected. Gravimetry, calorimetry, and mass spectrometry have been used in addition to support the conclusions made on the basis of Raman spectroscopic data.

  8. Resonance ionization spectroscopy in dysprosium

    Energy Technology Data Exchange (ETDEWEB)

    Studer, D., E-mail: dstuder@uni-mainz.de; Dyrauf, P.; Naubereit, P.; Heinke, R.; Wendt, K. [Johannes Gutenberg-Universität Mainz, Institut für Physik (Germany)

    2017-11-15

    We report on resonance ionization spectroscopy (RIS) of high-lying energy levels in dysprosium. We developed efficient excitation schemes and re-determined the first ionization potential (IP) via analysis of Rydberg convergences. For this purpose both two- and three-step excitation ladders were investigated. An overall ionization efficiency of 25(4) % could be demonstrated in the RISIKO mass separator of Mainz University, using a three-step resonance ionization scheme. Moreover, an extensive analysis of the even-parity 6sns- and 6snd-Rydberg-series convergences, measured via two-step excitation was performed. To account for strong perturbations in the observed s-series, the approach of multichannel quantum defect theory (MQDT) was applied. Considering all individual series limits we extracted an IP-value of 47901.76(5) cm{sup −1}, which agrees with the current literature value of 47901.7(6) cm{sup −1}, but is one order of magnitude more precise.

  9. The dysprosium-tin phase diagram

    Energy Technology Data Exchange (ETDEWEB)

    Eremenko, V.N.; Bulanova, M.V.; Martsenjuk, P.S. (I.N. Frantsevich Inst. for Problems of Materials Science, Kiev (Ukraine))

    1992-12-07

    The dysprosium-tin phase diagram was established by means of differential thermal, X-ray and microscopic analyses of 22 alloys. Seven intermetallic compounds were found to exist in the system. Dy[sub 5]Sn[sub 3] melts congruently at 1870 degC, and undergoes a polymorphous transformation at 1823 [+-] 6 degC. The intermetallics Dy[sub 5]Sn[sub 4], Dy[sub 11]Sn[sub 10], DySn, Dy[sub 4]Sn[sub 5], DySn[sub 2], DySn[sub 3] are formed peritectically at 1712 [+-]11, 1605 [+-]12, 1208 [+-]3, 1166 [+-]7, 1138 [+-]3 and 747 [+-]6 degC respectively. DySn[sub 3] exists in a narrow temperature range, in two polymorphous modifications. The transformation [beta]-DySn[sub 3] [yields] [alpha]-DySn[sub 3] occurs at 608 [+-] 12 degC, and at 499 [+-]2 degC [alpha]-DySn[sub 3] decomposes to DySn[sub 2] and the tin-rich melt. The dysprosium-rich eutectic crystallizes at 1204 [+-]10 degC and contains 13 at.% tin. The solid-state solubility of tin in dysprosium is about 3 at.%, and that of dysprosium in tin is negligible.

  10. Perchlorate Questions and Answers

    Science.gov (United States)

    ... Dietary Intake of Perchlorate and Iodine" in the Journal of Exposure Science and Environmental Epidemiology. This study reports on the ... Compliance Federal, State & Local Officials Consumers Health Professionals ... Blood & Biologics Animal & Veterinary Cosmetics Tobacco Products

  11. Widespread Occurrence of Plant Perchlorate

    Science.gov (United States)

    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

  12. Towards a new measurement of parity violation in dysprosium

    CERN Document Server

    Leefer, N; Antypas, D; Budker, D

    2014-01-01

    The dysprosium parity violation experiment concluded nearly 17 years ago with an upper limit on weak interaction induced mixing of nearly degenerate, opposite parity states in atomic dysprosium. While that experiment was limited in sensitivity by statistics, a new apparatus constructed in the interim for radio-frequency spectroscopy is expected to provide significant improvements to the statistical sensitivity. Preliminary work from the new PV experiment in dysprosium is presented with a discussion of the current statistical sensitivity and outlook.

  13. Dysprosium Modification of Cobalt Ferrite Ionic Magnetic Fluids

    Institute of Scientific and Technical Information of China (English)

    JIANG Rong-li; LIU Yong-chao; GENG Quan-rong; ZHAO Wen-tao

    2005-01-01

    Dysprosium composite cobalt ferrite ionic magnetic fluids were prepared by precipitation in the presence of Tri-sodium citrate. Influence of dysprosium modification on magnetic property is studied. The result shows that magnetic response toward exterior magnetic field can be improved by adding Dy3+. Studies also show that the increase of reaction temperature may improve the modification effect of dysprosium. By adding dysprosium ions, the average diameter of the magnetic nanoparticles will be decreased evidently. It is clear that the particles appear as balls, Cobalt ferrite with sizes of 12-15 nm, rare earth composite cobalt ferrite with sizes of 6-8 nm.

  14. Bioelectrical Perchlorate Remediation

    Science.gov (United States)

    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

  15. Can a dysprosium shortage threaten green energy technologies?

    NARCIS (Netherlands)

    Hoenderdaal, S.; Tercero Espinoza, L.; Marschneider-Weidemann, F.; Crijns - Graus, Wina

    2013-01-01

    Dysprosium, one of the various rare earth elements, is currently for more than 99% mined in China. As China is reducing its exports, new mining projects outside of China are needed to sustain supply and meet future demands. Dysprosium is mainly used in permanent magnets to retain the magnet's streng

  16. Phenalenyl-based mononuclear dysprosium complexes

    Directory of Open Access Journals (Sweden)

    Yanhua Lan

    2016-07-01

    Full Text Available The phenalenyl-based dysprosium complexes [Dy(PLN2(HPLNCl(EtOH] (1, [Dy(PLN3(HPLN]·[Dy(PLN3(EtOH]·2EtOH (2 and [Dy(PLN3(H2O2]·H2O (3, HPLN being 9-hydroxy-1H-phenalen-1-one, have been synthesized. All compounds were fully characterized by means of single crystal X-ray analysis, paramagnetic 1H NMR, MALDI-TOF mass spectrometry, UV–vis spectrophotometry and magnetic measurements. Both static (dc and dynamic (ac magnetic properties of these complexes have been investigated, showing slow relaxation of magnetization, indicative of single molecule magnet (SMM behavior. Attempts to synthesize sublimable phenalenyl-based dysprosium complexes have been made by implementing a synthetic strategy under anhydrous conditions. The sublimed species were characterized and their thermal stability was confirmed. This opens up the possibility to deposit phenalenyl-based lanthanides complexes by sublimation onto surfaces, an important prerequisite for ongoing studies in molecular spintronics.

  17. Anisotropy in the Interaction of Ultracold Dysprosium

    CERN Document Server

    Kotochigova, Svetlana

    2011-01-01

    The nature of the interaction between ultracold atoms with a large orbital and spin angular momentum has attracted considerable attention. It was suggested that such interactions can lead to the realization of exotic states of highly correlated matter. Here, we report on a theoretical study of the competing anisotropic dispersion, magnetic dipole-dipole, and electric quadrupole-quadrupole forces between two dysprosium atoms. Each dysprosium atom has an orbital angular momentum L=6 and magnetic moment $\\mu=10\\mu_B$. We show that the dispersion coefficients of the ground state adiabatic potentials lie between 1865 a.u. and 1890 a.u., creating a non-negligible anisotropy with a spread of 25 a.u. and that the electric quadrupole-quadrupole interaction is weak compared to the other interactions. We also find that for interatomic separations $R< 50\\,a_0$ both the anisotropic dispersion and magnetic dipole-dipole potential are larger than the atomic Zeeman splittings for external magnetic fields of order 10 G to ...

  18. An Enzymatic Bioassay for Perchlorate

    Science.gov (United States)

    2010-07-01

    equilibrated in 25 mM Trishydroxmethylamine buffer with 1 mM sodium dithionite (pH 8.5). Neither PCR nor chlorite dismutase bind to the resin, and...13  The  chlorite  bioassay... chlorite (ClO2-) with the purified perchlorate reductase from Dechloromonas agitata. It was hypothesized that the purified perchlorate reductase would

  19. Ammonium Perchlorate and Ammonium Perchlorate- Hydroxyl Terminated Polybutadiene Simulated Combustion

    Directory of Open Access Journals (Sweden)

    Rene Francisco Boschi Gonçalves

    2012-03-01

    Full Text Available The combustion simulation of ammonium perchlorate was carried out with the software Chemkin, in two steps: the burning behavior of pure ammonium perchlorate and the one of formulated ammonium perchlorate with hydroxyl terminated polybutadiene binder. In both cases, the room pressure varied in order to verify its influence in the system. The burning environment conditions were diverse. During the combustion process, the data obtained from the kinetic chemistry simulation software were compiled. The flame structure can be described by the molar fraction of the burning products and the temperature evolution from the surface of the material.

  20. Perchlorate Peer Review Frequent Questions

    Science.gov (United States)

    EPA believes that peer review is an important component of the scientific process. EPA will ask peer reviewers to comment on products that the agency will use to derive a Maximum Contaminant Level Goal (MCLG) for perchlorate.

  1. First search for double $\\beta$ decay of dysprosium

    CERN Document Server

    Belli, P; Cappella, F; Cerulli, R; Danevich, F A; d'Angelo, S; Di Vacri, M L; Incicchitti, A; Laubenstein, M; Nagorny, S S; Nisi, S; Tolmachev, A V; Tretyak, V I; Yavetskiy, R P

    2011-01-01

    A search for double $\\beta$ decay of dysprosium was realized for the first time with the help of an ultra low-background HP Ge $\\gamma$ detector. After 2512 h of data taking with a 322 g sample of dysprosium oxide limits on double beta processes in $^{156}$Dy and $^{158}$Dy have been established on the level of $T_{1/2}\\geq 10^{14}-10^{16}$ yr. Possible resonant double electron captures in $^{156}$Dy and $^{158}$Dy were restricted on a similar level. As a by-product of the experiment we have measured the radioactive contamination of the Dy$_2$O$_3$ sample and set limits on the $\\alpha$ decay of dysprosium isotopes to the excited levels of daughter nuclei as $T_{1/2}\\geq 10^{15} - 10^{17}$ yr.

  2. PERCHLORATE CROP INTERACTIONS VIA CONTAMINATED IRRIGATION WATER

    Science.gov (United States)

    Perchlorate has contaminated water and sods at several locations in the United States. Perchlorate is water 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 un...

  3. Perchlorate Reduction by Yeast for Mars Exploration

    Science.gov (United States)

    Sharma, Alaisha

    2015-01-01

    Martian soil contains high levels (0.6 percentage by mass) of calcium perchlorate (Ca(ClO4)2), which readily dissociates into calcium and the perchlorate ion (ClO4-) in water. Even in trace amounts, perchlorates are toxic to humans and have been implicated in thyroid dysfunction. Devising methods to lessen perchlorate contamination is crucial to minimizing the health risks associated with human exploration and colonization of Mars. We designed a perchlorate reduction pathway, which sequentially reduces perchlorate to chloride (Cl-) and oxygen (O2), for implementation in the yeast Saccharomyces cerevisiae. Using genes obtained from perchlorate reducing bacteria Azospira oryzae and Dechloromonas aromatica, we plan to assemble this pathway directly within S. cerevisiae through recombinational cloning. A perchlorate reduction pathway would enable S. cerevisiae to lower perchlorate levels and produce oxygen, which may be harvested or used directly by S. cerevisiae for aerobic growth and compound synthesis. Moreover, using perchlorate as an external electron acceptor could improve the efficiency of redox-imbalanced production pathways in yeast. Although several perchlorate reducing bacteria have been identified and utilized in water treatment systems on Earth, the widespread use of S. cerevisiae as a synthetic biology platform justifies the development of a perchlorate reducing strain for implementation on Mars.

  4. Neutron resonance parameters of dysprosium isotopes using neutron capture yields

    Energy Technology Data Exchange (ETDEWEB)

    Shin, S. G.; Kye, Y. U.; Cho, M. H. [POSTECH, Pohang (Korea, Republic of); Namkung, W. [Pohang Accelerator Laboratory, Pohang (Korea, Republic of); Kim, G. N. [Kyungpook National University, Daegu (Korea, Republic of); Lee, M. W.; Kang, Y. R. [Dongnam Inst. Of Radiological and Medical Science, Busan (Korea, Republic of)

    2015-10-15

    Dysprosium is used in the field of nuclear reactor system because it has a very large thermal neutron absorption cross-section. The dysprosium alloyed with special stainless steels is attractive for control in nuclear reactor because of the ability to absorb neutrons readily without swelling or contracting over time and its high melting point. Dysprosium is also one of fission products from the thermal fission of {sup 234}U, {sup 233}U, and {sup 239}Pu. The fission products are accumulated in the reactor core by the burn-up of the nuclear fuel and the poison effect is increased. Therefore, it is required to understand how Dysprosium as both a poison and an absorbing material in the control rod has an effect on the neutron population in a nuclear reactor system over all energy regions. Neutron Capture experiments on Dy isotopes were performed at the electron linear accelerator (LINAC) facility of the Rensselear Polytechnic Institute (RPI) in the neutron energy region from 10 eV to 1 keV. Resonance parameters were extracted by fitting the neutron capture data using the SAMMY multilevel R-matrix Bayesian code.

  5. Perchlorate natural attenuation in a riparian zone.

    Science.gov (United States)

    Borden, Robert C; Knox, Sheri L; Lieberman, M Tony; Ogles, Dora

    2014-01-01

    Multiple lines of evidence were used to document the natural attenuation of perchlorate in a shallow alluvial aquifer. In the upgradient, aerobic portion of the aquifer, perchlorate did not biodegrade. However, natural flushing by groundwater flow is reducing perchlorate concentrations in the aquifer over time. Perchlorate concentrations in the source area are expected to meet cleanup criteria in 11 to 27 years without active remedial measures. At the distal end of the plume, perchlorate is rapidly degraded as it migrates upward through organic rich littoral zone sediments. Apparent first-order degradation rates in groundwater were about 0.20 d(-1) and are consistent with laboratory macrocosm rates (0.12 d(-1)). qPCR results show a distinct region of the littoral zone where perchlorate degraders are elevated. The Eh within this zone varies from +0.1 to +0.3 V indicating perchlorate degraders can thrive in moderately oxidizing conditions. The study has shown that (i) there was no apparent perchlorate biodegradation in aerobic aquifer; (ii) perchlorate declines over time in aerobic aquifer due to flushing; (iii) there was a rapid perchlorate attenuation in organic rich littoral zone; and, (iv) qPCR results show large increases in perchlorate degraders in the littoral zone.

  6. ASSESSMENT OF PERCHLORATE IN FERTILIZERS

    Science.gov (United States)

    Perchlorate has been positively detected only in those materials known to be derived from Chilean caliche, which constitute less than 0.2% of U.S. fertilizer application. The data obtained in the preponderance of investigations suggest that fertilizers do not contribute to envir...

  7. Properties of Polydisperse Tin-doped Dysprosium and Indium Oxides

    Directory of Open Access Journals (Sweden)

    Malinovskaya Tatyana

    2017-01-01

    Full Text Available The results of investigations of the complex permittivity, diffuse-reflectance, and characteristics of crystal lattices of tin-doped indium and dysprosium oxides are presented. Using the methods of spectroscopy and X-ray diffraction analysis, it is shown that doping of indium oxide with tin results in a significant increase of the components of the indium oxide complex permittivity and an appearance of the plasma resonance in its diffuse-reflectance spectra. This indicates the appearance of charge carriers with the concentration of more than 1021 cm−3 in the materials. On the other hand, doping of the dysprosium oxide with the same amount of tin has no effect on its optical and electromagnetic properties.

  8. Dysprosium titanate as an absorber material for control rods

    Science.gov (United States)

    Risovany, V. D.; Varlashova, E. E.; Suslov, D. N.

    2000-09-01

    Disprosium titanate is an attractive control rod material for the thermal neutron reactors. Its main advantages are: insignificant swelling, no out-gassing under neutron irradiation, rather high neutron efficiency, a high melting point (˜1870°C), non-interaction with the cladding at temperatures above 1000°C, simple fabrication and easily reprocessed non-radioactive waste. It can be used in control rods as pellets and powder. The disprosium titanate control rods have worked off in the MIR reactor for 17 years, in VVER-1000 - for 4 years without any operating problems. After post-irradiation examinations this type of control rod having high lifetime was recommended for the VVER and RBMK. The paper presents the examination results of absorber element dummies containing dysprosium titanate, irradiated in the SM reactor to the neutron fluence of 3.4×10 22 cm -2 ( E>0.1 MeV) and, also, the data on structure, thermal-physical properties of dysprosium titanate, efficiency of dysprosium titanate control rods.

  9. Kinetics for a membrane reactor reducing perchlorate.

    Science.gov (United States)

    Padhye, Lokesh; Rainwater, Ken; Jackson, W Andrew; Morse, Audra

    2007-02-01

    The major objectives of this work were to operate and construct an autohydrogenotrophic reactor and estimate perchlorate degradation kinetics. The results show that autohydrogenotrophic bacteria were cultured in the reactor and capable of removing 3.6 mg/d of perchlorate in the presence of excess hydrogen (99% removal). The reactor was successful in treating the average influent perchlorate concentration of 532 microg/L to the level of 3 microg/L. A first-order relationship was obtained between the concentration of active biomass in the reactor and the hydraulic retention time for the given amount of substrate. During the kinetic loading study, perchlorate removal ranged from 100 to 50%. The kinetic rate of perchlorate degradation observed in this study was 1.62 hr(-1). The significant degradation of perchlorate in these samples indicates the ubiquity of perchlorate-reducing organisms. Additionally, nitrate was simultaneously removed during water treatment (greater than 90% removal). Because of the excess levels of hydrogen, simultaneous removal of nitrate was not believed to significantly affect perchlorate removal. The area of concern was the lack of complete control over biological treatment. The growth of sulfate-reducing organisms in the reactor negatively affected perchlorate removal efficiency. There were no significant effects observed on the dissolved organic carbon and total suspended solids concentration of the effluent, suggesting that the treatment did not produce a large amount of biomass washout.

  10. Aripiprazole salts. II. Aripiprazole perchlorate.

    Science.gov (United States)

    Freire, Eleonora; Polla, Griselda; Baggio, Ricardo

    2012-06-01

    The molecular structure of aripiprazole perchlorate (systematic name: 4-(2,3-dichlorophenyl)-1-{4-[(2-oxo-1,2,3,4-tetrahydroquinolin-7-yl)oxy]butyl}piperazin-1-ium perchlorate), C(23)H(28)Cl(2)N(3)O(2)(+)·ClO(4)(-), does not differ substantially from the recently published structure of aripiprazole nitrate [Freire, Polla & Baggio (2012). Acta Cryst. C68, o170-o173]. Both compounds have almost identical bond distances, bond angles and torsion angles. The two different counter-ions occupy equivalent places in the two structures, giving rise to very similar first-order `packing motifs'. However, these elemental arrangements interact with each other in different ways in the two structures, leading to two-dimensional arrays with quite different organizations.

  11. Biodegradation of rocket propellant waste, ammonium perchlorate

    Science.gov (United States)

    Naqvi, S. M. Z.; Latif, A.

    1975-01-01

    The short term effects of ammonium perchlorate on selected organisms were studied. A long term experiment was also designed to assess the changes incurred by ammonium perchlorate on the nitrogen and chloride contents of soil within a period of 3 years. In addition, an attempt was made to produce methane gas from anaerobic fermentation of the aquatic weed, Alternanthera philoxeroides.

  12. ACCUMULATION AND FATE OF PERCHLORATE IN PLANTS

    Science.gov (United States)

    Perchlorate, a component of solid rocket fuels, has emerged as a potential threat to surface water and groundwater at several locations in the U.S. Perchlorate levels up to 16 ug/L were detected in Lake Mead and 5-9 ug/L in the lower Colorado River. The water from the Colorado Ri...

  13. PHYTOREMEDIATION OF PERCHLORATE BY TOBACCO PLANTS

    Science.gov (United States)

    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,...

  14. PHYTOREMEDIATION OF PERCHLORATE BY TOBACCO PLANTS

    Science.gov (United States)

    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,...

  15. Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid

    Science.gov (United States)

    Berger, Claudia A.; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

    2016-07-01

    The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important

  16. Perchlorate reduction by microbes inhabiting oil reservoirs

    Science.gov (United States)

    Liebensteiner, Martin; Stams, Alfons; Lomans, Bart

    2014-05-01

    Microbial perchlorate and chlorate reduction is a unique type of anaerobic respiration as during reduction of (per)chlorate chlorite is formed, which is then split into chloride and molecular oxygen. In recent years it was demonstrated that (per)chlorate-reducing bacteria may employ oxygenase-dependent pathways for the degradation of aromatic and aliphatic hydrocarbons. These findings suggested that (per)chlorate may be used as oxygen-releasing compound in anoxic environments that contain hydrocarbons, such as polluted soil sites and oil reservoirs. We started to study perchlorate reduction by microbes possibly inhabiting oil reservoirs. One of the organisms studied was Archaeoglobus fulgidus. This extremely thermophilic archaeon is known as a major contributor to souring in hot oil reservoirs. A. fulgidus turned out to be able to use perchlorate as terminal electron acceptor for growth with lactate (Liebensteiner et al 2013). Genome based physiological experiments indicated that A. fulgidus possesses a novel perchlorate reduction pathway. Perchlorate is first reduced to chlorite, but chlorite is not split into chloride and molecular oxygen as occurs in bacteria. Rather, chlorite reacts chemically with sulfide, forming oxidized sulfur compounds, which are reduced to sulfide in the electron transport chain by the archaeon. The dependence of perchlorate reduction on sulfur compounds could be shown. The implications of our findings as novel strategy for microbiological enhanced oil recovery and for souring mitigation are discussed. Liebensteiner MG, Pinkse MWH, Schaap PJ, Stams AJM and Lomans BP (2013) Archaeal (per)chlorate reduction at high temperature, a matter of abiotic-biotic reactions. Science 340: 85-87

  17. Background Perchlorate Source Identification Technical Guidance

    Science.gov (United States)

    2013-12-01

    perchlorate was at one time used to treat thyroid dysfunction, particularly a hyperthyroidism condition known as Grave’s disease. Ecological impacts...Dispersion will cause the contaminant front to move faster than the average groundwater velocity. Perchlorate is kinetically very stable under...between the brine and groundwater may cause the brine to move vertically with minimal influence by groundwater movement and little or no dilution

  18. The Microbiology of Perchlorate in the Environment

    Science.gov (United States)

    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

  19. SURVEY OF FERTILIZERS AND RELATED MATERIALS FOR PERCHLORATE

    Science.gov (United States)

    The most comprehensive survey of fertilizers and other raw materials for perchlorate to date has been conducted to determine whether these could be significant contributors to environmental perchlorate contamination. Although the data span a large range of commercial products, th...

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

    Science.gov (United States)

    2010-07-01

    In the perchlorate breakdown study, chlorate, chlorite and chloride were analyzed. ERDC/EL TR-10-14 10 Chemicals Sodium perchlorate anhydrous...is the soluble anion associated with the solid salts of ammonium, potassium, and sodium perchlorate. Large-scale production of ammonium perchlorate...fertilizers, where it was probably a filler additive. Sodium hypochlorite solutions used in water and wastewater treatment plants have also been

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

    NARCIS (Netherlands)

    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

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

    NARCIS (Netherlands)

    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

  3. Experimental and molecular dynamics studies of dysprosium(III) salt solutions for a better representation of the microscopic features used within the binding mean spherical approximation theory.

    Science.gov (United States)

    Ruas, Alexandre; Guilbaud, Philippe; Den Auwer, Christophe; Moulin, Christophe; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

    2006-10-19

    This work is aimed at a predictive description of the thermodynamic properties of actinide(III) salt solutions at high concentration and 25 degrees C. A new solution of the binding mean spherical approximation (BIMSA) theory, based on the Wertheim formalism, for taking into account 1:1 and also 1:2 complex formation, is used to reproduce, from a simple procedure, experimental osmotic coefficient variation with concentration for three binary salt solutions of the same lanthanide(III) cation: dysprosium(III) perchlorate, nitrate, and chloride. The relevance of the fitted parameters is discussed, and their values are compared with available literature values. UV-vis/near-IR, time-resolved laser-induced fluorescence spectroscopy experiments, and molecular dynamics (MD) calculations were conducted for dilute to concentrated solutions (ca. 3 mol.kg-1) for a study of the microscopic behavior of DyCl3 binary solutions. Coupling MD calculations and extended X-ray absorption fine structure led to the determination of reliable distances. The MD results were used for a discussion of the parameters used in the BIMSA.

  4. Experimental and molecular dynamics studies of dysprosium(III) salt solutions for a better representation of the microscopic features used within the binding mean spherical approximation theory

    Energy Technology Data Exchange (ETDEWEB)

    Ruas, Alexandre; Guilbaud, Philippe; Den Auwer, Christophe; Moulin, Christophe; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe [DEN/DRCP/SCPS, CEA-Valrho Marcoule, BP 17171, 30207 Bagnols-sur-Ceze Cedex, DEN/DPC/SECR/LSRM, CEA-Saclay, Bat 391, BP 91191 Gif sur Yvette, Cedex (France); Laboratoire LI2C (UMR 7612), Universite Pierre et Marie Curie-Paris 6, Boite No. 51, 4 Place Jussieu, 75252 Paris Cedex 05 (France)

    2006-07-01

    This work is aimed at a predictive description of the thermodynamic properties of actinide (III) salt solutions at high concentration and 25 deg. C. A new solution of the binding mean spherical approximation (BIMSA) theory, based on the Wertheim formalism, for taking into account 1: 1 and also 1: 2 complex formation, is used to reproduce, from a simple procedure, experimental osmotic coefficient variation with concentration for three binary salt solutions of the same lanthanide (III) cation: dysprosium (III) perchlorate, nitrate, and chloride. The relevance of the fitted parameters is discussed, and their values are compared with available literature values. UV-vis/near-IR, time-resolved laser-induced fluorescence spectroscopy experiments, and molecular dynamics (MD) calculations were conducted for dilute to concentrated solutions (ca. 3 mol, kg{sup -1}) for a study of the microscopic behavior of DyCl{sub 3} binary solutions. Coupling MD calculations and extended X-ray absorption fine structure led to the determination of reliable distances. The MD results were used for a discussion of the parameters used in the BIMSA. (authors)

  5. Dysprosium detector for neutron dosimetry in external beam radiotherapy

    Science.gov (United States)

    Ostinelli, A.; Berlusconi, C.; Conti, V.; Duchini, M.; Gelosa, S.; Guallini, F.; Vallazza, E.; Prest, M.

    2014-09-01

    Radiotherapy treatments with high-energy (>8 MeV) photon beams are a standard procedure in clinical practice, given the skin and near-target volumes sparing effect, the accurate penetration and the uniform spatial dose distribution. On the other hand, despite these advantages, neutrons may be produced via the photo-nuclear (γ,n) reactions of the high-energy photons with the high-Z materials in the accelerator head, in the treatment room and in the patient, resulting in an unwanted dose contribution which is of concern, given its potential to induce secondary cancers, and which has to be monitored. This work presents the design and the test of a portable Dysprosium dosimeter to be used during clinical treatments to estimate the "in vivo" dose to the patient. The dosimeter has been characterized and validated with tissue-equivalent phantom studies with a Varian Clinical iX 18 MV photon beam, before using it with a group of patients treated at the S. Anna Hospital in Como. The working principle of the dosimeter together with the readout chain and the results in terms of delivered dose are presented.

  6. Dysprosium detector for neutron dosimetry in external beam radiotherapy

    Energy Technology Data Exchange (ETDEWEB)

    Ostinelli, A.; Berlusconi, C.; Conti, V.; Duchini, M.; Gelosa, S. [Medical Physics - Sant' Anna Hospital, Como (Italy); Guallini, F. [EL.SE s.r.l. (Italy); Vallazza, E. [INFN, Trieste (Italy); Prest, M. [University of Insubria, Como (Italy)

    2014-09-21

    Radiotherapy treatments with high-energy (>8MeV) photon beams are a standard procedure in clinical practice, given the skin and near-target volumes sparing effect, the accurate penetration and the uniform spatial dose distribution. On the other hand, despite these advantages, neutrons may be produced via the photo-nuclear (γ,n) reactions of the high-energy photons with the high-Z materials in the accelerator head, in the treatment room and in the patient, resulting in an unwanted dose contribution which is of concern, given its potential to induce secondary cancers, and which has to be monitored. This work presents the design and the test of a portable Dysprosium dosimeter to be used during clinical treatments to estimate the “in vivo” dose to the patient. The dosimeter has been characterized and validated with tissue-equivalent phantom studies with a Varian Clinical iX 18 MV photon beam, before using it with a group of patients treated at the S. Anna Hospital in Como. The working principle of the dosimeter together with the readout chain and the results in terms of delivered dose are presented.

  7. Low Field Magnetic and Thermal Hysteresis in Antiferromagnetic Dysprosium

    Directory of Open Access Journals (Sweden)

    Iuliia Liubimova

    2017-06-01

    Full Text Available Magnetic and thermal hysteresis (difference in magnetic properties on cooling and heating have been studied in polycrystalline Dy (dysprosium between 80 and 250 K using measurements of the reversible Villari effect and alternating current (AC susceptibility. We argue that measurement of the reversible Villari effect in the antiferromagnetic phase is a more sensitive method to detect magnetic hysteresis than the registration of conventional B(H loops. We found that the Villari point, recently reported in the antiferromagnetic phase of Dy at 166 K, controls the essential features of magnetic hysteresis and AC susceptibility on heating from the ferromagnetic state: (i thermal hysteresis in AC susceptibility and in the reversible Villari effect disappears abruptly at the temperature of the Villari point; (ii the imaginary part of AC susceptibility is strongly frequency dependent, but only up to the temperature of the Villari point; (iii the imaginary part of the susceptibility drops sharply also at the Villari point. We attribute these effects observed at the Villari point to the disappearance of the residual ferromagnetic phase. The strong influence of the Villari point on several magnetic properties allows this temperature to be ranked almost as important as the Curie and Néel temperatures in Dy and likely also for other rare earth elements and their alloys.

  8. Environmental Screening Assessment of Perchlorate Replacements

    Science.gov (United States)

    2007-08-01

    nitramido)dinitroethylene AP Ammonium perchlorate CAS Chemical Abstract Services DNNC 1,3,5,5-tetranitrohexahydropyrimidine EPI Estimation Program...can be created and pasted into the input screen or obtained from a linked file of Chemical Abstract Services (CAS) numbers. The EPI Suite Interface

  9. PERCHLORATE UPTAKE AND TRANSFORMATION IN AQUATIC PLANTS

    Science.gov (United States)

    Ammonium Perchlorate (AP) is produced on a large scale by the chemical industry, for a wide range of applications for example, as a strong oxidizing agent in solid rocket fuel. AP must be washed out of the inventory periodically due to its limited shelf-life,and replaced with a f...

  10. A Low-Symmetry Dysprosium Metallocene Single-Molecule Magnet with a High Anisotropy Barrier.

    Science.gov (United States)

    Pugh, Thomas; Chilton, Nicholas F; Layfield, Richard A

    2016-09-05

    The single-molecule magnet (SMM) properties of the isocarbonyl-ligated dysprosium metallocene [Cp*2 Dy{μ-(OC)2 FeCp}]2 (1Dy ), which contains a rhombus-shaped Dy2 Fe2 core, are described. Combining a strong axial [Cp*](-) ligand field with a weak equatorial field consisting of the isocarbonyl ligands leads to an anisotropy barrier of 662 cm(-1) in zero applied field. The dominant thermal relaxation pathways in 1Dy involves at least the fourth-excited Kramers doublet, thus demonstrating that prominent SMM behavior can be observed for dysprosium in low-symmetry environments.

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

    Science.gov (United States)

    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.

  12. Malonate complexes of dysprosium: synthesis, characterization and application for LI-MOCVD of dysprosium containing thin films.

    Science.gov (United States)

    Milanov, Andrian P; Seidel, Rüdiger W; Barreca, Davide; Gasparotto, Alberto; Winter, Manuela; Feydt, Jürgen; Irsen, Stephan; Becker, Hans-Werner; Devi, Anjana

    2011-01-07

    A series of malonate complexes of dysprosium were synthesized as potential metalorganic precursors for Dy containing oxide thin films using chemical vapor deposition (CVD) related techniques. The steric bulkiness of the dialkylmalonato ligand employed was systematically varied and its influence on the resulting structural and physico-chemical properties that is relevant for MOCVD was studied. Single crystal X-ray diffraction analysis revealed that the five homoleptic tris-malonato Dy complexes (1-5) are dimers with distorted square-face bicapped trigonal-prismatic geometry and a coordination number of eight. In an attempt to decrease the nuclearity and increase the solubility of the complexes in various solvents, the focus was to react these dimeric complexes with Lewis bases such as 2,2'-biypridyl and pyridine (6-9). This resulted in monomeric tris-malonato mono Lewis base adduct complexes with improved thermal properties. Finally considering the ease of synthesis, the monomeric nature and promising thermal characteristics, the silymalonate adduct complex [Dy(dsml)(3)bipy] (8) was selected as single source precursor for growing DySi(x)O(y) thin films by liquid injection metalorganic chemical vapor deposition (LI-MOCVD) process. The as-deposited films were analyzed for their morphology and composition by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, Rutherford backscattering (RBS) analysis and X-ray photoelectron spectroscopy.

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

    Science.gov (United States)

    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...

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

    Science.gov (United States)

    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...

  15. Exploration of dysprosium: the most critical element for Japan

    Science.gov (United States)

    Watanabe, Y.

    2012-04-01

    Dysprosium (Dy), one of the heavy rare earth elements, is used mainly as an additive for NdFeB permanent magnets which are installed in various modern industrial products such as voice coil motors in computers, factory automation machinery, hybrid and electric vehicles, home electronics, and wind turbine, to improve heat resistance of the magnets. Dy has been produced about 2,000t per year from the ores from ion adsorption type deposits in southern China. However, the produced amount of Dy was significantly reduced in 2011 in China due to reservation of heavy rare earth resources and protection of natural environment, resulting in soaring of Dy price in the world. In order to respond the increasing demand of Dy, unconventional supply sources are inevitably developed, in addition to heavy rare earth enriched ion adsorption type deposits outside China. Heavy rare earth elements including Dy are dominantly hosted in xenotime, fergusonite, zircon, eudialyte, keiviite, kainosite, iimoriite, etc. Concentration of xenotime is found in placer deposits in Malaysia and India, hydrothermal deposits associated with unconformity-type uranium mineralization (Athabasca basin in Canada, Western Australia), iron-oxide fluorite mineralization (South Africa) and Sn-bearing alkaline granite (Brazil). Zircon and fergusontie concentration is found as igneous and hydrothermal products in peralkaline syenite, alkaline granite and pegmatite (e.g., Nechalacho in Canada). Eudialyte concentration is found in some peralkaline syenite bodies in Greenland, Canada, Sweden and Russia. Among these sources, large Dy resources are estimated in the deposits hosted in peralkaline rocks (Nechalacho: 79,000t, Kvanefjeld: 49,000t, Norra Karr: 15,700t, etc.) compared to the present demand of Dy. Thus, Dy will be supplied from the deposits associated with peralkaline and alkaline deposits in future instead of ion adsorption type deposits in southern China.

  16. Long afterglow of trivalent dysprosium doped strontium aluminate

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yuan Ming, E-mail: dongshanisland@126.com [School of Mathematics and Physics, Changzhou University, Jiangsu 213164 (China); Ma, Qing-lan [School of Mathematics and Physics, Changzhou University, Jiangsu 213164 (China); School of Electronics and Information, Nantong University, Jiangsu 226019 (China)

    2015-04-15

    Trivalent dysprosium doped strontium aluminate (SrA1{sub 2}O{sub 4}:Dy{sup 3+}) was synthesized via the sol–gel combustion method to realize green afterglow in the absence of Eu{sup 2+} luminescent centers. The morphology, crystal structure, photoluminescence and long afterglow of the SrAl{sub 2}O{sub 4}:Dy{sup 3+} were characterized with scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy and photoluminescence spectroscopy, respectively. The bluish-green photoluminescence of SrAl{sub 2}O{sub 4}:Dy{sup 3+} consists of a broad emission band centered at about 520 nm and two characteristic emissions of Dy{sup 3+} ions centered at 480 and 575 nm, respectively. The green afterglow of SrAl{sub 2}O{sub 4}:Dy{sup 3+} is a broad emission band centered at around 520 nm, and the lifetime extracted from afterglow decay is found to be 53 s. The mechanism on the green afterglow from SrAl{sub 2}O{sub 4}:Dy{sup 3+} is discussed in terms of the possible defect levels in the host. - Highlights: • Broad band long-lasting afterglow is observed in SrAl{sub 2}O{sub 4}:Dy{sup 3+} phosphors. • Characteristic emissions of Dy{sup 3+} ions are superimposed on the broad PL of phosphors. • Dy{sup 3+} ions can also act as luminescent centers in addition to electron traps. • A mechanism on long afterglow of SrAl{sub 2}O{sub 4}:Dy{sup 3+} is proposed without Eu{sup 2+} activator.

  17. Low temperature spin reorientation in dysprosium iron garnet

    Energy Technology Data Exchange (ETDEWEB)

    Lahoubi, M; Younsi, W; Soltani, M L [Department of Physics, Badji-Mokhtar University, BP-12 Annaba, 23000 (Algeria); Voiron, J; Schmitt, D, E-mail: mlahoubi@gmail.co [Louis Neel Laboratory, CNRS-UJF, BP-166, 38042 Grenoble Cedex 9 (France)

    2009-03-01

    The spin reorientation (SR) phase transition in dysprosium iron garnet (Dy{sub 3}Fe{sub 5}O{sub 12} or DyIG) have been studied by specific heat C{sub p}(T) and high field magnetisation measurements M{sub T}(H) and M{sub H}(T) on single crystals at low temperature. A first order SR is observed with a sharp jump at T{sub SR} = 14.5+-0.5 K in the C{sub p}(T) curve which corresponds to a spontaneous change from the high temperature (HT) easy direction (111) to an (uuw) angular low temperature (LT) phases. Above T{sub SR}, the magnetic structure is described by the irreducible representation (IR) A{sub 2g} of the rhombohedral space group R 3 c. Below T{sub SR}, the magnetic structure changes in the monoclinic the space group C2/c with the IR A{sub g}. When the field H is kept aligned along the hard symmetry directions (100) and (110), we obtain respectively the variation of the angular positions theta(T) and theta'(T) from the total spontaneous magnetisation down to 1.5 K (theta = 39.23 deg. and theta' = 30.14 deg.) and the results are in good agreement with the previous observations in low fields. When the sample is allowed to rotate freely on itself, the critical field H{sub c}(T) between the HT(111) and the LT(uuw) angular phases permits us to precise the transition line up to 15 T and 40 K between the so called canted field induced (FI) and the associated collinear magnetic phases. The experimental magnetic phase diagram (MPD) is precisely determined in the (H{sub c}-T) plane and the domains of the existence and the stability of the two magnetic phases are specified.

  18. Anisotropic magnetic properties of dysprosium iron garnet (DyIG)

    Energy Technology Data Exchange (ETDEWEB)

    Lahoubi, M; Younsi, W; Soltani, M-L [Department of Physics, Badji-Mokhtar University, BP 12 - 23000 Annaba (Algeria); Ouladdiaf, B, E-mail: mlahoubi@gmail.co [Institut Laue Langevin, BP 156 - 38042 Grenoble Cedex 9 (France)

    2010-01-01

    The magnetic properties of dysprosium iron garnet (DyIG) have been studied by performing high resolution powder neutron diffraction experiments and high dc fields magnetizations on single crystals. Among all the reflections (hkl) indexed in the nuclear cubic space group (CSG) Ia 3-bar d with h+k+l=2n and k=[000], the superstructure lines (hkl)* forbidden by the symmetry (222)* and (622)* are not observed in the patterns at all temperatures. The pattern at 130 K is well interpreted within the magnetic modes F belonging to the irreducible representation (IR) T{sub 1g} of the CSG and identified to the room temperature ferrimagnetic Neel model. The high magnetic field behavior of the spontaneous collinear magnetic structure (MS) along the easy axis (EA) <111> is isotropic. Below 130 K, the patterns exhibit additional magnetic superstructure lines. They are associated to the appearance of the spontaneous non collinear MS which is described in the subgroup of the CSG, R 3-bar c within the IR A{sub 2g}. A strong magnetization anisotropy (MA) is observed at 1.5 K in the low symmetry phases were the spin reorientation transition (SR) occur at T{sub RS}=14.5 K. The onset of MA is detected below two characteristic temperatures, Ta{sub 1}=125 K and Ta{sub 2}=75 K respectively to the hard axis (HA) <100> and <110>. Symmetry arguments are used in the framework of the theory of representation analysis (RA) applied to the subgroup of R 3-bar c, C2/c within the IR A{sub g}. It seems that this MA results essentially from the difference between the spontaneous non collinear MS and the field induced (FI) configurations. All results are discussed with previous neutrons studies.

  19. The NAS perchlorate review: questions remain about the perchlorate RfD.

    Science.gov (United States)

    Ginsberg, Gary; Rice, Deborah

    2005-09-01

    Human exposure to perchlorate is commonplace because it is a contaminant of drinking water, certain foods, and breast milk. The U.S. Environmental Protection Agency (EPA) conducted a perchlorate risk assessment in 2002 that yielded a reference dose (RfD) based on both the animal and human toxicology data. This assessment has been superceded by a recent National Academy of Science (NAS) review that derived a perchlorate RfD that is 20-fold greater (less stringent) than that derived by the U.S. EPA in 2002. The NAS-derived RfD was put on the U.S. EPA's Integrated Risk Information System (IRIS) database very quickly and with no further public review. In this commentary we raise concerns about the NAS approach to RfD development in three areas of toxicity assessment: the dose that the NAS described as a no observable adverse-effect level is actually associated with perchlorate-induced effects; consideration of uncertainties was insufficient; and the NAS considered the inhibition of iodine uptake to be a nonadverse effect. We conclude that risk assessors should carefully evaluate whether the IRIS RfD is the most appropriate value for assessing perchlorate risk.

  20. Perchlorate Exposure and Thyroid Function in Ammonium Perchlorate Workers in Yicheng, China

    Directory of Open Access Journals (Sweden)

    Hongxia Chen

    2014-05-01

    Full Text Available The impact of low level dust on the thyroid function of workers chronically exposed to ammonium perchlorate (AP is uncertain and controversial. The aim of this study was to examine whether workers in China with long-term (>3 years occupational exposure to low levels of AP dust had affected thyroid homeostasis. Mean occupational exposures to AP dust ranged from 0.43 to 1.17 mg/m3. Geometric means of post-shift urinary perchlorate levels were 20.5 µg/L for those exposed and 12.8 µg/L for the controls. No significant differences were found for thyroid function parameters of FT3, FT4, or log TSH or for TPO prevalence or thyroglobulin levels. Additionally, no differences in findings were observed for complete blood count (CBC, serum biochemical profile, or pulmonary function test. Median urinary iodine levels of 172 and 184 µg/L showed that the workers had sufficient iodine intake. This study found no effect on thyroid function from long term, low-level documented exposure to ammonium perchlorate. It is the first study to report both thyroid status parameters and urinary perchlorate, a biomarker of internal perchlorate exposure, in occupationally exposed workers in China.

  1. Crystal structure of tin(II perchlorate trihydrate

    Directory of Open Access Journals (Sweden)

    Erik Hennings

    2014-12-01

    Full Text Available The title compound, [Sn(H2O3](ClO42, was synthesized by the redox reaction of copper(II perchlorate hexahydrate and metallic tin in perchloric acid. Both the trigonal–pyramidal [Sn(H2O3]2+ cations and tetrahedral perchlorate anions lie on crystallographic threefold axes. In the crystal, the cations are linked to the anions by O—H...O hydrogen bonds, generating (001 sheets.

  2. Dysprosium-containing layered double hydroxides nanoparticles intercalated with biologically active species as an approach for theranostic systems

    KAUST Repository

    Arratia-Quijada, Jenny

    2015-10-23

    A layered double hydroxide structure including dysprosium cations was prepared by co-precipitation. The nanoparticles showed a linear relationship with the reciprocal relaxation spin-lattice (T1) time of water protons which is reflected as contrast in aqueous suspensions analyzed by magnetic resonance imaging. The interlayer space of dysprosium containing LDH was successfully intercalated with folate, ibuprofen and gallate ions, which are key molecules for recognition of some cancer cells and treatment of diseases. The paramagnetic property of the dysprosium-containing LDH detected in this work beside the ability to transport drugs open up the opportunity to design theranostic materials in a single crystal phase with nanometric dimensions.

  3. Evidence for the distribution of perchlorates on Mars

    Science.gov (United States)

    Clark, Benton C.; Kounaves, Samuel P.

    2016-10-01

    Various Mars missions have detected Cl atoms, chlorides and perchlorates in martian surface materials. The global soils, in particular, always contain significant levels of observable Cl. Direct evidence points to this Cl being in the form of both chlorides and perchlorates, and possibly also chlorates and other oxychlorines. The most widespread measurements have been of Cl atoms, and cannot discern the chemical form. However, from separate evidence of perchlorate obtained at high latitudes (Phoenix lander) and low latitudes (Curiosity rover), it is likely that perchlorates are widespread, albeit in varying proportions relative to the total amount of ubiquitous Cl.

  4. Atmospheric Production of Perchlorate on Earth and Mars

    Science.gov (United States)

    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).

  5. Effects of Dysprosium Oxide Doping on Microstructure and Properties of Barium Titanate Ceramic

    Institute of Scientific and Technical Information of China (English)

    Pu Yongping; Ren Huijun; Chen Wei; Chen Shoutian

    2005-01-01

    Different amounts of dysprosium oxide were incorporated into barium titanate powders synthesized by hydrothermal method. Relations of substitution behaviors and lattice parameters with solid-solubility were studied. Furthermore, the influences of dysprosium oxide doping fraction on grain size and dielectric properties of barium titanate ceramic, including dielectric constant and breakdown electric field strength, were investigated via scanning electron microscope, X-ray diffraction and electric property tester. The results show that dysprosium oxide can restrain abnormal grain growth during sintering and that fine-grained and high density of barium titanate ceramic can result in excellent dielectric properties. As mass fraction of dysprosium oxide is 0.6%, the lattice parameters of grain increase to the maximum because of the lowest vacancy concentration. The electric property parameters are cited as following: dielectric constant (25 ℃) reaches 4100, the change in relative dielectric constant with temperature is -10% to 10% within the range of -15~100 ℃, breakdown electric field strength (alternating current) achieves 3.2 kV·mm-1, which can be used in manufacturing high voltage ceramic capacitors.

  6. Sandwich-type tetrakis(phthalocyaninato) dysprosium-cadmium quadruple-decker SMM.

    Science.gov (United States)

    Wang, Hailong; Qian, Kang; Wang, Kang; Bian, Yongzhong; Jiang, Jianzhuang; Gao, Song

    2011-09-14

    Homoleptic tetrakis[2,3,9,10,16,17,23,24-octa(butyloxy)phthalocyaninato] dysprosium-cadmium quadruple-decker complex 1 was isolated in relatively good yield of 43% from a simple one-pot reaction. This compound represents the first sandwich-type tetrakis(phthalocyaninato) rare earth-cadmium quadruple-decker SMM that has been structurally characterized.

  7. In situ characterization of the nitridation of dysprosium during mechanochemical processing

    Energy Technology Data Exchange (ETDEWEB)

    Jaques, Brian J.; Osterberg, Daniel D.; Alanko, Gordon A.; Tamrakar, Sumit; Smith, Cole R.; Hurley, Michael F.; Butt, Darryl P., E-mail: DarrylButt@BoiseState.edu

    2015-01-15

    Highlights: • A nitridation reaction in a high energy planetary ball mill was monitored in situ. • Dysprosium mononitride was synthesized from Dy at low temperatures in short times. • Ideal gas law and in situ temperature and pressure used to assess reaction extent. • It is proposed that reaction rate is proportional to the creation of new surface. - Abstract: Processing of advanced nitride ceramics traditionally requires long durations at high temperatures and, in some cases, in hazardous atmospheres. In this study, dysprosium mononitride (DyN) was rapidly formed from elemental dysprosium in a closed system at ambient temperatures. An experimental procedure was developed to quantify the progress of the nitridation reaction during mechanochemical processing in a high energy planetary ball mill (HEBM) as a function of milling time and intensity using in situ temperature and pressure measurements, SEM, XRD, and particle size analysis. No intermediate phases were formed. It was found that the creation of fresh dysprosium surfaces dictates the rate of the nitridation reaction, which is a function of milling intensity and the number of milling media. These results show clearly that high purity nitrides can be synthesized with short processing times at low temperatures in a closed system requiring a relatively small processing footprint.

  8. Perchlorate Remediation Using New Nanoscale Polymer Technology

    Science.gov (United States)

    2009-11-01

    conditions to give a total of 101 g product. Reduce Amount of Reagents The propargyl tosylate initiated PEOX was analyzed for acetylene content. There...the copper(I) catalyzed reaction between azide functional groups (-N3) and propargyl or acetylenic functional groups (-C≡C-), has become a major...available at an affordable price . This potential perchlorate binding site was reacted with PEOX DP= 100 as a model compound in methanol. 1H-NMR and SEC

  9. Monitored Natural Attenuation of Perchlorate in Groundwater

    Science.gov (United States)

    2010-09-01

    Center ORP oxidation-reduction potential P&T pump-and-treat pcrA perchlorate reductase RAO remedial action objective SCM site conceptual... SCM ) should be formulated and then calibrated against local data. Physical conditions of the aquifer, groundwater flow characteristics (e.g., flow...8 disadvantage . Flushing and dilution can reduce concentrations rapidly, but solubility can result in extended plumes with low concentrations that

  10. Dysprosium complexes with the tetraphenylporphyrin macrocyclic ligand; Complejos de disprosio con el ligante macrociclico tetrafenilporfirina

    Energy Technology Data Exchange (ETDEWEB)

    Martinez M, V.; Padilla, J.; Ramirez, F.M

    1992-04-15

    In this report, the results obtained on the synthesis, characterization and study of the chemical behavior of dysprosium complex with the acetylacetone chelating agent (Hacac) and the tetraphenylporphyrin macrocyclic ligand (H{sub 2}TFP) are given. Based on the literature but according to our necessities and interest, the appropriate methodology settled down from the synthesis of prime matters until the obtaining and characterization of the products. The acetyl acetonate complex was obtained of mono hydrated dysprosium [Dy(acac){sub 3}. H{sub 2}0] and trihydrated [Dy(acac){sub 3} .3 H{sub 2}0], the mono tetra phenyl porphyrinate [Dy(TFP)(acac). 2 ac] the double sandwich of the dysprosium porphyrinate [Dy(TFP){sub 2}] and the triple sandwich of the dysprosium porphyrinate [Dy(TFP){sub 3}. 2 TCB] (TCB = trichlorobenzene). Its were characterized by their melting points, solubility, IR, UV, TGA and DTA both first and besides the techniques already mentioned for NMR'H, RPE and Magnetic susceptibility the three last complexes. From the spectroscopic point of view, IR and RPE its suggested the existence of a complex of inverse mixed valence [Dy(TFP){sup 2-} (TFP) {sup 1-}] for the Dy(TFP){sub 2} as a result of the existence of the free radical (TFP' {sup 1-} and that it was not in none of the other porphyrin compounds. In the NMR'H spectra of the compounds were not observed signals in the region from 0 to 10 ppm that which shows that the dysprosium complexes in special those of the porphyrin type are highly paramagnetic and its could be used as displacement reagents, creators of images and contrast agents of great utility in these days in studies of NMR, technique today by today used in medical diagnoses. (Author)

  11. Synthesis, structural characterization and in vitro testing of dysprosium containing silica particles as potential MRI contrast enhancing agents

    Science.gov (United States)

    Chiriac, L. B.; Trandafir, D. L.; Turcu, R. V. F.; Todea, M.; Simon, S.

    2016-11-01

    The work is focused on synthesis and structural characterization of novel dysprosium-doped silica particles which could be considered as MRI contrast agents. Sol-gel derived silica rich particles obtained via freeze-drying and spray-drying processing methods were structurally characterized by XRD, 29Si MAS-NMR and XPS methods. The occurrence of dysprosium on the outermost layer of dysprosium containing silica particles was investigated by XPS analysis. The MRI contrast agent characteristics have been tested using RARE-T1 and RARE-T2 protocols. The contrast of MRI images delivered by the investigated samples was correlated with their local structure. Dysprosium disposal on microparticles with surface structure characterised by decreased connectivity of the silicate network units favours dark T2-weighted MRI contrast properties.

  12. Dysprosium-containing layered double hydroxides nanoparticles intercalated with biologically active species as an approach for theranostic systems

    Energy Technology Data Exchange (ETDEWEB)

    Arratia-Quijada, Jenny [Departamento de Ciencias de la Salud, Centro Universitario Tonalá, Universidad de Guadalajara, Av. Nuevo Periférico No. 555, C.P. 48525, Tonalá, Jalisco (Mexico); Sánchez Jiménez, Cecilia [Departamento de Química, Universidad de Guadalajara, Boulevard Marcelino García Barragán 1421, C.P. 44430, Guadalajara, Jalisco (Mexico); Gurinov, Andrey [Research Resources Center for Magnetic Resonance, St. Petersburg State University, Universitetskiy pr. 26, 198504 St. Petersburg (Russian Federation); NMR Core Lab, King Abdullah University of Science and Technology, Thuwal 23955-6900 (Saudi Arabia); Pérez Centeno, Armando; Ceja Andrade, Israel [Departamento de Física, Universidad de Guadalajara, Boulevard Marcelino García Barragán 1421, C.P. 44430, Guadalajara, Jalisco (Mexico); Carbajal Arízaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.mx [Departamento de Química, Universidad de Guadalajara, Boulevard Marcelino García Barragán 1421, C.P. 44430, Guadalajara, Jalisco (Mexico)

    2016-01-15

    Graphical abstract: - Highlights: • LDH structure including dysprosium was prepared by co-precipitation. • LDH was capable to produce contrast in the T1 mode of MRI. • LDH were intercalated with folate, ibuprofen and gallate ions. - Abstract: A layered double hydroxide structure including dysprosium cations was prepared by co-precipitation. The nanoparticles showed a linear relationship with the reciprocal relaxation spin-lattice (T1) time of water protons which is reflected as contrast in aqueous suspensions analyzed by magnetic resonance imaging. The interlayer space of dysprosium containing LDH was successfully intercalated with folate, ibuprofen and gallate ions, which are key molecules for recognition of some cancer cells and treatment of diseases. The paramagnetic property of the dysprosium-containing LDH detected in this work beside the ability to transport drugs open up the opportunity to design theranostic materials in a single crystal phase with nanometric dimensions.

  13. Slow magnetic relaxation in a hydrogen-bonded 2D array of mononuclear dysprosium(III) oxamates.

    Science.gov (United States)

    Fortea-Pérez, Francisco R; Vallejo, Julia; Julve, Miguel; Lloret, Francesc; De Munno, Giovanni; Armentano, Donatella; Pardo, Emilio

    2013-05-01

    The reaction of N-(2,6-dimethylphenyl)oxamic acid with dysprosium(III) ions in a controlled basic media afforded the first example of a mononuclear lanthanide oxamate complex exhibiting a field-induced slow magnetic relaxation behavior typical of single-ion magnets (SIMs). The hydrogen-bond-mediated self-assembly of this new bifunctional dysprosium(III) SIM in the solid state provides a unique example of 2D hydrogen-bonded polymer with a herringbone net topology.

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

    NARCIS (Netherlands)

    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

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

    NARCIS (Netherlands)

    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

  16. Validation of Chlorine and Oxygen Isotope Ratio Analysis to Differentiate Perchlorate Sources and to Document Perchlorate Biodegradation

    Science.gov (United States)

    2011-12-01

    67 ii 4.5 SUMMARY OF LONG ISLAND PERCHLORATE SOURCE STUDY .......................... 67 5.0 SUMMARY AND CONCLUSIONS...Chilean nitrate fertilizer. 4.5 SUMMARY OF LONG ISLAND PERCHLORATE SOURCE STUDY The stable isotope results (δ37Cl, δ18O, and Δ17O) for ClO4- and key

  17. Alternative Causes of Wide-Spread, Low Concentration Perchlorate Impacts to Groundwater

    Science.gov (United States)

    2007-11-02

    substances such as titanium slags Acid digestion Ammonium perchlorate, high purity metal perchlorates Starting material for the manufacture of pure...ammonium perchlorate and in the production of high purity metal perchlorates Pickling and passivation of iron and steels Oxidant Determination of...Potassium Nitrate 13 White Sparks Potassium Perchlorate 42.1 Titanium 42.1 Dextrine 15.8 White Sparks “water fall” Potassium

  18. Dysprosium-Catalyzed Growth of Single-Walled Carbon Nanotube Arrays on Substrates

    Directory of Open Access Journals (Sweden)

    Qian Yong

    2009-01-01

    Full Text Available Abstract In this letter, we report that dysprosium is an effective catalyst for single-walled carbon nanotubes (SWNTs growth via a chemical vapor deposition (CVD process for the first time. Horizontally superlong well-oriented SWNT arrays on SiO2/Si wafer can be fabricated by EtOH-CVD under suitable conditions. The structure and properties are characterized by scanning electron microscopy, transition electron microscopy, Raman spectroscopy and atomic force microscopy. The results show that the SWNTs from dysprosium have better structural uniformity and better conductivity with fewer defects. This rare earth metal provides not only an alternative catalyst for SWNTs growth, but also a possible method to generate high percentage of superlong semiconducting SWNT arrays for various applications of nanoelectronic device.

  19. Direct Search for keV Sterile Neutrino Dark Matter with a Stable Dysprosium Target

    CERN Document Server

    Lasserre, T; Cribier, M; Merle, A; Mertens, S; Vivier, M

    2016-01-01

    We investigate a new method to search for keV-scale sterile neutrinos that could account for Dark Matter. Neutrinos trapped in our galaxy could be captured on stable $^{163}$Dy if their mass is greater than 2.83~keV. Two experimental realizations are studied, an integral counting of $^{163}$Ho atoms in dysprosium-rich ores and a real-time measurement of the emerging electron spectrum in a dysprosium-based detector. The capture rates are compared to the solar neutrino and radioactive backgrounds. An integral counting experiment using several kilograms of $^{163}$Dy could reach a sensitivity for the sterile-to-active mixing angle $\\sin^2\\theta_{e4}$ of $10^{-5}$ significantly exceeding current laboratory limits. Mixing angles as low as $\\sin^2\\theta_{e4} \\sim 10^{-7}$ / $\\rm m_{^{163}\\rm Dy}\\rm{(ton)}$ could possibly be explored with a real-time experiment.

  20. Preparation of Dysprosium Ferrite/Polyacrylamide Magnetic Composite Microsphere and Its Characterization

    Institute of Scientific and Technical Information of China (English)

    Hidehiro Kumazawa; Wang Zhifeng; Zhou Lanxiang; Zhang Hong; Li Yourong; Zhang Ming

    2005-01-01

    Using the technique of microemulsion polymerization with nano-reactor, dysprosium ferrite/polyacrylamide magnetic composite microsphere was prepared by one-step method in a single inverse microemulsion. The structure, average particle size, morphology of composite microsphere were characterized by FTIR, XRD, TEM and TGA. The magnetic responsibility of composite microsphere was also investigated. The results indicate that the magnetic composite microsphere possess high magnetic responsibility and suspension stability.

  1. {Delta}I = 2 energy staggering in normal deformed dysprosium nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Riley, M.A.; Brown, T.B.; Archer, D.E. [Florida State Univ., Tallahassee, FL (United States)] [and others

    1996-12-31

    Very high spin states (I{ge}50{Dirac_h}) have been observed in {sup 155,156,157}Dy. The long regular band sequences, free from sharp backbending effects, observed in these dysprosium nuclei offer the possibility of investigating the occurence of any {Delta}I = 2 staggering in normal deformed nuclei. Employing the same analysis techniques as used in superdeformed nuclei, certain bands do indeed demonstrate an apparent staggering and this is discussed.

  2. Poly[[[μ3-N′-(carboxymethylethylenediamine-N,N,N′-triacetato]dysprosium(III] trihydrate

    Directory of Open Access Journals (Sweden)

    Xiaomei Zhuang

    2010-11-01

    Full Text Available In the title coordination polymer, {[Dy(C10H13N2O8]·3H2O}n, the dysprosium(III ion is coordinated by two N atoms and six O atoms from three different (carboxymethylethylenediaminetriacetate ligands in a distorted square-antiprismatic geometry. The ligands connect the metal atoms, forming layers parallel to the ab plane. O—H...O hydrogen bonds further assemble adjacent layers into a three-dimensional supramolecular network.

  3. Making two dysprosium atoms rotate - Einstein-de Haas effect revisited

    OpenAIRE

    Górecki, Wojciech; Rzążewski, Kazimierz

    2016-01-01

    We present a numerical study of the behaviour of two magnetic dipolar atoms trapped in a harmonic potential and exhibiting the standard Einstein-de Haas effect while subject to a time dependent homogeneous magnetic field. Using a simplified description of the short range interaction and the full expression for the dipole-dipole forces we show, that under experimentally realisable conditions two dysprosium atoms may be pumped to a high ($l>20$) value of the relative orbital angular momentum.

  4. Phosphor Dysprosium-Doped Layered Double Hydroxides Exchanged with Different Organic Functional Groups

    Directory of Open Access Journals (Sweden)

    David Ricardo Martínez Vargas

    2013-01-01

    Full Text Available The layers of a Zn/Al layered double hydroxide (LDH were doped with Dy3+ cations. Among some compositions, the Zn2+ : Al3+ : Dy3+ molar ratio equal to 30 : 9 : 1 presented a single crystalline phase. Organic anions with carboxylic, amino, sulfate, or phosphate functional groups were intercalated as single layers between LDH layers as confirmed by X-ray diffraction and infrared spectroscopy. Photoluminescence spectra of the nitrate intercalated LDH showed a wide emission band with strong intensity in the yellow region (around 574 nm, originated due to symmetry distortion of the octahedral coordination in dysprosium centers. Moreover, a broad red band emission was also detected apparently due to the presence of zinc oxide. The distorted symmetry of the dysprosium coordination environment, also confirmed by X-ray photoelectron spectroscopy analysis, was modified after the intercalation with phenyl phosphonate (PP, aspartate (Asp, adipate (Adip, and serinate (Ser anions; the emission as measured from PL spectra of these LDH was more intense in the blue region (ca. 486 nm, thus indicating an increase in symmetry of dysprosium octahedrons. The red emission band from zinc oxide kept the same intensity after intercalation of dodecyl sulfate (DDS. An additional emission of unknown origin at λ = 767 nm was present in all LDHs.

  5. Perchlorates as Powerful Catalysts in Many Important Organic Transformations

    Institute of Scientific and Technical Information of China (English)

    G. Bartoli; L. Sambri; M. Locatelli

    2005-01-01

    @@ 1Introduction For long times, metallic perchlorates have been considered dangerous compounds[1] in that they function as explosives and as incontrollable oxidizers. Therefore, the fear of the great hazard connected with their manufacture and uses had prevented an extensive use both in research laboratories and in industrial processes[2].However, recently it has been cleared that this bad reputation is due to the mistaken association of metallic perchlorates with the oxidizing potential of perchloric acid and the pyrotechnic performances of NH4ClO4.

  6. Systematic study on surface and magnetostructural changes in Mn-substituted dysprosium ferrite by hydrothermal method

    Energy Technology Data Exchange (ETDEWEB)

    Rekha, G. [Department of Physics, College of Engineering Guindy, Anna University, Sardar Patel Road, Chennai 600025 (India); Tholkappiyan, R. [Department of Physics, College of Engineering Guindy, Anna University, Sardar Patel Road, Chennai 600025 (India); Department of Physics, College of Science, UAE University, Al-Ain 15551 (United Arab Emirates); Vishista, K., E-mail: raovishista@gmail.com [Department of Physics, College of Engineering Guindy, Anna University, Sardar Patel Road, Chennai 600025 (India); Hamed, Fathalla [Department of Physics, College of Science, UAE University, Al-Ain 15551 (United Arab Emirates)

    2016-11-01

    Highlights: • Garnet type Dy{sub 3}Fe{sub 5-x}Mn{sub x}O{sub 12} (x = 0–0.06) nanoparticles of 88.4–86.8 nm were synthesized by hydrothermal method. • The Dy, Mn, Fe and O elements in the ferrites were confirmed from XPS. • The multiple oxidation states of Fe and Mn ions, bonding energy and cationic distributions of the samples were examined by XPS. • The magnetic property shows ferromagnetic behavior from VSM technique. • The results from these studies are correlated with respect to Mn dopant. - Abstract: Dysprosium iron garnets are of scientific importance because of the wide range of magnetic properties that can be obtained in substituting dysprosium by a rare earth metal. In the present work, the effect of Mn substitution on magnetostructural changes in dysprosium ferrite nanoparticles is studied. Highly crystalline pure and Mn doped dysprosium ferrite nanoparticles were synthesized by hydrothermal method. The samples were calcined at 1100 °C for 2 h in air atmosphere which is followed by characterization using XRD, FT-IR analysis, SEM, XPS and VSM. The average crystallite size of synthesized samples were calculated by X-ray diffraction falls in the range of 88.4–86.8 nm and was found to be in cubic garnet structure. For further investigation of the structure and corresponding changes in the tetrahedral and octahedral stretching vibrational bonds, FT-IR was used. The synthesized samples consist of multiple oxidation (Fe{sup 3+} and Fe{sup 2+}) states for Fe ions and (Mn{sup 3+} and Mn{sup 2+}) Mn ions analyzed in three ways of Fe 2p and Mn 2p spectra from the XPS analysis. With respect to Mn dopant in Dy{sub 3}Fe{sub 5}O{sub 12}, the cationic distributions of elements were discussed from high resolution XPS spectra by peak position and shift, area, width. To find out the porous/void surface morphology of the sample, scanning electron microscopy was used. From XPS analysis, the presence of elements (Dy, Mn, Fe and O) and their composition in the

  7. Synthesis, structural characterization and in vitro testing of dysprosium containing silica particles as potential MRI contrast enhancing agents

    Energy Technology Data Exchange (ETDEWEB)

    Chiriac, L.B.; Trandafir, D.L. [Faculty of Physics & National Magnetic Resonance Center, Babeş-Bolyai University, Cluj-Napoca, RO-400084 (Romania); Interdisciplinary Research Institute on Bio-Nano-Sciences & Faculty of Physics, Babeş-Bolyai University, Cluj-Napoca, RO-400084 (Romania); Turcu, R.V.F. [Faculty of Physics & National Magnetic Resonance Center, Babeş-Bolyai University, Cluj-Napoca, RO-400084 (Romania); Todea, M. [Interdisciplinary Research Institute on Bio-Nano-Sciences & Faculty of Physics, Babeş-Bolyai University, Cluj-Napoca, RO-400084 (Romania); Simon, S., E-mail: simons@phys.ubbcluj.ro [Faculty of Physics & National Magnetic Resonance Center, Babeş-Bolyai University, Cluj-Napoca, RO-400084 (Romania); Interdisciplinary Research Institute on Bio-Nano-Sciences & Faculty of Physics, Babeş-Bolyai University, Cluj-Napoca, RO-400084 (Romania)

    2016-11-01

    Highlights: • Dysprosium containing silica microparticles obtained by freeze and spray drying. • Higher structural units interconnection achieved in freeze vs. spray dried samples. • Dy occurance on the outermost layer of the microparticles evidenced by XPS. • Enhanced MRI contrast observed for freeze dried samples with 5% mol Dy{sub 2}O{sub 3}. - Abstract: The work is focused on synthesis and structural characterization of novel dysprosium-doped silica particles which could be considered as MRI contrast agents. Sol-gel derived silica rich particles obtained via freeze-drying and spray-drying processing methods were structurally characterized by XRD, {sup 29}Si MAS-NMR and XPS methods. The occurrence of dysprosium on the outermost layer of dysprosium containing silica particles was investigated by XPS analysis. The MRI contrast agent characteristics have been tested using RARE-T{sub 1} and RARE-T{sub 2} protocols. The contrast of MRI images delivered by the investigated samples was correlated with their local structure. Dysprosium disposal on microparticles with surface structure characterised by decreased connectivity of the silicate network units favours dark T{sub 2}-weighted MRI contrast properties.

  8. POLISHING THE EFFLUENT FROM AN ANAEROBIC BIOLOGICAL PERCHLORATE TREATMENT PROCESS

    Science.gov (United States)

    Anaerobic biological processes effectively reduce perchlorate to chloride. However, the effluent can be biologically unstable, high in particulates and high in disinfection by-product precursor compounds. Such an effluent would be unsuitable for transmission into a drinking water...

  9. Assembled cross-species perchlorate dose-response data

    Data.gov (United States)

    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...

  10. High pressure studies of potassium perchlorate

    Science.gov (United States)

    Pravica, Michael; Wang, Yonggang; Sneed, Daniel; Reiser, Sharissa; White, Melanie

    2016-09-01

    Two experiments are reported on KClO4 at extreme conditions. A static high pressure Raman study was first conducted to 18.9 GPa. Evidence for at least two new phases was observed: one between 2.4 and 7.7 GPa (possibly sluggish), and the second near 11.7 GPa. Then, the X-ray induced decomposition rate of potassium perchlorate (KClO4 → hν KCl + 2O2) was studied up to 15.2 GPa. The time-dependent growth of KCl and O2 was monitored. The decomposition rate slowed at higher pressures. We present the first direct evidence for O2 crystallization at higher pressures, demonstrating that O2 molecules aggregate at high pressure.

  11. Dimethylammonium perchlorate 18-crown-6 monohydrate clathrate

    Directory of Open Access Journals (Sweden)

    Jia-Zhen Ge

    2010-07-01

    Full Text Available The reaction of dimethylamine, 18-crown-6, and perchloric acid in methanol yields the title compound, C2H8N+·ClO4−·C12H24O6·H2O. The dimethylammonium cation and the water molecule interact with the 18-crown-6 unit: N—H...O hydrogen bonds are formed between the ammonium NH2+ group and four O atoms of the crown ether, while the water molecule on the other side of 18-crown-6 ring forms O—H...O hydrogen bonds with two other O atoms of the crown ether. All conventional donors and acceptors in the cations are thus engaged in hydrogen bonding. The ClO4− anion is disordered over two sites, and occupancies for the disordered O atoms were fixed at 0.5. In the crystal, the cations and anions are arranged in alternating layers.

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

    Science.gov (United States)

    2011-03-06

    technology combines ion exchange and electrochemistry to provide a selective and reversible method for removing target species from wastewater. In...nanotube nanocomposite for removing perchlorate from drinking water and wastewater. The ESIX technology combines ion exchange and electrochemistry to...potential for perchlorate occurrence in drinking water and food supplies is a human health concern because it can interfere with iodide uptake by the

  13. Engineered Intrinsic Bioremediation of Ammonium Perchlorate in Groundwater

    Science.gov (United States)

    2010-12-01

    synthetic symbiotic ecosystem. IET Syst. Biol. 2:33–38 Keller, L. and Surette, M.G. 2006. Communication in bacteria : an ecological and...degradation involves perchlorate reducing bacteria (PRBs), which are widespread in the environment. PRBs have the ability to grow in either the presence...LIST OF TABLES TABLE 1. EXAMPLES OF KNOWN PERCHLORATE- AND CHLORATE-DEGRADING BACTERIA , USED IN THE GA OPTIMIZATION EXPERIMENT

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

    Science.gov (United States)

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

    2016-04-22

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

  15. Determination of Perchlorate in Bottled Water from Italy

    Directory of Open Access Journals (Sweden)

    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.

  16. Thermal and Evolved Gas Analysis of Magnesium Perchlorate: Implications for Perchlorates in Soils at the Mars Phoenix Landing Site

    Science.gov (United States)

    Ming, Douglas W.; Morris, R.V.; Lauer, H. V.; Sutter, B.; Golden, D.C.; Boynton, W.V.

    2009-01-01

    Perchlorate salts were discovered in the soils around the Phoenix landing site on the northern plains of Mars [1]. Perchlorate was detected by an ion selective electrode that is part of the MECA Wet Chemistry Laboratory (WCL). The discovery of a mass 32 fragment (likely 02) by the Thermal and Evolved-Gas Analyzer (TEGA) provided additional confirmation of a strong oxidizer in the soils around the landing site. The purpose of this paper is to evaluate the thermal and evolved gas behavior of perchlorate salts using TEGA-like laboratory testbed instruments. TEGA ovens were fabricated from high purity Ni. Hence, an additional objective of this paper is to determine the effects that Ni might have on the evolved gas behavior of perchlorate salts.

  17. Perchlorate in The Great Lakes: Distribution, Isotopic Composition and Origin

    Science.gov (United States)

    Poghosyan, A.; Sturchio, N. C.; Jackson, W. A.; Guan, Y.; Eiler, J. M.; Hatzinger, P. B.

    2013-12-01

    Concentrations, stable chlorine and oxygen isotopic compositions, and 36Cl abundances of perchlorate were investigated in the five Laurentian Great Lakes. Samples were collected during monitoring cruises in 2007 and 2008 of the U.S. EPA's RV Lake Guardian and in 2010 at the water supply intake of Marquette, MI on the southern shore of Lake Superior. Concentrations of perchlorate were measured by IC/MS/MS at 24 locations, including one or two depth profiles in each lake. Mean concentrations (μg/L) are: Superior, 0.06 × 0.01; Michigan, 0.10 × 0.01; Huron, 0.11 × 0.01; Erie, 0.08 × 0.01, and Ontario, 0.09 × 0.01. Concentration vs. depth is nearly constant in each lake, indicating well-mixed conditions. Perchlorate was extracted from near-surface water by passing 15,000 to 80,000 L of water through 1-L cartridges containing Purolite A530E bifunctional anion-exchange resin. In the laboratory, perchlorate was eluted from the resin, purified, and precipitated as a >99% pure crystalline phase. Milligram amounts were recovered from each lake. Chlorine and oxygen isotopic analyses were performed at Caltech using the Cameca 7f-GEO SIMS instrument, following validation of the SIMS method with analyses of USGS-37 and USGS-38 isotopic reference materials. Results indicate a relatively narrow range in δ37Cl values (+2.9 to +3.9 ‰) and a wider range in δ18O values (-4.0 to +4.1 ‰), with a general geographic trend of increasing δ18O from west to east. Oxygen-17 was measured at UIC using dual-inlet IRMS of O2 produced by decomposition of KClO4. Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ17O values (+1.6 ‰ to +2.7 ‰) divided into two distinct groups: Lake Superior (+2.7 ‰) and the other four lakes (~ +1.7 ‰). The isotopic data indicate that perchlorate is dominantly of natural origin, having stable isotopic compositions resembling those of perchlorate from pre-industrial groundwaters in the western USA. The 36Cl

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Influence of exchange splitting on optical properties in gadolinium and dysprosium single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Knyazev, Yu.V.; Bolotin, G.A. (AN SSSR, Sverdlovsk. Inst. Fiziki Metallov)

    1984-12-01

    The temperature dependences of optical conductivity in gadolinium and dysprosium single crystals at the light wave vector polarization along a hexagonal axis and in the basis plane are considered. A substantial anisotropy of interzonal absorption has been found. The sample transition into magnetically ordered state is shown to be accompanied by the emergence of resonance absorption peaks in the near infrared spectral region. The manifestation of these peculiarities is associated with quantum electron transitions between the s-, d-f- interaction-split energy bands near the Fermi level. Main peculiarities of the experimental spectrum of gadolinium optical conductivity found their reflection in theoretically calculated dispersion dependence.

  1. Therapeutic application of dysprosium-165-FHMA in the treatment of rheumatoid knee effusions

    Energy Technology Data Exchange (ETDEWEB)

    English, R.J.; Zalutsky, M.; Venkatesan, P.; Sledge, C.B.

    1986-03-01

    Radiation synovectomy utilizing a variety of radionuclides has proven to be an effective technique in the treatment of rheumatoid arthritis. The recent introduction of the short-lived radionuclide, Dysprosium-165 (/sup 165/Dy), as a replacement for the longer-lived radiocolloids has reduced nontarget dosimetry caused by leakage of the agent from the articular cavity. A review of the methods and status of radiation synovectomy, and the application of /sup 165/Dy-ferric hydroxide macroaggregates (FHMA) as an alternative therapeutic agent is described.

  2. Properties of dysprosium-doped gallium lanthanum sulfide fiber amplifiers operating at 1.3 microm.

    Science.gov (United States)

    Samson, B N; Schweizer, T; Hewak, D W; Laming, R I

    1997-05-15

    In light of recent progress in the fabrication of gallium lanthanum sulfide (GaLaS) fibers, we have modeled the performance of dysprosium-doped GaLaS fiber amplifiers operating at 1.3 microm . Based on experimental data, we find that the incorporation of a codopant (terbium) in the fiber core significantly shortens the optimum amplifier length from >30 m to approximately 3 m . Such a device may be practical, given the fiber losses currently achieved in GaLaS fibers.

  3. Oxygen and Chlorine Isotopic Fractionation During Microbial Reduction of Perchlorate

    Science.gov (United States)

    Beloso, A. D.; Sturchio, N. C.; Böhlke, J. K.; Streger, S. H.; Heraty, L. J.; Hatzinger, P. B.

    2006-12-01

    Perchlorate is a widespread environmental contaminant that has both anthropogenic and natural sources. Stable isotope ratios of O and Cl in perchlorate have been used recently to distinguish perchlorate of different origins. Isotopic ratios may also be useful for identifying the occurrence and extent of biodegradation of perchlorate in natural environments, information that is critical for assessing natural attenuation of this contaminant. For this approach to be useful, however, the extent of isotopic fractionation of both Cl and O by bacteria must be determined, and the influence of environmental variables on this process must be defined. During this laboratory study, the O and Cl isotope ratios of perchlorate were monitored as a function of degradation by two separate bacterial species (Azospira suillum JPLRND and Dechlorospirillum sp. FBR2) at both 10 °C and 22 °C with acetate as the electron donor. Perchlorate was completely degraded by both strains within 280 hr at 22 °C and 615 hr at 10 °C. Measured values of isotopic fractionation factors were ɛ18O = -36.6 to -29.0 ‰ and ɛ37Cl = -14.5 to - 11.5 ‰, and these showed no apparent systematic variation with either temperature or bacterial strain. One experiment using 18O-enriched water (δ18O = 200‰) gave results indistinguishable from those observed in isotopically normal water, indicating little or no isotopic exchange between perchlorate and water during biodegradation. The fractionation factor ratio ɛ18O/ɛ37Cl was nearly invariant in all experiments at 2.50 ± 0.04. These data indicate that isotopic analysis will be useful for documenting perchlorate biodegradation in soils and groundwater. The establishment of a microbial fractionation factor ratio (ɛ18O/ɛ37Cl) also has significance for forensic studies, as these data indicate that fractionation via biodegradation will not cause the reported mass-dependent Cl and O isotopic signatures of synthetic and natural perchlorate to overlap.

  4. Perchlorates are compatible with life on Earth: Why not Mars?

    Science.gov (United States)

    Kolb, Vera M.; Hoover, Richard

    2013-09-01

    Perchlorates have been found on the surface of Mars. Since they are strongly oxidizing, it is important to discuss how this fact is reflected both on the existence of organic compounds on the surface of Mars and possibly life. We have previously reported that perchlorates, although strongly oxidizing, do not destroy some amino acids, such as glycine and alanine, among others, and also spare other classes of organic compounds. Others have found that perchlorates are utilized by bacteria and Archaea as energy sources. Particularly important are the findings about Archaea, since they show a combination of a biotic and abiotic processing of perchlorates, which implies ancient origins of these pathways, which may have been typical on prebiotic Earth. There are also numerous reports of the presence of organohalogen compounds on Earth which are made by natural sources or living organisms. Such compounds may be simple, such as chloromethane, or very complicated. They are utilized or produced by living organisms on Earth. Significantly, some such compounds are extremely stable to high temperatures, over 400oC, which should be taken into account for the chemical analyses on Mars. Finally, organohalogen compounds have been also detected on the meteorites. This combined evidence indicates that eventual finding of the organohalogen compounds on Mars is expected, and that the presence of the strongly oxidizing perchlorates does not rule out life on Mars.

  5. PERCHLORATE-CROP INTERACTIONS FROM CONTAMINATED IRRIGATION WATER AND FERTILIZER APPLICATIONS

    Science.gov (United States)

    Perchlorate has contaminated water and soils at several locations in the United States. Perchlorate is water 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 un...

  6. A perchlorate sensitive iodide transporter in frogs.

    Science.gov (United States)

    Carr, Deborah L; Carr, James A; Willis, Ray E; Pressley, Thomas A

    2008-03-01

    Nucleotide sequence comparisons have identified a gene product in the genome database of African clawed frogs (Xenopus laevis) as a probable member of the solute carrier family of membrane transporters. To confirm its identity as a putative iodide transporter, we examined the function of this sequence after heterologous expression in mammalian cells. A green monkey kidney cell line transfected with the Xenopus nucleotide sequence had significantly greater (125)I uptake than sham-transfected control cells. The uptake in carrier-transfected cells was significantly inhibited in the presence of perchlorate, a competitive inhibitor of mammalian Na(+)/iodide symporter. Tissue distributions of the sequence were also consistent with a role in iodide uptake. The mRNA encoding the carrier was found to be expressed in the thyroid gland, stomach, and kidney of tadpoles from X. laevis, as well as the bullfrog Rana catesbeiana. The ovaries of adult X. laevis also were found to express the carrier. Phylogenetic analysis suggested that the putative X. laevis iodide transporter is orthologous to vertebrate Na(+)-dependent iodide symporters. We conclude that the amphibian sequence encodes a protein that is indeed a functional Na(+)/iodide symporter in X. laevis, as well as R. catesbeiana.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Effect of dysprosium on the kinetics and structural transformations during the decomposition of the supersaturated solid solution in magnesium-samarium alloys

    Science.gov (United States)

    Rokhlin, L. L.; Luk'yanova, E. A.; Tabachkova, N. Yu.; Dobatkina, T. V.; Tarytina, I. E.; Korol'kova, I. G.

    2017-03-01

    The effect of dysprosium added in the amounts such that it does not form an individual phase in equilibrium with solid magnesium on the decomposition of the supersaturated magnesium solid solution in Mg-Sm alloys is studied. The presence of dysprosium in Mg-Sm alloys is found to retard the decomposition of the supersaturated magnesium solid solution and to increase the hardening effect upon aging. When these alloys are aged, dysprosium is partly retained in the magnesium solid solution and partly enters into the compositions of the phases that form during the decomposition of the solid solution and are characteristic of Mg-Sm alloys.

  9. Cyclic single-molecule magnets: from the odd-numbered heptanuclear to a dimer of heptanuclear dysprosium clusters.

    Science.gov (United States)

    Tian, Haiquan; Bao, Song-Song; Zheng, Li-Min

    2016-02-01

    A heptanuclear and a dimer of heptanuclear dysprosium clusters (Dy7 and Dy14) have been successfully synthesized by ingenious coalescence of the single and double pyrazinyl hydrazone as well as phosphonate ligands. The complexes feature the largest odd-numbered cyclic lanthanide clusters reported thus far. Both exhibit single molecule magnet behaviors at low temperature.

  10. A comparison of the effects of symmetry and magnetoanisotropy on paramagnetic relaxation in related dysprosium single ion magnets.

    Science.gov (United States)

    Williams, Ursula J; Mahoney, Brian D; DeGregorio, Patrick T; Carroll, Patrick J; Nakamaru-Ogiso, Eiko; Kikkawa, James M; Schelter, Eric J

    2012-06-07

    Dysprosium complexes of the tmtaa(2-) ligand were synthesized and characterized by X-band EPR and magnetism studies. Both complexes demonstrate magnetoanisotropy and slow paramagnetic relaxation. Comparison of these compounds with the seminal phthalocyanine complex [Dy(Pc)(2)](-) shows the azaannulide complexes are more susceptible to relaxation through non-thermal pathways.

  11. Dual responsive dysprosium-doped hydroxyapatite particles and toxicity reduction after functionalization with folic and glucuronic acids

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez Lafarga, Ana Karen; Pacheco Moisés, Fermín P. [Departamento de Química, Universidad de Guadalajara, Marcelino García Barragán 1421, C.P. 44430, Guadalajara, Jalisco (Mexico); Gurinov, Andrey [Research Resources Center for Magnetic Resonance, Saint Petersburg State University, Universitetskij pr. 26, 198504 St. Petersburg (Russian Federation); Ortiz, Genaro Gabriel [Laboratorio Desarrollo-Envejecimiento, Enfermedades Neurodegenerativas, Centro de Investigación Biomédica de Occidente (CIBO), Instituto Mexicano de Seguro Social (IMSS), Guadalajara, Jalisco (Mexico); Carbajal Arízaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.mx [Departamento de Química, Universidad de Guadalajara, Marcelino García Barragán 1421, C.P. 44430, Guadalajara, Jalisco (Mexico)

    2015-03-01

    The development of probes for biomedical applications demands materials with low toxicity levels besides fluorescence or magnetic properties to be detected by confocal microscopes or MRI resonators. Several drug delivery systems or other biomedical materials prepared with hydroxyapatite have been proposed, however, toxicity effects might arise when the size of particles is nanometric. In this study, hydroxyapatite functionalized with glucuronic or folic acids presented lower oxidative stress, measured from lipoperoxides and nitric oxide indicators in rats than pure hydroxyapatite. In separated experiments, hydroxyapatite was doped with dysprosium cations by coprecipitation producing a single crystal phase with fluorescent properties easily visualized by confocal microscopy when excited at 488 nm. These particles also presented the ability to modify the proton relaxation time in T1 maps collected by magnetic resonance imaging. These modified hydroxyapatite nanoparticles could be candidates to design bimodal probes with low toxicity. - Highlights: • Hydroxyapatite functionalized with glucuronic acid reduced oxidative stress in rats. • Functionalization with folic acid reduced oxidative stress in rats. • Dysprosium doping does not affect the crystalline structure of hydroxyapatite. • Dysprosium doped particles are visible in fluorescent microscope. • Dysprosium doped particles act as MRI contrast agents.

  12. Tuning Slow Magnetic Relaxation in a Two-Dimensional Dysprosium Layer Compound through Guest Molecules.

    Science.gov (United States)

    Chen, Qi; Li, Jian; Meng, Yin-Shan; Sun, Hao-Ling; Zhang, Yi-Quan; Sun, Jun-Liang; Gao, Song

    2016-08-15

    A novel two-dimensional dysprosium(III) complex, [Dy(L)(CH3COO)]·0.5DMF·H2O·2CH3OH (1), has been successfully synthesized from a new pyridine-N-oxide (PNO)-containing ligand, namely, N'-(2-hydroxy-3-methoxybenzylidene)pyridine-N-oxidecarbohydrazide (H2L). Single-crystal X-ray diffraction studies reveal that complex 1 is composed of a dinuclear dysprosium subunit, which is further extended by the PNO part of the ligand to form a two-dimensional layer. Magnetic studies indicate that complex 1 shows well-defined temperature- and frequency-dependent signals under a zero direct-current (dc) field, typical of slow magnetic relaxation with an effective energy barrier Ueff of 33.6 K under a zero dc field. Interestingly, powder X-ray diffraction and thermogravimetric analysis reveal that compound 1 undergoes a reversible phase transition that is induced by the desorption and absorption of methanol and water molecules. Moreover, the desolvated sample [Dy(L)(CH3COO)]·0.5DMF (1a) also exhibits slow magnetic relaxation but with a higher anisotropic barrier of 42.0 K, indicating the tuning effect of solvent molecules on slow magnetic relaxation.

  13. Dosimetric properties of dysprosium doped calcium magnesium borate glass subjected to Co-60 gamma ray

    Energy Technology Data Exchange (ETDEWEB)

    Omar, R. S., E-mail: ratnasuffhiyanni@gmail.com; Wagiran, H., E-mail: husin@utm.my; Saeed, M. A. [Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, 81310 Johor Bahru (Malaysia)

    2016-01-22

    Thermoluminescence (TL) dosimetric properties of dysprosium doped calcium magnesium borate (CMB:Dy) glass are presented. This study is deemed to understand the application of calcium as the modifier in magnesium borate glass with the presence of dysprosium as the activator to be performed as TL dosimeter (TLD). The study provides fundamental knowledge of a glass system that may lead to perform new TL glass dosimetry application in future research. Calcium magnesium borate glass systems of (70-y) B{sub 2}O{sub 3} − 20 CaO – 10 MgO-(y) Dy{sub 2}O{sub 3} with 0.05  mol % ≤ y ≤ 0.7  mol % of dyprosium were prepared by melt-quenching technique. The amorphous structure and TL properties of the prepared samples were determined using powder X-ray diffraction (XRD) and TL reader; model Harshaw 4500 respectively. The samples were irradiated to Co-60 gamma source at a dose of 50 Gy. Dosimetric properties such as annealing procedure, time temperature profile (TTP) setting, optimization of Dy{sub 2}O{sub 3} concentration of 0.5 mol % were determined for thermoluminescence dosimeter (TLD) reader used.

  14. Direct measurement of perchlorate exposure biomarkers in a highly exposed population: a pilot study.

    Directory of Open Access Journals (Sweden)

    Paul English

    Full Text Available Exposure to perchlorate is ubiquitous in the United States and has been found to be widespread in food and drinking water. People living in the lower Colorado River region may have perchlorate exposure because of perchlorate in ground water and locally-grown produce. Relatively high doses of perchlorate can inhibit iodine uptake and impair thyroid function, and thus could impair neurological development in utero. We examined human exposures to perchlorate in the Imperial Valley among individuals consuming locally grown produce and compared perchlorate exposure doses to state and federal reference doses. We collected 24-hour urine specimen from a convenience sample of 31 individuals and measured urinary excretion rates of perchlorate, thiocyanate, nitrate, and iodide. In addition, drinking water and local produce were also sampled for perchlorate. All but two of the water samples tested negative for perchlorate. Perchlorate levels in 79 produce samples ranged from non-detect to 1816 ppb. Estimated perchlorate doses ranged from 0.02 to 0.51 µg/kg of body weight/day. Perchlorate dose increased with the number of servings of dairy products consumed and with estimated perchlorate levels in produce consumed. The geometric mean perchlorate dose was 70% higher than for the NHANES reference population. Our sample of 31 Imperial Valley residents had higher perchlorate dose levels compared with national reference ranges. Although none of our exposure estimates exceeded the U. S. EPA reference dose, three participants exceeded the acceptable daily dose as defined by bench mark dose methods used by the California Office of Environmental Health Hazard Assessment.

  15. A bioinspired iron catalyst for nitrate and perchlorate reduction.

    Science.gov (United States)

    Ford, Courtney L; Park, Yun Ji; Matson, Ellen M; Gordon, Zachary; Fout, Alison R

    2016-11-11

    Nitrate and perchlorate have considerable use in technology, synthetic materials, and agriculture; as a result, they have become pervasive water pollutants. Industrial strategies to chemically reduce these oxyanions often require the use of harsh conditions, but microorganisms can efficiently reduce them enzymatically. We developed an iron catalyst inspired by the active sites of nitrate reductase and (per)chlorate reductase enzymes. The catalyst features a secondary coordination sphere that aids in oxyanion deoxygenation. Upon reduction of the oxyanions, an iron(III)-oxo is formed, which in the presence of protons and electrons regenerates the catalyst and releases water.

  16. Preliminary assessment of perchlorate in ecological receptors at the Longhorn Army Ammunition Plant (LHAAP), Karnack, Texas.

    Science.gov (United States)

    Smith, P N; Theodorakis, C W; Anderson, T A; Kendall, R J

    2001-10-01

    There have been increasing human health and ecological concerns about ionic perchlorate (ClO4-) since it was detected in drinking water sources in 1997. Perchlorate is known to affect thyroid function, causing subsequent hormone disruption and potential perturbations of metabolic activities. According to current estimates, perchlorate is found in the surface of groundwater of 14 states, including Texas. Longhorn Army Ammunition Plant, located in east central Texas, was a facility historically associated with perchlorate-containing propellants and rocket motors. Subsequently, perchlorate contamination in ground and surface waters at the facility has been reported. Soil, sediment, water, vegetation, and animal tissue samples were collected from several locations within the plant for a preliminary site assessment of perchlorate contamination. Perchlorate concentrations ranged from 555-5,557,000 ppb in vegetation, 811-2038 ppb in aquatic insects, below detection limits (ND) to 207 ppb in fish, ND-580 ppb in frogs, and ND-2328 ppb in mammals. Consistent with our hypothesis, aquatic organisms inhabiting perchlorate-contaminated surface water bodies contained detectable concentrations of perchlorate. Additionally, terrestrial organisms were exposed through pathways not necessarily related to contaminated surface waters. Therefore, these data demonstrate that aquatic and terrestrial species are exposed to perchlorate in the environment. To our knowledge, this represents the first incidence of perchlorate exposure among wild animals reported in the scientific literature.

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

    Science.gov (United States)

    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.

  18. Simultaneous detection of perchlorate and bromate using rapid high-performance ion exchange chromatography-tandem mass spectrometry and perchlorate removal in drinking water.

    Science.gov (United States)

    West, Danielle M; Mu, Ruipu; Gamagedara, Sanjeewa; Ma, Yinfa; Adams, Craig; Eichholz, Todd; Burken, Joel G; Shi, Honglan

    2015-06-01

    Perchlorate and bromate occurrence in drinking water causes health concerns due to their effects on thyroid function and carcinogenicity, respectively. The purpose of this study was threefold: (1) to advance a sensitive method for simultaneous rapid detection of perchlorate and bromate in drinking water system, (2) to systematically study the occurrence of these two contaminants in Missouri drinking water treatment systems, and (3) to examine effective sorbents for minimizing perchlorate in drinking water. A rapid high-performance ion exchange chromatography-tandem mass spectrometry (HPIC-MS/MS) method was advanced for simultaneous detection of perchlorate and bromate in drinking water. The HPIC-MS/MS method was rapid, required no preconcentration of the water samples, and had detection limits for perchlorate and bromate of 0.04 and 0.01 μg/L, respectively. The method was applied to determine perchlorate and bromate concentrations in total of 23 selected Missouri drinking water treatment systems during differing seasons. The water systems selected include different source waters: groundwater, lake water, river water, and groundwater influenced by surface water. The concentrations of perchlorate and bromate were lower than or near to method detection limits in most of the drinking water samples monitored. The removal of perchlorate by various adsorbents was studied. A cationic organoclay (TC-99) exhibited effective removal of perchlorate from drinking water matrices.

  19. POLISHING EFFLUENT FROM A PERCHLORATE-REDUCING ANAEROBIC BIOLOGICAL CONTACTOR

    Science.gov (United States)

    The U.S. Environmental Protection Agency undertook at 3 ½ year pilot-scale biological perchlorate treatment study that included two long (311 and 340 days) examinations of anaerobic effluent polishing. The polishing system consisted of hydrogen peroxide addition and aeration, fo...

  20. The Impact of Temperature on Anaerobic Biological Perchlorate Treatment

    Science.gov (United States)

    A 20-month pilot-scale study was conducted to examine the impact of temperature on the performance of an anaerobic biological contactor used to treat perchlorate-contaminated water. The contactor was successfully acclimated with indigenous micro-organisms. Influent temperatures...

  1. Structure of aqueous sodium perchlorate solutions.

    Science.gov (United States)

    General, Ignacio J; Asciutto, Eliana K; Madura, Jeffry D

    2008-12-01

    Salt solutions have been the object of study of many scientists through history, but one of the most important findings came along when the Hofmeister series were discovered. Their importance arises from the fact that they influence the relative solubility of proteins, and solubility is directly related to one of today's holy grails: protein folding. In this work we characterize one of the more-destabilizing salts in the series, sodium perchlorate, by studying it as an aqueous solution at various concentrations ranging from 0.08 to 1.60 mol/L. Molecular dynamics simulations at room temperature permitted a detailed study of the organization of solvent and cosolvent, in terms of its radial distribution functions, along with the study of the structure of hydrogen bonds in the ions' solvation shells. We found that the distribution functions have some variations in their shape as concentration changes, but the position of their peaks is mostly unaffected. Regarding water, the most salient fact is the noticeable (although small) change in the second hydration shell and even beyond, especially for g(O(w)***O(w)), showing that the locality of salt effects should not be restricted to considerations of only the first solvation shell. The perturbation of the second shell also appears in the study of the HB network, where the difference between the number of HBs around a water molecule and around the Na(+) cation gets much smaller as one goes from the first to the second solvation shell, yet the difference is not negligible. Nevertheless, the effect of the ions past their first hydration shell is not enough to make a noticeable change in the global HB network. The Kirkwood-Buff theory of liquids was applied to our system, in order to calculate the activity derivative of the cosolvent. This coefficient, along with a previously calculated preferential binding, allowed us to establish that if a folded AP peptide is immersed in the studied solution, becoming the solute, then

  2. Luminescent properties of dysprosium(Ⅲ) ions in LaAlO3 nanocrystallites

    Institute of Scientific and Technical Information of China (English)

    K. Lema(n)ski; P.J. Dere(n)

    2011-01-01

    The absorption and emission spectra as well as decay time profile of Dy3+ ions in LaAlO3 nanocrystals were analyzed.The crystal structure of LaAlO3 was confirmed from XRD measurement.The emission peaks from blue to red came from main emitting level of dysprosium 4F9/2 to the ground and other excited levels of Dy3+ ions.Cross relaxation process led to non-radiative quenching of luminescence,so that the lifetime of the 4F9/2 energy level ions decreased with increasing amount of doped Dy3+ ions.The cross relaxation transfer rates were experimentally determined as a function of Dy3+ concentration.

  3. Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

    Science.gov (United States)

    Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; Vohra, Yogesh K.

    2014-04-01

    Magnetic ordering temperatures in heavy rare earth metal dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to a pressure of 69 GPa and a temperature of 10 K. Previous studies using magnetic susceptibility measurements at high pressures were able to track magnetic ordering temperature only till 7 GPa in the hexagonal close packed (hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. This is followed by a rapid increase in the magnetic ordering temperatures in the double hcp phase and finally leveling off in the distorted face centered cubic phase of Dy. Our studies reaffirm that 4f-shell remains localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.

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

    KAUST Repository

    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.

  5. Electrochemical behaviour of dysprosium in the eutectic LiCl-KCl at W and Al electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Castrillejo, Y. [Dpto de Quimica Analitica, Facultad de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain)]. E-mail: ycastril@qa.uva.es; Bermejo, M.R. [Dpto de Quimica Analitica, Facultad de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Barrado, A.I. [Dpto de Quimica Analitica, Facultad de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Pardo, R. [Dpto de Quimica Analitica, Facultad de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Barrado, E. [Dpto de Quimica Analitica, Facultad de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Martinez, A.M. [Department of Materials Technology, Sem Saelands vei 6, 7491 Trondheim (Norway)

    2005-03-15

    The electrochemical behaviour of DyCl{sub 3} was studied in the eutectic LiCl-KCl at different temperatures. The cathodic reaction can be written:Dy(III)+3e-bar Dy(0)which can be divided in two very close cathodic steps:Dy(III)+1e-bar Dy(II)andDy(II)+2e-bar Dy(0)Transient electrochemical techniques, such as cyclic voltammetry, chronopotentiometry, and chronoamperometry were used in order to study the reaction mechanism and the transport parameters of electroactive species at a tungsten electrode. The results showed that in the eutectic LiCl-KCl, electrocrystallization of dysprosium seems to be the controlling electrochemical step. Chronoamperometric studies indicated instantaneous nucleation of dysprosium with three dimensional growth of the nuclei whatever the applied overpotential.Mass transport towards the electrode is a simple diffusion process, and the diffusion coefficient of the electroactive species, i.e. Dy(III), has been calculated. The validity of the Arrhenius law was also verified by plotting the variation of the logarithm of the diffusion coefficient versus 1/T.In addition, the electrode reactions of the LiCl-KCl-DyCl{sub 3} solutions at an Al wire were also investigated by cyclic voltammetry and open circuit chronopotentiometry. The redox potential of the Dy(III)/Dy couple at the Al electrode was observed at more positive potentials values than those at the inert electrode. This potential shift was thermodynamically analyzed by a lowering of activity of Dy in the metal phase due to the formation of intermetallic compounds.

  6. Thyroid function and reproductive success in rodents exposed to perchlorate via food and water.

    Science.gov (United States)

    Smith, Philip N; Severt, Scott A; Jackson, J W Andrew; Anderson, Todd A

    2006-04-01

    The purpose of the present study was to determine if exposure to perchlorate via food items would have effects on mammals similar to those caused by exposure through drinking water at approximately equivalent doses. Prairie voles (Microtus ochrogaster) and deer mice (Peromyscus maniculatus) were used to assess the potential toxicity of perchlorate-contaminated food items. Voles and mice were divided randomly into three treatment groups--perchlorate-contaminated food (PCF), perchlorate-contaminated water (PCW), and control groups--such that each treatment group contained equal numbers of males and females. Rodents in PCF treatment groups were fed chow formulated with soybean plant matter that had been grown with perchlorate-contaminated irrigation water. Individuals in the control and PCF groups were provided distilled/deionized drinking water, whereas the PCW group received drinking water containing sodium perchlorate. Only slight differences among treatment groups were observed in a variety of endpoints, including reproductive success, tissue perchlorate concentrations, thyroid hormone concentrations, and thyroid histology. However, trends observed in the present study suggest that perchlorate exposure via water may result in slightly greater effects than exposure to perchlorate via food. These data and recent reports of perchlorate in a wide variety of food items indicate that exposure via food intake is an important consideration when examining cumulative risk among humans, livestock, and wildlife.

  7. Exogenous iodide ameliorates perchlorate-induced thyroid phenotypes in threespine stickleback.

    Science.gov (United States)

    Gardell, Alison M; von Hippel, Frank A; Adams, Elise M; Dillon, Danielle M; Petersen, Ann M; Postlethwait, John H; Cresko, William A; Buck, C Loren

    2017-03-01

    Perchlorate is a ubiquitous environmental contaminant that has widespread endocrine disrupting effects in vertebrates, including threespine stickleback (Gasterosteus aculeatus). The target of perchlorate is thyroid tissue where it induces changes in the organization, activation, and morphology of thyroid follicles and surrounding tissues. To test the hypothesis that some phenotypes of perchlorate toxicity are not mediated by thyroid hormone, we chronically exposed stickleback beginning at fertilization to perchlorate (10, 30, 100ppm) or control water with and without supplementation of either iodide or thyroxine (T4). Stickleback were sampled across a one-year timespan to identify potential differences in responses to treatment combinations before and after sexual maturation. We found that most thyroid histomorphological phenotypes induced by perchlorate (follicle proliferation, reduced follicle area (adults only), colloid depletion, thyrocyte hypertrophy (subadults only)) were significantly ameliorated by exogenous iodide supplementation. In contrast, treatment with exogenous T4 did not correct any of the thyroid-specific histopathologies induced by perchlorate. Whole-body thyroid hormone concentrations were not significantly affected by perchlorate exposure; however, supplementation with iodide and T4 significantly increased T4 concentrations. This study also revealed an increased erythrocyte area in the thyroid region of perchlorate-exposed adults, while lipid droplet number increased in perchlorate-exposed subadults. Increased erythrocyte area was ameliorated by both iodide and T4, while neither supplement was able to correct lipid droplet number. Our finding on lipid droplets indicates that exposure to perchlorate in early development may have obesogenic effects. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Interaction between perchlorate and iodine in the metamorphosis of Hyla versicolor

    Science.gov (United States)

    Sparling, D.W.; Harvey, G.; Nzengung, V.; Linder, Gregory L.; Krest, Sherry K.; Sparling, Donald W.; Little, Edward E.

    2003-01-01

    Perchlorate (ClO4-) is a water-soluble, inorganic anion that is often combined with ammonium, potassium or other cations for use in industry and agriculture. Ammonium perchlorate, for example, is a potent oxidizer and is used in various military applications including rocket fuel. It has also been found in an historically widely used fertilizer, Chilean nitrate and in other fertilizers. It has been found in ground and surface waters of over 30 states and is considered a human health risk. Because of its similar atomic radius and volume, perchlorate competes with iodide for thyroid uptake and storage and thereby inhibits production of thyroid hormones. Amphibians may be particularly affected by perchlorate because they rely on the thyroid for metamorphosis. This study exposed early larval Hyla versicolor to concentrations of perchlorate ranging from 2.2 to 50 ppm to determine the effects of perchlorate on a native amphibian. In addition, three controls, 0 perchlorate, 0 perchlorate with 0.10 ppm iodide (C + I) and 50 ppm perchlorate + 0.10 ppm iodide (50 + I) were tested. Mortality (<11% with all treatments) and growth appeared to be unaffected by perchlorate. Inhibition of development started with 2.2 ppm perchlorate and little or no development occurred at 22.9 ppm and above. This inhibition was particularly apparent at the latter stages of development including hindlimb formation and metamorphosis. The estimated EC50 for total inhibition of metamorphosis at 70 days of treatment was 3.63 ppm. There was no evidence of inhibition of development with the 50 + I, C + I, or controls, indicating that the presence of small concentrations of iodide could counter the effects of perchlorate. When tadpoles that had been inhibited by perchlorate were subsequently treated with iodide, development through prometamorphosis progressed but mortality was very high.

  9. Sensitivity and adaptability of methanogens to perchlorates: Implications for life on Mars

    Science.gov (United States)

    Kral, Timothy A.; Goodhart, Timothy H.; Harpool, Joshua D.; Hearnsberger, Christopher E.; McCracken, Graham L.; McSpadden, Stanley W.

    2016-01-01

    In 2008, the Mars Phoenix Lander discovered perchlorate at its landing site, and in 2012, the Curiosity rover confirmed the presence of perchlorate on Mars. The research reported here was designed to determine if certain methanogens could grow in the presence of three different perchlorate salt solutions. The methanogens tested were Methanothermobacter wolfeii, Methanosarcina barkeri, Methanobacterium formicicum and Methanococcus maripaludis. Media were prepared containing 0%, 0.5%, 1.0%, 2%, 5% and 10% wt/vol magnesium perchlorate, sodium perchlorate, or calcium perchlorate. Organisms were inoculated into their respective media followed by incubation at each organism's growth temperature. Methane production, commonly used to measure methanogen growth, was measured by gas chromatography of headspace gas samples. Methane concentrations varied with species and perchlorate salt tested. However, all four methanogens produced substantial levels of methane in the presence of up to 1.0% perchlorate, but not higher. The standard procedure for growing methanogens typically includes sodium sulfide, a reducing agent, to reduce residual molecular oxygen. However, the sodium sulfide may have been reducing the perchlorate, thus allowing for growth of the methanogens. To investigate this possibility, experiments were conducted where stainless steel nails were used instead of sodium sulfide as the reducing agent. Prior to the addition of perchlorate and inoculation, the nails were removed from the liquid medium. Just as in the prior experiments, the methanogens produced methane at comparable levels to those seen with sodium sulfide as the reductant, indicating that sodium sulfide did not reduce the perchlorate to any significant extent. Additionally, cells metabolizing in 1% perchlorate were transferred to 2%, cells metabolizing in 2% were transferred to 5%, and finally cells metabolizing in 5% were transferred to 10%. All four species produced methane at 2% and 5%, but not 10

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. Structural, optical, thermal, mechanical and dielectric studies of Sulfamic acid single crystals: An influence of dysprosium (Dy3+) doping

    Science.gov (United States)

    Singh, Budhendra; Shkir, Mohd.; AlFaify, S.; Kaushal, Ajay; Nasani, Narendar; Bdikin, Igor; Shoukry, H.; Yahia, I. S.; Algarni, H.

    2016-09-01

    Sulfamic acid is a potential material that exhibits excellent optical properties. A good quality, pure and dysprosium (Dy3+) doped (2.5 and 5 mol %) Sulfamic acid (SA) single crystals were grown successfully by slow cooling method. Structural study revealed a slight change in its lattice parameters and volume, suggesting the successful incorporation of Dy3+ in crystal system. The existence of dysprosium in the system was also confirmed. Presence of various vibrational modes was confirmed. Optical transparency was found to have a significant effect with variation in the doping concentration. Furthermore, a marked enhancement in its mechanical parameters with doping was also identified by nanoindentation technique. Etching study was also performed on the grown crystals to study the etch-pit formation and growth mechanism. Effect of doping on the thermal stability was analysed. All the results were compared and discussed in detail to get insight of the effect of doping concentration on Sulfamic acid crystal.

  12. Optical trapping of ultracold dysprosium atoms: transition probabilities, dynamic dipole polarizabilities and van der Waals $C_6$ coefficients

    CERN Document Server

    Li, Hui; Dulieu, Olivier; Nascimbene, Sylvain; Lepers, Maxence

    2016-01-01

    The efficiency of optical trapping of ultracold atoms depend on the atomic dynamic dipole polarizability governing the atom-field interaction. In this article, we have calculated the real and imaginary parts of the dynamic dipole polarizability of dysprosium in the ground and first excited level. Due to the high electronic angular momentum of those two states, the polarizabilities possess scalar, vector and tensor contributions that we have computed, on a wide range of trapping wavelengths, using the sum-over-state formula. Using the same formalism, we have also calculated the $C_6$ coefficients characterizing the van der Waals interaction between two dysprosium atoms in the two lowest levels. We have computed the energies of excited states and the transition probabilities appearing in the sums, using a combination of \\textit{ab initio} and least-square-fitting techniques provided by the Cowan codes and extended in our group. Regarding the real part of the polarizability, for field frequencies far from atomic...

  13. Mixed (phthalocyaninato)(Schiff-base) di-dysprosium sandwich complexes. Effect of magnetic coupling on the SMM behavior.

    Science.gov (United States)

    Wang, Hailong; Liu, Chenxi; Liu, Tao; Zeng, Suyuan; Cao, Wei; Ma, Qi; Duan, Chunying; Dou, Jianmin; Jiang, Jianzhuang

    2013-11-21

    Reaction between Schiff-base ligand and half-sandwich complex M(Pc)(acac) led to the isolation of new sandwich-type mixed (phthalocyaninato)(Schiff-base) di-lanthanide compounds M2(Pc)2(L)H2O (M = Dy, Gd) (1, 2) [H2Pc = metal free phthalocyanine, Hacac = acetylacetone, H2L = N,N'-bis(3-methyloxysalicylidene)benzene-1,2-diamine] with the triple-decker molecular structure clearly revealed by single crystal X-ray diffraction analysis. For the comparative studies, sandwich triple-decker analogues with pure Schiff-base ligand M2(L)3H2O (M = Dy, Gd) (3, 4) were also prepared. Dynamic magnetic measurement result reveals the single-molecule magnet (SMM) nature of the di-dysprosium derivative 1, while the static magnetic investigation over both pure and the diamagnetic diluted samples of this compound discloses the interionic ferromagnetic coupling between the two dysprosium ions, which in turn effectively suppresses the QTM and enhances the energy barrier of this SMM. Nevertheless, comparative studies over the static magnetic properties of the di-dysprosium triple-decker complexes 1 and 3 indicate the stronger magnetic coupling between the two lanthanide ions in mixed (phthalocyaninato)(Schiff-base) species than in the pure Schiff-base triple-decker analogue, suggesting the special coordination sphere around the dysprosium ions in the former compound over the latter one on the more intense inter-ionic ferromagnetic coupling. As a very small step towards understanding the structure-property relationship, the present result will be surely helpful for the design and synthesis of the multinuclear lanthanide-based SMMs with good properties.

  14. Environmental impacts of perchlorate with special reference to fireworks--a review.

    Science.gov (United States)

    Sijimol, M R; Mohan, Mahesh

    2014-11-01

    Perchlorate is an inorganic anion that is used in solid rocket propellants, fireworks, munitions, signal flares, etc. The use of fireworks is identified as one of the main contributors in the increasing environmental perchlorate contamination. Although fireworks are displayed for entertainment, its environmental costs are dire. Perchlorates are also emerging as potent thyroid disruptors, and they have an impact on the ecology too. Many studies have shown that perchlorate contaminates the groundwater and the surface water, especially in the vicinity of fireworks manufacturing sites and fireworks display sites. The health and ecological impacts of perchlorate released in fireworks are yet to be fully assessed. This paper reviews fireworks as a source of perchlorate contamination and its expected adverse impacts.

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

    Science.gov (United States)

    2008-10-01

    hyperthyroidism , gas generators, electrolytes for lithium cells, and as chemical reagents. The occurrence of perchlorate in the environment is... treatments for the remediation of perchlorate in the environment (Refs. 10, 11). The debate on the acceptable levels of perchlorate in drinking...Biodegradation for Water Treatment ”, Environ. Sci. and Tecnol., Vol. 39 pp. 239A-247A, 2005. [11] Hatzinger, P.B., Whittier, C.M., Arkins, M.D., Bryan

  16. A Potential Mechanism for Perchlorate Formation on Mars: Surface-Radiolysis-Initiated Atmospheric Chemistry

    Science.gov (United States)

    Wilson, Eric; Atreya, Sushil K.; Kaiser, Ralf-Ingo; Mahaffy, Paul

    2016-10-01

    Perchlorate (ClO4-) is prevalent on Earth, and with observations of perchlorate on lunar samples and chondrite meteorites, along with recent observations indicating the presence of perchlorate (ClO4-) in the Martian surface by the Phoenix lander and the Sample Analysis at Mars (SAM) on the Mars Science Laboratory (MSL) rover, it appears that the existence of perchlorate is widespread throughout the solar system. However, the abundance and isotopic composition of Martian perchlorate suggest that the perchlorate formation mechanism on Mars may involve a different path than perchlorate found elsewhere in the solar system. Motivated by this, we employ a one-dimensional chemical model to investigate the viability of perchlorate formation in the atmosphere of Mars, instigated by the radiolysis of the Martian surface by galactic cosmic rays. The surface-atmosphere interaction to produce Martian perchlorate involves the sublimation of chlorine oxides into the atmosphere, through surface radiolysis, and their subsequent synthesis to form perchloric acid (HClO4), followed by surface deposition and mineralization to form surface perchlorates. Considering the chlorine oxide, OClO, we find an OClO surface flux as low as 3.2x107 molecules cm-2 s-1, sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.

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

    Science.gov (United States)

    2010-09-01

    Perchlorate-Impacted Groundwater for Base Case 8-4 Cost Components for Extraction and Treatment of Perchlorate-Impacted Groundwater for Base Case 8-5...consumed, increasing the likelihood of perchlorate biodegradation in the natural environment (Coates and Jackson, 2009). Trace amounts of molybdenum are...chlorinated solvents (USEPA, 1998) have been in use for many years. These documents describe systematic steps for delineating contaminant plumes

  18. Kinetics analysis of a salt-tolerant perchlorate-reducing bacterium: effects of sodium, magnesium, and nitrate.

    Science.gov (United States)

    Xiao, Yeyuan; Roberts, Deborah J

    2013-08-06

    Salt-tolerant perchlorate-reducing bacteria can be used to regenerate ion-exchange brines or resins exhausted with perchlorate. A salt-tolerant perchlorate-reducing Marinobacter vinifirmus strain P4B1 was recently purified. This study determined the effects of Na(+) and Mg(2+) concentrations on the perchlorate reduction rate of P4B1. The results showed that strain P4B1 could utilize perchlorate and grow in the presence of 1.8% to 10.2% NaCl. Lower NaCl concentrations allowed faster perchlorate reduction. The addition of Mg(2+) to the culture showed significant effects on perchlorate reduction when perchlorate was the sole electron acceptor. A molar Mg(2+)/Na(+) ratio of ∼0.11 optimized perchlorate degradation and cell growth. When perchlorate and nitrate were both present, nitrate reduction did not start significantly until perchlorate was below 100 mg/L. Tests with washed cell suspensions indicated that strain P4B1 had both perchlorate and nitrate reduction enzymes. When the culture was exposed to both perchlorate and nitrate, the nitrate reduction enzyme activity was low. The maximum specific substrate utilization rate (Vm) and the half saturation coefficient (KS) for P4B1 (30 g/L NaCl) determined in this study were 0.049 ± 0.003 mg ClO4(-)/mg VSS-h and 18 ± 4 mg ClO4(-)/L, respectively.

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

    Science.gov (United States)

    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 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.

  20. 4-(2-Azaniumylethylpiperazin-1-ium bis(perchlorate

    Directory of Open Access Journals (Sweden)

    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.

  1. Parameters for the Pyrolysis of Organic Material - Perchlorate Mixtures

    Science.gov (United States)

    Steininger, Harald; Goesmann, Fred; Goetz, Walter

    2013-04-01

    The ESA-lead Mars rover ExoMars (launch in 2018) will carry a suit of instruments, one of the in-struments is the Mars Organic Molecule Analyzer MOMA. Organic material in the Martian soil will be either pyrolyzed at temperatures of up to 1000°C and separated by gas chromatography or volatilized with the help of an UV-laser. A mass spectrometer will be the detector for both methods. Chlorinated organics have been detected in pyroly-sis GC-MS experiments on Mars two times. The first time during the Viking mission in 1976 and a second time with the Sample Analysis on Mars (SAM) in-strument onboard the Curiosity rover in 2012. [1] [2] The presence of perchlorates found by the Phoenix mission in 2008 [3] lead to the discovery that organic molecules not only get oxidized during pyrolysis, but also chlorinated organic compounds can be pro-duced. [4] The parameters used for pyrolysis and the sample composition especially the distribution of organics and perchlorates within the sample and the concentrations of organics and perchlorate have a huge influence on the products created. It is possible to change the condi-tions of the pyrolysis by spatially separating the organ-ics from the perchlorates that the chloromethanes get the major product of the pyrolysis. This might help to understand the results of the (SAM) instrument yield-ing mono-, di- and trichloromethane and a chlorinated 4-hydrocarbon molecule. References: [1] Biemann K et al. (1977) JGR, 82, 4641-4658. [2] Grotzinger J. P et al. (2011) AGU Fall Meeting U13A-01 [3] Hecht M. H., et al. (2009) Science, 325 64-67. [4] Steininger H., Goesmann F., Goetz W. (2011) Planet. & Space Sci., 71, 9-17. Acknowledgments: This work was funded by DLR (FKZ 50QX1001)

  2. Spectroscopic and Visual Evidence of Perchlorate Deliquescence Under Martian Conditions

    Science.gov (United States)

    Nikolakakos, George; Whiteway, James

    2015-04-01

    One of the key findings during the Phoenix and Mars Science Laboratory landed Mars missions has been the detection of perchlorate, a highly deliquescent salt. Perchlorates are of great interest on Mars due to their high affinity for water vapour as well as their ability to greatly depress the freezing point of water when in solution. This has intriguing biological implications as resulting brines could potentially provide a habitable environment for living organisms. Additionally, it has been speculated that these salts may play a significant role in influencing the hydrological cycle on Mars. In order to experimentally study water exchange processes between the surface and atmosphere on Mars and assess the feasibility of a future landed detection tool, a stand-off Raman spectroscopy instrument and environmental simulation chamber have been developed at York University. A sample of magnesium perchlorate consistent with the size of patches found at the Phoenix site has been subjected to the low water vapour pressure and temperatures found at polar Martian latitudes. Results indicate that at a water vapour pressure of ~2 Pa (-54°C frost point temperature), Raman spectroscopy is able to detect the onset of brine formation and provide a relative estimate of the quantity of water taken up by the sample until complete deliquescence is reached. Significant uptake of water from the atmosphere is observed to occur prior to the frost point temperature being reached and on time scales relevant to the Martian diurnal cycle. This result suggests that perchlorates in the Martian regolith can contribute to the hydrological cycle, pre-emptively reducing the water vapour pressure before saturation is reached.

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

    Science.gov (United States)

    2008-10-16

    ppb standard in October 2007. Several states have issued health goals or advisory levels ranging from 1 ppb in Maryland (advisory level) and New Mexico ...Environmental Medicine, 2003, p. 1117. 6 Benjamin C. Blount, James L. Pirkle, et al., “Urinary Perchlorate and Thyroid Hormone Levels in Adolescent ...concern is that impairment of thyroid function in pregnant women can affect fetuses and nursing infants and can result in delayed development and

  4. Using Stable Isotope Ratio Analysis to Distinguish Perchlorate Sources

    Science.gov (United States)

    2011-03-30

    Death Valley caliche West Texas OCl - + O 3 ClO 2 + O 3 -5.0 0.0 5.0 10 15 20 -30 -20 -10 0 10 20 30 40 50  1 7 O ( p e r m i l ) 18O (per mil...Synthetic solids Atacama caliche/ fertilizer Death Valley caliche West Texas OCl - + UV ClO 2 + UV Perchlorate generated with UV 36Cl Analysis Long

  5. 1-Benzylpiperazine-1,4-diium bis(perchlorate monohydrate

    Directory of Open Access Journals (Sweden)

    Kamel Kaabi

    2010-07-01

    Full Text Available In the title compound, C11H18N22+·2ClO4−·H2O, one perchlorate anion is disordered over two orientations in a 0.66 (3:0.34 (3 ratio. Intermolecular O—H...O, N—H...O and C—H...O hydrogen bonds link the cations, anions and water molecules into ribbons extending along [100].

  6. Evaluating United States and world consumption of neodymium, dysprosium, terbium, and praseodymium in final products

    Science.gov (United States)

    Hart, Matthew

    This paper develops scenarios of future rare-earth-magnet metal (neodymium, dysprosium, terbium, and praseodymium) consumption in the permanent magnets used in wind turbines and hybrid electric vehicles. The scenarios start with naive base-case scenarios for growth in wind-turbine and hybrid-electric-vehicle sales over the period 2011 to 2020, using historical data for each good. These naive scenarios assume that future growth follows time trends in historical data and does not depend on any exogenous variable. Specifically, growth of each technological market follows historical time trends, and the amount of rare earths used per unit of technology remains fixed. The chosen reference year is 2010. Implied consumptions of the rare earth magnet metals are calculated from these scenarios. Assumptions are made for the material composition of permanent magnets, the market share of permanent-magnet wind turbines and vehicles, and magnet weight per unit of technology. Different scenarios estimate how changes in factors like the material composition of magnets, growth of the economy, and the price of a substitute could affect future consumption. Each scenario presents a different method for reducing rare earth consumption and could be interpreted as potential policy choices. In 2010, the consumption (metric tons, rare-earth-oxide equivalent) of each rare-earth-magnet metal was as follows. Total neodymium consumption in the world for both technologies was 995 tons; dysprosium consumption was 133 tons; terbium consumption was 50 tons; praseodymium consumption was zero tons. The base scenario for wind turbines shows there could be strong, exponential growth in the global wind turbine market. New U.S. sales of hybrid vehicles would decline (in line with the current economic recession) while non-U.S. sales increase through 2020. There would be an overall increase in the total amount of magnetic rare earths consumed in the world. Total consumption of each rare earth in the short

  7. Formation Of Perchlorate By Ozonation Of Aqueous Oxy-chlorine Anions: An Insight To Natural Perchlorate Formation

    Science.gov (United States)

    Rao, B.; Jackson, A.; Kang, N.; Redder, A.

    2007-12-01

    Perchlorate (ClO4-) is a natural and anthropogenic contaminant of increasing concern. Natural perchlorate was first identified in Chilean nitrates from the Atacama dessert over 100 years ago. However, only in the last two years has the occurrence of natural perchlorate been seriously considered as a potential exposure source. Although there has been considerable research effort in understanding the occurrence, remediation, and impact of ClO4- in the environment, relatively little information is available regarding the mechanism(s) responsible for ClO4- formation. Perchlorate productions from ozone oxidation of chlorine and oxy- chlorine anions (Cl-, OCl-, ClO2-and ClO3-) were conducted in continuous flow reactors at constant ozone concentrations (approximately 6 mg L-1) and at varying concentrations of chlorine materials (ranging from 10 to 1000 mg L-1). Sub samples from both the main reaction flask and alkaline trapping flasks were taken over varying time intervals and the concentrations of oxy-chlorine anions including ClO4- were measured using various ion chromatographic methods whereas OCl- was determined iodometrically using the spectrophotometer. The experiment time ranged from 6 hrs to 7 days depending on the rate of decomposition of the reactants. Results indicate that ClO4- is readily formed during the ozonation of ClO2- and OCl- solutions (maximum conversion of 2.7 %) whereas the Cl- and ClO3- solutions produced relatively lower quantities of ClO4- ( maximum conversion of 0.02 %) . Further the presence of ClO2- in the initial OCl- solution is suspected to significantly contribute the total ClO4- generated augmenting the role of ClO2- in ClO4- formation as mentioned in recent study on the photochemical reactions of oxy-chlorine anions.

  8. Perchlorate in the Hydrologic Cycle - An Overview of Sources and Occurrence

    Science.gov (United States)

    Stonestrom, D. A.; Jackson, W.; Mayer, K.; Orris, G. J.

    2007-12-01

    Perchlorate (ClO4-) in water and food is of concern due to deleterious health affects associated with hypothyroidism. The presence of widespread perchlorate in 0-to-28 ka-old pristine ground water of the Middle Rio Grande Basin (Plummer et al., 2006, ES&T, DOI:10.1021/es051739h), in ground water >1 mile from agricultural activities in the Southern High Plains (Rajagapolan et al., 2006, ES&T, DOI:10.1021/es052155i), and in unsaturated zones throughout the arid and semiarid southwestern United States (Rao et al., 2007, ES&T, DOI:10.1021/es062853i) clearly indicates that perchlorate is a non-exotic component of the hydrologic cycle, at least in dry environments. The natural system has been greatly perturbed in places by human activities. Most anthropogenic inputs are associated with the manufacture and use of explosives and rocket fuel, providing concentrated sources of excess perchlorate to the hydrologic cycle. Perchlorate-containing fertilizers and irrigation provide dispersed sources within and down-gradient from agricultural areas. Natural sources include photochemically mediated reactions involving ozone at the land surface and in the lower atmosphere. A growing body of work indicates that a small, but persistent, meteoric source acting over thousands of years can explain observed accumulations of unsaturated-zone perchlorate in arid regions. In addition to meteoric sources, oxyanions produced during volcanogenic processes can include appreciable amounts of natural perchlorate. Terrestrial plants take up perchlorate in soil water, with some species of xerophytic succulents concentrating the anion to high levels. Similarly, perchlorate in marine plants indicates that perchlorate is part of marine biochemical cycles. Perchlorate-bearing marine sediments of late Tertiary age suggest that perchlorate has been part of global geochemical cycles for millions of years and, furthermore, can be preserved in the subsurface despite the nearly ubiquitous presence of

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Containerized Wetland Bioreactor Evaluated for Perchlorate and Nitrate Degradation

    Energy Technology Data Exchange (ETDEWEB)

    Dibley, V R; Krauter, P W

    2004-12-02

    The U.S. Department of Energy (DOE) and Lawrence Livermore Laboratory (LLNL) designed and constructed an innovative containerized wetlands (bioreactor) system that began operation in November 2000 to biologically degrade perchlorate and nitrate under relatively low-flow conditions at a remote location at Site 300 known as Building 854. Since initial start-up, the system has processed over 3,463,000 liters of ground water and treated over 38 grams of perchlorate and 148 kilograms of nitrate. Site 300 is operated by the University of California as a high-explosives and materials testing facility supporting nuclear weapons research. The 11-square mile site located in northern California was added to the NPL in 1990 primarily due to the presence of elevated concentrations of volatile organic compounds (VOCs) in ground water. At the urging of the regulatory agencies, perchlorate was looked for and detected in the ground water in 1999. VOCs, nitrate and perchlorate were released into the soil and ground water in the Building 854 area as the result of accidental leaks during stability testing of weapons or from waste discharge practices that are no longer permitted at Site 300. Design of the wetland bioreactors was based on earlier studies showing that indigenous chlorate-respiring bacteria could effectively degrade perchlorate into nontoxic concentrations of chlorate, chlorite, oxygen, and chloride. Studies also showed that the addition of organic carbon would enhance microbial denitrification. Early onsite testing showed acetic acid to be a more effective carbon source than dried leaf matter, dried algae, or milk replacement starter; a nutrient and carbon source used in a Department of Defense phytoremediation demonstration. No inocula were added to the system. Groundwater was allowed to circulate through the bioreactor for three weeks to acclimate the wetland plants and to build a biofilm from indigenous flora. Using solar energy, ground water is pumped into granular

  11. Modeling aqueous perchlorate chemistries with applications to Mars

    Science.gov (United States)

    Marion, G. M.; Catling, D. C.; Zahnle, K. J.; Claire, M. W.

    2010-06-01

    NASA's Phoenix lander identified perchlorate and carbonate salts on Mars. Perchlorates are rare on Earth, and carbonates have largely been ignored on Mars following the discovery by NASA's Mars Exploration Rovers of acidic precipitated minerals such as jarosite. In light of the Phoenix results, we updated the aqueous thermodynamic model FREZCHEM to include perchlorate chemistry. FREZCHEM models the Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO 4-NO 3-OH-HCO 3-CO 3-CO 2-O 2-CH 4-Si-H 2O system, with 95 solid phases. We added six perchlorate salts: NaClO 4·H 2O, NaClO 4·2H 2O, KClO 4, Mg(ClO 4) 2·6H 2O, Mg(ClO 4) 2·8H 2O, and Ca(ClO 4) 2·6H 2O. Modeled eutectic temperatures for Na, Mg, and Ca perchlorates ranged from 199 K (-74 °C) to 239 K (-34 °C) in agreement with experimental data. We applied FREZCHEM to the average solution chemistry measured by the Wet Chemistry Laboratory (WCL) experiment at the Phoenix site when soil was added to water. FREZCHEM was used to estimate SO42- and alkalinity concentrations that were missing from the WCL data. The amount of SO42- is low compared to estimates from elemental abundance made by other studies on Mars. In the charge-balanced solution, the dominant cations were Mg 2+ and Na + and the dominant anions were ClO4-,SO42-, and alkalinity. The abundance of calcite measured at the Phoenix site has been used to infer that the soil may have been subject to liquid water in the past, albeit not necessarily locally; so we used FREZCHEM to evaporate (at 280.65 K) and freeze (from 280.65 to 213.15 K) the WCL-measured solution to provide insight into salts that may have been in the soil. Salts that precipitated under both evaporation and freezing were calcite, hydromagnesite, gypsum, KClO 4, and Mg(ClO 4) 2·8H 2O. Epsomite (MgSO 4·7H 2O) and NaClO 4·H 2O were favored by evaporation at temperatures >0 °C, while meridianite (MgSO 4·11H 2O), MgCl 2·12H 2O, and NaClO 4·2H 2O were favored at subzero temperatures. Incongruent melting

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

    Science.gov (United States)

    2012-01-01

    become a concern of the US Department of Defense is the “perchlorate issue.” Potassium perchlorate and ammonium perchlorate oxidizers, once believed to be...amongst ideal oxi- dizers owing to their inherent reactivity, stability , low cost, low hygroscopicity, and large positive oxygen balances, have now...groundwater, thus posing a po- tential risk to drinking supplies. Perchlorates are believed to be teratogenic and the anion is believed to compete with iodide

  13. Luminescence features of dysprosium and phosphorus oxide co-doped lithium magnesium borate glass

    Science.gov (United States)

    Hashim, S.; Mhareb, M. H. A.; Ghoshal, S. K.; Alajerami, Y. S. M.; Saripan, M. I.; Bradley, D. A.

    2017-08-01

    Lithium magnesium borate (LMB) glass system co-doped with the oxides of dysprosium (Dy2O3) and phosphorus (P2O5) were synthesized using melt-quenching method. Prepared samples were characterized using various techniques to determine the effects of co-dopants concentration variation on their thermoluminescence (TL) and photoluminescence (PL) properties. TL glow curves of LMB:0.5Dy sample revealed a single prominent peak at Tm=190 °C, where TL intensity was enhanced by a factor of 2.5 with the increase of P2O5 concentration up to 1 mol%. This enhancement was accompanied by a shift in Tm towards higher temperature. Good linearity in the range of 1-100 Gy with linear correlation coefficient of 0.998 was achieved. PL spectra displayed two significant peaks centred at 481 nm and 573 nm. These attractive luminescence features of the proposed glass system may be useful for the development of radiation dosimetry.

  14. Single-molecule magnet behavior for an antiferromagnetically superexchange-coupled dinuclear dysprosium(III) complex.

    Science.gov (United States)

    Long, Jérôme; Habib, Fatemah; Lin, Po-Heng; Korobkov, Ilia; Enright, Gary; Ungur, Liviu; Wernsdorfer, Wolfgang; Chibotaru, Liviu F; Murugesu, Muralee

    2011-04-13

    A family of five dinuclear lanthanide complexes has been synthesized with general formula [Ln(III)(2)(valdien)(2)(NO(3))(2)] where (H(2)valdien = N1,N3-bis(3-methoxysalicylidene)diethylenetriamine) and Ln(III) = Eu(III)1, Gd(III)2, Tb(III)3, Dy(III)4, and Ho(III)5. The magnetic investigations reveal that 4 exhibits single-molecule magnet (SMM) behavior with an anisotropic barrier U(eff) = 76 K. The step-like features in the hysteresis loops observed for 4 reveal an antiferromagnetic exchange coupling between the two dysprosium ions. Ab initio calculations confirm the weak antiferromagnetic interaction with an exchange constant J(Dy-Dy) = -0.21 cm(-1). The observed steps in the hysteresis loops correspond to a weakly coupled system similar to exchange-biased SMMs. The Dy(2) complex is an ideal candidate for the elucidation of slow relaxation of the magnetization mechanism seen in lanthanide systems.

  15. A comparative study of donor formation in dysprosium, holmium, and erbium implanted silicon

    Energy Technology Data Exchange (ETDEWEB)

    Emtsev, V.V.; Emtsev, V.V. Jr.; Poloskin, D.S.; Shek, E.I.; Sobolev, N.A. [Division of Solid State Electronics, Ioffe Physicotechnical Institute, Russian Academy of Sciences, 194021 St. Petersburg (Russian Federation)

    1998-12-01

    Formation of donor centers in Czochralski grown silicon doped with dysprosium, holmium, and erbium is discussed. Donor states of three kinds are introduced in the implanted layers after annealing at T=700C. Shallow donor states with ionization energies between 20 and 40 meV are attributed to oxygen -related thermal donors. Other donor centers in the energy range of E{sub C}-(60...70) meV and E{sub C}-(100...120) meV appear to be dependent on dopants. After a 900C anneal strong changes in the donor formation are observed only in silicon doped with erbium. Instead of donors at E{sub C}-(118{+-}5) meV, new donor centres at E{sub C}-(145{+-}5) meV are formed. Reportedly, the latter ones are involved in the excitation process of the Er{sup 3+} ions with a characteristic luminescence line at {approx}1.54 {mu}m. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  16. Thermoluminescence properties of lithium magnesium borate glasses system doped with dysprosium oxide.

    Science.gov (United States)

    Mhareb, M H A; Hashim, S; Ghoshal, S K; Alajerami, Y S M; Saleh, M A; Razak, N A B; Azizan, S A B

    2015-12-01

    We report the impact of dysprosium (Dy(3+)) dopant and magnesium oxide (MgO) modifier on the thermoluminescent properties of lithium borate (LB) glass via two procedures. The thermoluminescence (TL) glow curves reveal a single prominent peak at 190 °C for 0.5 mol% of Dy(3+). An increase in MgO contents by 10 mol% enhances the TL intensity by a factor of 1.5 times without causing any shift in the maximum temperature. This enhancement is attributed to the occurrence of extra electron traps created via magnesium and the energy transfer to trivalent Dy(3+) ions. Good linearity in the range of 0.01-4 Gy with a linear correlation coefficient of 0.998, fading as low as 21% over a period of 3 months, excellent reproducibility without oven annealing and tissue equivalent effective atomic numbers ~8.71 are achieved. The trap parameters, including geometric factor (μg), activation energy (E) and frequency factor (s) associated with LMB:Dy are also determined. These favorable TL characteristics of prepared glasses may contribute towards the development of Li2O-MgO-B2O3 radiation dosimeters.

  17. Optical properties of zinc borotellurite glass doped with trivalent dysprosium ion

    Science.gov (United States)

    Ami Hazlin, M. N.; Halimah, M. K.; Muhammad, F. D.; Faznny, M. F.

    2017-04-01

    The zinc borotellurite doped with dysprosium oxide glass samples with chemical formula {[(TeO2) 0 . 7(B2O3) 0 . 3 ] 0 . 7(ZnO) 0 . 3 } 1 - x(Dy2O3)x (where x=0.01, 0.02, 0.03, 0.04 and 0.05 M fraction) were prepared by using conventional melt quenching technique. The structural and optical properties of the proposed glass systems were characterized by using X-ray diffraction (XRD) spectroscopy, Fourier Transform Infrared (FTIR) spectroscopy, and UV-VIS spectroscopy. The amorphous nature of the glass systems is confirmed by using XRD technique. The infrared spectra of the glass systems indicate three obvious absorption bands which are assigned to BO3 and TeO4 vibrational groups. Based on the absorption spectra obtained, the direct and indirect optical band gaps, as well as the Urbach energy were calculated. It is observed that both the direct and indirect optical band gaps increase with the concentration of Dy3+ ions. On the other hand, the Urbach energy is observed to decrease as the concentration of Dy3+ ions increases.

  18. Isolation of {sup 163}Ho from dysprosium target material by HPLC for neutrino mass measurements

    Energy Technology Data Exchange (ETDEWEB)

    Mocko, Veronika; Taylor, Wayne A.; Nortier, Francois M.; Engle, Jonathan W.; Pollington, Anthony D.; Kunde, Gerd J.; Rabin, Michael W.; Birnbaum, Eva R. [Los Alamos National Laboratory, Los Alamos, NM (United States). Chemistry Div.; Barnhart, Todd E.; Nickles, Robert J. [Univ. Wisconsinn, Madison, WI (United States). Dept. of Medical Physics

    2015-07-01

    The rare earth isotope {sup 163}Ho is of interest for neutrino mass measurements. This report describes the isolation of {sup 163}Ho from a proton-irradiated dysprosium target and its purification. A Dy metal target was irradiated with 16 MeV protons for 10 h. After target dissolution, {sup 163}Ho was separated from the bulk Dy via cation-exchange high performance liquid chromatography using 70 mmol dm{sup -3} α-hydroxyisobutyric acid as the mobile phase. Subsequent purification of the collected Ho fraction was performed to remove the α-hydroxyisobutyrate chelating agent and to concentrate the Ho in a low ionic strength aqueous matrix. The final solution was characterized by MC-ICP-MS to determine the {sup 163}Ho/{sup 165}Ho ratio, {sup 163}Ho and the residual Dy content. The HPLC purification process resulted in a decontamination factor 1.4 x 10{sup 5} for Dy. The isolated Ho fraction contained 24.8 ± 1.3 ng of {sup 163}Ho corresponding to holmium recovery of 72 ± 3%.

  19. Anaerobic Treatment of Wastewaters Containing Perchlorate from Munitions Handling and Production

    Science.gov (United States)

    2008-01-01

    1 Background ...ERDC/CERL TR-08-3 1 1 Introduction Background Perchlorate is an oxidant that is widely used in propellants such as solid rocket motors, and in...result in hypothyroidism , mental retardation, and speech and hearing degradation. Treatment technology Perchlorate treatment technologies are

  20. Photodimerization and photooxygenation of 9-vinylcarbazole catalyzed by titanium dioxide and magnesium perchlorate

    Institute of Scientific and Technical Information of China (English)

    Hajime; Maeda; Mio; Yamamoto; Hideyuki; Nakagawa; Kazuhiko; Mizuno

    2010-01-01

    Photoreaction of 9-vinylcarbazole in acetonitrile in the presence of titanium dioxide and a catalytic amount of magnesium perchlorate gave 3,6-di(9-carbazolyl)-1,2-dioxane as a photooxygenated product via photodimerization of 9-vinylcarbazole.The photoreaction proceeds via an electron transfer mechanism,where magnesium perchlorate accelerated formation of the photo-oxygenated product.

  1. Hybrid Adsorption-Membrane Biological Reactors for Improved Performance and Reliability of Perchlorate Removal Processes

    Science.gov (United States)

    2008-12-01

    carbon supply for the autotrophic perchlorate reducing bacteria. The membrane used in the reactor is a hollow-fiber microfiltration membrane made from...1 HYBRID ADSORPTION- MEMBRANE BIOLOGICAL REACTORS FOR IMPROVED PERFORMANCE AND RELIABILITY OF PERCHLORATE REMOVAL PROCESSES L.C. Schideman...Center Champaign, IL 61826, USA ABSTRACT This study introduces the novel HAMBgR process (Hybrid Adsorption Membrane Biological Reactor) and

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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, ...

  5. Perchlorate in groundwater: a synoptic survey of "pristine" sites in the coterminous United States.

    Science.gov (United States)

    Parker, David R; Seyfferth, Angelia L; Reese, Brandi Kiel

    2008-03-01

    Perchlorate is widely used as an oxidant in solid rocket propellants and energetic applications, and it has frequently been detected in groundwaters at concentrations relevant to human health. The possibility of naturally occurring perchlorate has only recently received significant attention. Relying primarily on domestic, agricultural, and recreational wells, we utilized a network of volunteers to help collect 326 groundwater samples from across the coterminous United States. Care was taken to avoid known, USEPA-documented sites of perchlorate use or release, as well as perchlorate contamination due to disinfection using hypochlorite. Using IC-ESI-MS and a Cl18O4- internal standard, we achieved a method detection limit (MDL) of 40 ng/L perchlorate and a minimum reporting level (MRL) of 120 ng/L. Of the 326 samples, 147 (45%) were below the MDL, while 42 (13%) were between the MDL and the MRL. Of the 137 samples that could be quantified, most (109) contained 10000 ng/L) previously reported for the west-central Texas area appear to be anomalous. Perchlorate concentrations were positively correlated with nitrate levels (P < 0.001) but not with chloride concentrations. Opportunities exist for follow-up studies of perchlorate's origins using isotope forensics and for further elucidation of the role of atmospheric processes in the formation or transport of perchlorate.

  6. Tailored Granular Activated Carbon Treatment of Perchlorate in Drinking Water. ESTCP Cost and Performance Report

    Science.gov (United States)

    2011-08-01

    improvements in the perchlorate capacity and decreases in the market price of perchlorate selective IX resins, the operating cost of conventional...Representative Frank Lajutis Fontana Water Company 8440 Nuevo Avenue Fontana, CA 92335 Phone: (909) 822-2201, ext. 332 E-mail: cdiggs@fontanawater.com

  7. Perchlorate reduction by the sulfite/ultraviolet light advanced reduction process

    Energy Technology Data Exchange (ETDEWEB)

    Vellanki, Bhanu Prakash, E-mail: bhanuprakashvellanki@gmail.com [Zachry Department of Civil Engineering, 3136 TAMU, Texas A and M University, College Station, TX 77803-3136 (United States); Batchelor, Bill, E-mail: bill-batchelor@neo.tamu.edu [Zachry Department of Civil Engineering, 3136 TAMU, Texas A and M University, College Station, TX 77803-3136 (United States)

    2013-11-15

    Highlights: • Perchlorate removal by sulfite/UV-L advanced reduction process documented. • Perchlorate removal efficiency increases with increasing pH and temperature. • Increasing pH results in decreasing quantum yield for sulfite loss. • An optimal sulfite concentration exists for maximum perchlorate degradation. • Satisfactory chlorine recovery was obtained with chlorate and chloride the major products. • Oxygen abstraction mechanism to reduce perchlorate proposed. -- Abstract: Advanced reduction processes (ARPs) are a new class of water treatment processes that combine activation methods and reducing agents to form highly reactive reducing radicals that degrade oxidized contaminants. The combination of sulfite with low-pressure ultraviolet light (UV-L) is the most effective ARP tested to date. In this study, batch kinetic experiments were conducted to characterize the kinetics of perchlorate destruction by the sulfite/UV-L ARP. Experimental variables were pH, sulfite concentration, temperature and UV-L irradiance. The rate of perchlorate degradation by sulfite/UV-L increases with increasing pH and temperature and increases with increasing sulfite concentration to a maximum and then decreases due to lack of mixing within the reactor system used. Efficiency of perchlorate degradation was measured as a quantum yield and was observed to decrease with increasing sulfite concentration. The ultimate product of perchlorate degradation by the sulfite/UV-L ARP is chloride, but chlorate was detected as an intermediate.

  8. PERFORMANCE OF POLYVINYL ALCOHOL GEL COLUMNS ON THE ION CHROMATOGRAPHIC DETERMINATION OF PERCHLORATE IN FERTILIZERS

    Science.gov (United States)

    Interest in possible sources of perchlorate (ClO4-) that could lead to environmental release has been heightened since the EPA placed this anion on its Contaminant Candidate List (CCL) for drinking water. Besides its association with defense and aerospace activities, perchlorate ...

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

    Science.gov (United States)

    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.

  10. The impact of temperature on the performance of anaerobic biological treatment of perchlorate in drinking water.

    Science.gov (United States)

    Dugan, Nicholas R; Williams, Daniel J; Meyer, Maria; Schneider, Ross R; Speth, Thomas F; Metz, Deborah H

    2009-04-01

    A 20-month pilot-scale study was conducted to examine the impact of temperature on the performance of an anaerobic biological contractor used to treat perchlorate-contaminated water. The contractor was successfully acclimated with indigenous microorganisms. Influent temperatures varied from 1.4 to 30 degrees C. The objectives of the study were to investigate the effects of temperature on perchlorate removal, nitrate removal, nitrite formation, dissolved oxygen consumption, sulfide production, and nutrient acetate consumption. The results confirmed that consistent biological perchlorate removal to 2 microg /L is feasible at temperatures above 10 degrees C. Effluent concentrations of perchlorate, nitrate, and dissolved oxygen varied inversely with temperature, while sulfide varied positively with temperature. Under the conditions that prevailed during this study, 10 degrees C was a threshold temperature below which microbial activity, including perchlorate reduction, decreased dramatically.

  11. Specific adsorption of perchlorate anions on Pt{hkl} single crystal electrodes.

    Science.gov (United States)

    Attard, Gary A; Brew, Ashley; Hunter, Katherine; Sharman, Jonathan; Wright, Edward

    2014-07-21

    The voltammetry of Pt{111}, Pt{100}, Pt{110} and Pt{311} single crystal electrodes as a function of perchloric acid concentration (0.05-2.00 M) has been studied in order to test the assertion made in recent reports by Watanabe et al. that perchlorate anions specifically adsorb on polycrystalline platinum. Such an assertion would have significant ramifications for our understanding of electrocatalytic processes at platinum surfaces since perchlorate anions at low pH have classically been assumed not to specifically adsorb. For Pt{111}, it is found that OHad and electrochemical oxide states are both perturbed significantly as perchloric acid concentration is increased. We suggest that this is due to specific adsorption of perchlorate anions competing with OHad for adsorption sites. The hydrogen underpotential deposition (H UPD) region of Pt{111} however remains unchanged although evidence for perchlorate anion decomposition to chloride on Pt{111} is reported. In contrast, for Pt{100} no variation in the onset of electrochemical oxide formation is found nor any shift in the potential of the OHad state which normally results from the action of specifically adsorbing anions. This suggests that perchlorate anions are non-specifically adsorbed on this plane although strong changes in all H UPD states are observed as perchloric acid concentration is increased. This manifests itself as a redistribution of charge from the H UPD state situated at more positive potential to the one at more negative potential. For Pt{110} and Pt{311}, marginal changes in the onset of electrochemical oxide formation are recorded, associated with specific adsorption of perchlorate. Specific adsorption of perchlorate anions on Pt{111} is deleterious to electrocatalytic activity in relation to the oxygen reduction reaction (ORR) as measured using a rotating disc electrode (RDE) in a hanging meniscus configuration. This study supports previous work suggesting that a large component of the ORR

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

    Science.gov (United States)

    Ahn, Se Chang; Cha, Daniel K; Kim, Byung J; Oh, Seok-Young

    2011-08-30

    US Army and the Department of Defense (DoD) facilities generate perchlorate (ClO(4)(-)) 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 wastewater was rapidly decreased to an undetectable level in 2 days. This result demonstrated that iron treatment not only removed energetic compounds but also eliminated the toxic constituents that inhibited the subsequent microbial process.

  13. CRYSTALLIZATION KINETICS OF AMMONIUM PERCHLORATE IN AN AGITATED VESSEL

    Directory of Open Access Journals (Sweden)

    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.

  14. Tailored Granular Activated Carbon Treatment of Perchlorate in Drinking Water

    Science.gov (United States)

    2010-10-01

    Dekker, Inc, NY Seader , J. D. and E.J. Henley. 1998. Separation Process Principles . John Wiley and Sons, Inc. New York. Sheng, G., X. Wang, S. Wu...Properties of GAC and Tailoring Process 6  2.1.2  Schematic Diagram of the Technology 10  2.1.3  Chronological Summary of TGAC Technology Development to date...of Perchlorate in Drinking Water iii January 2010 5.4.4.1.4  Tailoring Process 58  5.4.4.1.5  Washing Process 59  5.4.4.2  38 GPM System 59  5.4.4.3

  15. Long-Range Transport of Perchlorate Observed in the Atmospheric Aerosols Collected at Okinawa Island, Japan

    Science.gov (United States)

    Handa, D.; Okada, K.; Kuroki, Y.; Nakama, Y.; Nakajima, H.; Arakaki, T.; Tanahara, A.; Oomori, T.; Miyagi, T.; Kadena, H.; Ishizaki, T.; Nakama, F.

    2007-12-01

    The study of perchlorate has become quite active in the U.S. in the last several years. Perchlorate has been recognized as a new environmental pollutant and it attracted much attention quickly in the world. The health concern about perchlorate stems from the fact that it displaces iodide in the thyroid gland, while iodine-containing thyroid hormones are essential for proper neural development from the fetal stage through the first years of life. In this study, we determined the concentrations of perchlorate ion present in the atmospheric aerosols collected in Okinawa Island, Japan. We then examined the relationships between the perchlorate concentrations and the environmental parameters and the climatic conditions peculiar to Okinawa. Bulk aerosol samples were collected on quartz filters by using a high volume air sampler at Cape Hedo Atmosphere and Aerosol Monitoring Station (CHAAMS). Each sampling duration was one week. The quartz filters with aerosols were stirred with Milli-Q pure water for three hours before perchlorate ion was extracted. The extracted perchlorate ion concentrations were determined by ion chromatography (ICS-2000, DIONEX). The mean perchlorate concentration for the samples collected at CHAAMS was 1.83 ng/m3, and the minimum was 0.18 ng/m3. The samples collected during November 21-27, 2005, January 23-30, 2006 and April 24-01, 2006 had highest perchlorate concentrations. For these three samples, we performed back trajectory analysis, and found that the air mass for the three samples arrived from the Asian continent. A relatively strong correlation (r2 = 0.55) was found between perchlorate and nss-sulfate concentrations for the CHAAMS samples. Furthermore, we analyzed perchlorate in the soils and the fertilizers used for sugar cane farming around the CHAAMS area. The Milli-Q extract of the soil and the fertilizers did not contain any detectable levels of perchlorate ions. Therefore, it was suggested that perchlorate found in the atmospheric

  16. Acute dysprosium toxicity to Daphnia pulex and Hyalella azteca and development of the biotic ligand approach.

    Science.gov (United States)

    Vukov, Oliver; Smith, D Scott; McGeer, James C

    2016-01-01

    The toxicological understanding of rare earth elements (REEs) in the aquatic environment is very limited but of increasing concern. The objective of this research is to compare the toxicological effect of the REE dysprosium to the freshwater invertebrates Daphnia pulex and Hyalella azteca and in the more sensitive organism, understand the toxicity modifying influence of Ca, Na, Mg, pH and dissolved organic matter (DOM). Standard methods (Environment Canada) were followed for testing and culture in media of intermediate hardness (60mg CaCO3 mg/L) at pH 7.8 with Ca at 0.5, Na 0.5, Mg 0.125 (mM) and 23°C. Acute toxicity tests were done with azteca and D. pulex revealed Hyalella to be 1.4 times more sensitive than Daphnia. Additions of Ca and Na but not Mg provided significant protection against Dy toxicity to Hyalella. Similarly, low pH was associated with reduction in toxicity. Exposures which were pH buffered with and without MOPS were significantly different and indicated that MOPS enhanced Dy toxicity. DOM also mitigated Dy toxicity. Biotic ligand based parameters (LogK values) were calculated based on free ion relationships as determined by geochemical equilibrium modeling software (WHAM ver. 7.02). The logK value for Dy(3+) toxicity to Hyalella was 7.75 while the protective influence of Ca and Na were 3.95 and 4.10, respectively. This study contributes data towards the development of site specific water quality guidelines and criteria for Dy and possibly REEs in general and offers insight into the complex bio-geochemical nature of this element.

  17. The relationship between perchlorate in drinking water and cord blood thyroid hormones: First experience from Iran

    Directory of Open Access Journals (Sweden)

    Ashraf Javidi

    2015-01-01

    Full Text Available Background: Considering the controversial information regarding the effects of perchlorate on thyroid function of high risk population as neonates, and given the high prevalence rate of thyroid disorders specially congenital hypothyroidism in our region, this study aims to investigate for the first time in Iran, the relationship between drinking groundwater perchlorate and cord blood thyroid hormones level in an industrial region. Methods: In this cross-sectional study, drinking groundwater perchlorate level of rural areas of Zarinshahr, Isfahan was measured. Simultaneously, cord blood level of thyroid hormones of neonates born in the studied region was measured. Thyroid function test of neonates in regions with low and high perchlorate level were compared. Results: In this study, 25 tap water samples were obtained for perchlorate measurement. Level of cord blood thyroid stimulating hormone (TSH, T4 and T3 of 25 neonates were measured. Mean (standard deviation of perchlorate, TSH, T4 and T3 was 3.59 (5.10 μg/l, 7.81 (4.14 mIU/m, 6.06 (0.85 mg/dl, and 63.46 (17.53 mg/dl, respectively. Mean levels of thyroid function tests were not different in low ( 0.05. Conclusions: Perchlorate did not appear to be related to thyroid function of neonates in the studied industrial region. It seems that iodine status of the regions, as well as other environmental contaminants and genetic background, could impact on its relation with thyroid function of neonates.

  18. [Surveillance of perchlorate level in wine, seafood, polished rice, milk, powdered milk and yogurt].

    Science.gov (United States)

    Takatsuki, Satoshi; Watanabe, Takahiro; Matsuda, Rieko

    2011-01-01

    Perchlorate, which may be naturally occurring or artificial in origin, inhibits iodide uptake into the thyroid gland and disturbs thyroid function. In order to investigate perchlorate contamination in foods in Japan, perchlorate levels in 28 wine samples, 20 seafood samples, 10 polished rice samples, 30 milk (include whole milk, composition modified milk, low fat milk, processed milk, milk drink) samples, 10 powdered milk samples and 10 yogurt samples were measured. Perchlorate was found in all wine, milk, powdered milk and yogurt samples tested. Perchlorate levels ranged from 0.2 ng/g to 103 ng/g in wine samples, from 2 ng/g to 11 ng/g in milk samples, from 3 ng/g to 35 ng/g in powdered milk samples, and from 2 ng/g to 11 ng/g in yogurt samples. Perchlorate levels in the seafood samples were under the LOQ (0.8 ng/g) in 8 samples and ranged from 0.8 ng/g to 72 ng/g in 12 samples. In all polished rice samples, perchlorate level was under the LOQ (1.0 ng/g).

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

    Science.gov (United States)

    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. Optical trapping of ultracold dysprosium atoms: transition probabilities, dynamic dipole polarizabilities and van der Waals C 6 coefficients

    Science.gov (United States)

    Li, H.; Wyart, J.-F.; Dulieu, O.; Nascimbène, S.; Lepers, M.

    2017-01-01

    The efficiency of the optical trapping of ultracold atoms depends on the atomic dynamic dipole polarizability governing the atom-field interaction. In this article, we have calculated the real and imaginary parts of the dynamic dipole polarizability of dysprosium in the ground and first excited levels. Due to the high electronic angular momentum of those two states, the polarizabilities possess scalar, vector and tensor contributions that we have computed, on a wide range of trapping wavelengths, using the sum-over-state formula. Using the same formalism, we have also calculated the C 6 coefficients characterizing the van der Waals interaction between two dysprosium atoms in the two lowest levels. We have computed the energies of excited states and the transition probabilities appearing in the sums, using a combination of ab initio and least-square-fitting techniques provided by the Cowan codes and extended in our group. Regarding the real part of the polarizability, for field frequencies far from atomic resonances, the vector and tensor contributions are two-orders-of-magnitude smaller than the scalar contribution, whereas for the imaginary part, the vector and tensor contributions represent a noticeable fraction of the scalar contribution. Finally, our anisotropic C 6 coefficients are much smaller than those published in the literature.

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

    Science.gov (United States)

    Petersen, Ann M; Earp, Nathanial C; Redmond, Mandy E; Postlethwait, John H; von Hippel, Frank A; Buck, C Loren; Cresko, William A

    2016-01-01

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  3. Kinetics of nitrate and perchlorate removal and biofilm stratification in an ion exchange membrane bioreactor.

    Science.gov (United States)

    Ricardo, Ana R; Carvalho, Gilda; Velizarov, Svetlozar; Crespo, João G; Reis, Maria A M

    2012-09-15

    The biological degradation of nitrate and perchlorate was investigated in an ion exchange membrane bioreactor (IEMB) using a mixed anoxic microbial culture and ethanol as the carbon source. In this process, a membrane-supported biofilm reduces nitrate and perchlorate delivered through an anion exchange membrane from a polluted water stream, containing 60 mg/L of NO₃⁻ and 100 μg/L of ClO₄⁻. Under ammonia limiting conditions, the perchlorate reduction rate decreased by 10%, whereas the nitrate reduction rate was unaffected. Though nitrate and perchlorate accumulated in the bioreactor, their concentrations in the treated water (2.8 ± 0.5 mg/L of NO₃⁻ and 7.0 ± 0.8 μg/L of ClO₄⁻, respectively) were always below the drinking water regulatory levels, due to Donnan dialysis control of the ionic transport in the system. Kinetic parameters determined for the mixed microbial culture in suspension showed that the nitrate reduction rate was 35 times higher than the maximum perchlorate reduction rate. It was found that perchlorate reduction was inhibited by nitrate, since after nitrate depletion perchlorate reduction rate increased by 77%. The biofilm developed in the IEMB was cryosectioned and the microbial population was analyzed by fluorescence in situ hybridization (FISH). The results obtained seem to indicate that the kinetic advantage of nitrate reduction favored accumulation of denitrifiers near the membrane, whereas per(chlorate) reducing bacteria were mainly positioned at the biofilm outer surface, contacting the biomedium. As a consequence of the biofilm stratification, the reduction of perchlorate and nitrate occur sequentially in space allowing for the removal of both ions in the IEMB.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  7. Dissimilatory reduction of perchlorate and other common pollutants by a consortium enriched from tidal flats of the Yellow Sea

    Institute of Scientific and Technical Information of China (English)

    Nirmala Bardiya; Jae-Ho Bae

    2015-01-01

    Objective: To enrich a facultative anaerobic bacterial consortium from the Yellow Sea and assess its ability to reduce perchlorate and other co-pollutants. Methods: Bacterial consortium collected from the tidal flats of the Yellow Sea was enriched in an anoxic medium containing perchlorate as the electron (e-) acceptor and acetate as the electron (e-) donor. The enriched consortium was then tested for perchlorate reduction under different perchlorate concentrations and in the presence of nitrate by using standard anaerobic techniques. The complete enzymatic reduction of perchlorate to chloride was confirmed by chlorite dismutation. Ability of the consortium to grow with alternate e- acceptors was also tested with acetate as the e- donor. Results: The enriched consortium could rapidly reduce perchlorate up to the initial concentration of 25.65 mmol/L. In the presence of nitrate, perchlorate reduction did not occur immediately and reduction of nitrate started after a lag phase, with concomitant accumulation of nitrite. The perchlorate-enriched consortium could reduce chlorate, oxygen, Cr (VI), and selenate as the alternate e- acceptors but failed to utilize sulfate, thiosulfate, sulfite, and nitrite. Conclusions: The consortium from the tidal flats of the Yellow Sea could reduce perchlorate and co-contaminants such as chlorate, nitrate, Cr (VI), and selenate under heterotrophic conditions with acetate as the e- donor and carbon source. While perchlorate was completely dismutated into innocuous chloride and oxygen, accumulation of nitrite occurred during the reduction of nitrate.

  8. Acute dysprosium toxicity to Daphnia pulex and Hyalella azteca and development of the biotic ligand approach

    Energy Technology Data Exchange (ETDEWEB)

    Vukov, Oliver, E-mail: vuko3930@mylaurier.ca [Biology Department, Wilfrid Laurier University, Waterloo, Ontario N2L 3C5 (Canada); Smith, D. Scott [Chemistry Department, Wilfrid Laurier University, Waterloo, Ontario N2L 3C5 (Canada); McGeer, James C. [Biology Department, Wilfrid Laurier University, Waterloo, Ontario N2L 3C5 (Canada)

    2016-01-15

    The toxicological understanding of rare earth elements (REEs) in the aquatic environment is very limited but of increasing concern. The objective of this research is to compare the toxicological effect of the REE dysprosium to the freshwater invertebrates Daphnia pulex and Hyalella azteca and in the more sensitive organism, understand the toxicity modifying influence of Ca, Na, Mg, pH and dissolved organic matter (DOM). Standard methods (Environment Canada) were followed for testing and culture in media of intermediate hardness (60 mg CaCO{sub 3} mg/L) at pH 7.8 with Ca at 0.5, Na 0.5, Mg 0.125 (mM) and 23 °C. Acute toxicity tests were done with <24 h old neonates for 48 h in the case of D. pulex and with 2–9 days old offspring for 96 h tests with Hyalella. The potential protective effect of cationic competition was tested with Ca (0.5–2.0 mM), Na (0.5–2.0 mM) and Mg (0.125–0.5 mM). The effect of pH (6.5–8.0) and Suwannee River DOM complexation (at dissolved organic carbon (DOC) concentrations of 9 and 13 mg C/L) were evaluated. Dissolved Dy concentrations were lower than total (unfiltered) indicating precipitation, particularly at higher concentrations. Acute toxicity of Dy to H. azteca and D. pulex revealed Hyalella to be 1.4 times more sensitive than Daphnia. Additions of Ca and Na but not Mg provided significant protection against Dy toxicity to Hyalella. Similarly, low pH was associated with reduction in toxicity. Exposures which were pH buffered with and without MOPS were significantly different and indicated that MOPS enhanced Dy toxicity. DOM also mitigated Dy toxicity. Biotic ligand based parameters (Log K values) were calculated based on free ion relationships as determined by geochemical equilibrium modeling software (WHAM ver. 7.02). The log K value for Dy{sup 3+} toxicity to Hyalella was 7.75 while the protective influence of Ca and Na were 3.95 and 4.10, respectively. This study contributes data towards the development of site specific

  9. White light emission of dysprosium doped lanthanum calcium phosphate oxide and oxyfluoride glasses

    Science.gov (United States)

    Luewarasirikul, N.; Kim, H. J.; Meejitpaisan, P.; Kaewkhao, J.

    2017-04-01

    Lanthanum calcium phosphate oxide and oxyfluoride glasses doped with dysprosium oxide were prepared by melt-quenching technique with chemical composition 20La2O3:10CaO:69P2O5:1Dy2O3 and 20La2O3:10CaF2:69P2O5:1Dy2O3. The physical, optical and luminescence properties of the glass samples were studied to evaluate their potential to using as luminescence materials for solid-state lighting applications. The density, molar volume and refractive index of the glass samples were carried out. The optical and luminescence properties were studied by investigating absorption, excitation, and emission spectra of the glass samples. The absorption spectra were investigated in the UV-Vis-NIR region from 300 to 2000 nm. The excitation spectra observed under 574 nm emission wavelength showed the highest peak centered at 349 nm (6H15/2 → 6P7/2). The emission spectra, excited with 349 nm excitation wavelength showed two major peaks corresponding to 482 nm blue emission (4F9/2 → 6H15/2) and 574 nm yellow emission (4F9/2 → 6H13/2). The experimental lifetime were found to be 0.539 and 0.540 for oxide and oxyfluoride glass sample, respectively. The x,y color coordinates under 349 nm excitation wavelength were (0.38, 0.43) for both glass samples, that be plotted in white region of CIE 1931 chromaticity diagram. The CCT values obtained from the glass samples are 4204 K for oxide glass and 4228 K for oxyfluoride glass corresponding to the commercial cool white light (3100-4500 K). Judd-Ofelt theory had also been employed to obtain the J-O parameters (Ω2, Ω4 and Ω6), oscillator strength, radiative transition possibility, stimulated emission cross section and branching ratio. The Ω2 > Ω4 > Ω6 trend of J-O parameters of both glass samples may indicate the good quality of a glass host for using as optical device application. Temperature dependence of emission spectra was studied from 300 K to 10 K and found that the intensity of the emission peak was found to be increased with

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

    Directory of Open Access Journals (Sweden)

    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.

  11. POLISHING THE EFFLUENT FROM AN ANAEROBIC BIOLOGICAL PERCHLORATE TREATMENT PROCESS - SLIDES

    Science.gov (United States)

    Anaerobic biological processes effectively reduce perchlorate to chloride. However, the effluent can be biologically unstable, high in particulates and high in disinfection by-product precursor compounds. Such an effluent would be unsuitable for transmission into a drinking water...

  12. Perchlorate Selectivity of Anion Exchange Resins as Evaluated Using Ion-Selective Electrodes.

    Science.gov (United States)

    Yamamoto, Kenji; Mitsuda, Shin'ya; Ohtake, Naomi; Murashige, Natsuki; Ohmuro, Satoshi; Yuchi, Akio

    2017-01-01

    The selectivity coefficients reported for perchlorate of the high selectivity on anion exchange resins (AXRs) have not been consistent with one another. Possible errors by the unique use of four parameters (concentrations of two anions in two phases) were experimentally verified. The concentrations of perchlorate buffered at low levels (10(-6) - 10(-4) mol L(-1)) by two forms of AXRs were successfully determined by potentiometry with a perchlorate ion-selective electrode. This gave reasonable coefficients. The coefficients for perchlorate on several AXRs were independent of the relative exchange (RE), in contrast to the previous reports. On the other hand, the coefficients for fluoride of the low selectivity that were examined for comparison decreased with an increase in RE, and the dependency was more remarkable for the resins of large exchange capacity.

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

    Science.gov (United States)

    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...

  14. The Impact of Temperature on the Performance of Anaerobic Biological Treatment of Perchlorate in Drinking Water

    Science.gov (United States)

    A 20 month pilot-scale study was conducted to examine the impact of temperature on the performance of an anaerobic biological contactor used to treat perchlorate-contaminated water. The contactor was successfully acclimated with indigenous microorganisms. Influent temperatures ...

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

    Science.gov (United States)

    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...

  16. Perchlorate in dust fall and indoor dust in Malta: An effect of fireworks.

    Science.gov (United States)

    Vella, Alfred J; Chircop, Cynthia; Micallef, Tamara; Pace, Colette

    2015-07-15

    We report on the presence of perchlorate in the settleable dust of Malta, a small central Mediterranean island. Both dust fall collected directly as it precipitated from atmosphere over a period of one month and deposited indoor dust from domestic residences were studied. Perchlorate was determined by ion chromatography of water extracts of the collected dusts. Dust fall was collected from 43 towns during 2011 to 2013 and indoor dust was sampled from homes in the same localities. Perchlorate was detected in 108 of 153 samples of dust fall (71%) and in 28 of 37 indoor dust samples (76%). Detectable perchlorate in dust fall ranged from 0.52μgg(-1) to 561μgg(-1) with a median value of 6.2μgg(-1); in indoor dust, levels were from 0.79μgg(-1) to 53μgg(-1) with a median value of 7.8μgg(-1), the highest recorded anywhere to date. Statistical analysis suggested that there was no significant difference in perchlorate content of indoor dust and dust fall. Perchlorate levels in dust fall escalate during the summer in response to numerous religious feasts celebrated with fireworks and perchlorate persists at low μgg(-1) concentrations for several months beyond the summer festive period. In Malta, perchlorate derives exclusively from KClO4, imported for fireworks manufacture. Its residue in dust presents an exposure risk to the population, especially via ingestion by hand to mouth transfer. Our results suggest that wherever intensive burning of fireworks takes place, the environmental impact may be much longer lived than realised, mainly due to re-suspension and deposition of contaminated settled dust in the urban environment.

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

    Science.gov (United States)

    Navarro-Gonzalex, Rafael; Sutter, Brad; Archer, Doug; Ming, Doug; Eigenbrode, Jennifer; Franz, Heather; Glavin, Daniel; McAdam, Amy; Stern, Jennifer; McKay, Christopher; Coll, Patrice; Cabane, Michel; Mahaffy, Paul; Conrad, Pamela; Martin-Torres, Francisco; Zorzano-Mier, Maria; Grotzinger, John

    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 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 chlorides catalyzed by mineral catalysts [7]. The presence of soil perchlorates in the Martian surface has important implications for the detection of organics [2], carbonates [8] and nitrates [9] by SAM.

  18. Preparation of perlite-based magnesium perchlorate desiccant with colour indicator.

    Science.gov (United States)

    Wu, L; He, H

    1994-05-01

    A new desiccant consisting of magnesium perchlorate, expanded perlite and metal chelate was prepared. The performance tests show that the desiccant is superior to magnesium perchlorate desiccant in dehydration efficiency, absorption capacity for water, flow resistance, color indicator and regeneration. It can reduce the amount of water in gases to approximately 0.7 ppm(v/v). Its applications in gas analysis and purification were investigated.

  19. Evaluation of Potential for Monitored Natural Attenuation of Perchlorate in Groundwater (Indian Head)

    Science.gov (United States)

    2010-07-01

    material. There are a wide variety of microorganisms can degrade perchlorate to chloride and oxygen under oxygen limiting conditions (Coates et al., 1999...anaerobic respiration when oxygen is not present. This metabolic versatility suggests that 2 perchlorate reducing microorganisms will be active...consisted of mottled light to olive brown clay to sandy silts. The clay and sand fractions of the silts varied horizontally and vertically. Fine

  20. 1-Benzyl-piperazine-1,4-diium bis-(perchlorate) monohydrate.

    Science.gov (United States)

    Kaabi, Kamel; El Glaoui, Meher; Jeanneau, Erwann; Rzaigui, Mohamed; Ben Nasr, Cherif

    2010-06-23

    In the title compound, C(11)H(18)N(2) (2+)·2ClO(4) (-)·H(2)O, one perchlor-ate anion is disordered over two orientations in a 0.66 (3):0.34 (3) ratio. Inter-molecular O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds link the cations, anions and water mol-ecules into ribbons extending along [100].

  1. Anaerobic treatment of army ammunition production wastewater containing perchlorate and RDX.

    Science.gov (United States)

    Atikovic, Emina; Suidan, Makram T; Maloney, Stephen W

    2008-08-01

    Perchlorate is an oxidizer that has been routinely used in solid rocket motors by the Department of Defense and National Aeronautics and Space Administration. Royal Demolition Explosive (RDX) is a major component of military high explosives and is used in a wide variety of munitions. Perchlorate bearing wastewater typically results from production of solid rocket motors, while RDX is transferred to Army industrial wastewaters during load, assemble and pack operations for new munitions, and hot water or steam washout for disposal and deactivation of old munitions (commonly referred to as demilitarization, or simply demil). Biological degradation in Anaerobic Fluidized Bed Reactors (AFBR), has been shown to be an effective method for the removal of both perchlorate and RDX in contaminated wastewater. The focus of this study was to determine the effectiveness of removal of perchlorate and RDX, individually and when co-mingled, using ethanol as an electron donor under steady state conditions. Three AFBRs were used to assess the effectiveness of this process in treating the wastewater. The performance of the bioreactors was monitored relative to perchlorate, RDX, and chemical oxygen demand removal effectiveness. The experimental results demonstrated that the biodegradation of perchlorate and RDX was more effective in bioreactors receiving the single contaminant than in the bioreactor where both contaminants were fed.

  2. An improved ion chromatographic method for determination of trace levels of perchlorate in environmental water

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    An improved ion chromatographic (IC)method was developed to determine trace levels of perchlorate in environmental water samples.Perchlorate was separated in the hydroxide selective column IonPac AS 16 using NaOH as an eluent with an organic modifier.To eliminate the coelution of perchlorate and 4-chlorobenzene sulfonate (4-CBS),an organic solvent as modifier was added to the eluent.Of four organic solvents studied,acetonitrile proved to be the most efficient based on the retention time of perchlorate and 4-CBS.To improve the method sensitivity,a concentrator column (AGI9) was used to concentrate perchlorate online.With the adoption of a preconcentration step,the sensitivity of our method was improved and the method detection limit (MDL) was reduced to 0.1 μg/L.The linear range was from 0.2 μg/L to 200/.μg/L with a linear correlation coefficient of 0.9989 and the relative standard deviation (RSD) of peak area for eleven successive injections of 0.5 μg/L perehlorate was 4.2%.The method had been applied to the determination of perchlorate in some real environmental water samples and recovery was between 93% and 113%.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  5. Perchlorate contamination of groundwater from fireworks manufacturing area in South India.

    Science.gov (United States)

    Isobe, Tomohiko; Ogawa, Shohei P; Sugimoto, Rina; Ramu, Karri; Sudaryanto, Agus; Malarvannan, Govindan; Devanathan, Gnanasekaran; Ramaswamy, Babu Rajendran; Munuswamy, Natesan; Ganesh, Deavaraj Sankar; Sivakumar, Jeyaraj; Sethuraman, A; Parthasarathy, V; Subramanian, Annamalai; Field, Jennifer; Tanabe, Shinsuke

    2013-07-01

    Perchlorate contamination was investigated in groundwater and surface water from Sivakasi and Madurai in the Tamil Nadu State of South India. Sensitive determination of perchlorate (LOQ = 0.005 μg/L) was achieved by large-volume (500 μL) injection ion chromatography coupled with tandem mass spectrometry. Concentrations of perchlorate were <0.005-7,690 μg/L in groundwater (n = 60), <0.005-30.2 μg/L in surface water (n = 11), and 0.063-0.393 μg/L in tap water (n = 3). Levels in groundwater were significantly higher in the fireworks factory area than in the other locations, indicating that the fireworks and safety match industries are principal sources of perchlorate pollution. This is the first study that reports the contamination status of perchlorate in this area and reveals firework manufacture to be the pollution source. Since perchlorate levels in 17 out of 57 groundwater samples from Sivakasi, and none from Madurai, exceeded the drinking water guideline level proposed by USEPA (15 μg/L), further investigation on human health is warranted.

  6. PERCHLORATE: Occurrence is Widespread but at Varying Levels; Federal Agencies Have Taken Some Actions to Respond to and Lessen Releases

    Science.gov (United States)

    2010-08-01

    tomatoes and spinach, having higher perchlorate levels than others. According to researchers, concentrations of perchlorate at or above 100 parts per...These food items represent the major components of the American diet, such as dairy, meat, fruits, and vegetables. Certain foods, such as tomatoes ...Administration’s Total Diet Study: Dietary intake of perchlorate and iodine ,” Journal of Exposure Science and Environmental Epidemiology, vol. 18 (2008

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Limits on violations of Lorentz symmetry and the Einstein equivalence principle using radio-frequency spectroscopy of atomic dysprosium.

    Science.gov (United States)

    Hohensee, M A; Leefer, N; Budker, D; Harabati, C; Dzuba, V A; Flambaum, V V

    2013-08-02

    We report a joint test of local Lorentz invariance and the Einstein equivalence principle for electrons, using long-term measurements of the transition frequency between two nearly degenerate states of atomic dysprosium. We present many-body calculations which demonstrate that the energy splitting of these states is particularly sensitive to violations of both special and general relativity. We limit Lorentz violation for electrons at the level of 10(-17), matching or improving the best laboratory and astrophysical limits by up to a factor of 10, and improve bounds on gravitational redshift anomalies for electrons by 2 orders of magnitude, to 10(-8). With some enhancements, our experiment may be sensitive to Lorentz violation at the level of 9 × 10(-20).

  9. Nonlinear optical properties of lutetium and dysprosium bisphthalocyanines at 1550 nm with femto- and nanosecond pulse excitation

    Science.gov (United States)

    Plekhanov, A. I.; Basova, T. V.; Parkhomenko, R. G.; Gürek, A. G.

    2017-02-01

    In this work, the nonlinear optical properties of unsubstituted lutetium (LuPc2) and dysprosium (DyPc2) bisphthalocyanines as well as octasubstituted Lu(PcR8)2 derivative with R=-S(C6H13) were studied at a wavelength of 1550 nm with 10 ns and 300 fs pulses. Based on Z-scan measurements the nonlinear absorption and refraction coefficient as well as the nature of nonlinear optical properties were analyzed for these materials. Open aperture Z-scan indicates strong two-photon absorption in all three bisphthalocyanines in nano- and femtosecond regimes. With good nonlinear optical coefficients, bisphthalocyanines of rare earth elements are expected to be promising materials for the creation of optical limiters.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. Soil Flushing Through a Thick Vadose Zone: Perchlorate Removal Documented at Edwards AFB, California

    Science.gov (United States)

    Battey, T. F.; Shepard, A. J.; Tait, R. J.

    2007-12-01

    There are currently few viable alternatives for perchlorate remediation in the vadose zone, particularly for the relatively thick vadose zones that are typical in the arid southwest where many perchlorate sites occur. Perchlorate in the vadose zone occurs in the form of highly soluble salts that may represent a risk to human or ecological receptors, and may also represent a threat to the underlying groundwater. A soil flushing treatability study was conducted at Edwards Air Force Base in the Mojave Desert of southern California at a site with a 129-foot thick vadose zone consisting primarily of clayey sand. This study utilized an infiltration gallery in conjunction with extraction, treatment, and re-injection of groundwater at the site, which contained perchlorate-contaminated soil and groundwater. The study objective was to evaluate the effectiveness of the infiltration gallery to 1) introduce treated groundwater back into the aquifer and 2) wash the perchlorate from the vadose zone soils to the aquifer. The infiltration gallery consisted of slotted PVC pipes within a highly permeable engineered bed of washed gravel. The initial water introduced into the gallery was amended with potassium bromide tracer. A downhole neutron probe was used to track the movement of the wetting front downward and outward from the gallery. Successive neutron measurements in vertical access tubes revealed that the introduced water reached the 125-foot bottom of the access tubes 14 weeks after the water was introduced into the gallery. The bromide tracer was detected in groundwater immediately below the gallery approximately 1 week later. The infiltration gallery was able to sustain an average flow rate of 2.3 gallons per minute. Prior to infiltration, the perchlorate concentration in groundwater below the gallery was 4,500 µg/L. Approximately 18 weeks after the start of infiltration, a perchlorate spike of 72,400 µg/L was detected below the gallery. The increase in perchlorate

  12. Spectroscopic data of the 1.8-, 2.9-, and 4.3- mu m transitions in dysprosium-doped gallium lanthanum sulfide glass

    Science.gov (United States)

    Schweizer, T.; Hewak, D. W.; Samson, B. N.; Payne, D. N.

    1996-10-01

    Infrared emission at 1.8, 2.9, and 4.3 mu m is measured in dysprosium-doped gallium lanthanum sulfide (Ga:La:S) glass excited at 815 nm. Emission cross sections were calculated by Judd-Ofelt analysis, the Fuchtbauer-Ladenburg equation, and the theory of McCumber. The sigma tau value for the 4.3- mu m transition is \\similar 4000 times larger in the Ga:La:S glass than in a dysprosium-doped LiYF4 crystal, which has lased on this transition. The large sigma tau value and the recently reported ability of Ga:La:S glass to be fabricated into fiber form show the potential for an efficient, low-threshold mid-infrared fiber laser. The fluorescence peak at 4.3 mu m coincides with the fundamental absorption of atmospheric carbon dioxide, making the glass a potential laser source for gas-sensing applications.

  13. Spectroscopic data of the 1.8-, 2.9-, and 4.3-microm transitions in dysprosium-doped gallium lanthanum sulfide glass.

    Science.gov (United States)

    Schweizer, T; Hewak, D W; Samson, B N; Payne, D N

    1996-10-01

    Infrared emission at 1.8, 2.9, and 4.3 microm is measured in dysprosium-doped gallium lanthanum sulfide (Ga:La:S) glass excited at 815 nm. Emission cross sections were calculated by Judd-Ofelt analysis, the Füchtbauer- Ladenburg equation, and the theory of McCumber. The sigmatau value for the 4.3-microm transition is ~4000 times larger in the Ga:La:S glass than in a dysprosium-doped LiYF(4) crystal, which has lased on this transition. The large sigmatau value and the recently reported ability of Ga:La:S glass to be fabricated into fiber form show the potential for an efficient, low-threshold mid-infrared fiber laser. The f luorescence peak at 4.3 microm coincides with the fundamental absorption of atmospheric carbon dioxide, making the glass a potential laser source for gas-sensing applications.

  14. On-line complexation/cloud point preconcentration for the sensitive determination of dysprosium in urine by flow injection inductively coupled plasma-optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ortega, Claudia; Cerutti, Soledad; Silva, Maria F. [Departamento de Quimica Analitica, Facultad de Quimica, Bioquimica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700, San Luis (Argentina); Olsina, Roberto A.; Martinez, Luis D. [Departamento de Quimica Analitica, Facultad de Quimica, Bioquimica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, 5700, San Luis (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Avda. Rivadavia 1917, CP C1033AAJJ, Buenos Aires (Argentina)

    2003-01-01

    An on-line dysprosium preconcentration and determination system based on the hyphenation of cloud point extraction (CPE) to flow injection analysis (FIA) associated with ICP-OES was studied. For the preconcentration of dysprosium, a Dy(III)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex was formed on-line at pH 9.22 in the presence of nonionic micelles of PONPE-7.5. The micellar system containing the complex was thermostated at 30 C in order to promote phase separation, and the surfactant-rich phase was retained in a microcolumn packed with cotton at pH 9.2. The surfactant-rich phase was eluted with 4 mol L{sup -1} nitric acid at a flow rate of 1.5 mL min{sup -1}, directly in the nebulizer of the plasma. An enhancement factor of 50 was obtained for the preconcentration of 50 mL of sample solution. The detection limit value for the preconcentration of 50 mL of aqueous solution of Dy was 0.03 {mu}g L{sup -1}. The precision for 10 replicate determinations at the 2.0 {mu}g L{sup -1}Dy level was 2.2% relative standard deviation (RSD), calculated from the peak heights obtained. The calibration graph using the preconcentration system for dysprosium was linear with a correlation coefficient of 0.9994 at levels near the detection limits up to at least 100 {mu}g L {sup -1}. The method was successfully applied to the determination of dysprosium in urine. (orig.)

  15. 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

    NARCIS (Netherlands)

    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 o

  16. Effects of lanthanum nitrate on growth and chlorophyll fluorescence characteristics of Alternanthera philoxeroides under perchlorate stress

    Institute of Scientific and Technical Information of China (English)

    谢寅峰; 蔡贤雷; 刘伟龙; 陶功胜; 陈倩; 张强

    2013-01-01

    To investigate the effects of exogenous lanthanum (La) on Alternanthera philoxeroides (Mart.) Griseb under perchlorate stress, changes in the growth and physiological parameters were investigated in solution culture experiments under controlled condi-tions. Different concentrations of La (NO3)3 were used in our study. It was shown that 0.1 and 0.5 mg/L La3+alleviated the inhibition effect of perchlorate on A. philoxeroides, including relative growth yield, dry weight of different organs, leaf area and root activity. And La3+prevented decline in the relative chlorophyll content and chlorophyll fluorescence parameters including Fv/Fm, Fv'/Fm',ΦPSI and ETR induced by perchlorate stress. Moreover, 0.5 mg/L La3+showed an optimal mitigative effect, while excess La3+(5.0 mg/L) led to synergistic effect on stress. Correlation analysis revealed a significant positive relationship between growth indexes and the chlorophyll fluorescence parameters, root activity and relative chlorophyll content (p<0.05). The results suggested that appropriate concentration of La3+could effectively alleviate growth inhibition and injury of A. philoxeroides caused by perchlorate stress, and the mitigative effect of La3+might be achieved by improving root activity, maintaining chlorophyll content and promoting photochemical efficiency of photosystem II of A. philoxeroides under perchlorate stress.

  17. Highly Selective Perchlorate Membrane Electrode Based on Cobalt(Ⅲ) Schiff Base as a Neutral Carrier

    Institute of Scientific and Technical Information of China (English)

    SHOKROLLAHI Ardeshir; GHAEDI Mehrorang; RAJABI, Harold Reza; KIANFAR, Ali Hossein

    2009-01-01

    A highly selective poly(vinyl chloride) (PVC) membrane electrode based on Co(Ⅲ)-Schiff base [Co(5-NO2-Salen)(PBu3)]ClO4·H2O (where 5-NO2-SalenH=bis(5-nitrosalycilaldehyde)ethylenediamine) as a new carrier for construction of perchlorate-selective electrode by incorporating the membrane ingredients on the surface of a graphite electrodes has been reported. The proposed electrode possesses a very wide Nernestian potential linear range to perchlorate from 1.0×10-6 to 5.0×10-1 mol·L-1 with a slope of (59.4±0.9) mV per decade of perchlo-rate concentration with a low detection limit of 5.0×10-7 mol·L-1 and good perchlorate selectivity over the wide variety of other anions. The developed electrode has an especially fast response (<5 s) and a wide pH independent range (3.0-12.0) in comparison with recent reported electrodes and can be used for at least 2 months without any considerable divergence in their potential response. This electrode was used for the determination of perchlorate in river water, drinking water, sludgy water and human urine with satisfactory results without complicated and time consuming pretreatment.

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

    Science.gov (United States)

    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.

  19. [Determination of iodide, thiocyanate and perchlorate ions in environmental water by two-dimensional ion chromatography].

    Science.gov (United States)

    Lin, Li; Wang, Haibo; Shi, Yali

    2013-03-01

    A procedure for the determination of iodide, thiocyanate and perchlorate ions in environmental water by two-dimensional ion chromatography has been developed. At first the iodide, thiocyanate and perchlorate ions were separated from interfering ions by a column (IonPac AS16, 250 mm x 4 mm). The iodide ion, thiocyanate and perchlorate ions were then enriched with an enrichment column (MAC-200, 80 mm x 0.75 mm). In the 2nd-dimensional chromatography, iodide thiocyanate and perchlorate ions were separated and quantified by a capillary column (IonPac AS20 Capillary, 250 mm x 0.4 mm). The linear ranges were 0.05 -100 pg/L with correlation coefficients of 0. 999 9, and the detection limits were 0. 02 - 0.05 micro gg/L. The spiked recoveries of iodide, thiocyanate and perchlorate ions were in the range of 85.1% to 100.1%. The relative standard deviations of the recoveries were 1.7% to 4.9%.

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

    Science.gov (United States)

    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.

  1. Perchlorate and Nitrate Remediation Efficiency and Microbial Diversity in a Containerized Wetland Bioreactor

    Energy Technology Data Exchange (ETDEWEB)

    Jr., B D; Dibley, V; Pinkart, H; Legler, T

    2004-06-09

    We have developed a method to remove perchlorate (14 to 27 {micro}g/L) and nitrate (48 mg/L) from contaminated groundwater using a wetland bioreactor. The bioreactor has operated continuously in a remote field location for more than two years with a stable ecosystem of indigenous organisms. This study assesses the bioreactor for long-term perchlorate and nitrate remediation by evaluating influent and effluent groundwater for reduction-oxidation conditions and nitrate and perchlorate concentrations. Total community DNA was extracted and purified from 10-g sediment samples retrieved from vertical coring of the bioreactor during winter. Analysis by denaturing gradient gel electrophoresis of short, 16S rDNA, polymerase-chain-reaction products was used to identify dominant microorganisms. Bacteria genera identified were closely affiliated with bacteria widely distributed in soils, mud layers, and fresh water. Of the 17 dominant bands sequenced, most were gram negative and capable of aerobic or anaerobic respiration with nitrate as the terminal electron acceptor (Pseudomonas, Acinetobacter, Halomonas, and Nitrospira). Several identified genera (Rhizobium, Acinetobactor, and Xanthomonas) are capable of fixing atmospheric nitrogen into a combined form (ammonia) usable by host plants. Isolates were identified from the Proteobacteria class, known for the ability to reduce perchlorate. Initial bacterial assessments of sediments confirm the prevalence of facultative anaerobic bacteria capable of reducing perchlorate and nitrate in situ.

  2. Chlorine-36 abundance in natural and synthetic perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

  4. Hydrogen oxidation on gold electrode in perchloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    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)

  5. Kinetics of chlorite dismutase in a perchlorate degrading reactor sludge.

    Science.gov (United States)

    Nadaraja, Anupama Vijaya; Veetil, Prajeesh Gangadharan Puthiya; Vidyadharan, Athira; Bhaskaran, Krishnakumar

    2013-01-01

    Kinetics of chlorite dismutase (CD), the terminal enzyme involved in the perchlorate (ClO4(-)) reduction pathway, in a ClO4(-)-degrading bioreactor are reported in this study. Enzyme activity was determined from dissolved oxygen released during disproportionation of chlorite (ClO2(-)). CD activity was in the range 29.8-36.4 U/mg dry weight sludge, and kinetic constants Vmax and K(m) of the enzyme were 37.83 U/mg dry weight and 0.28 mM, respectively. Among reactor operational conditions, enzyme activity was observed at pH 4.0-9.0, with an optimum at pH 6.0. Redox potential in the range -50 to +120mV and NaCl up to 3.5 g/L had no significant effect on CD activity. However, co-occurring pollutants such as ammonium at 10 ppm, nitrite at 50 ppm and EDTA at 100 microM reduced CD activity substantially. The present study highlights ideal bioreactor conditions to avoid ClO2(-) toxicity, while indicating the buffering potential of a mixed microbial system against inhibiting factors to maintain stable CD activity in bioreactors.

  6. SURVEY OF BOTTLED WATERS FOR PERCHLORATE BY ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS) AND ION CHROMATOGRAPHY (IC)

    Science.gov (United States)

    Perchlorate has been identified in ground and surface waters around the US, including some that serve as supplies for drinking water. Because perchlorate salts are used as solid oxidants in rockets and ordnance, water contamination may occur near military or aerospace installatio...

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

    Science.gov (United States)

    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...

  8. Kinetics of nitrate and perchlorate reduction in ion exchange brine using the membrane biofilm reactor (MBfR)

    Science.gov (United States)

    Several sources of bacterial inocula were tested for their ability to reduce nitrate and perchlorate in synthetic ion-exchange spent brine (3-4.5% salinity) using a hydrogen-based membrane biofilm reactor (MBfR). Nitrate and perchlorate removal fluxes reached as high as 5.4 g N ...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Preparation, characterization and thermolysis of nitrate and perchlorate salts of 2,4,6-trimethylaniline.

    Science.gov (United States)

    Kapoor, Inder Pal Singh; Kapoor, Manisha; Singh, Gurdip; Singh, Udai P; Goel, Nidhi

    2010-01-15

    Nitrate and perchlorate salts of 2,4,6-trimethylaniline have been prepared and characterized by X-ray crystallography and gravimetric analyses. Their thermal decomposition has been studied by TG, TG-DSC and ignition/explosion delays. It has been observed that proton transfer from substituted anilinium ion to nitrate and perchlorate ion regenerate amine, HNO(3) and HClO(4) in condensed phase at higher temperature, where oxidation-reduction between amine and acids leads to ignition and explosion. The kinetics of thermal decomposition was evaluated by applying model fitting as well as isoconversional methods. The values of calculated activation energy of nitrate and perchlorate salts are 77.9 and 118.2 kJ mol(-1) respectively. The possible pathways of thermolysis of these salts have also been proposed.

  11. Preparation, characterization and thermolysis of nitrate and perchlorate salts of 2,4,6-trimethylaniline

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Inder Pal Singh; Kapoor, Manisha [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273009 (India); Singh, Gurdip, E-mail: gsingh4us@yahoo.com [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273009 (India); Singh, Udai P.; Goel, Nidhi [Department of Chemistry, Indian Institute of Technology, Roorkee, Roorkee 247667 (India)

    2010-01-15

    Nitrate and perchlorate salts of 2,4,6-trimethylaniline have been prepared and characterized by X-ray crystallography and gravimetric analyses. Their thermal decomposition has been studied by TG, TG-DSC and ignition/explosion delays. It has been observed that proton transfer from substituted anilinium ion to nitrate and perchlorate ion regenerate amine, HNO{sub 3} and HClO{sub 4} in condensed phase at higher temperature, where oxidation-reduction between amine and acids leads to ignition and explosion. The kinetics of thermal decomposition was evaluated by applying model fitting as well as isoconversional methods. The values of calculated activation energy of nitrate and perchlorate salts are 77.9 and 118.2 kJ mol{sup -1} respectively. The possible pathways of thermolysis of these salts have also been proposed.

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

    Science.gov (United States)

    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.

  13. Microbial perchlorate reduction: A precise laboratory determination of the chlorine isotope fractionation and its possible biochemical basis

    Science.gov (United States)

    Ader, Magali; Chaudhuri, Swades; Coates, John D.; Coleman, Max

    2008-05-01

    Perchlorate-reducing bacteria fractionate chlorine stable isotopes giving a powerful approach to monitor the extent of microbial consumption of perchlorate in contaminated sites undergoing remediation or natural perchlorate containing sites. This study reports the full experimental data and methodology used to re-evaluate the chlorine isotope fractionation of perchlorate reduction in duplicate culture experiments of Azospira suillum strain PS at 37 °C (Δ 37Cl Cl --ClO 4-) previously reported, without a supporting data set by Coleman et al. [Coleman, M.L., Ader, M., Chaudhuri, S., Coates, J.D., 2003. Microbial Isotopic Fractionation of Perchlorate Chlorine. Appl. Environ. Microbiol. 69, 4997-5000] in a reconnaissance study, with the goal of increasing the accuracy and precision of the isotopic fractionation determination. The method fully described here for the first time, allows the determination of a higher precision Δ 37Cl Cl --ClO 4- value, either from accumulated chloride content and isotopic composition or from the residual perchlorate content and isotopic composition. The result sets agree perfectly, within error, giving average Δ 37Cl Cl --ClO 4- = - 14.94 ± 0.15‰. Complementary use of chloride and perchlorate data allowed the identification and rejection of poor quality data by applying mass and isotopic balance checks. This precise Δ 37Cl Cl --ClO 4- value can serve as a reference point for comparison with future in situ or microcosm studies but we also note its similarity to the theoretical equilibrium isotopic fractionation between a hypothetical chlorine species of redox state + 6 and perchlorate at 37 °C and suggest that the first electron transfer during perchlorate reduction may occur at isotopic equilibrium between an enzyme-bound chlorine and perchlorate.

  14. Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

    Science.gov (United States)

    Bohlke, Johnkarl F.; Hatzinger, P.B.; Sturchio, N.C.; Gu, B.; Heraty, L.J.; Borden, R.C.

    2009-01-01

    An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br– as a conservative tracer of the injectate), perchlorate concentrations decreased by 78% and nitrate concentrations decreased by 82% during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (e18O/e37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of ~0.8 (e18O/e15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (e18O/e37Cl, e18O/e15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent e values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion.

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

    Science.gov (United States)

    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.

  16. Linking methane oxidation with perchlorate reduction: a microbial base for possible Martian life

    Science.gov (United States)

    Miller, L. G.; Carlstrom, C.; Baesman, S. M.; Coates, J. D.; Oremland, R. S.

    2011-12-01

    Recent observations of methane (CH4) and perchlorate (ClO4-) within the atmosphere and surface of Mars, respectively, provide impetus for establishing a metabolic linkage between these compounds whereby CH4 acts as an electron donor and perchlorate acts as an electron acceptor. Direct linkage through anaerobic oxidation of methane (AOM) has not been observed. However, indirect syntrophic oxygenase-dependent oxidation of CH4 with an aerobic methane oxidizer is feasible. The pathway for anaerobic dissimilatory perchlorate reduction includes 3 steps. The first 2 are sequential reductions of (1) perchlorate to chlorate and (2) chlorate to chlorite, mediated by perchlorate reductase. The third step is disproportionation of chlorite to chloride and molecular oxygen, mediated by chlorite dismutase. Utilization of thusly derived oxygen by hydrocarbon-degrading organisms in anoxic environments was first demonstrated by Coates et. al. (1998)1, however the link to aerobic methane oxidation was not examined at that time. Here, we systematically explore the potential for several species of aerobic methanotrophs to couple with chlorite during dissimilatory perchlorate reduction. In one experiment, 0.5 kPa CH4 was completely removed in one day from the headspace of combined cell suspensions of Dechloromonas agitata strain CKB and Methylococcus capsulatus in the presence of 5 mM chlorite. Oxidation of labeled 14CH4 to 14CO2 under similar conditions was later confirmed. Another experiment demonstrated complete removal of 0.2 kPa CH4 over several days by Methylobacter albus strain BG8 with strain CKB in the presence of 5 mM chlorite. Finally, we observed complete removal of 0.2 kPa CH4 in bottles containing natural soil (enriched in methanotrophs by CH4 additions over several weeks) and strain CKB and in the presence of 10 mM chlorite. This soil, collected from a pristine lake shoreline, demonstrated endogenous methane, perchlorate, chlorate and chlorite uptake. Other soil and

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

    Science.gov (United States)

    2016-05-12

    amino-4,6-dinitrotoluene 73 3 2-nitrotoluene 0.046 3 3-nitrotoluene 120 3 4-amino-2,6-dinitrotoluene 73 3 4-nitrotoluene 0.62 3 Ethylene glycol dinitrate... chlorinated ethenes, and in one DoD demonstration, perchlorate and 1,1,1-trichloroethane (Borden, 2007). ESTCP Final Report ER-201028 12 May 2016 During this...of 7 days. Emulsified oil in an permeable reactive barrier was examined previously for comingled chlorinated solvents and perchlorate (Borden et al

  18. Contact Electrification of Regolith Particles and Chloride Electrolysis: Synthesis of Perchlorates on Mars

    Science.gov (United States)

    Tennakone, K.

    2016-10-01

    Contact electrification of chloride-impregnated martian regolith particles due to eolian agitation and moisture condensation on coalesced oppositely charged grains may lead to spontaneous electrolysis that generates hypochlorite, chlorite, chlorate, and perchlorate with a concomitant reduction of water to hydrogen. This process is not curtailed even if moisture condenses as ice because chloride ionizes on the surface of ice. Limitations dictated by potentials needed for electrolysis and breakdown electric fields enable estimation of the required regolith grain size. The estimated dimension turns out to be of the same order of magnitude as the expected median size of martian regolith, and a simple calculation yields the optimum rate of perchlorate production.

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

    Science.gov (United States)

    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. Synthesis and Crystal Structure of Tri-(2-mercaptopyridine N-oxide)bis(dimethyl sulfoxide) Dysprosium(Ⅲ)

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A range of rare earth metal complexes of 2-mercaptopyridine N-oxide (Hmpo) have been synthesized, and studied by elemental analysis and IR spectroscopic technique. Crystal structure of Dy(mpo)3(DMSO)2 (DMSO = dimethyl sulfoxide) has been determined. The complex crystallizes in the triclinic system, space group Pī with lattice parameters: a = 9.602(3), b = 9.803(3), c = 15.498(5)A, α= 89.51(1), β= 85.73(1), γ= 62.99(1)°, Dc = 1.787 g/cm3, C19H24N3O5S5Dy, Mr = 697.21, Z = 2, F(000) = 690, μ = 3.321mm-1, the final R = 0.0237 and wR = 0.0587 for 4116 reflections with I>σ2(I). The coordination number of dysprosium Ⅲ is eight, and its coordination geometry is a somewhat distorted square antiprism with O(3), O(4), O(5), S(3) and O(1), O(2), S(1), S(2) at the tetragonal bases (dihedral angle between their mean planes is 2.9(1)0). Around the Dy atom, three five-membered ring planes (Dy, O, N, C, S) make the dihedral angles of 74.42, 11.31 and 83.72, respectively.

  1. Photo-, cathodo- and thermoluminescent properties of dysprosium-doped HfO2 films deposited by ultrasonic spray pyrolysis.

    Science.gov (United States)

    Manríquez, R Reynoso; Góngora, J A I Díaz; Guzmán-Mendoza, J; Montalvo, T Rivera; Olguín, J C Guzmán; Ramírez, P V Cerón; García-Hipólito, M; Falcony, C

    2014-09-01

    In this work, the photoluminescent (PL), cathodoluminescent (CL) and thermoluminescent (TL) properties of hafnium oxide films doped with trivalent dysprosium ions are reported. The films were deposited on glass substrates at temperatures ranging from 300 to 600°C, using chlorides as precursor reagents. The surface morphology of films showed a veins shaped microstructure at low deposition temperatures, while at higher temperatures the formation of spherical particles was observed on the surface. X-ray diffraction showed the presence of HfO2 monoclinic phase in the films deposited at temperatures greater than 400°C. The PL and CL spectra of the doped films showed the highest emission band centered at 575nm corresponding to the transitions (4)F9/2→(6)H13/2, which is a characteristic transition of Dy(3+) ion. The greatest emission intensities were observed in samples doped with 1 atomic percent (at%) of DyCl3 in the precursor solution. Regarding the TL behavior, the glow curve of HfO2:Dy(+3) films exhibited spectrum with one broad band centered at about 150°C. The highest intensity TL response was observed on the films deposited at 500°C. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Workplace testing of the new single sphere neutron spectrometer based on Dysprosium activation foils (Dy-SSS)

    Science.gov (United States)

    Bedogni, R.; Gómez-Ros, J. M.; Esposito, A.; Gentile, A.; Chiti, M.; Palacios-Pérez, L.; Angelone, M.; Tana, L.

    2012-08-01

    A photon insensitive passive neutron spectrometer consisting of a single moderating polyethylene sphere with Dysprosium activation foils arranged along three perpendicular axes was designed by CIEMAT and INFN. The device is called Dy-SSS (Dy foil-based Single Sphere Spectrometer). It shows nearly isotropic response in terms of neutron fluence up to 20 MeV. The first prototype, previously calibrated with 14 MeV neutrons, has been recently tested in workplaces having different energy and directional distributions. These are a 2.5 MeV nearly mono-chromatic and mono-directional beam available at the ENEA Frascati Neutron Generator (FNG) and the photo-neutron field produced in a 15 MV Varian CLINAC DHX medical accelerator, located in the Ospedale S. Chiara (Pisa). Both neutron spectra are known through measurements with a Bonner Sphere Spectrometer. In both cases the experimental response of the Dy-SSS agrees with the reference data. Moreover, it is demonstrated that the spectrometric capability of the new device are independent from the directional distribution of the neutron field. This opens the way to a new generation of moderation-based neutron instruments, presenting all advantages of the Bonner sphere spectrometer without the disadvantage of the repeated exposures. This concept is being developed within the NESCOFI@BTF project of INFN (Commissione Scientifica Nazionale 5).

  3. Ferroelectric properties of dysprosium-doped Bi4Ti3O12 thin films crystallized in various atmospheres

    Institute of Scientific and Technical Information of China (English)

    CHENG Chuan-pin; TANG Ming-hua; YE Zhi; ZHOU Yic-hun; ZHENG Xue-jun; ZHONG Xiang-li; HU Zeng-shun

    2006-01-01

    Dysprosium-doped Bi4Ti3O12 (Bi3.4Dy0.6Ti3O12,BDT) ferroelectric thin films were deposited on Pt(111)/Ti/SiO2/Si(111) substrates by chemical solution deposition (CSD) and crystallized in nitrogen,air and oxygen atmospheres,respectively. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to identify the crystal structure,the surface and cross-section morphology of the deposited ferroelectric films. The results show that the crystallization atmosphere has significant effect on determining the crystallization and ferroelectric properties of the BDT films. The film crystallized in nitrogen at a relatively low temperature of 650 ℃,exhibits excellent crystallinity and ferroelectricity with a remanent polarization of 2Pr = 24.9 μC/cm2 and a coercive field of 144.5 kV/cm. While the films annealed in air and oxygen at 650 ℃ do not show good crystallinity and ferroelectricity until they are annealed at 700 ℃. The structure evolution and ferroelectric properties of BDT thin films annealed under different temperatures (600-750 ℃) were also investigated. The crystallinity of the BDT films is improved and the average grain size increases when the annealing temperature increases from 600 ℃ to 750 ℃ at an interval of 50 ℃. However,the polarization of the films is not monotonous function of the annealing temperature.

  4. Kinetics of nitrate and perchlorate reduction in ion-exchange brine using the membrane biofilm reactor (MBfR).

    Science.gov (United States)

    Van Ginkel, Steven W; Ahn, Chang Hoon; Badruzzaman, Mohammad; Roberts, Deborah J; Lehman, S Geno; Adham, Samer S; Rittmann, Bruce E

    2008-09-01

    Several sources of bacterial inocula were tested for their ability to reduce nitrate and perchlorate in synthetic ion-exchange spent brine (30-45 g/L) using a hydrogen-based membrane biofilm reactor (MBfR). Nitrate and perchlorate removal fluxes reached as high as 5.4 g Nm(-2)d(-1) and 5.0 g ClO(4)m(-2)d(-1), respectively, and these values are similar to values obtained with freshwater MBfRs. Nitrate and perchlorate removal fluxes decreased with increasing salinity. The nitrate fluxes were roughly first order in H(2) pressure, but roughly zero-order with nitrate concentration. Perchlorate reduction rates were higher with lower nitrate loadings, compared to high nitrate loadings; this is a sign of competition for H(2). Nitrate and perchlorate reduction rates depended strongly on the inoculum. An inoculum that was well acclimated (years) to nitrate and perchlorate gave markedly faster removal kinetics than cultures that were acclimated for only a few months. These results underscore that the most successful MBfR bioreduction of nitrate and perchlorate in ion-exchange brine demands a well-acclimated inoculum and sufficient hydrogen availability.

  5. Systematics of Natural Perchlorate in Precipitation, Soils, and Plants at the Amargosa Desert Research Site, Nye County, Nevada

    Science.gov (United States)

    Andraski, B. J.; Stonestrom, D. A.; Jackson, W. A.; Rajagopalan, S.; Taylor, E. M.

    2007-12-01

    Naturally occurring perchlorate is known to be associated with nitrate deposits of the hyperarid Atacama Desert in Chile, and recent large-scale sampling has identified a substantial reservoir (up to 1 kg/ha) of natural perchlorate in diverse unsaturated zones of the arid and semiarid Southwestern United States (Rao et al., 2007, ES&T, DOI: 10.1021/es062853i). The objective of the Amargosa Desert work is to develop a better understanding of the deposition, accumulation, and biological cycling of perchlorate in arid environments. Occurrence of perchlorate was evaluated by sampling shallow soil profiles up to 3 m in depth at four different locations and at two different time periods, and by sampling dominant plant species growing near the subsurface profiles. Deposition of perchlorate was evaluated by analyzing both bulk deposition (precipitation plus dry fall, collected under oil) collected on site and wet deposition samples collected by the National Atmospheric Deposition program at a nearby site. Soil samples and atmospheric-deposition samples were tested for both perchlorate (ClO4- ) and major anions. Perchlorate concentrations (0.2-20 µg/kg) were variable with depth in soil profiles and generally correlated most highly with chloride (Cl-) and nitrate (NO3-), although the intensity of these relations differed among profiles. Plant concentrations were generally above 1 mg/kg, suggesting ClO4- accumulation. Concentrations of ClO4- were generally much greater in total deposition than wet deposition samples, indicating a substantial dryfall component of meteoric deposition. This presentation will present the mass distribution and variability of perchlorate in bulk deposition, soils, and plants. Reasons for observed relations between subsurface concentrations of perchlorate and other anions will be explored.

  6. 高氯酸诺氟沙星铜(Ⅱ)%Norfloxacin Coppe(Ⅱ) Perchlorate

    Institute of Scientific and Technical Information of China (English)

    谢永荣; 叶琼; 熊仁根

    2004-01-01

    The hydrothermal treatment of Cu(ClO4)2·6H2O and Norfloxacin (H-Norf) afforded [Cu(H-Noff)2(ClO4)2] (1) in which center Cu has a square planar geometry while perchlorate just acts as charge balance anions. CCDC:140821.

  7. The Impact of Temperature on Anaerobic Biological Perchlorate Removal and Aerobic Polishing of the Effluent

    Science.gov (United States)

    This abstract describes a pilot-scale evaluation of anaerobic biological perchlorate (C1O4) removal followed by aerobic effluent polishing. The anaerobic biological contactor operated for 3.5 years. During that period, two effluent polishing evaluations, lasting 311 an...

  8. The Impact of Temperature on Anaerobic Biological Perchlorate Removal and Aerobic Polishing of the Effluent - paper

    Science.gov (United States)

    This abstract describes a pilot-scale evaluation of anaerobic biological perchlorate (C1O4) removal followed by aerobic effluent polishing. The anaerobic biological contactor operated for 3.5 years. During that period, two effluent polishing evaluations, lasting 311 an...

  9. Regioselective iodination of aromatic compounds with potassium iodide in the presence of benzyltriphenylphosphonium perchlorate

    Institute of Scientific and Technical Information of China (English)

    Jalal Albadi; Masoumeh Abedini; Nasir Iravani

    2012-01-01

    A simple and efficient method for the selective iodination of various aromatic compounds by using potassium iodide in the presence of benzyltriphenylphosphonium perchlorate,is reported.This method provides several advantages such as good selectivity between ortho and para positions of aromatic compounds and high yields of the products.

  10. NATIONAL ACADEMY OF SCIENCES (NAS) REVIEW OF THE HEALTH IMPLICATIONS OF PERCHLORATE INGESTION (2005)

    Science.gov (United States)

    In the interest of resolving scientific questions, the EPA, the Department of Defense, the Department of Energy, and the National Aeronautics and Space Administration - members of a broader Interagency Working Group on Perchlorate led by the Office of Science and Technology Polic...

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

    Science.gov (United States)

    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 ...

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

    KAUST Repository

    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. Heterotrophic-autotrophic sequential system for reductive nitrate and perchlorate removal.

    Science.gov (United States)

    Ucar, Deniz; Cokgor, Emine Ubay; Sahinkaya, Erkan

    2016-01-01

    Nitrate and perchlorate were identified as significant water contaminants all over the world. This study aims at evaluating the performances of the heterotrophic-autotrophic sequential denitrification process for reductive nitrate and perchlorate removal from drinking water. The reduced nitrate concentration in the heterotrophic reactor increased with increasing methanol concentrations and the remaining nitrate/nitrite was further removed in the following autotrophic denitrifying process. The performances of the sequential process were studied under varying nitrate loads of [Formula: see text] at a fixed hydraulic retention time of 2 h. The C/N ratio in the heterotrophic reactor varied between 1.24 and 2.77 throughout the study. Nitrate and perchlorate reduced completely with maximum initial concentrations of [Formula: see text] and 1000 µg/L, respectively. The maximum denitrification rate for the heterotrophic reactor was [Formula: see text] when the bioreactor was fed with [Formula: see text] and 277 mg/L methanol. For the autotrophic reactor, the highest denitrification rate was [Formula: see text] in the first period when the heterotrophic reactor performance was low. Perchlorate reduction was initiated in the heterotrophic reactor, but completed in the following autotrophic process. Effluent sulphate concentration was below the drinking water standard level of 250 mg/L and pH was in the neutral level.

  14. A screened hybrid density functional study on energetic complexes: cobalt, nickel and copper carbohydrazide perchlorates.

    Science.gov (United States)

    Huang, Huisheng; Zhang, Tonglai; Zhang, Jianguo; Wang, Liqiong

    2010-07-15

    The molecular geometry, electronic structure, infrared spectra and thermochemical properties of cobalt and nickel tris(carbohydrazide) perchlorates (CoCP and NiCP) as well as copper bis(carbohydrazide) perchlorate (CuCP) were investigated using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional. The results show that both perchlorate ions coordinate with the copper atom, and the interactions between copper and perchlorate are ionic, whereas all the metal-carbohydrazide interactions are covalent. Due to the delocalization from the sigma(N-H) bond orbital to the n*(M) antibond orbital, the amino stretching vibrations of these complexes show considerable red-shift compared with those of free carbohydrazide ligand. The calculated heats of reaction and formation indicate that the formations of these complexes are exothermic, and the order of their thermal stability is NiCP>CoCP>CuCP. These agree well with the experimental results. Finally, we find that there is a relationship between the energy gap and impact sensitivity.

  15. ION CHROMATOGRAPHIC DETERMINATION OF PERCHLORATE ION: ANALYSIS OF FERTILIZERS AND RELATED MATERIALS

    Science.gov (United States)

    A solid fertilizer sample is dissolved or leached to solutilize the perchlorate as the aqueous anion. If needed, the liquid is filtered or centrifuged. The rsulting solution is subjected to ion chromatography using an adaptation of EPA Method 314.0. Preliminary screenng is requir...

  16. Double-Polymer-Modified Pencil Lead for Stripping Voltammetry of Perchlorate in Drinking Water

    Science.gov (United States)

    Izadyar, Anahita; Kim, Yushin; Ward, Michelle M.; Amemiya, Shigeru

    2012-01-01

    The inexpensive and disposable electrode based on a double-polymer-modified pencil lead is proposed for upper-division undergraduate instrumental laboratories to enable the highly sensitive detection of perchlorate. Students fabricate and utilize their own electrodes in the 3-4 h laboratory session to learn important concepts and methods of…

  17. Double-Polymer-Modified Pencil Lead for Stripping Voltammetry of Perchlorate in Drinking Water

    Science.gov (United States)

    Izadyar, Anahita; Kim, Yushin; Ward, Michelle M.; Amemiya, Shigeru

    2012-01-01

    The inexpensive and disposable electrode based on a double-polymer-modified pencil lead is proposed for upper-division undergraduate instrumental laboratories to enable the highly sensitive detection of perchlorate. Students fabricate and utilize their own electrodes in the 3-4 h laboratory session to learn important concepts and methods of…

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

    DEFF Research Database (Denmark)

    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...

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

    Science.gov (United States)

    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

  20. High Pressure Burn Rate Measurements on an Ammonium Perchlorate Propellant

    Energy Technology Data Exchange (ETDEWEB)

    Glascoe, E A; Tan, N

    2010-04-21

    High pressure deflagration rate measurements of a unique ammonium perchlorate (AP) based propellant are required to design the base burn motor for a Raytheon weapon system. The results of these deflagration rate measurements will be key in assessing safety and performance of the system. In particular, the system may experience transient pressures on the order of 100's of MPa (10's kPSI). Previous studies on similar AP based materials demonstrate that low pressure (e.g. P < 10 MPa or 1500 PSI) burn rates can be quite different than the elevated pressure deflagration rate measurements (see References and HPP results discussed herein), hence elevated pressure measurements are necessary in order understand the deflagration behavior under relevant conditions. Previous work on explosives have shown that at 100's of MPa some explosives will transition from a laminar burn mechanism to a convective burn mechanism in a process termed deconsolidative burning. The resulting burn rates that are orders-of-magnitude faster than the laminar burn rates. Materials that transition to the deconsolidative-convective burn mechanism at elevated pressures have been shown to be considerably more violent in confined heating experiments (i.e. cook-off scenarios). The mechanisms of propellant and explosive deflagration are extremely complex and include both chemical, and mechanical processes, hence predicting the behavior and rate of a novel material or formulation is difficult if not impossible. In this work, the AP/HTPB based material, TAL-1503 (B-2049), was burned in a constant volume apparatus in argon up to 300 MPa (ca. 44 kPSI). The burn rate and pressure were measured in-situ and used to calculate a pressure dependent burn rate. In general, the material appears to burn in a laminar fashion at these elevated pressures. The experiment was reproduced multiple times and the burn rate law using the best data is B = (0.6 {+-} 0.1) x P{sup (1.05{+-}0.02)} where B is the burn

  1. Investigation of Perchlorate and Water at the Surface of Mars with Raman Scattering

    Science.gov (United States)

    Nikolakakos, G.; Whiteway, J. A.

    2015-12-01

    A major accomplishment of the NASA Phoenix Mars mission was the identification of perchlorate (ClO4-) in the regolith by the Wet Chemistry Laboratory instrument. More recently, the Sample Analysis at Mars instrument on the NASA Curiosity Rover detected the presence of perchlorate in Gale Crater, suggesting that it is globally distributed. Perchlorates are of great interest on Mars due to their high affinity for water vapor (deliquescence) as well as their ability to greatly depress the freezing point of water when in solution. This has intriguing biological implications as resulting brines could potentially provide a habitable environment for living organisms. Additionally, it has been speculated that these salts may play a significant role in the hydrological cycle on Mars. A sample of magnesium perchlorate was subjected to the water vapor pressure and temperatures found at the landing site of the Phoenix Mars mission. Laser Raman scattering was applied to detect the onset of deliquescence and provide a relative estimate of the quantity of water taken up and subsequently released by the sample. As the temperature of the sample decreased at the same rate as measured on Mars during the evening, significant uptake of water from the atmosphere was observed to occur prior to the frost point temperature being reached. As the temperature was lowered, water uptake continued as saturation was reached and frost formed on the surface surrounding the perchlorate sample. Freezing of the brine film was observed at the eutectic temperature of -67°C and thawing occurred at a temperature of -62°C.

  2. Contribution of tap water to chlorate and perchlorate intake: a market basket study.

    Science.gov (United States)

    Asami, Mari; Yoshida, Nobue; Kosaka, Koji; Ohno, Koichi; Matsui, Yoshihiko

    2013-10-01

    The contributions of water to total levels of chlorate and perchlorate intake were determined using food and water samples from a market basket study from 10 locations in Japan between 2008 and 2009. Foods were categorized into 13 groups and analyzed along with tap water. The average total chlorate intake was 333 (min. 193-max. 486) μg/day for samples cooked with tap water. The contribution of tap water to total chlorate intake was as high as 47%-58%, although total chlorate intake was less than 32% of the tolerable daily intake, 1500 μg/day for body weight of 50 kg. For perchlorate, daily intake from water was 0.7 (0.1-4.4) μg/day, which is not high compared to the average total intake of 14 (2.5-84) μg/day, while the reference dose (RfD) is 35 μg/day and the provisional maximum tolerable daily intake (PMTDI) is 500 μg/day for body weight of 50 kg. The highest intake of perchlorate was 84 μg/day, where concentrations in foods were high, but not in water. The contribution of water to total perchlorate intake ranged from 0.5% to 22%, while the ratio of highest daily intake to RfD was 240% and that to PMTDI was 17%. Eight baby formulas were also tested--total chlorate and perchlorate intakes were 147 (42-332) μg/day and 1.11 (0.05-4.5) μg/day, respectively, for an ingestion volume of 1 L/day if prepared with tap water.

  3. Removing perchlorate from samples to facilitate organics detection by pyrolitic methods

    Science.gov (United States)

    von Kiparski, Guntram R.; Parker, David R.; Tsapin, Alexandre I.

    2013-07-01

    Thermal volatilization or pyrolysis of solid samples followed by gas chromatography-mass spectrometry (TV-GC-MS) or other downstream analyses has proven robustness and has been adopted for the extraction of organic compounds for their detection in planetary lander science missions (e.g., Viking Lander GC-MS, Phoenix TEGA, MSL SAM, and the future ExoMars MOMA). Pyrolysis to extract organic compounds from soil has limitations when oxidants co-occur in the analyzed sample unless the desired end product is CO2. Pyrolysis of such soils may result in oxidation of organics to CO2 during heating, and thus make organics characterization difficult, if not impossible. Analytical investigations seeking to identify organics in martian soils containing oxidants could benefit from the deployment of technologies that remove known and putative oxidants prior to thermal volatilization. We conducted a series of experiments in order to determine if a polymeric anion exchange resin, commonly used for removing the perchlorate anion from contaminated municipal water supplies, could sustain its substantial perchlorate removal capability while keeping organic compounds intact for downstream detection. We demonstrated that this resin can strongly bind perchlorate from aqueous solution while simultaneously leaving amino acids substantially unaltered. The perchlorate-binding resin could be easily adopted as a pre-treatment for martian soil extracts to create analytical systems with improved organics characterization capabilities compatible with existing TV-GC-MS systems. We propose this strategy to aid detection and characterization of putative martian organics co-situated with perchlorate at sampling sites.

  4. An Ion-selective Electrode for Anion Perchlorate in Thick-film Technology

    Directory of Open Access Journals (Sweden)

    Luís Gil

    2006-04-01

    Full Text Available The ionophore 1,4,7,10,13-penta(n-octyl-1,4,7,10,13-pentaazacyclopentadecane(L1 was used for the development of miniaturised perchlorate-selective electrodes in thick-film technology. Different PVC membranes containing L1 and the plasticizers o-nitrophenyloctyl ether (NPOE, dibutyl phthalate (DBP, bis(2-ethylhexylsebacate (DOS and dibutylsebacate (DBS were prepared and placed on a graphite working electrode manufactured byusing thick film serigraphic technology. The perchlorate selective electrode containing DBSas plasticizer showed a potentiometric Nernstian response of -57 mV per decade in a rangeof perchlorate concentration from 1 x 10-4 to 1 x 10-1 M with a detection limit of 5 x 10-5 M.The ion selective electrodes containing DBP and NPOE as plasticizers exhibit a workingrange from 6.3 x 10-5 to 1 x 10-1 M and 7.4 x 10-5 to 1 x 10-1 M for perchlorate, respectively,with a detection limit of ca. 2.2 x 10-5 M. For all three electrodes a response time of ca. 5 s was found. The prepared electrodes do not show appreciable decay of the slope for at least 25 days. Potentiometric selectivity coefficients (log KpotClO4-,X- with respect to the primaryanion perchlorate were evaluated using the fixed interference method. These coefficients areof the order of 10-1.7 or smaller, indicating the relatively poor interference of the differentanions studied.

  5. Sensitive search for the temporal variation of the fine structure constant using radio-frequency E1 transitions in atomic dysprosium

    CERN Document Server

    Nguyen, A T; Lamoreaux, S K; Torgerson, J R

    2003-01-01

    It has been proposed that the radio-frequency electric-dipole (E1) transition between two nearly degenerate opposite-parity states in atomic dysprosium should be highly sensitive to possible temporal variation of the fine structure constant ($\\alpha$) [V. A. Dzuba, V. V. Flambaum, and J. K. Webb, Phys. Rev. A {\\bf 59}, 230 (1999)]. We discuss here an experimental realization of the proposed search, which involves monitoring the E1 transition frequency over a period of time using direct frequency counting techniques. We estimate that a statistical sensitivity of $|\\adota| \\sim 10^{-18}$/yr may be achieved and discuss possible systematic effects in such a measurement.

  6. In situ bioremediation of nitrate and perchlorate in vadose zone soil for groundwater protection using gaseous electron donor injection technology.

    Science.gov (United States)

    Evans, Patrick J; Trute, Mary M

    2006-12-01

    When present in the vadose zone, potentially toxic nitrate and perchlorate anions can be persistent sources of groundwater contamination. Gaseous electron donor injection technology (GEDIT), an anaerobic variation of petroleum hydrocarbon bioventing, involves injecting electron donor gases, such as hydrogen or ethyl acetate, into the vadose zone, to stimulate biodegradation of nitrate and perchlorate. Laboratory microcosm studies demonstrated that hydrogen and ethanol promoted nitrate and perchlorate reduction in vadose zone soil and that moisture content was an important factor. Column studies demonstrated that transport of particular electron donors varied significantly; ethyl acetate and butyraldehyde were transported more rapidly than butyl acetate and ethanol. Nitrate removal in the column studies, up to 100%, was best promoted by ethyl acetate. Up to 39% perchlorate removal was achieved with ethanol and was limited by insufficient incubation time. The results demonstrate that GEDIT is a promising remediation technology warranting further validation.

  7. Potential Influence of Perchlorate on Heavy Metals and Organic Carbon in Serpentine Soil; Implications for Martian Regolith

    Science.gov (United States)

    Oze, C.; Kumarathilaka, P. R.; Indraratne, S.; Vithanage, M. S.

    2015-12-01

    Prasanna Kumarathilaka Chemical and Environmental Systems Modeling Research Group, National Institute of Fundamental Studies, Kandy, Sri LankaPerchlorate (ClO4-) concentrations as high as 1 Wt.% have been reported in Martian regolith. Perchlorate is a strong oxidizer capable of accelerating heavy and/or trace metal release into regolith/soil and reacting with organic matter/compounds (if present). Here, we assess interactions between perchlorate and an analogous Martian regolith (i.e., serpentine soil) to simulate and understand the fate of Mn, Ni and Co and organic carbon. Pre-characterized serpentine soil collected from Sri Lanka was used for this study. Incubation experiments were performed with three perchlorate concentrations (1, 0.75 and 0.5 w/w) and sequential and single extractions assessed solid phase metal fractionation in serpentine sediments after 3 weeks and 1 year, respectively. Additionally, total organic carbon (TOC) of the residues were analyzed. These experiments demonstrate a high release of Mn compared to Ni and Co. Metal concentrations in exchangeable and bioavailable fractions increased with increasing perchlorate concentrations. Exchangeable Ni, Mn and Co increased 5.9, 69.6 and 44.6% and bioavailable Ni, Mn and Co increased 5.5, 92.3 and 72.8%, respectively, after 1 year compared to 3 weeks. Additionally, TOC decreased with increasing perchlorate concentration. For example, TOC decreased by 14.3% after 1 year compared to a 3 week incubation period. Overall, this study confirms the accelerated release of metals and the removal of organic carbon with increasing perchlorate concentrations. Furthermore, this study illustrates how perchlorate may present additional challenges to current Martian life studies and the future human habitation of Mars.Prasanna Kumarathilaka Chemical and Environmental Systems Modeling Research Group, National Institute of Fundamental Studies, Kandy, Sri LankaPerchlorate (ClO4-) concentrations as high as 1 Wt.% have

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

    Science.gov (United States)

    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...

  9. Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

    Science.gov (United States)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.

    2013-12-01

    The presence of methane (CH4) in the atmosphere of Mars is controversial yet the evidence has aroused scientific interest, as CH4 could be a harbinger of extant or extinct microbial life. There are various oxidized compounds present on the surface of Mars that could serve as electron acceptors for the anaerobic oxidation of CH4, including perchlorate (ClO4-). We examined the role of perchlorate, chlorate (ClO3-) and chlorite (ClO2-) as oxidants linked to CH4 oxidation. Dissimilatory perchlorate reduction begins with reduction of ClO4- to ClO2- and ends with dismutation of chlorite to yield chloride (Cl-) and molecular oxygen (O2). We explored the potential for aerobic CH4 oxidizing bacteria to couple with oxygen derived from chlorite dismutation during dissimilatory perchlorate reduction. Methane (0.2 kPa) was completely removed within several days from the N2-flushed headspace above cell suspensions of methanotrophs (Methylobacter albus strain BG8) and perchlorate reducing bacteria (Dechloromonas agitata strain CKB) in the presence of 5 mM ClO2-. Similar rates of CH4 consumption were observed for these mixed cultures whether they were co-mingled or segregated under a common headspace, indicating that direct contact of cells was not required for methane consumption to occur. We also observed complete removal of 0.2 kPa CH4 in bottles containing dried soil (enriched in methanotrophs by CH4 additions over several weeks) and D. agitata CKB and in the presence of 10 mM ClO2-. This soil (seasonally exposed sediment) collected from the shoreline of a freshwater lake (Searsville Lake, CA) demonstrated endogenous CH4 uptake as well as perchlorate, chlorate and chlorite reduction/dismutation. However, these experiments required physical separation of soil from the aqueous bacterial culture to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although dissimilatory reduction of ClO4- and ClO3- could be inferred from the

  10. Physiological and genetic description of dissimilatory perchlorate reduction by the novel marine bacterium Arcobacter sp. strain CAB.

    Science.gov (United States)

    Carlström, Charlotte I; Wang, Ouwei; Melnyk, Ryan A; Bauer, Stefan; Lee, Joyce; Engelbrektson, Anna; Coates, John D

    2013-05-21

    A novel dissimilatory perchlorate-reducing bacterium (DPRB), Arcobacter sp. strain CAB, was isolated from a marina in Berkeley, CA. Phylogenetically, this halophile was most closely related to Arcobacter defluvii strain SW30-2 and Arcobacter ellisii. With acetate as the electron donor, strain CAB completely reduced perchlorate (ClO4(-)) or chlorate (ClO3(-)) [collectively designated (per)chlorate] to innocuous chloride (Cl(-)), likely using the perchlorate reductase (Pcr) and chlorite dismutase (Cld) enzymes. When grown with perchlorate, optimum growth was observed at 25 to 30°C, pH 7, and 3% NaCl. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) preparations were dominated by free-swimming straight rods with 1 to 2 polar flagella per cell. Strain CAB utilized a variety of organic acids, fructose, and hydrogen as electron donors coupled to (per)chlorate reduction. Further, under anoxic growth conditions strain CAB utilized the biogenic oxygen produced as a result of chlorite dismutation to oxidize catechol via the meta-cleavage pathway of aerobic catechol degradation and the catechol 2,3-dioxygenase enzyme. In addition to (per)chlorate, oxygen and nitrate were alternatively used as electron acceptors. The 3.48-Mb draft genome encoded a distinct perchlorate reduction island (PRI) containing several transposases. The genome lacks the pcrC gene, which was previously thought to be essential for (per)chlorate reduction, and appears to use an unrelated Arcobacter c-type cytochrome to perform the same function. IMPORTANCE The study of dissimilatory perchlorate-reducing bacteria (DPRB) has largely focused on freshwater, mesophilic, neutral-pH environments. This study identifies a novel marine DPRB in the genus Arcobacter that represents the first description of a DPRB associated with the Campylobacteraceae. Strain CAB is currently the only epsilonproteobacterial DPRB in pure culture. The genome of strain CAB lacks the pcrC gene found in all

  11. Oxygen and chlorine isotopic fractionation during perchlorate biodegradation: Laboratory results and implications for forensics and natural attenuation studies

    Science.gov (United States)

    Sturchio, N.C.; Böhlke, J.K.; Beloso, A.D.; Streger, S.H.; Heraty, L.J.; Hatzinger, P.B.

    2007-01-01

    Perchlorate is a widespread environmental contaminant having both anthropogenic and natural sources. Stable isotope ratios of O and Cl in a given sample of perchlorate may be used to distinguish its source(s). Isotopic ratios may also be useful for identifying the extent of biodegradation of perchlorate, which is critical for assessing natural attenuation of this contaminant in groundwater. For this approach to be useful, however, the kinetic isotopic fractionations of O and Cl during perchlorate biodegradation must first be determined as a function of environmental variables such as temperature and bacterial species. A laboratory study was performed in which the O and Cl isotope ratios of perchlorate were monitored as a function of degradation by two separate bacterial strains (Azospira suillum JPLRND and Dechlorospirillum sp. FBR2) at both 10??C and 22??C with acetate as the electron donor. Perchlorate was completely reduced by both strains within 280 h at 22??C and 615 h at 10??C. Measured values of isotopic fractionation factors were ??18O = -36.6 to -29.0??? and ??37Cl = -14.5 to -11.5???, and these showed no apparent systematic variation with either temperature or bacterial strain. An experiment using 18O-enriched water (??18O = +198???) gave results indistinguishable from those observed in the isotopically normal water (??18O = -8.1???) used in the other experiments, indicating negligible isotope exchange between perchlorate and water during biodegradation. The fractionation factor ratio ??18O/??37Cl was nearly invariant in all experiments at 2.50 ?? 0.04. These data indicate that isotope ratio analysis will be useful for documenting perchlorate biodegradation in soils and groundwater. The establishment of a microbial fractionation factor ratio (??18O/??37Cl) also has significant implications for forensic studies. ?? 2007 American Chemical Society.

  12. Adsorption of perchlorate from aqueous solution by the calcination product of Mg/(Al-Fe) hydrotalcite-like compounds.

    Science.gov (United States)

    Yang, Yiqiong; Gao, Naiyun; Chu, Wenhai; Zhang, Yongji; Ma, Yan

    2012-03-30

    The calcination products containing Mg(II), Al(III), and Fe(III) in the brucite-like layers with varying Mg/Al/Fe molar ratios at 550°C were used as the adsorbent to remove perchlorate from aqueous solution, while the Mg/(Al-Fe) hydrotalcite compounds were synthesized by co-precipitation method at a constant pH value. The Mg/(Al-Fe) hydrotalcite compounds (HMAF) were characterized by XRD, FT-IR and TG-DTA. The characteristics showed that the layered double hydroxides structures in the HMAF were lost during calcination at 550°C, but were reconstructed subsequent to adsorption of perchlorate, indicating that the 'memory effect' appeared to play an important role in perchlorate adsorption. Batch adsorption studies were conducted under various equilibration conditions, such as molar ratios of Mg/Al/Fe, calcined temperature, different initial solution pH, adsorbent dose, initial perchlorate concentration, and co-existing anions. It was found that the existence of ferric iron in calcined Mg/(Al-Fe) hydrotalcite compound (CHMAF) was favorable to removal of perchlorate from water, and the best ratio of Mg/Al/Fe is 3:0.8:0.2 (CHMAF5%). This study demonstrated that the calcination product of Mg/(Al-Fe) hydrotalcite-like compound was a promising adsorbent for control of the perchlorate pollution in water.

  13. Dysprosium doping induced shape and magnetic anisotropy of Fe3-xDyxO4 (x=0.01-0.1) nanoparticles

    Science.gov (United States)

    Jain, Richa; Luthra, Vandna; Gokhale, Shubha

    2016-09-01

    The effect of dysprosium doping on evolution of structural and magnetic properties of magnetite (Fe3O4) nanoparticles is reported. A standard route of co-precipitation was used for the synthesis of undoped and doped magnetite nanoparticles Fe3-xDyxO4 (x=0.0-0.1). Transmission electron microscopy (TEM) shows formation of round shaped particles with diameter in the range of 8-14 nm for undoped sample. On doping beyond x=0.01, the formation of rod like structures is initiated along with the round shaped particles. The number of rods is found to increase with increasing doping concentration. Magnetic characterization using Vibrating Sample Magnetometer (VSM) revealed doping dependent magnetic properties which can be correlated with the crystallite size as determined from X-ray diffraction (XRD). Enhancement in the saturation magnetization in the initial stages of doping can be explained on the basis of incorporation of Dy3+ ions in the inverse spinel structure at the octahedral site in place of Fe3+ ions. Subsequent decrease in saturation magnetization observed beyond x=0.03 could be attributed to precipitation of excess Dy in form of dysprosium ferrite phase.

  14. Research Advances: Perchlorate in Dairy and Breast Milk Samples; NO Glow on Mars; Physical Chemistry to the Rescue: Differentiating Nicotinic and Cholinergic Agonists

    Science.gov (United States)

    King, Angela G.

    2005-07-01

    Perchlorate levels in milk suggest widespread presence of the chemical. NO emissions indicate circulation in Martian atmosphere. Modeling reveals subtle differences in drug membrane receptor interactions.

  15. Effect of sodium chloride, chlorite, and perchlorate on the hypochlorite-induced peroxidation of phospholipid liposomes.

    Science.gov (United States)

    Panasenko, O M; Arnhold, J; Sergienko, V I

    1997-01-01

    The abilities of sodium hypochlorite (NaClO), chlorite (NaClO2), chlorate (NaClO3), and perchlorate (NaClO4) to initiate lipid peroxidation (LP) in liposomes formed from unsaturated phosphatidylcholine were compared. It was shown that only NaClO induced an intensive accumulation of LP products (thiobarbituric acid-reactive substances and diene conjugates) in the liposomes as a result of their co-incubation. The other oxochlorates produced no similar effects and did not affect the hypochlorite-induced LP. This indicates that the observed hypochlorite-induced LP does not result from the presence of chlorite, chlorate, or perchlorate anion admixtures in the medium.

  16. Tetranitroacetimidic acid: a high oxygen oxidizer and potential replacement for ammonium perchlorate.

    Science.gov (United States)

    Vo, Thao T; Parrish, Damon A; Shreeve, Jean'ne M

    2014-08-27

    Considerable work has been focused on developing replacements for ammonium perchlorate (AP), a primary choice for solid rocket and missile propellants, due to environmental concerns resulting from the release of perchlorate into groundwater systems [corrected]. Additionally, the generation of hydrochloric acid contributes to high concentrations of acid rain and to ozone layer depletion. En route to synthesizing salts that contain cationic FOX-7, a novel, high oxygen-containing oxidizer, tetranitroacetimidic acid (TNAA), has been synthesized and fully characterized. The properties of TNAA were found to be exceptional, with a calculated specific impulse exceeding that of AP, leading to its high potential as a replacement for AP. TNAA can be synthesized easily in a one-step process by the nitration of FOX-7 in high yield (>93%). The synthesis, properties, and chemical reactivity of TNAA have been examined.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. Relevance of a perchloric acid extraction scheme to determine mineral and organic phosphorus in swine slurry.

    Science.gov (United States)

    Daumer, Marie-Line; Béline, Fabrice; Spérandio, Mathieu; Morel, Christian

    2008-03-01

    To increase the phosphorus recycling potential from swine slurry, mineral phosphorus products which could be used as fertilizers should be obtained and new processes need to be investigated. A routine method is needed to better evaluate the dissolved and solid mineral phosphorus in swine slurry. Cold perchloric acid extraction method previously developed for wastewater or sludge analysis was adapted. Ionic chromatography was used to measure orthophosphate in extracts. Only one extraction step was needed to distinguish between mineral and organic phosphorus in slurry. Reproducibility of the method was high (less than 5% of variation on the measured fractions). Selectivity was assessed by adding several organic and mineral phosphorus sources in the slurry. Cold perchloric extraction followed by ionic chromatography was very selective in quantifying both the mineral and organic forms of phosphorus in swine slurry.

  19. The processing, properties and use of the pyrotechnic mixture titanium subhydride/potassium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Massis, T.M.

    1996-07-01

    Development of this pyrotechnic occurred because of the need for a static insensitive material to meet personnel safety requirements and related system safety issues in nuclear weapon energetic material component designs. Ti subhydride materials are made by the thermal dehydrding of commercial Ti hydride powder to the desired equivalent hydrogen composition in the Ti lattice. These Ti subhydrides, when blended with K perchlorate, meet the static insensitivity requirement of not being initiated from an equivalent human body electrostatic discharge. Individual material and blend qualification requirements provide a reproducible material from lot to lot. These pyrotechnic formulations meet the high reliability requirements (0.9995) for initiation and performance parameters and have the necessary stability and compatibility to meet long lived requirements of more than 25 years. Various experiences and problems are also discussed that have led to a mature technology for Ti subhydride/K perchlorate during its use in energetic material component designs.

  20. Widespread occurrence of perchlorate in water, foodstuffs and human urine collected from Kuwait and its contribution to human exposure.

    Science.gov (United States)

    Alomirah, Husam F; Al-Zenki, Sameer F; Alaswad, Marivi C; Alruwaih, Noor A; Wu, Qian; Kannan, Kurunthachalam

    2016-06-01

    Perchlorate is a thyroid hormone-disrupting compound and is reported to occur widely in the environment. Little is known on human exposure to perchlorate in Kuwait. In this study, 218 water samples, 618 commonly consumed foodstuffs and 532 urine samples collected from Kuwait were analysed to assess the exposure of the Kuwaiti population to perchlorate. For the estimation of daily intake of perchlorate, food consumption rates were obtained from the National Nutrition Survey in the State of Kuwait (NNSSK). The results showed that leafy vegetables accounted for a major share of perchlorate exposure among the Kuwaiti population at 0.062 µg kg(-)(1) bw day(-)(1) (36.2%), followed by fruits at 0.026 µg kg(-)(1) bw day(-)(1) (15.3%) and non-leafy vegetables at 0.017 µg kg(-)(1) bw day(-)(1) (10.1%). The urinary perchlorate geometric mean (GM) concentrations ranged from 8.51 to 17.1 µg l(-)(1) for the five age groups, which were higher than those reported in other countries. The estimated urinary perchlorate exposure for the Kuwaiti general population was 0.42 µg kg(-)(1) bw day(-)(1), which was higher than that reported for the United States. The dietary intake of perchlorate for the Kuwaiti population ranged from 0.14 to 0.67 µg kg(-)(1) bw day(-)(1) for the five age groups, with a mean total daily intake of 0.17 µg kg(-)(1) bw day(-)(1) for the general population. The highest estimated dietary mean daily intake of perchlorate (0.67 µg kg(-)(1) bw day(-)(1)) was found for children at 3-5 years. The estimated dietary perchlorate exposure in Kuwait is higher than the recommended mean reference dose (RfD) but lower than that of provisional maximum tolerable daily intake (PMTDI) set by the Joint FAO/WHO Expert Committee on Food Additives (JECFA).

  1. Potentiometric Electronic Tongue to Resolve Mixtures of Sulfide and Perchlorate Anions

    OpenAIRE

    2011-01-01

    This work describes the use of an array of potentiometric sensors and an artificial neural network response model to determine perchlorate and sulfide ions in polluted waters, by what is known as an electronic tongue. Sensors used have been all-solid-state PVC membrane selective electrodes, where their ionophores were different metal-phtalocyanine complexes with specific and anion generic responses. The study case illustrates the potential use of electronic tongues in the quantification of mi...

  2. Composition change of uranium perchlorates with organic ligands upon mechanochemical activation of exchange processes

    Science.gov (United States)

    Zazhogin, A. P.; Zazhogin, A. A.; Komyak, A. I.; Umreiko, D. S.

    2008-03-01

    Results of studies on the effect of mechanochemical activation of ligand exchange processes in uranyl perchlorate-dimethylsulfoxide are presented. Spectroscopic data show that mechanical activation of the exchange process in this system results in the replacement of H2O in the first coordination sphere of uranyl UO{2/2+} by DMSO to form nanocrystals with a defined ligand sphere. Possible factors governing the noted features are considered.

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

    Science.gov (United States)

    2008-04-01

    to Aquifer Material..................................................................... 14 3.4.3 Biodegradation Processes...perchlorate is occurring. In situ columns isolate an intact column of soil and groundwater from the rest of the aquifer and can be used to monitor the...Natural Attenuation of MTBE in the Subsurface under Methanogenic Conditions. USEPA, EPA/600/R-00/006. • Pennington, J.C. et al., 1999. Draft Protocol

  4. Mechanism of H2S Oxidation by the Dissimilatory Perchlorate-Reducing Microorganism Azospira suillum PS

    Science.gov (United States)

    Mehta-Kolte, Misha G.; Loutey, Dana; Wang, Ouwei; Youngblut, Matthew D.; Hubbard, Christopher G.; Wetmore, Kelly M.; Conrad, Mark E.

    2017-01-01

    ABSTRACT The genetic and biochemical basis of perchlorate-dependent H2S oxidation (PSOX) was investigated in the dissimilatory perchlorate-reducing microorganism (DPRM) Azospira suillum PS (PS). Previously, it was shown that all known DPRMs innately oxidize H2S, producing elemental sulfur (So). Although the process involving PSOX is thermodynamically favorable (ΔG°′ = −206 kJ ⋅ mol−1 H2S), the underlying biochemical and genetic mechanisms are currently unknown. Interestingly, H2S is preferentially utilized over physiological electron donors such as lactate or acetate although no growth benefit is obtained from the metabolism. Here, we determined that PSOX is due to a combination of enzymatic and abiotic interactions involving reactive intermediates of perchlorate respiration. Using various approaches, including barcode analysis by sequencing (Bar-seq), transcriptome sequencing (RNA-seq), and proteomics, along with targeted mutagenesis and biochemical characterization, we identified all facets of PSOX in PS. In support of our proposed model, deletion of identified upregulated PS genes traditionally known to be involved in sulfur redox cycling (e.g., Sox, sulfide:quinone reductase [SQR]) showed no defect in PSOX activity. Proteomic analysis revealed differential abundances of a variety of stress response metal efflux pumps and divalent heavy-metal transporter proteins, suggesting a general toxicity response. Furthermore, in vitro biochemical studies demonstrated direct PSOX mediated by purified perchlorate reductase (PcrAB) in the absence of other electron transfer proteins. The results of these studies support a model in which H2S oxidation is mediated by electron transport chain short-circuiting in the periplasmic space where the PcrAB directly oxidizes H2S to So. The biogenically formed reactive intermediates (ClO2− and O2) subsequently react with additional H2S, producing polysulfide and So as end products. PMID:28223460

  5. Optimization of Perchlorate Biodegradation: Performance and Cost Assessment for the Thiokol Prototype

    Science.gov (United States)

    2000-03-01

    and startup on December 8, 1997. Incorporation of this prototype into the Thiokol’s perchlorate recovery and wastewater treatment processes has...carbohydrate byproduct (CBP), was identified and evaluated as the best replacement for the brewer’s yeast and cheese whey mixture in use at that time. CBP...was converted from the yeast- whey nutrient blend to CBP in May 1999. Since conversion, good performance has been maintained. Actual nutrient and

  6. IONIC CONDUCTIVITY OF METHYLSILOXANE TERMINATED POLYETHYLENE OXIDE WITH LITHIUM PERCHLORATE NETWORK FILMS

    Institute of Scientific and Technical Information of China (English)

    LI Yongjun; FU Yingwen; FANG Shibi; JIANG Yingyan

    1988-01-01

    Complex films of crosslinked poly(methylsiloxane-co-ethylene oxide) and lithium perchlorate were prepared. These solid state polymeric electrolytes show a markedly higher ionic conductivity, and excellent flexibility. The ionic conductivity of the network films closed to 10-5 Scm-1 at room temperature. The effects of Li + content, species and contents of crosslinking agents, molecular weight of poly(ethylene oxide)and temperature on the ionic conductivity of the network films were also investigated.

  7. The ionic product of water in highly concentrated sodium perchlorate solutions.

    Science.gov (United States)

    Turonek, M L; Hefter, G T; May, P M

    1998-03-01

    The ionic product of water, pK(w)=-log[H(+)][OH(-)], has been determined in aqueous solutions of sodium perchlorate over the concentration range of 1.0-8.0 M at 25 degrees C from high-precision potentiometric titrations carried out in cells with liquid junction using both glass and hydrogen electrodes. The glass electrode results are systematically lower probably as a result of interference by Na(+) ions.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.)

  9. 1-Benzyl­piperazine-1,4-diium bis­(perchlorate) monohydrate

    Science.gov (United States)

    Kaabi, Kamel; El Glaoui, Meher; Jeanneau, Erwann; Rzaigui, Mohamed; Ben Nasr, Cherif

    2010-01-01

    In the title compound, C11H18N2 2+·2ClO4 −·H2O, one perchlor­ate anion is disordered over two orientations in a 0.66 (3):0.34 (3) ratio. Inter­molecular O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link the cations, anions and water mol­ecules into ribbons extending along [100]. PMID:21587939

  10. Field Demonstration of a Novel Biotreatment Process for Perchlorate Reduction in Groundwater

    Science.gov (United States)

    2010-12-01

    Certification Program FeCO3 siderite FOB freight on board ID inside diameter Mo molybdenum MPN most probably number NaHCO3 sodium bicarbonate...of an organic substrate.  Possibility of treating both perchlorate and possible co-contaminants such as nitrate, chlorinated solvents such as TCE...continuously extracted from a single well, from where it was distributed to the different demonstration projects. The water average contaminant

  11. Comparative assessment of the environmental sustainability of existing and emerging perchlorate treatment technologies for drinking water.

    Science.gov (United States)

    Choe, Jong Kwon; Mehnert, Michelle H; Guest, Jeremy S; Strathmann, Timothy J; Werth, Charles J

    2013-05-07

    Environmental impacts of conventional and emerging perchlorate drinking water treatment technologies were assessed using life cycle assessment (LCA). Comparison of two ion exchange (IX) technologies (i.e., nonselective IX with periodic regeneration using brines and perchlorate-selective IX without regeneration) at an existing plant shows that brine is the dominant contributor for nonselective IX, which shows higher impact than perchlorate-selective IX. Resource consumption during the operational phase comprises >80% of the total impacts. Having identified consumables as the driving force behind environmental impacts, the relative environmental sustainability of IX, biological treatment, and catalytic reduction technologies are compared more generally using consumable inputs. The analysis indicates that the environmental impacts of heterotrophic biological treatment are 2-5 times more sensitive to influent conditions (i.e., nitrate/oxygen concentration) and are 3-14 times higher compared to IX. However, autotrophic biological treatment is most environmentally beneficial among all. Catalytic treatment using carbon-supported Re-Pd has a higher (ca. 4600 times) impact than others, but is within 0.9-30 times the impact of IX with a newly developed ligand-complexed Re-Pd catalyst formulation. This suggests catalytic reduction can be competitive with increased activity. Our assessment shows that while IX is an environmentally competitive, emerging technologies also show great promise from an environmental sustainability perspective.

  12. Solubility of PdI/sub 2/ in nitrate and perchlorate solutions. [For use in spent fuels processing; solvents are water, nitric acid, calcium nitrate, and sodium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Horner, D.E.; Mailen, J.C.; Bigelow, H.R.

    1976-01-01

    This paper reports the solubilities of PdI/sub 2/ as measured in nitric acid by a tracer technique and in water, calcium nitrate, and sodium perchlorate solutions by a specific ion electrode technique. The tracer technique measures all the soluble iodine species, whereas the specific ion electrode measures only simple iodide ions (I/sup -/). When compared on the basis of ionic strength, the values obtained in the nitrate solutions by the two methods were in reasonable agreement. The solubilities in perchlorate solution were much higher than in nitrate, possibly because of ionic equilibria involving Pd/sup 4 +/, but this was not resolved in this work. The activity product constant, K/sub ap(PdI/sub 2/)/ = (2.5 +- 0.4) x 10/sup -23/ (25/sup 0/C), was calculated from PdI/sub 2/ solubility in water. With this value and the standard electrode potentials from the literature, the free energy of formation for PdI/sub 2/ was calculated to be --13.6 kcal/mol.

  13. Rapid measurement of perchlorate in polar ice cores down to sub-ng L(-1) levels without pre-concentration.

    Science.gov (United States)

    Peterson, Kari; Cole-Dai, Jihong; Brandis, Derek; Cox, Thomas; Splett, Scott

    2015-10-01

    An ion chromatography-electrospray ionization-tandem mass spectrometry (IC-ESI-MS/MS) method has been developed for rapid and accurate measurement of perchlorate in polar snow and ice core samples in which perchlorate concentrations are expected to be as low as 0.1 ng L(-1). Separation of perchlorate from major inorganic species in snow is achieved with an ion chromatography system interfaced to an AB SCIEX triple quadrupole mass spectrometer operating in multiple reaction monitoring mode. Under optimized conditions, the limit of detection and lower limit of quantification without pre-concentration have been determined to be 0.1 and 0.3 ng L(-1), respectively, with a linear dynamic range of 0.3-10.0 ng L(-1) in routine measurement. These represent improvements over previously reported methods using similar analytical techniques. The improved method allows fast, accurate, and reproducible perchlorate quantification down to the sub-ng L(-1) level and will facilitate perchlorate measurement in the study of natural perchlorate production with polar ice cores in which perchlorate concentrations are anticipated to vary in the low and sub-ng L(-1) range. Initial measurements of perchlorate in ice core samples from central Greenland show that typical perchlorate concentrations in snow dated prior to the Industrial Revolution are about 0.8 ng L(-1), while perchlorate concentrations are significantly higher in recent (post-1980) snow, suggesting that anthropogenic sources are a significant contributor to perchlorate in the current environment.

  14. Mechanism of H2S Oxidation by the Dissimilatory Perchlorate-Reducing Microorganism Azospira suillum PS.

    Science.gov (United States)

    Mehta-Kolte, Misha G; Loutey, Dana; Wang, Ouwei; Youngblut, Matthew D; Hubbard, Christopher G; Wetmore, Kelly M; Conrad, Mark E; Coates, John D

    2017-02-21

    The genetic and biochemical basis of perchlorate-dependent H2S oxidation (PSOX) was investigated in the dissimilatory perchlorate-reducing microorganism (DPRM) Azospira suillum PS (PS). Previously, it was shown that all known DPRMs innately oxidize H2S, producing elemental sulfur (S(o)). Although the process involving PSOX is thermodynamically favorable (ΔG°' = -206 kJ ⋅ mol(-1) H2S), the underlying biochemical and genetic mechanisms are currently unknown. Interestingly, H2S is preferentially utilized over physiological electron donors such as lactate or acetate although no growth benefit is obtained from the metabolism. Here, we determined that PSOX is due to a combination of enzymatic and abiotic interactions involving reactive intermediates of perchlorate respiration. Using various approaches, including barcode analysis by sequencing (Bar-seq), transcriptome sequencing (RNA-seq), and proteomics, along with targeted mutagenesis and biochemical characterization, we identified all facets of PSOX in PS. In support of our proposed model, deletion of identified upregulated PS genes traditionally known to be involved in sulfur redox cycling (e.g., Sox, sulfide:quinone reductase [SQR]) showed no defect in PSOX activity. Proteomic analysis revealed differential abundances of a variety of stress response metal efflux pumps and divalent heavy-metal transporter proteins, suggesting a general toxicity response. Furthermore, in vitro biochemical studies demonstrated direct PSOX mediated by purified perchlorate reductase (PcrAB) in the absence of other electron transfer proteins. The results of these studies support a model in which H2S oxidation is mediated by electron transport chain short-circuiting in the periplasmic space where the PcrAB directly oxidizes H2S to S(o) The biogenically formed reactive intermediates (ClO2(-) and O2) subsequently react with additional H2S, producing polysulfide and S(o) as end products.IMPORTANCE Inorganic sulfur compounds are

  15. Comparison of biotic and abiotic treatment approaches for co-mingled perchlorate, nitrate, and nitramine explosives in groundwater

    Science.gov (United States)

    Schaefer, C. E.; Fuller, M. E.; Condee, C. W.; Lowey, J. M.; Hatzinger, P. B.

    2007-01-01

    Biological and abiotic approaches for treating co-mingled perchlorate, nitrate, and nitramine explosives in groundwater were compared in microcosm and column studies. In microcosms, microscale zero-valent iron (mZVI), nanoscale zero-valent iron (nZVI), and nickel catalyzed the reduction of RDX and HMX from initial concentrations of 9 and 1 mg/L, respectively, to below detection (0.02 mg/L), within 2 h. The mZVI and nZVI also degraded nitrate (3 mg/L) to below 0.4 mg/L, but none of the metal catalysts were observed to appreciably reduce perchlorate (˜ 5 mg/L) in microcosms. Perchlorate losses were observed after approximately 2 months in columns of aquifer solids treated with mZVI, but this decline appears to be the result of biodegradation rather than abiotic reduction. An emulsified vegetable oil substrate was observed to effectively promote the biological reduction of nitrate, RDX and perchlorate in microcosms, and all four target contaminants in the flow-through columns. Nitrate and perchlorate were biodegraded most rapidly, followed by RDX and then HMX, although the rates of biological reduction for the nitramine explosives were appreciably slower than observed for mZVI or nickel. A model was developed to compare contaminant degradation mechanisms and rates between the biotic and abiotic treatments.

  16. Bioregeneration of perchlorate-laden gel-type anion-exchange resin in a fluidized bed reactor.

    Science.gov (United States)

    Venkatesan, Arjun K; Sharbatmaleki, Mohamadali; Batista, Jacimaria R

    2010-05-15

    Selective ion-exchange resins are very effective to remove perchlorate from contaminated waters. However, these resins are currently incinerated after one time use, making the ion-exchange process incomplete and unsustainable for perchlorate removal. Resin bioregeneration is a new concept that combines ion-exchange with biological reduction by directly contacting perchlorate-laden resins with a perchlorate-reducing bacterial culture. In this research, feasibility of the bioregeneration of perchlorate-laden gel-type anion-exchange resin was investigated. Bench-scale bioregeneration experiments, using a fluidized bed reactor and a bioreactor, were performed to evaluate the feasibility of the process and to gain insight into potential mechanisms that control the process. The results of the bioregeneration tests suggested that the initial phase of the bioregeneration process might be controlled by kinetics, while the later phase seems to be controlled by diffusion. Feasibility study showed that direct bioregeneration of gel-type resin was effective in a fluidized-bed reactor, and that the resin could be defouled, reused, and repeatedly regenerated using the method applied in this research.

  17. Bioregeneration of perchlorate-laden gel-type anion-exchange resin in a fluidized bed reactor

    Energy Technology Data Exchange (ETDEWEB)

    Venkatesan, Arjun K.; Sharbatmaleki, Mohamadali [Department of Civil and Environmental Engineering, University of Nevada Las Vegas (UNLV), 4505 Maryland Parkway, Las Vegas, NV 89154-4015 (United States); Batista, Jacimaria R., E-mail: jaci@ce.unlv.edu [Department of Civil and Environmental Engineering, University of Nevada Las Vegas (UNLV), 4505 Maryland Parkway, Las Vegas, NV 89154-4015 (United States)

    2010-05-15

    Selective ion-exchange resins are very effective to remove perchlorate from contaminated waters. However, these resins are currently incinerated after one time use, making the ion-exchange process incomplete and unsustainable for perchlorate removal. Resin bioregeneration is a new concept that combines ion-exchange with biological reduction by directly contacting perchlorate-laden resins with a perchlorate-reducing bacterial culture. In this research, feasibility of the bioregeneration of perchlorate-laden gel-type anion-exchange resin was investigated. Bench-scale bioregeneration experiments, using a fluidized bed reactor and a bioreactor, were performed to evaluate the feasibility of the process and to gain insight into potential mechanisms that control the process. The results of the bioregeneration tests suggested that the initial phase of the bioregeneration process might be controlled by kinetics, while the later phase seems to be controlled by diffusion. Feasibility study showed that direct bioregeneration of gel-type resin was effective in a fluidized-bed reactor, and that the resin could be defouled, reused, and repeatedly regenerated using the method applied in this research.

  18. Single-molecule magnet behavior in an octanuclear dysprosium(iii) aggregate inherited from helical triangular Dy3 SMM-building blocks.

    Science.gov (United States)

    Zhang, Li; Zhang, Peng; Zhao, Lang; Wu, Jianfeng; Guo, Mei; Tang, Jinkui

    2016-06-28

    An unprecedented octanuclear dysprosium(iii) cluster with the formula [Dy8L6(μ3-OH)4(μ2-CH3O)2(CH3OH)6(H2O)2]·6H2O·10CH3OH·2CH3CN () based on a nonlinearly tritopic aroylhydrazone ligand H3L has been isolated, realizing the successful linking of pairwise interesting triangular Dy3 SMMs. It is noteworthy that two enantiomers (Λ and Δ configurations) individually behaving as a coordination-induced chirality presented in the Dy3 helicate are connected in the meso Dy8 cluster. Remarkably, alternating-current magnetic susceptibility measurements revealed that the Dy8 cluster shows typical SMM behavior inherited from its Dy3 helical precursor. It is one of the rare polynuclear Lnn SMMs (n > 7) under zero dc field.

  19. Another challenge to paramagnetic relaxation theory: a study of paramagnetic proton NMR relaxation in closely related series of pyridine-derivatised dysprosium complexes.

    Science.gov (United States)

    Rogers, Nicola J; Finney, Katie-Louise N A; Senanayake, P Kanthi; Parker, David

    2016-02-14

    Measurements of the relaxation rate behaviour of two series of dysprosium complexes have been performed in solution, over the field range 1.0 to 16.5 Tesla. The field dependence has been modelled using Bloch-Redfield-Wangsness theory, allowing estimates of the electronic relaxation time, T1e, and the size of the magnetic susceptibility, μeff, to be made. Changes in relaxation rate of the order of 50% at higher fields were measured, following variation of the para-substituent in the single pyridine donor. The magnetic susceptibilities deviated unexpectedly from the free-ion values for certain derivatives in each series examined, in a manner that was independent of the electron-releasing/withdrawing ability of the pyridine substituent, suggesting that the polarisability of just one pyridine donor in octadenate ligands can play a significant role in defining the magnetic susceptibility anisotropy.

  20. Development of a Screening Model for Design and Costing of an Innovative Tailored Granular Activated Carbon Technology to Treat Perchlorate-Contaminated Water

    Science.gov (United States)

    2007-03-01

    1 Background ...Granular Activated Carbon Technology to Treat Perchlorate-Contaminated Water I. Introduction 1.1 Background Perchlorate is commonly used... Hypothyroidism is a condition where the thyroid makes insufficient amounts of these hormones with varying health effects, including impaired

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

    Science.gov (United States)

    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.

  2. Returning perchlorate-contaminated fume hood systems to service. Part II. Disassembly, decontamination, disposal, and analytical procedures.

    Science.gov (United States)

    Bader, M; Phillips, C C; Mueller, T R; Underwood, W S; Whitson, S D

    1999-06-01

    Part I presented work leading up to and including a pilot study for remediation of laboratory fume hood systems contaminated with residues from processes that used fuming perchloric acid. Since publication of Part I, three incidents involving explosions and fires related to perchlorates have come to the attention of the authors. Experience has been gained through decontamination/remediation of 41 additional systems. This article expands on previous one and includes (1) administrative details that need to be addressed before and during the execution of the decontamination itself, (2) a seven-step procedure for decontamination-remediation/disposal, (3) some precautions associated with the use of methylene blue as a diagnostic tool for perchlorates, and-specific electrode to augment or replace the methylene blue test.

  3. 3,12-Diaza-6,9-diazo-nia-2,13-dioxotetra-decane bis-(perchlorate).

    Science.gov (United States)

    Söhnel, Tilo; Wichmann, Kathrin A; Doert, Thomas; Cooper, Garth J S

    2012-02-01

    The crystal structure of the title diprotonated diacetyl-triethyl-ene-tetra-mine (DAT) perchorate salt, C(10)H(24)N(4)O(2) (2+)·2ClO(4) (-), can be described as a three-dimensional assembly of alternating layers consisting of diprotonated diacetyl-triethyl-ene-tetra-mine (H(2)DAT)(2+) strands along [100] and the anionic species ClO(4) (-). The (H(2)DAT)(2+) cations in the strands are connected via N-H⋯O hydrogen bonding between the acetyl groups and the amine groups of neighbouring (H(2)DAT)(2+) cations. Layers of (H(2)DAT)(2+) strands and perchlorate anions are connected by a network of hydrogen bonds between the NH and NH(2) groups and the O atoms of the perchlorate anion. The asymmetric unit consits of one perchlorate anion in a general position, as well as of one cation that is located on a center of inversion.

  4. Light and variable 37Cl/35Cl ratios in rocks from Gale Crater, Mars: Possible signature of perchlorate

    Science.gov (United States)

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

    2016-03-01

    Cl isotope ratios measured on HCl thermally evolved from as-yet-unknown phases in sedimentary rocks and sand in Gale Crater provide unexpected insights to the Martian surficial Cl cycle. The seven samples yield δ37Cl values ranging from - 1 ± 25 ‰ to - 51 ± 5 ‰. Five analyses from two samples of the Sheepbed mudstone (Yellowknife Bay study area) are analytically indistinguishable with a mean δ37Cl of - 11 ± 7 ‰ (1 σ). In contrast, four mudstones/sandstones from the Kimberley and Pahrump study areas also yielded indistinguishable ratios, but with a mean δ37Cl of - 43 ± 6 ‰. The Rocknest sand deposit gave a highly uncertain δ37Cl value of - 7 ± 44 ‰. These light and highly variable δ37Cl values are unique among known solar system materials. Two endmember models are offered to account for these observations, and in both, perchlorate, with its extreme ability to fractionate Cl isotopes, is critical. In the first model, SAM is detecting HCl from an oxychlorine compound (e.g., perchlorate) produced from volcanic gas emissions by atmospheric chemical reactions. Similar reactions in Earth's atmosphere may be responsible for the isotopically lightest known Cl outside of this study, in perchlorate from the Atacama Desert. Some of the Gale Crater δ37Cl values are more negative than those in Atacama perchlorate, but because reaction mechanisms and associated fractionation factors are unknown, it is impossible to assess whether this difference is prohibitive. If the negative δ37Cl signal is produced in this fashion, the isotopic variability among samples could arise either from variations in the relative size of the reactant chloride and product perchlorate reservoirs, or from variations in the fraction of perchlorate reduced back to chloride after deposition. Such reduction strongly enriches 37Cl in the residual perchlorate. Perchlorate reduction alone offers an alternative endmember model that can explain the observed data if SAM measured HCl derived

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  6. Formation of oxidizing species via irradiation of perchlorates using high-energy electrons and D 2 + ions

    Science.gov (United States)

    Crandall, Parker B.; Gillis-Davis, Jeffrey J.; Kaiser, Ralf-Ingo

    2016-10-01

    The perchlorate ion (ClO4-) has garnered particular interest in recent years following the discovery of perchlorate salts in the Martian regolith at levels of 0.4-0.6 wt% by the Phoenix lander in 2006 and Mars Science Laboratory's Curiosity rover in 2013. Due to their oxidizing properties, perchlorates are suspected to play a contributing role to the surprising lack of organics on the Martian surface. In this study, magnesium perchlorate hexahydrate (Mg(ClO4)2●6H2O) samples were irradiated with monoenergetic beams of 5 keV electrons and D2+ ions separately, sequentially, and simultaneously to simulate the effects of galactic cosmic ray exposure of perchlorates. The irradiation experiments were carried out under ultra-high vacuum conditions at 50 K, after which the samples were slowly heated to 300 K (0.5 K min-1) while desorbing products were monitored by quadrupole mass spectrometry. In all cases, molecular oxygen (O2) was detected upon the onset of irradiation and again during the warmup phase. In the case of simultaneous irradiation, deuterated water (D2O) and deuterium peroxide (D2O2) were also detected as the sample was heated whereas in the D2+ experiment small amounts of D2O2 was found exclusively. When samples were irradiated sequentially, the production of D2O2 was dependent upon the sample being irradiated with D2+ ions prior to electrons. These experiments show that perchlorates are capable of producing multiple oxidizing agents (O2, D2O2) which may also account for the lack of organics on the Martian surface.

  7. Effect of environmental perchlorate on thyroid function in pregnant women from Córdoba, Argentina, and Los Angeles, California.

    Science.gov (United States)

    Pearce, Elizabeth N; Spencer, Carole A; Mestman, Jorge H; Lee, Richard H; Bergoglio, Liliana M; Mereshian, Paula; He, Xuemei; Leung, Angela M; Braverman, Lewis E

    2011-01-01

    To determine whether environmental perchlorate exposure adversely affects thyroid function in women in the first trimester of pregnancy. First-trimester pregnant women were recruited from prenatal clinics in the Los Angeles County Hospital, Los Angeles, California, and in the Hospital Universitario de Maternidad dependent Universidad Nacional de Córdoba, Córdoba, Argentina, between 2004 and 2007. Spot urine and blood specimens were obtained during the clinic visit. Urinary perchlorate, iodine, and creatinine were measured, and thyroid function tests were performed. The study included 134 pregnant women from Los Angeles, California (mean gestational age ± SD = 9.1 ± 2.2 weeks), and 107 pregnant women from Córdoba, Argentina (mean gestational age = 10.0 ± 2.0 weeks). Median urinary iodine values were 144 μg/L in California and 130 μg/L in Argentina. Urinary perchlorate levels were detectable in all women (California: median, 7.8 μg/L [range, 0.4-284 μg/L] and Argentina: median, 13.5 μg/L [range, 1.1-676 μg/L]). Serum thyroperoxidase antibodies were detectable in 21 women from California (16%) and in 17 women from Argentina (16%). Using Spearman rank correlation analyses, there was no association between urinary perchlorate concentrations and serum thyrotropin, free thyroxine index, or total triiodothyronine values, including within the subset of women with urinary iodine values less than 100 μg/L. In multivariate analyses using the combined Argentina and California data sets and adjusting for urinary iodine concentrations, urinary creatinine, gestational age, and thyroperoxidase antibody status, urinary perchlorate was not a significant predictor of thyroid function. Low-level perchlorate exposure is ubiquitous, but is not associated with altered thyroid function among women in the first trimester of pregnancy.

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

    Directory of Open Access Journals (Sweden)

    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.

  9. In Situ Bioremediation of Perchlorate in Vadose Zone Soil Using Gaseous Electron Donors

    Science.gov (United States)

    2009-11-01

    90% propane) CH3CH2CH3 44.1 6.00E-01 5700 Ethanol C2H5OH 46.07 5.00E-06 40 17 chlorate, chlorite , and chloride concentration, moisture content...C. Perchlorate, chlorate, chlorite , chloride, nitrate, and nitrite were extracted from 5-g soil by vortexing for 1 minute in a 50-mL centrifuge...equipped with an AS-11 column, and an ED40 Electrochemical Detector. A sodium hydroxide solution eluent with a flow rate of 1 mL/min was used to

  10. 2-(2-Hydroxy-3-methoxyphenyl-1H-benzimidazol-3-ium perchlorate

    Directory of Open Access Journals (Sweden)

    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].

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

    Science.gov (United States)

    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

  12. Purification of human genomic DNA from whole blood using sodium perchlorate in place of phenol.

    Science.gov (United States)

    Johns, M B; Paulus-Thomas, J E

    1989-08-01

    We have developed a new, rapid method for the extraction of human genomic DNA from whole blood samples. Traditionally, genomic DNA has been extracted from blood by overnight proteinase K digestion of lysed peripheral lymphocytes followed by phenol/chloroform extraction. In addition to being time consuming, the use of phenol involves inherent risks due to the toxic nature of the reagent. Our method for the extraction of DNA from whole blood uses sodium perchlorate and chloroform instead of phenol with a significant time savings realized as well as fewer hazards to the technician. Furthermore, DNA prepared by this new method is an excellent substrate for restriction endonuclease digestion and Southern hybridization analysis.

  13. Bis[N-(2-pyridylcarbonylpyridine-2-carboximidato]iron(III perchlorate methanol solvate

    Directory of Open Access Journals (Sweden)

    Dayu Wu

    2009-11-01

    Full Text Available In the title complex, [Fe(C12H8N3O22]ClO4·CH3OH, the iron(III ion is surrounded by two tridentate N-(2-pyridylcarbonylpyridine-2-carboximidate (bpca ligands and exhibits a distorted octahedral coordination by six bpca N atoms. A classical O—H...O hydrogen bond exists between the methanol solvent molecule and the perchlorate anion. Magnetic susceptibility measurements indicated the complex to be in the low-spin state in the temperature range 5–400 K.

  14. Preparation, X-ray crystallography, and thermal decomposition of some transition metal perchlorate complexes of hexamethylenetetramine.

    Science.gov (United States)

    Singh, Gurdip; Baranwal, B P; Kapoor, I P S; Kumar, Dinesh; Fröhlich, Roland

    2007-12-20

    The perchlorate complexes of manganese, nickel, and zinc with hexamethylenetetramine (HMTA) of the general formula [M(H2O-HMTA-H2O)2(H2O-ClO4)2(H2O)2] (where M=Mn, Ni, and Zn) have been prepared and characterized by X-ray crystallography. Thermal studies were undertaken using thermogravimetry (TG), differential thermal analysis (DTA), and explosion delay (DE) measurements. The kinetics of thermal decomposition of these complexes was investigated using isothermal TG data by applying isoconversional method. The decomposition pathways of the complexes have also been proposed. These were found to explode when subjected to higher temperatures.

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

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. Nano-Ammonium Perchlorate: Preparation, Characterization, and Evaluation in Composite Propellant Formulation

    Science.gov (United States)

    Kumari, A.; Mehilal; Jain, S.; Jain, M. K.; Bhattacharya, B.

    2013-07-01

    Nanomaterials are finding applications in explosives and propellant formulations due to their large surface area and high surface energy. This high surface energy is responsible for the low activation energy and increase in burning rate of the composition. Therefore, a successful attempt has been made to prepare nano-ammonium perchlorate using a nonaqueous method by dissolving ammonium perchlorate (AP) in methanol followed by adding the dissolved AP to the hydroxyl-terminated polybutadiene (HTPB), homogenization, and vacuum distillation of the solvent. The nano-AP thus formed was characterized using a NANOPHOX particle size analyzer (Sympatec, Germany), transmission electron microscopy (FEI, Hillsboro, OR), X-ray diffraction (PANalytical B.V., The Netherlands) and scanning electron microscopy (Ikon Analytical Equipment Pvt. Ltd., Mumbai, India) for particle size, purity, and morphology, respectively. The thermal behavior of nano-AP was also studied using differential thermal analysis-thermo gravimetric analysis (DTA-TGA). The data indicated that the particle size of the prepared AP was in the range of 21-52 nm and the thermal decomposition temperature was lower than that of coarse AP. Characterized nano-AP was subsequently used in composite propellant formulation up to 5% with 86% solid loading and studied for different properties. The results showed a 14% increase in burning rate in comparison to standard propellant composition with desired mechanical properties.

  18. Adsorption of Chloride,Nitrate and Perchlorate by Variable Charge Soils

    Institute of Scientific and Technical Information of China (English)

    JIGUO-LIANG; KONGXIAO-LING

    1992-01-01

    Two cells consisting of a chloride-selective eloectrode and a nitrate-selective electrode or of a chloride-selectrive electrode and a perchlorate-selective electrode were directly put in the soil suspension to determine the concentration rations Cl-/NO3- or Cl-/ClO4- for studying the adsorption of the three anions by variable charge soils.It was found that all the concentration ration CCl-/CNO3- and CCl-/CClO4- in suspension were smaller than unity when soil samples were in equilibrium with mixed KCl and KNO3 or KCl and KClO4 solutions of equal concentration.The order of the amount of chloride,nitrate and perchlorate adsorbed by variable charge soils was Cl->NO3->ClO4- when the soils adsorbed these anions from the solution containing equal concentrations of Cl-,NO3- and ClO4-.Such factors as the pH of the suspension,the iron oxide content of the soil etc.Could affect the amounts and the ratios of anions adsorbed.The adsorption was chiefly caused by coulombic attraction,but a covalent force between the anion and the metal atom on the surface of soil particles may also be involved,at least for Cl- ions,even for NO3- ions.

  19. Lithium perchlorate ion pairing in a model of amorphous polyethylene oxide

    Energy Technology Data Exchange (ETDEWEB)

    Halley, J.W.; Duan, Y. [School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States); Curtiss, L.A.; Baboul, A.G. [Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    1999-08-01

    We report a molecular dynamics study of pairing and dynamics of lithium cation and perchlorate anion in a previously reported model of amorphous polyethylene oxide. We are particularly interested in the question of whether these ions pair in the model, as previously reported experimentally. We calculate the potential of mean force between a lithium and perchlorate ion in the system for several temperatures when a pair of ions is at various separation distances in our model. We find evidence for two minima in the potential of mean force, one at lithium{endash}chlorine separations of 3.5 {Angstrom} and about 6.5 {Angstrom}. We studied the same system with five ion pairs in the system and again find two minima at the same separation distances but in this case there is evidence of entropic effects in the binding free energy of the pairs at 3.5 {Angstrom}. A study of radial distribution functions permits us to deduce information concerning the structure of the paired states. {copyright} {ital 1999 American Institute of Physics.}

  20. Diaquasodium(I perchlorate bis[μ-2-(carboxylatomethyliminomethylphenolato]bis[(3-methylpyridinecopper(II

    Directory of Open Access Journals (Sweden)

    Zhengyi Li

    2008-12-01

    Full Text Available In the title compound, [Na(H2O2]ClO4·[Cu2(C9H7NO32(C6H7N2], the CuII atom is coordinated by one N atom and two O atoms from a tridentate N-salicylideneglycinate Schiff base dianion and one N atom from a 3-methylpyridine ligand. Longer Cu...O contacts [2.680 (2 Å] complete an approximate square-based pyramidal coordination geometry around CuII, forming a dimeric complex across a centre of inversion. The dimeric complexes form stacks along the a axis, with Cu...O contacts of 3.332 (2 Å between them. The Na+ cations and perchlorate anions lie on twofold rotation axes between the stacks. The former are coordinated by two disordered water molecules (each with half-occupancy, and form Na...O contacts of 3.698 (3 Å to the perchlorate anions and Na...π contacts to neighbouring salicylideneglycinate ligands [shortest Na...C = 3.516 (3 Å].

  1. Change of iodine load and thyroid homeostasis induced by ammonium perchlorate in rats.

    Science.gov (United States)

    Chen, Hong-Xia; Ding, Miao-Hong; Liu, Qin; Peng, Kai-Liang

    2014-10-01

    Ammonium perchlorate (AP), mainly used as solid propellants, was reported to interfere with homeostasis via competitive inhibition of iodide uptake. However, detailed mechanisms remain to be elucidated. In this study, AP was administered at 0, 130, 260 and 520 mg/kg every day to 24 male SD rats for 13 weeks. The concentrations of iodine in urine, serum thyroid hormones levels, total iodine, relative iodine and total protein, and malondialdehyde (MDA), superoxide dismutase (SOD) and catalase (CAT) activity in thyroid tissues were measured, respectively. Our results showed that high-dose perchlorate induced a significant increase in urinary iodine and serum thyroid stimulating hormone (TSH), with a decrease of total iodine and relative iodine content. Meanwhile, free thyroxine (FT4) was decreased and CAT activity was remarkably increased. Particularly, the CAT activity was increased in a dose-dependent manner. These results suggested that CAT might be enhanced to promote the synthesis of iodine, resulting in elevated urinary iodine level. Furthermore, these findings suggested that iodine in the urine and CAT activity in the thyroid might be used as biomarkers for exposure to AP, associated with thyroid hormone indicators such as TSH, FT4.

  2. Environmentally relevant concentrations of ammonium perchlorate inhibit thyroid function and alter sex ratios in developing Xenopus laevis.

    Science.gov (United States)

    Goleman, Wanda L; Carr, James A; Anderson, Todd A

    2002-03-01

    Embryos and larvae of the South African frog Xenopus laevis were exposed to ammonium perchlorate (AP) or control medium for 70 d. The dosage levels (59 ppb, 14,140 ppb) bracketed a range of perchlorate concentrations measured in surface waters at the Longhorn Army Ammunition Plant (LHAAP) in Karnack, Texas, USA. The experiment also included a 28-d nontreatment recovery period to assess the reversibility of AP effects. There were no significant effects of AP on mortality or hatching success. There were no effects of AP on developmental abnormalities such as bent/asymmetric tails or edema. Ammonium perchlorate inhibited forelimb emergence, the percentage of animals completing tail resorption, and hindlimb development during the 70-d exposure period. Only the upper AP concentration reduced whole-body thyroxine content, whereas both concentrations caused significant hypertrophy of the thyroid follicular epithelium. Both concentrations of AP caused a skewed sex ratio, significantly reducing the percentage of males at metamorphosis. The effects of AP on metamorphosis and thyroid function were reversed during the 28-d nontreatment recovery period. We conclude that AP inhibits thyroid activity and alters gonadal differentiation in developing X. laevis. These effects were observed at concentrations at or below concentrations reported in surface waters contaminated with ammonium perchlorate, suggesting that this contaminant may pose a threat to normal development and growth in natural amphibian populations.

  3. Chitosan Derivatives as Important Biorefinery Intermediates. Quaternary Tetraalkylammonium Chitosan Derivatives Utilized in Anion Exchange Chromatography for Perchlorate Removal

    Science.gov (United States)

    Sayed, Shakeela; Jardine, Anwar

    2015-01-01

    There has recently been great interest in the valorization of biomass waste in the context of the biorefinery. The biopolymer chitosan, derived from chitin, is present in large quantities of crustacean waste. This biomass can be converted into value-added products with applications in energy, fuel, chemicals and materials manufacturing. The many reported applications of this polymer can be attributed to its unique properties, such as biocompatibility, chemical versatility, biodegradability and low toxicity. Cost effective water filters which decontaminate water by removal of specific impurities and microbes are in great demand. To address this need, the development of ion exchange resins using environmentally friendly, renewable materials such as biopolymers as solid supports was evaluated. The identification and remediation of perchlorate contaminated water using an easy, inexpensive method has come under the spotlight recently. Similarly, the use of a low cost perchlorate selective solid phase extraction (SPE) cartridge that can be rapidly employed in the field is desirable. Chitosan based SPE coupled with colorimetric analytical methods showed promise as a renewable anion exchange support for perchlorate analysis or removal. The polymers displayed perchlorate retention comparable to the commercial standard whereby the quaternized iron loaded polymer TMC-Fe(III) displayed the best activity. PMID:25915024

  4. Tuning the composition and magnetostructure of dysprosium iron garnets by Co-substitution: An XRD, FT-IR, XPS and VSM study

    Energy Technology Data Exchange (ETDEWEB)

    Tholkappiyan, R.; Vishista, K., E-mail: raovishista@gmail.com

    2015-10-01

    Graphical abstract: - Highlights: • Garnet type Dy{sub 3}Fe{sub 5−x}Co{sub x}O{sub 12} (x = 0–0.06) nanoparticles were synthesized by glycine assisted combustion method. • To investigate and confirm the phases in the synthesized ferrite nanoparticles by FT-IR and XRD analysis. • To investigate the compositional and oxidation state of the samples by X-ray photoelectron spectroscopy. • The detailed core level spectra of Dy 4d, Fe 2p, Co 2p and O 1s were analyzed using XPS. • The magnetic property was studied by VSM technique. - Abstract: We report the Co-substituting on the synthesis and properties of garnet type dysprosium ferrite nanoparticles by basic composition Dy{sub 3}Fe{sub 5−x}Co{sub x}O{sub 12} (x = 0–0.06) synthesized through glycine assisted combustion method. A possible formation mechanism of synthesized Dy{sub 3}Fe{sub 5−x}Co{sub x}O{sub 12} samples by controlling the synthesis process has been proposed. XRD, FT-IR, XPS and VSM studies were used to investigate the compositional and magnetostructural properties of the prepared nanoparticles. XRD results confirm that all the samples are single-phase cubic garnet structure with mean crystallite size of 97–105 nm obtained from Scherrer method and 95–102 nm from W–H method. FT-IR analysis shows the presence of three expected bands in the frequency limit of 450–600 cm{sup −1} attributed to metal–O stretching vibration in tetrahedral site of garnet structure. A typical survey spectrum from XPS results confirmed the presence of Dy, Fe, Co and O elements in the samples. This study also to characterize the different oxidation states of the samples by fitting the parameters of high resolution Dy 4d, Fe 2p, Co 2p and O 1s XPS spectra. The XPS data of Dy 4d spectrum show that Dy{sup 3+} ion occupy in dodecahedral (D) site. The XPS analysis of Fe 2p and Co 2p data suggests that (Fe{sup 3+} and Fe{sup 2+}), (Co{sup 3+} and Co{sup 2+}) are distributed in tetrahedral and octahedral sites

  5. Perchlorate and selected metals in water and soil within Mount Rushmore National Memorial, South Dakota, 2011–15

    Science.gov (United States)

    Hoogestraat, Galen K.; Rowe, Barbara L.

    2016-04-14

    Mount Rushmore National Memorial is located in the east-central part of the Black Hills area of South Dakota and is challenged to provide drinking water to about 3 million annual visitors and year-round park personnel. An environmental concern to water resources within Mount Rushmore National Memorial has been the annual aerial fireworks display at the memorial for the Independence Day holiday during 1998–2009. A major concern of park management is the contamination of groundwater and surface water by perchlorate, which is used as an oxidizing agent in firework displays. A study by the U.S. Geological Survey, in cooperation with the National Park Service, was completed to characterize the occurrence of perchlorate and selected metals (constituents commonly associated with fireworks) in groundwater and surface water within and adjacent to Mount Rushmore National Memorial during 2011–15. Concentrations of perchlorate and metals in 106 water samples (collected from 6 groundwater sites and 14 surface-water sites) and 11 soil samples (collected from 11 soil sites) are reported.Within the Mount Rushmore National Memorial boundary, perchlorate concentrations were greatest in the Lafferty Gulch drainage basin, ranging from less than 0.20 to 38 micrograms per liter (μg/L) in groundwater samples and from 2.2 to 54 μg/L in surface-water samples. Sites within the Starling Gulch drainage basin also had some evidence of perchlorate contamination, with concentrations ranging from 0.61 to 19 μg/L. All groundwater and surface-water samples within the unnamed tributary to Grizzly Bear Creek drainage basin and reference sites outside the park boundary had concentrations less than 0.20 μg/L. Perchlorate concentrations in samples collected at the 200-foot-deep production well (Well 1) ranged from 17 to 38 μg/L with a median of 23 μg/L, whereas perchlorate concentrations in samples from the 500-foot-deep production well (Well 2) ranged from 2.1 to 17 μg/L, with a median of 6

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

    Science.gov (United States)

    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 (water, sorption to the 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

  7. Monitoring Performance of a Dual Wall Permeable Reactive Barrier for Treating Perchlorate and TCE

    Science.gov (United States)

    Dowman, C. E.; Hashimoto, Y.; Warner, S.; Bennett, P.; Gandhi, D.; Szerdy, F.; Neville, S.; Fennessy, C.; Scow, K. M.

    2008-12-01

    AMEC Geomatrix, through collaboration with Aerojet General Corporation and the University of California, Davis (UCD), has performed work leading to the installation of a dual wall permeable reactive barrier (PRB) system capable of treating perchlorate and chlorinated aliphatic hydrocarbon compounds (CAHs), including trichloroethylene (TCE), at Aerojet's Area 40 site in Sacramento, California. This unique system consisted of an upgradient zero-valent iron (ZVI) permeable reactive barrier (PRB) that is intended to not only degrade CAHs, but also, provide hydrogen generated from the ZVI corrosion process, to a downgradient bio-effective PRB (carbohydrate solution circulated through a gravel-packed trench) for destroying perchlorate. The subsurface was characterized during a site investigation, and numerous logistical and site-specific challenges of installation were addressed. The site-specific challenges included installation of a passive remediation system in a remote location with no access to electricity. The selected remediation system was keyed into the undulating bedrock 20 to 25 feet below the ground surface without the use of shoring. Under a collaborative effort, UCD provided initial bench testing. AMEC Geomatrix designed and installed the dual wall system consisting of two approximately parallel 50-foot long by 2-foot thick by 25-foot deep PRB segments which are separated by about 8 feet perpendicular to the approximate direction of groundwater flow. AMEC Geomatrix performed the installation of performance monitoring network, which consisted of 21 wells, and monitored these points for a 6-month period. Monitoring and sampling techniques were designed to measure water levels and water quality parameters in the subsurface during sampling events, to better assess the hydrologic and chemical processes. The monitoring results indicate that the upgradient ZVI PRB effectively treats groundwater with TCE concentrations approaching 60 mg/L, and in addition, may

  8. METHOD 332.0: DETERMINATION OF PERCHLORATE IN DRINKING WATER BY ION CHROMATOGRAPHY WITH SUPPRESSED CONDUCTIVITY AND ELECTROSPRAY IONIZATION MASS SPECTROMETRY

    Science.gov (United States)

    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)

  9. A dysprosium-based metal-organic framework: Synthesis, characterization, crystal structure and interaction with calf thymus-DNA and bovine serum albumin

    Indian Academy of Sciences (India)

    Biplab Mondal; Buddhadeb Sen; Ennio Zangrando; Pabitra Chattopadhyay

    2014-07-01

    A dysprosium-based metallo-organic framework (MOF) containing calcium ions formulated as {Dy(pyda)3Ca1.5(H2O)6} · 5.5H2O (1) (H2pyda = pyridine-2,6-dicarboxylic acid) was solvothermally synthesized in ethanolic medium and characterized by physico-chemical and spectroscopic tools. A detailed structural analysis of the solid state structure of 1 by single crystal X-ray diffraction study showed a tricapped trigonal prism geometry for lanthanide in the [Dy(pyda)3]3− fragment. The mode of interaction of 1 with calf thymus- DNA and with protein bovine serum albumin (BSA) was investigated by using absorption and emission spectroscopic tools. The apparent association constant of complex 1 with CT-DNA was deduced from an absorption spectral study (b = 4.08 × 104 M-1). Spectral and viscosity measurements indicated a groove-binding mode of 1 with CT-DNA, and from spectroscopic study the formation of a metal complex-BSA adduct was assumed to be the result of the interaction of 1 with BSA.

  10. Dual-mode T1 and T2 magnetic resonance imaging contrast agent based on ultrasmall mixed gadolinium-dysprosium oxide nanoparticles: synthesis, characterization, and in vivo application

    Science.gov (United States)

    Tegafaw, Tirusew; Xu, Wenlong; Wasi Ahmad, Md; Baeck, Jong Su; Chang, Yongmin; Bae, Ji Eun; Chae, Kwon Seok; Kim, Tae Jeong; Lee, Gang Ho

    2015-09-01

    A new type of dual-mode T1 and T2 magnetic resonance imaging (MRI) contrast agent based on mixed lanthanide oxide nanoparticles was synthesized. Gd3+ (8S7/2) plays an important role in T1 MRI contrast agents because of its large electron spin magnetic moment resulting from its seven unpaired 4f-electrons, and Dy3+ (6H15/2) has the potential to be used in T2 MRI contrast agents because of its very large total electron magnetic moment: among lanthanide oxide nanoparticles, Dy2O3 nanoparticles have the largest magnetic moments at room temperature. Using these properties of Gd3+ and Dy3+ and their oxide nanoparticles, ultrasmall mixed gadolinium-dysprosium oxide (GDO) nanoparticles were synthesized and their potential to act as a dual-mode T1 and T2 MRI contrast agent was investigated in vitro and in vivo. The D-glucuronic acid coated GDO nanoparticles (davg = 1.0 nm) showed large r1 and r2 values (r2/r1 ≈ 6.6) and as a result clear dose-dependent contrast enhancements in R1 and R2 map images. Finally, the dual-mode imaging capability of the nanoparticles was confirmed by obtaining in vivo T1 and T2 MR images.

  11. Elucidation of Dual Magnetic Relaxation Processes in Dinuclear Dysprosium(III) Phthalocyaninato Triple-Decker Single-Molecule Magnets Depending on the Octacoordination Geometry.

    Science.gov (United States)

    Katoh, Keiichi; Aizawa, Yu; Morita, Takaumi; Breedlove, Brian K; Yamashita, Masahiro

    2017-08-07

    When applying single-molecule magnets (SMMs) to spintronic devices, control of the quantum tunneling of the magnetization (QTM) as well as a spin-lattice interactions are important. Attempts have been made to use not only coordination geometry but also magnetic interactions between SMMs as an exchange bias. In this manuscript, dinuclear dysprosium(III) (Dy(III) ) SMMs with the same octacoordination geometry undergo dual magnetic relaxation processes at low temperature. In the dinuclear Dy(III) phthalocyaninato (Pc(2-) ) triple-decker type complex [(Pc)Dy(ooPc)Dy(Pc)] (1) (ooPc(2-) =2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato) with a square-antiprismatic (SAP) geometry, the ground state is divided by the Zeeman effect, and level intersection occurs when a magnetic field is applied. Due to the ground state properties of 1, since the Zeeman diagram where the levels intersect in an Hdc of 2500 Oe, two kinds of QTM and direct processes occur. However, dinuclear Dy(III) -Pc systems with C4 geometry, which have a twist angle (ϕ) of less than 45° do not undergo dual magnetic relaxation processes. From magnetic field and temperature dependences, the dual magnetic relaxation processes were clarified. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Annealing behaviour and crystal structure of RF-sputtered Bi-substituted dysprosium iron-garnet films having excess co-sputtered Bi-oxide content

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliev, M; Nur-E-Alam, M; Alameh, K [Electron Science Research Institute, Edith Cowan University, 270 Joondalup Drive, Joondalup, WA, 6027 (Australia); Premchander, P; Lee, Y T [Department of Information and Communications, Gwangju Institute of Science and Technology (GIST), Gwangju, 500-712 (Korea, Republic of); Kotov, V A [Institute of Radio Engineering and Electronics, Russian Academy of Sciences, 11 Mohovaya St, Moscow, 125009 (Russian Federation); Lee, Y P, E-mail: m.vasiliev@ecu.edu.au [Quantum Photonic Science Research Center, Department of Physics, Hanyang University, 133-791 (Korea, Republic of)

    2011-02-23

    We investigate the magneto-optic properties, crystal structure and annealing behaviour of nano-composite media with record-high magneto-optic quality exceeding the levels reported so far in sputtered iron-garnet films. Bi-substituted dysprosium-gallium iron-garnet films having excess bismuth oxide content are deposited using RF co-sputtering, and a range of garnet materials are crystallized using conventional oven-annealing processes. We report, for the first time ever, the results of optimization of thermal processing regimes for various high-performance magneto-optic iron-garnet compositions synthesized and describe the evolution of the optical and magneto-optical properties of garnet-Bi-oxide composite-material films occurring during the annealing processes. The crystallization temperature boundaries of the system (BiDy){sub 3}(FeGa){sub 5}O{sub 12} : Bi{sub 2}O{sub 3} are presented. We also report the results of x-ray diffraction and energy-dispersive x-ray spectroscopy studies of this recently developed class of high-performance magneto-optic composites. Our hypothesis of iron oxides being the cause of excess optical absorption in sputtered Bi-iron-garnet films is confirmed experimentally.

  13. Potentiometric Electronic Tongue to Resolve Mixtures of Sulfide and Perchlorate Anions

    Directory of Open Access Journals (Sweden)

    Deivy Wilson

    2011-03-01

    Full Text Available This work describes the use of an array of potentiometric sensors and an artificial neural network response model to determine perchlorate and sulfide ions in polluted waters, by what is known as an electronic tongue. Sensors used have been all-solid-state PVC membrane selective electrodes, where their ionophores were different metal-phtalocyanine complexes with specific and anion generic responses. The study case illustrates the potential use of electronic tongues in the quantification of mixtures when interfering effects need to be counterbalanced: relative errors in determination of individual ions can be decreased typically from 25% to less than 5%, if compared to the use of a single proposed ion-selective electrode.

  14. Potentiometric electronic tongue to resolve mixtures of sulfide and perchlorate anions.

    Science.gov (United States)

    Wilson, Deivy; Abbas, Mohammed N; Radwan, Abdel Latief A; del Valle, Manel

    2011-01-01

    This work describes the use of an array of potentiometric sensors and an artificial neural network response model to determine perchlorate and sulfide ions in polluted waters, by what is known as an electronic tongue. Sensors used have been all-solid-state PVC membrane selective electrodes, where their ionophores were different metal-phtalocyanine complexes with specific and anion generic responses. The study case illustrates the potential use of electronic tongues in the quantification of mixtures when interfering effects need to be counterbalanced: relative errors in determination of individual ions can be decreased typically from 25% to less than 5%, if compared to the use of a single proposed ion-selective electrode.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. Kinetics of Thermolysis of Nickel(II Perchlorate Complex with n-Propylamine

    Directory of Open Access Journals (Sweden)

    Chandra Prakash Singh

    2014-01-01

    Full Text Available Complex of nickel perchlorate with n-propylamine has been synthesised with molecular formula [Ni(n-pa3(ClO4(H2O]ClO4. It has been characterised by elemental analysis, thermogravimetry, UV-VIS, and IR spectroscopic data. Thermal properties have been investigated by thermogravimetry (TG in static air and by simultaneous thermogravimetry-derivative thermogravimetry-differential thermal analysis (TG-DTG-DTA in flowing nitrogen atmosphere. Kinetics of thermolysis has been analysed applying model-fitting and model-free isoconversional method on isothermal TG data recorded at five different temperatures. To observe the response of complex towards fast heating, explosion delay time has been recorded at various temperatures and kinetics of explosion has been studied using these data.

  17. Electrochemical synthesis and characterization of cubic magnetite nanoparticle in aqueous ferrous perchlorate medium

    Directory of Open Access Journals (Sweden)

    D. Gopi

    2016-09-01

    Full Text Available Electrochemical synthesis of cubic magnetite nanoparticle (MNP in ferrous perchlorate aqueous medium and its spectral investigations have been carried out. The structural property of MNP is evidenced by X-ray diffraction pattern shows the characteristic peaks. Further the vibrational frequencies of MNP are evaluated using FT-IR and Raman spectroscopic techniques. UV–visible spectroscopic studies show the possibility of surface plasmon resonance effect. The cubic structure of MNP has been confirmed by transmission electron microscope (TEM technique and it is also evidenced by scanning electron microscope (SEM. The as-synthesized MNP shows superparamagnetic property which is confirmed by the vibrating sample magnetometer, hence it could be useful for synthesis of very ultra superparamagnetic iron oxide solution (VUSPIO for cancer treatment.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lebrini, Mounim [Laboratoire de Cristallochimie et Physicochimie du Solide UMR 8012 ENSCL, BP. 108, F-59652 Villeneuve d' Ascq Cedex (France); Bentiss, Fouad [Laboratoire de Cristallochimie et Physicochimie du Solide UMR 8012 ENSCL, BP. 108, F-59652 Villeneuve d' Ascq Cedex (France); Laboratoire de Chimie de Coordination et d' Analytique, Universite Chouaib Doukkali, Faculte des Sciences, B.P. 20, El Jadida (Morocco); Vezin, Herve [Laboratoire de Chimie Organique et Macromoleculaire, CNRS UMR 8009, USTL Ba-hat t C4, F-59655 Villeneuve d' Ascq Cedex (France); Lagrenee, Michel [Laboratoire de Cristallochimie et Physicochimie du Solide UMR 8012 ENSCL, BP. 108, F-59652 Villeneuve d' Ascq Cedex (France)]. E-mail: michel.lagrenee@ensc-lille.fr

    2005-11-15

    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{sub 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{sub 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)

  19. Large Angular Jump Mechanism Observed for Hydrogen Bond Exchange in Aqueous Perchlorate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Minbiao; /SLAC, PULSE /Stanford U., Phys. Dept.; Odelius3, Michael; /Stockholm U.; Gaffney1, K.J.; /aff SLAC, PULSE

    2010-06-11

    The mechanism for hydrogen bond (H-bond) switching in solution has remained subject to debate despite extensive experimental and theoretical studies. We have applied polarization-selective multidimensional vibrational spectroscopy to investigate the H-bond exchange mechanism in aqueous NaClO{sub 4} solution. The results show that a water molecule shifts its donated H-bonds between water and perchlorate acceptors by means of large, prompt angular rotation. Using a jump-exchange kinetic model, we extract an average jump angle of 49 {+-} 4{sup o}, in qualitative agreement with the jump angle observed in molecular dynamics simulations of the same aqueous NaClO{sub 4} solution.

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

    Science.gov (United States)

    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.; Zorzano, M.-P.; Martin-Torres, F. J.

    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.

  1. USE OF A UNIQUE BIOBARRIER TO REMEDIATE NITRATE AND PERCHLORATE IN GROUNDWATER

    Energy Technology Data Exchange (ETDEWEB)

    Strietelmeier, E. A. (Elizabeth A.); Espinosa, Melissa L. (Melissa L.); Adams, J. D. (Joshua D. ); Leonard, P. A. (Patricia A.); Hodge, E. M. (Evangeline M.)

    2001-01-01

    Research was conducted to evaluate a multiple-layer system of volcanic rock, limestone, Apatite mineral and a 'biobarrier' to impede migration of radionuclides, metals and colloids through shallow alluvial groundwater, while simultaneously destroying contaminants such as nitrate and perchlorate. The 'bio' portion of this Multi-Barrier system uses highly porous, slowly degradable, carbon-based material (pecan shells) that serves as an energy source and supports the growth of indigenous microbial populations capable of destroying biodegradable compounds. The studies, using elevated nitrate concentrations in groundwater, have demonstrated reduction from levels of 6.5-9.7 mM nitrate (400-600 mg/L) to below discharge limits (0.16 mM nitrate). Perchlorate levels of 4.3 {micro}M (350 {micro}g/L) were also greatly reduced. Elevated levels of nitrate in drinking water are a public health concern, particularly for infants and adults susceptible to gastric cancer. Primary sources of contamination include feedlots, agriculture (fertilization), septic systems, mining and nuclear operations. A major source of perchlorate contamination in water is ammonium perchlorate from manufacture/use of rocket propellants. Perchlorate, recently identified as an EPA contaminant of concern, may affect thyroid function and cause tumor formation. A biobarrier used to support the growth of microbial populations (i.e. a biofilm) is a viable and inexpensive tool for cleaning contaminated groundwater. Aquatic ecosystems and human populations worldwide are affected by contaminated water supplies. One of the most frequent contaminants is nitrate. Remediation of nitrate in groundwater and drinking water by biodegradation is a natural solution to this problem. Microbial processes play an extremely important role in in situ groundwater treatment technologies. The assumption of carbon limitation is the basis for addition of carbon-based substrates to a system in the development of

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

    Science.gov (United States)

    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 (sensors show high selectivity in the presence of some inorganic ions (e.g., PO4(3-), SO4(2-), S2O3(2-), NO2(-), NO3(-), N3(-), CN(-), Cl(-), Br(-), I(-)) and automation feasibility. Indium-porphyrin based membrane sensor (sensor III) is used as a detector in a wall-jet flow injection set-up to enable accurate flow injection analysis (FIA) of perchlorate in some fireworks without interferences from the associated reducing agents (sulfur and charcoal), binders (dextrin, lactose), coloring agents (calcium, strontium, 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.

  3. Thermal Diffusivity and Specific Heat Measurements of Titanium Potassium Perchlorate Titanium Subhydride Potassium Perchlorate 9013 Glass 7052 Glass SB-14 Glass and C-4000 Muscovite Mica Using the Flash Technique

    Energy Technology Data Exchange (ETDEWEB)

    Specht, Paul Elliott [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Cooper, Marcia A. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2015-02-01

    The flash technique was used to measure the thermal diffusivity and specific heat of titanium potassium perchlorate (TKP) ignition powder (33wt% Ti - 67wt% KP) with Ventron sup- plied titanium particles, TKP ignition powder (33wt% Ti - 67wt% KP) with ATK supplied titanium particles, TKP output powder (41wt% Ti - 59wt% KP), and titanium subhydride potassium perchlorate (THKP) (33wt% TiH 1.65 - 67wt% KP) at 25°C. The influence of density and temperature on the thermal diffusivity and specific heat of TKP with Ventron supplied titanium particles was also investigated. Lastly, the thermal diffusivity and specific heats of 9013 glass, 7052 glass, SB-14 glass, and C-4000 Muscovite mica are presented as a function of temperature up to 300° C.

  4. Thermal Diffusivity and Specific Heat Measurements of Titanium Potassium Perchlorate Titanium Subhydride Potassium Perchlorate 9013 Glass 7052 Glass SB-14 Glass and C-4000 Muscovite Mica Using the Flash Technique.

    Energy Technology Data Exchange (ETDEWEB)

    Specht, Paul Elliott; Cooper, Marcia A.

    2015-02-01

    The flash technique was used to measure the thermal diffusivity and specific heat of titanium potassium perchlorate (TKP) ignition powder (33wt% Ti - 67wt% KP) with Ventron sup- plied titanium particles, TKP ignition powder (33wt% Ti - 67wt% KP) with ATK supplied titanium particles, TKP output powder (41wt% Ti - 59wt% KP), and titanium subhydride potassium perchlorate (THKP) (33wt% TiH 1.65 - 67wt% KP) at 25 o C. The influence of density and temperature on the thermal diffusivity and specific heat of TKP with Ventron supplied titanium particles was also investigated. Lastly, the thermal diffusivity and specific heats of 9013 glass, 7052 glass, SB-14 glass, and C-4000 Muscovite mica are presented as a function of temperature up to 300 o C.

  5. Perchlorate and selected metals in water and soil within Mount Rushmore National Memorial, South Dakota, 2011–15

    Science.gov (United States)

    Hoogestraat, Galen K.; Rowe, Barbara L.

    2016-04-14

    Mount Rushmore National Memorial is located in the east-central part of the Black Hills area of South Dakota and is challenged to provide drinking water to about 3 million annual visitors and year-round park personnel. An environmental concern to water resources within Mount Rushmore National Memorial has been the annual aerial fireworks display at the memorial for the Independence Day holiday during 1998–2009. A major concern of park management is the contamination of groundwater and surface water by perchlorate, which is used as an oxidizing agent in firework displays. A study by the U.S. Geological Survey, in cooperation with the National Park Service, was completed to characterize the occurrence of perchlorate and selected metals (constituents commonly associated with fireworks) in groundwater and surface water within and adjacent to Mount Rushmore National Memorial during 2011–15. Concentrations of perchlorate and metals in 106 water samples (collected from 6 groundwater sites and 14 surface-water sites) and 11 soil samples (collected from 11 soil sites) are reported.Within the Mount Rushmore National Memorial boundary, perchlorate concentrations were greatest in the Lafferty Gulch drainage basin, ranging from less than 0.20 to 38 micrograms per liter (μg/L) in groundwater samples and from 2.2 to 54 μg/L in surface-water samples. Sites within the Starling Gulch drainage basin also had some evidence of perchlorate contamination, with concentrations ranging from 0.61 to 19 μg/L. All groundwater and surface-water samples within the unnamed tributary to Grizzly Bear Creek drainage basin and reference sites outside the park boundary had concentrations less than 0.20 μg/L. Perchlorate concentrations in samples collected at the 200-foot-deep production well (Well 1) ranged from 17 to 38 μg/L with a median of 23 μg/L, whereas perchlorate concentrations in samples from the 500-foot-deep production well (Well 2) ranged from 2.1 to 17 μg/L, with a median of 6

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

    Directory of Open Access Journals (Sweden)

    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].

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

    Directory of Open Access Journals (Sweden)

    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.

  8. Vibrational Spectroscopic Study on Ion Solvation and Association of Lithium Perchlorate in 4-Methoxymethyl-ethylene Carbonate

    Institute of Scientific and Technical Information of China (English)

    QIAO,Hong-Wei; LUAN,He-Lin; ZHOU,Zhi-Ming; YAO,Wen

    2007-01-01

    Solvation interaction and ion association in solutions of lithium perchlorate/4-methoxymethyl-ethylene carbonate(MEC)have been studied by using Infrared and Raman spectra as a function of concentration of lithium perchlorate.The splitting of ring deformation band and ring ether asymmetric stretching band,and the change of Carbonyl stretching band suggest that there should be a strong interaction between Li+ and the solvent molecules,and the site of solvation should be the oxygen atom of carbonyl group.The apparent solvation number of Li+ was calculated by using band fitting technique.The solvation number was decreased from 3.3 to 1.1 with increasing the concentration of LiClO4/MEC solutions.On the other hand,the band fitting for the ClO ̄4 band revealed the presence of contact ion pair,and free ClO ̄4 anion in the concentrated solutions.

  9. Global use structures of the magnetic materials neodymium and dysprosium. A scenario-based analysis of the effect of the diffusion of electromobility on the demand for rare earths; Globale Verwendungsstrukturen der Magnetwerkstoffe Neodym und Dysprosium. Eine szenariobasierte Analyse der Auswirkung der Diffusion der Elektromobilitaet auf den Bedarf an Seltenen Erden

    Energy Technology Data Exchange (ETDEWEB)

    Gloeser-Chahoud, Simon; Kuehn, Andre; Tercero Espinoza, Luis

    2016-06-15

    Neodymium-iron-boron magnets (NdFeB) have experienced a significant demand as the most powerful permanent magnet in recent years, especially for the manufacture of compact electric servomotors with high efficiency and high power density, especially for mobile applications in hybrid traction motors and electric vehicles or for electric bikes. However, NdFeB magnets are also increasingly being used in general mechanical engineering (conveying and pumping systems, tools, air conditioning systems, lift motors, etc.), in the small electric motors of conventional passenger cars or in the generators of large wind power plants with permanent magnetic direct drive. Nevertheless, there is still high uncertainty in the use structures of NdFeB magnets and the contained rare earth elements neodymium and dysprosium. An effective instrument for increasing the market transparency and the understanding of complex anthropogenic material cycles is the dynamic material flow modeling. In the present work paper, this instrument is used for an in-depth analysis of the use structures of NdFeB magnets and the contained rare earths on a global scale. The dynamic modeling of product usage cycles reveals today's usage structures and quantifies future magnetic quantities in obsolete product flows. It could be shown that the magnets in today's scrap volume are mainly contained in obsolete electronics applications such as hard disks (HDD), CD and DVD drives, which makes the recycling hardly seem to be economical due to the small magnets and the high material spread, but in the foreseeable future with larger magnetic quantities from synchronous servomotors and generators can be expected, which significantly increases the recycling potential. In a further step, the effect of the diffusion of alternative drives in the automotive market on the dysprosium requirement is analyzed using a system dynamics model and possible adaptation mechanisms in the form of different substitution effects in

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

    Energy Technology Data Exchange (ETDEWEB)

    Blount, Benjamin C. [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA 30341 (United States)]. E-mail: bblount@cdc.gov; Valentin-Blasini, Liza [Division of Laboratory Sciences, National Center for Environmental Health, Centers for Disease Control and Prevention, Atlanta, GA 30341 (United States)

    2006-05-10

    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{sup 18}O{sub 4} {sup -}, S{sup 13}CN{sup -} and {sup 15}NO{sub 3} {sup -} 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 {mu}g/L), thiocyanate (<10-5860, 89 {mu}g/L), nitrate (650-8900, 1620 {mu}g/L) and iodide (1.7-170, 8.1 {mu}g/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.

  11. Demonstration of New, Highly Perchlorate-Selective Ion Exchange Resin Coupled with Resin-Optimized, Single-Vessel Engineering Design

    Science.gov (United States)

    2013-03-01

    this issue less of a risk and concern for the success of the demonstration. Another factor affecting the overall cost performance equation is...aquifers in populated areas and hence entered some potable water sources. Health studies have found that perchlorate can mimic iodine in the human thyroid...entering the top of the vessels and exiting to bottom. This operational mode has two deficiencies . First, the long operating time in the down-flow

  12. Evaluation of Perchlorate Sources in the Rialto-Colton and Chino California Subbasins using Chlorine and Oxygen Isotope Ratio Analysis

    Science.gov (United States)

    2015-03-01

    then collected by filtration and rinsed with a few drops of 90 % methanol (by volume, in water ). The purified KClO4 was then dissolved in DIW and a...Ridley, M.; Tock, R. 2005. Perchlorate occurrence in the Texas southern high plains aquifer system. Ground Water Monit. Remed. 25:137-149...monoxide CO2 carbon dioxide DI dual-inlet DI-IRMS dual-inlet isotope ratio mass spectrometry DIW deionized water DO dissolved oxygen DoD

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

    Science.gov (United States)

    2012-12-01

    adding ultraviolet ( UV ) disinfection to disinfect groundwater before it is introduced to the ion exchange vessels; and adding granulated activated...carbon (GAC) vessels to remove VOC that has been detected in upstream monitoring wells. The WBA demonstration system treated water upstream of the UV ...Perchlorate Removal, Destruction, and Field Monitoring Demonstration.” 5.4.3 System Disinfection Prior to delivering water from the WBA demonstration

  14. Supercritical Carbon Dioxide Extraction of Coronene in the Presence of Perchlorate for In Situ Chemical Analysis of Martian Regolith

    Science.gov (United States)

    McCaig, Heather C.; Stockton, Amanda; Crilly, Candice; Chung, Shirley; Kanik, Isik; Lin, Ying; Zhong, Fang

    2016-09-01

    The analysis of the organic compounds present in the martian regolith is essential for understanding the history and habitability of Mars, as well as studying the signs of possible extant or extinct life. To date, pyrolysis, the only technique that has been used to extract organic compounds from the martian regolith, has not enabled the detection of unaltered native martian organics. The elevated temperatures required for pyrolysis extraction can cause native martian organics to react with perchlorate salts in the regolith and possibly result in the chlorohydrocarbons that have been detected by in situ instruments. Supercritical carbon dioxide (SCCO2) extraction is an alternative to pyrolysis that may be capable of delivering unaltered native organic species to an in situ detector. In this study, we report the SCCO2 extraction of unaltered coronene, a representative polycyclic aromatic hydrocarbon (PAH), from martian regolith simulants, in the presence of 3 parts per thousand (ppth) sodium perchlorate. PAHs are a class of nonpolar molecules of astrobiological interest and are delivered to the martian surface by meteoritic infall. We also determined that the extraction efficiency of coronene was unaffected by the presence of perchlorate on the regolith simulant, and that no sodium perchlorate was extracted by SCCO2. This indicates that SCCO2 extraction can provide de-salted samples that could be directly delivered to a variety of in situ detectors. SCCO2 was also used to extract trace native fluorescent organic compounds from the martian regolith simulant JSC Mars-1, providing further evidence that SCCO2 extraction may provide an alternative to pyrolysis to enable the delivery of unaltered native organic compounds to an in situ detector on a future Mars rover.

  15. Influence of rhenium speciation on the stability and activity of Re/Pd bimetal catalysts used for perchlorate reduction.

    Science.gov (United States)

    Choe, Jong Kwon; Shapley, John R; Strathmann, Timothy J; Werth, Charles J

    2010-06-15

    Recent work demonstrates reduction of aqueous perchlorate by hydrogen at ambient temperatures and pressures using a novel rhenium-palladium bimetal catalyst immobilized on activated carbon (Re/Pd-AC). This study examines the influence of Re speciation on catalyst activity and stability. Rates of perchlorate reduction are linearly dependent on Re content from 0-6 wt %, but no further increases are observed at higher Re contents. Surface-immobilized Re shows varying stability and speciation both in oxic versus H(2)-reducing environments and as a function of Re content. In oxic solutions, Re immobilization is dictated by sorption of the Re(VII) precursor, perrhenate (ReO(4)(-)), to activated carbon via electrostatic interactions. Under H(2)-reducing conditions, Re immobilization is significantly improved and leaching is minimized by ReO(4)(-) reduction to more reduced species on the catalyst surface. X-ray photoelectron spectroscopy shows two different Re binding energy states under H(2)-reducing conditions that correspond most closely to Re(V)/Re(IV) and Re(I) reference standards, respectively. The distribution of the two redox states varies with Re content, with the latter predominating at lower Re contents where catalyst activity is more strongly dependent on Re content. Results demonstrate that both lower Re contents and the maintenance of H(2)-reducing conditions are key elements in stabilizing the active Re surface species that are needed for sustained catalytic perchlorate treatment.

  16. Detection of trace organics in Mars analog samples containing perchlorate by laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    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.

  17. N,N′-Bis(2-ammoniobenzylethane-1,2-diammonium–nitrate–perchlorate (1/1.5/2.5

    Directory of Open Access Journals (Sweden)

    Nancy Pérez Rodríguez

    2009-12-01

    Full Text Available The title compound, C16H26N44+·2.5ClO4−·1.5NO3−, is an organic salt in which the cation is a fully protonated tetramine. The cation lies on an inversion center and, as a consequence, both benzene rings are parallel. The central chain is found in an all-trans arrangement, a conformation different from that observed in the crystal structure of the non-protonated molecule. The charges are balanced by a mixture of nitrate and perchlorate ions. One site is occupied by an ordered perchlorate ion, while the other contains both nitrate and perchlorate ions, with occupancies of 0.75 and 0.25, respectively. In the crystal, the NH2+ groups of the cation form N—H...O hydrogen bonds with the anions. The NH3+ groups also behave as donor groups, allowing the building of chains along [100], alternating cations and disordered anions being connected via N—H...O hydrogen bonds.

  18. Microbial respiration with chlorine oxyanions: diversity and physiological and biochemical properties of chlorate- and perchlorate-reducing microorganisms.

    Science.gov (United States)

    Liebensteiner, Martin G; Oosterkamp, Margreet J; Stams, Alfons J M

    2016-02-01

    Chlorine oxyanions are valuable electron acceptors for microorganisms. Recent findings have shed light on the natural formation of chlorine oxyanions in the environment. These suggest a permanent introduction of respective compounds on Earth, long before their anthropogenic manufacture. Microorganisms that are able to grow by the reduction of chlorate and perchlorate are affiliated with phylogenetically diverse lineages, spanning from the Proteobacteria to the Firmicutes and archaeal microorganisms. Microbial reduction of chlorine oxyanions can be found in diverse environments and different environmental conditions (temperature, salinities, pH). It commonly involves the enzymes perchlorate reductase (Pcr) or chlorate reductase (Clr) and chlorite dismutase (Cld). Horizontal gene transfer seems to play an important role for the acquisition of functional genes. Novel and efficient Clds were isolated from microorganisms incapable of growing on chlorine oxyanions. Archaea seem to use a periplasmic Nar-type reductase (pNar) for perchlorate reduction and lack a functional Cld. Chlorite is possibly eliminated by alternative (abiotic) reactions. This was already demonstrated for Archaeoglobus fulgidus, which uses reduced sulfur compounds to detoxify chlorite. A broad biochemical diversity of the trait, its environmental dispersal, and the occurrence of relevant enzymes in diverse lineages may indicate early adaptations of life toward chlorine oxyanions on Earth.

  19. The role of dysprosium on the structural and magnetic properties of (Nd1-xDyx)2Fe14B nanoparticles

    Science.gov (United States)

    Rahimi, Hamed; Ghasemi, Ali; Mozaffarinia, Reza; Tavoosi, Majid

    2017-02-01

    In current work, Nd2Fe14B nanoparticles was synthesized by sol-gel method. Dysprosium powders were added into Nd2Fe14B nanoparticles by mechanical alloying process in order to enhancement of coercivity. The phase analysis, structure, and magnetic properties of annealed (Nd1-xDyx)2Fe14B nanoparticles with different Dy-content (x=0.1, 0.2, 0.3, 0.4, 0.5, 0.6) were investigated by employing X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive spectroscopy, field emission scanning electron microscope, transmission electron microscope and vibrating sample magnetometer techniques. The results showed that with an increase in Dy amounts, the coercivity of particles increased from 2.9 kOe to 13.4 kOe and then decreased to 5.6 kOe. By adding an optimum amount of Dy (x=0.4), the coercivity was significantly increased from 2.9 kOe to 13.4 kOe. The average particle size of annealed (Nd1-xDyx)2Fe14B nanoparticles was below 10 nm. Magnetization reversal studies indicate that the coercivity of milled and annealed (Nd1-xDyx)2Fe14B nanoparticles is controlled by the nucleation of reversed magnetic domains. The experimental results in the angular dependence of coercivity for (Nd1-xDyx)2Fe14B permanent magnets showed that the normalized coercivity of the permanent magnets Hc(θ)/Hc(0) increases from 1 to about 1.2-1.5 with increasing θ from 0 to about π/3, for x=0.4-0.6.

  20. Evaluation of potassium iodide (KI) and ammonium perchlorate (NH4ClO4) to ameliorate 131I- exposure in the rat.

    Science.gov (United States)

    Harris, C A; Fisher, J W; Rollor, E A; Ferguson, D C; Blount, B C; Valentin-Blasini, L; Taylor, M A; Dallas, C E

    2009-01-01

    Nuclear reactor accidents and the threat of nuclear terrorism have heightened the concern for adverse health risks associated with radiation poisoning. Potassium iodide (KI) is the only pharmaceutical intervention that is currently approved by the Food and Drug Administration for treating (131)I(-) exposure, a common radioactive fission product. Though effective, KI administration needs to occur prior to or as soon as possible (within a few hours) after radioactive exposure to maximize the radioprotective benefits of KI. During the Chernobyl nuclear reactor accident, KI was not administered soon enough after radiation poisoning occurred to thousands of people. The delay in administration of KI resulted in an increased incidence of childhood thyroid cancer. Perchlorate (ClO(4)(-)) was suggested as another pharmaceutical radioprotectant for 131I- poisoning because of its ability to block thyroidal uptake of iodide and discharge free iodide from the thyroid gland. The objective of this study was to compare the ability of KI and ammonium perchlorate to reduce thyroid gland exposure to radioactive iodide (131I-). Rats were dosed with 131I- tracer and 0.5 and 3 h later dosed orally with 30 mg/kg of either ammonium perchlorate or KI. Compared to controls, both anion treatments reduced thyroid gland exposure to 131I- equally, with a reduction ranging from 65 to 77%. Ammonium perchlorate was more effective than stable iodide for whole-body radioprotectant effectiveness. KI-treated animals excreted only 30% of the (131)I(-) in urine after 15 h, compared to 47% in ammonium perchlorate-treated rats. Taken together, data suggest that KI and ammonium perchlorate are both able to reduce thyroid gland exposure to 131I- up to 3 h after exposure to 131I-. Ammonium perchlorate may offer an advantage over KI because of its ability to clear 131I- from the body.

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

    KAUST Repository

    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

  2. Thermodynamics of the complexation of ciprofloxacin with calcium and magnesium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    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.

  3. Spectroscopic study of perchlorates and other oxygen chlorides in a Martian environmental chamber

    Science.gov (United States)

    Wu, Zhongchen; Wang, Alian; Ling, Zongcheng

    2016-10-01

    We report a study where the molecular spectral features of nine anhydrous and hydrous oxygen chlorides were analyzed both under Mars atmospheric pressure and temperature conditions in a Planetary Environment and Analysis Chamber (PEACh) and, for comparison, under ambient laboratory conditions. The goal is to understand the effect of Mars environmental conditions (mainly temperature T and CO2 pressure P) on their spectral features as determined by both Raman and NIR spectroscopy. These results will be used for in situ simultaneous identification of the Cl O4- and other intermediate oxygen chloride products generated during a dynamic electrostatic discharge (ESD) experiment. We have three major findings from the first phase of this study: (1) the ν1 Raman peak position is the most sensitive parameter for identifying the cation speciation in perchlorates (e.g., Na, Mg, Ca), the hydration state of magnesium perchlorate (e.g., Mg(ClO4)2 ṡ xH2O, x = 0 , 2 , 4 , 6), and the degree of oxidation of sodium oxygen chlorides (e.g., NaClOy, y = 1 , 2 , 3 , 4); (2) ν1 Raman peak positions of most tested hydrous and anhydrous oxygen chlorides show no detectable changes within the tested T and P ranges relevant to the environmental conditions at Mars surface and shallow subsurface, but water Raman peaks of the hydrated salts change following T decreases; (3) under the P &T conditions relevant to current surface and shallow subsurface at Mars mid-latitude regions, both Mg(ClO4)2 ṡ 6H2O and Ca(ClO4)2 ṡ 2H2O are stable against dehydration, while NaClO4 ṡ H2O dehydrates, with a dehydration rate that is a function of T which was quantified by in situ NIR spectroscopy. These results are useful for the interpretations of the data from current orbital remote sensing (Vis-NIR spectra) and from future landed missions (Raman spectra). Furthermore, we have designed a set of systematic ESD experiments to be conducted in PEACh for studying the pathways and the rates of oxygen chloride

  4. Purification of apyrase from yellow lupin cotyledons after extraction with perchloric acid.

    Science.gov (United States)

    Guranowski, A; Starzyńska, E; Rataj-Guranowska, M; Günther Sillero, M A

    1991-08-01

    Neutralized 1 M perchloric acid (PCA) extracts of yellow lupin (Lupinus luteus) seedling cotyledons contain considerable amounts of apyrase (EC 3.6.1.5). Investigators who use PCA extraction for the estimation of nucleotide levels, particularly in plant tissues, should be aware of this danger. Only when the material is treated with 1.8-2 M PCA are the extracts obtained free of apyrase activity. Chromatography of neutralized 1 M extracts obtained from 7-day-old seedling cotyledons on DEAE-Sephacel and Sephadex G-100 yields almost homogeneous apyrase that shows a band of M(r) 51,000 on sodium dodecyl sulfate-polyacrylamide gel electrophoresis gels. The molecular weight of the native enzyme is also about 51,000. The apyrase preparation is free of nonspecific phosphatases, nucleotidases, and adenosine nucleosidase, as well as dinucleoside polyphosphate-degrading enzymes. The apyrase exhibits a broad pH optimum between 6 and 8. Mg2+ and Ca2+ are required for maximum activity; Zn2+ and Mn2+ are less effective and Co2+, Ni2+, and Cd2+ are without effect. The Km values for ATP and ADP are about 20 microM. All common 5'-nucleoside tri- and diphosphates as well as adenosine 5'-tetraphosphate are substrates.

  5. [An investigation on fast thermolysis of ammonium perchlorate (AP) by FTIR spectroscopy].

    Science.gov (United States)

    Zhang, La-ying; Liu, Zi-ru; Wang, Xiao-hong; Heng, Shu-yun; Pan, Qing; Shao, Ying-hui; Zhang, Gao; Zhao, Feng-qi

    2010-08-01

    The fast thermolysis processes of ammonium perchlorate (AP) and its chemical reaction mechanism under certain simulated conditions of combustion were systematically studied by means of T-Jump/FTIR technique. AP was flash-pyrolyzed under different pressure nitrogen atmosphere, with the heating rate of 1000 K x s(-1) and the set temperatures of 874 and 1 274 K. Thereafter, the real time species and concentration of its gaseous products were obtained and identified by using rapid scanning Fourier transform infrared (FTIR) in-situ spectroscopy. It was indicated that the main gaseous products of AP thermolysis is composed of NO2, N2O, NO, HCl and NClO. Interestingly, the values of N2O/NO2, NO/NO2 and NO/NClO are increased while the test temperature or pressure is elevated. It is suggested that the transformation of condensed phase and heterogeneous gas/condensed phase was probably arises and the "following reactions" among the main gaseous products may also take place in the fast thermolysis process of AP.

  6. Widespread presence of naturally occurring perchlorate in high plains of Texas and New Mexico

    Science.gov (United States)

    Rajagopalan, S.; Anderson, T.A.; Fahlquist, L.; Rainwater, K.A.; Ridley, M.; Jackson, W.A.

    2006-01-01

    Perchlorate (ClO4-) occurrence in groundwater has previously been linked to industrial releases and the historic use of Chilean nitrate fertilizers. However, recently a number of occurrences have been identified for which there is no obvious anthropogenic source. Groundwater from an area of 155 000 km2 in 56 counties in northwest Texas and eastern New Mexico is impacted by the presence of ClO4-. Concentrations were generally low (anions (e.g., IO3-, Cl-, SO4-2) and ClO4-. The ClO4- distribution appears to be mainly related to evaporative concentration and unsaturated transport. This process has led to higher ClO4- and other ion concentrations in groundwater where the water table is relatively shallow, and in areas with lower saturated thickness. Irrigation may have accelerated this process in some areas by increasing the transport of accumulated salts and by increasing the number of evaporative cycles. Results from this study highlight the potential for ClO4- to impact groundwater in arid and semiarid areas through long-term atmospheric deposition. ?? 2006 American Chemical Society.

  7. Morphological control of zinc tricarbohydrazide perchlorate crystals:Theoretical and experimental study

    Institute of Scientific and Technical Information of China (English)

    LIU Rui; QI ShuYuan; ZHANG TongLai; ZHOU ZunNing; YANG Li; ZHANG JianGuo

    2013-01-01

    The theoretical crystal-morphology of zinc tricarbohydrazide perchlorate (ZnCP) was studied using the morphology simulation software.The growth trends and surface characteristics were calculated using the Bravais-Friedel-Donnay-Harker (BFDH),Growth Morphology,and Equilibrium Morphology methods; these provide theoretical guidance for the choice of crystal-control reagents.On the basis of the simulations,experiments were carried out to study the effects of five different crystal-control reagents,including carboxymethylcellulose (A),polyacrylamide (B),dextrin (C),Tween 40 (D),and Tween 60 (E),in the control of the crystal-morphology of ZnCP.Mixtures of two reagents and higher temperatures were used to further optimize the ZnCP crystals.The results show that ZnCP crystals are well dispersed,and have a large apparent density and regular crystal-morphology under the control of a mixture of reagents A and E in a mass ratio of 1 ∶ 4 at 80℃.

  8. Synthesis, growth and characterization of a nonlinear optical crystal: l-Leucinium perchlorate

    Directory of Open Access Journals (Sweden)

    P. Baskaran

    2017-01-01

    Full Text Available An amino acid based semiorganic nonlinear optical family single crystal of l-leucinium perchlorate (LLPCl was grown by the solvent evaporation method at ambient temperature. Good optical quality single crystals up to a size of 6 mm × 5 mm × 3 mm were obtained. The single-crystal XRD analysis shows that the grown crystals have a monoclinic structure. Fourier transform infrared (FTIR spectral analysis and UV–vis spectral studies were also carried out. Microhardness mechanical studies show that the hardness number (Hv of a LLPCl single crystal decreases with the load as measured by the Vickers microhardness method. The dielectric properties of the grown crystal were analysed by varying the frequency. Photoconductivity analysis gives the variation of the photocurrent and dark current. The nonlinear optical properties were studied using the Kurtz and Perry powder method and the second harmonic generation efficiency was found to be 2.6 times higher than that of KDP crystals.

  9. Carbon-coated copper nanoparticles prepared by detonation method and their thermocatalysis on ammonium perchlorate

    Directory of Open Access Journals (Sweden)

    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.

  10. Size and Shape of Ammonium Perchlorate and their Influence on Properties of Composite Propellant

    Directory of Open Access Journals (Sweden)

    Sunil Jain

    2009-05-01

    Full Text Available Most of the composite propellant compositions contain solid loading up to 86 per cent. The main solid ingredients of composite propellant are ammonium perchlorate (AP and aluminium powder. Therefore, it is a must to characterise these to improve processibility and quality of composite propellant. Effect of particle size on propellants slurry viscosity and ballistic parameters are well documented, however, the effect of oxidizer particle shape is not reported. In the present study, different methods for size and shape characterisation are discussed and effect of size and shape of AP on composite propellant properties are studied. The data indicate that as size of AP decreases, propellant slurry viscosity increases and burn rate increases. The particles having higher shape factor provides less endof mix (EOM viscosity of propellant slurry and burn rate. Further, effect of size of ground AP on shape is also investigated. From the data thus obtained, it is inferred that as size of ground AP decreases, shape factor decreases, and particles become more irregular in shape.Defence Science Journal, 2009, 59(3, pp.294-299, DOI:http://dx.doi.org/10.14429/dsj.59.1523

  11. Combustion Characteristics and Propulsive Performance of Boron/Ammonium Perchlorate Mixtures in Microtubes

    Science.gov (United States)

    Liang, Daolun; Liu, Jianzhong; Zhou, Junhu; Wang, Yang; Yang, Yuxin

    2016-07-01

    A microthruster is used for the operation tracking and posture control of microsatellites. In this work, the combustion characteristics and propulsive performance of a boron/ammonium perchlorate (B/AP) propellant mixture for a microthruster were investigated. Amorphous B and AP were used in different mass ratios to prepare the propellant samples. A laser-ignition solid micropropulsion test system was set up, and a differential scanning calorimeter was used. The solid combustion products of the samples with good performance were collected. Microstructural and component analyses of the combustion products were performed. Various performance parameters, including the combustion temperature, combustion velocity, spectral intensity, ignition delay time, thrust, specific impulse, density specific impulse, and heat flow, changed with the fuel-oxidant ratio. The optimal fuel-oxidant mass ratio of the propellant samples was 40%, with a density specific impulse of 0.474 kg/m2•s and a maximum heat flow of 4.4913 mW/mg. Analysis of the combustion products revealed that the clearance between particles significantly diminished after combustion. During combustion, the AP completely decomposed, and a large amount of H3BO3, B2O3, and HBO2 was generated.

  12. Effect of Surface Microstructure on the Temperature sensitivity of Burning Rate of Ammonium Perchlorate

    Directory of Open Access Journals (Sweden)

    K. Kishore

    1997-04-01

    Full Text Available Considering Vielle's law and the new thermodynamic model which the authors have developed recently the true dependence of temperature sensitivity of burning rate of ammonium perchlorate (AP on pressure is resolved and experimentally verified for bellet burning. The value of decreases with pressure steeply in regime I' (below 20 atm, but gently in regime I (above 20 atm. The value of powder AP has been determined and it is observed that (powder > (pellet, which clearly suggests that of is innuenced by the surface temperature sensitive parameter and hence by the surface/subsurface microstructure. In powder burning, the buoyant lifting of the particles into the gas phase occurs, Which constitutes the so-called 'free board region' (FER extending just above the true surface. Consequent to the decomposition of AP particles in FER, the condensed phase heat release gets curtailed and (powder becomes larger. A general relationship for in terms of density and surface temperature is suggested, which is applicable to both pellet and powder AP.

  13. The influence of VO2(B nanobelts on thermal decomposition of ammonium perchlorate

    Directory of Open Access Journals (Sweden)

    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

  14. Kinetic calculations and mechanism definition for reactions in an ammonium perchlorate flame

    Energy Technology Data Exchange (ETDEWEB)

    Ermolin, N.E.; Fomin, V.M.; Korobeinichev, O.P.; Tereshchenko, A.G.

    1982-09-01

    This article reports on detailed calculations on the reaction kinetics in APC flames on the basis of a wide set of possible reactions and experimental data on the initial composition of the gas mixture (gasification products from APC). The purpose is to select the most important reactions in this system by comparing the calculations on the kinetics with experimental data on the concentration profiles in APC flames. Discusses kinetic equations; rate constants as the reaction mechanism; results from kinetic calculations; and identification of major stages. A laminar flame such as that provided by ammonium perchlorate is described in general form by a system of differential equations that incorporate the transport of heat and matter in the presence of chemical reactions. APC is a system consisting of 4 elements (N,H,Cl and O). Points out that the scheme enables one to determine which reactions are responsible for producing the final products. Suggests that in the future one will be able to analyze experimental data on the reaction-rate profiles for stable components in order to determine either the atom and radical concentrations or the rate constants of the reactions involving them.

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

    KAUST Repository

    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

  16. Biomarker expression in lung of rabbit with pulmonary fibrosis induced by ammonium perchlorate.

    Science.gov (United States)

    Wu, Feng-hong; Guo, Hui-xia; Lin, Ming-fang; Chen, Zhi-ze; Zhou, Xuan; Peng, Kai-liang

    2011-04-01

    Ammonium perchlorate (AP), an oxidizer, has been used in solid propellants. Although AP exposure has been suspected as a risk factor for the development of pulmonary fibrosis, data are still inconclusive. To evaluate the pulmonary toxicity and the potential pulmonary fibrosis caused by occupational exposure to this compound, 25 male rabbits were randomly allocated into five groups to receive AP or bleomycin or saline by intratracheal injection. All rabbits were sacrificed and total RNA from the lungs was extracted. Expressions of types I and III collagens, transforming growth factor-β(1) (TGF-β(1)) and tumour necrosis factor-α (TNF-α) messenger RNA (mRNA) were measured by reverse transcription-polymerase chain reaction (RT-PCR). The expressions of type I and III collagen mRNA in low, moderate and high dose AP groups were significantly higher (p < 0.01 or p < 0.05) than that in the saline group. There was also a significant increased level of TGF-β(1) and TNF-α mRNA in the three AP groups compared with saline control group (p < 0.01 or p < 0.05). These results reveal that AP can increase gene expressions of types I, III collagens, TGF-β(1) and TNF-α in lung of rabbits exposed to AP. The overexpression of these biomarkers were considered as effective indicator linking to the development of pulmonary fibrosis and finally demonstrated that AP has potential to induce pulmonary fibrosis.

  17. (μ-1,4,7,10-Tetraoxacyclododecanebis[(1,4,7,10-tetraoxacyclododecanelithium] bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Ilia A. Guzei

    2010-04-01

    Full Text Available 12-Crown-4 ether (12C4 and LiClO4 combine to form the ionic title compound, [Li2(C8H16O43](ClO42, which is composed of discrete Li/12C4 cations and perchlorate anions. In the [Li2(12C43]2+ cation there are two peripheral 12C4 ligands, which each form four Li—O bonds with only one Li+ atom. Additionally there is a central 12C4 in which diagonal O atoms form one Li—O bond each with both Li+ atoms. Therefore each Li+ atom is pentacoordinated in a distorted square-pyramidal geometry, forming four longer bonds to the O atoms on the peripheral 12C4 and one shorter bond to an O atom of the central 12C4. The cation occupies a crystallographic inversion centre located at the center of the ring of the central 12C4 ligand. The Li+ atom lies above the cavity of the peripheral 12C4 by 0.815 (2 Å because it is too large to fit in the cavity.

  18. (2,2′-Bipyridine(2-formyl-6-methoxyphenolatonickel(II perchlorate

    Directory of Open Access Journals (Sweden)

    Cui-Juan Wang

    2009-01-01

    Full Text Available In the title compound, [Ni(C8H7O3(C10H8N2]ClO4, the NiII atom is in a slightly distorted square-planar coordination by two N atoms from the 2,2′-bipyridine (bipy ligand and two O atoms from the deprotonated 2-formyl-6-methoxyphenolate (mbd ligand. The bipy ligand is nearly coplanar with the NiII square plane, the Ni atom being only 0.042 (2 Å from the mean plane, whereas the benzaldehyde plane is folded with respect to the square plane, making a dihedral angle of 19.17 (8°. One of the O atoms of the perchlorate anion is involved in a weak interaction with the Ni atom, with an Ni—O distance of 2.5732 (18 Å. The packing is stabilized by weak C—H...O interactions.

  19. In Situ Detection of Chlorine Dioxide (C1O2) in the Radiolysis of Perchlorates and Implications for the Stability of Organics on Mars

    Science.gov (United States)

    Góbi, Sándor; Bergantini, Alexandre; Kaiser, Ralf I.

    2016-12-01

    Magnesium perchlorate hexahydrate (Mg(ClO4)2 · 6H2O) samples were exposed to energetic electrons to investigate the products of the decomposition of perchlorates in the Martian soil and to infer their role in the degradation of organics on Mars. The samples were monitored online and in situ via infrared spectroscopy as well as electron impact (EI-QMS) and reflectron time-of-flight mass spectrometry coupled with single photon ionization (PI-ReTOF-MS). Our study reveals that besides chlorates ({{{ClO}}3}-) and molecular oxygen (O2), the chlorine dioxide radical (ClO2) was observed online and in situ for the first time as a radiolysis product of solid perchlorates. Chlorine dioxide, which is used on Earth as a strong oxidizing agent in water disinfection and bleaching, represents a proficient oxidizer—potentially more powerful than molecular oxygen—to explain the lack of abundant organics in the Martian soil.

  20. Crystal structure of (perchlorato-κO)(1,4,7,10-tetra-aza-cyclo-dodecane-κ(4)N)copper(II) perchlorate.

    Science.gov (United States)

    Gray, Jessica L; Gerlach, Deidra L; Papish, Elizabeth T

    2017-01-01

    The crystal structure of the title salt, [Cu(ClO4)(C8H20N4)]ClO4, is reported. The Cu(II) ion exhibits a square-pyramidal geometry and is coordinated by the four N atoms of the neutral 1,4,7,10-tetra-aza-cyclo-dodecane (cyclen) ligand and an O atom from one perchlorate anion, with the second perchlorate ion hydrogen-bonded to one of the amine N atoms of the cyclen ligand. Additional N-H⋯O hydrogen bonds between the amine H atoms and the coordinating and non-coordinating perchlorate groups create a three-dimensional network structure. Crystals were grown from a concentrated methanol solution at ambient temperature, resulting in no co-crystallization of solvent.

  1. Dysprosium(III) complexes with a square-antiprism configuration featuring mononuclear single-molecule magnetic behaviours based on different β-diketonate ligands and auxiliary ligands.

    Science.gov (United States)

    Zhang, Sheng; Ke, Hongshan; Shi, Quan; Zhang, Jangwei; Yang, Qi; Wei, Qing; Xie, Gang; Wang, Wenyuan; Yang, Desuo; Chen, Sanping

    2016-03-28

    Three mononuclear dysprosium(III) complexes derived from three β-diketonate ligands, 4,4,4-trifluoro-1-(4-methylphenyl)-1,3-butanedione (tfmb), 4,4,4-trifluoro-1-(4-fluorophenyl)-1,3-butanedione (tffb) and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (tfnb) as well as auxiliary ligands, 5-nitro-1,10-phenanthroline (5-NO2-Phen), DMF and 2,2'-bipyridine (bpy) have been synthesized and structurally characterized, namely [Dy(5-NO2-Phen)(tfmb)3] (1), [Dy(DMF)2(tffb)3] (2) and [Dy(bpy)2(tfnb)3]·0.5(1,4-dioxane) (3). The metal ions in 1-3 adopt an approximately square-antiprismatic (SAP) coordination environment with D4d axial symmetry. The magnetic properties of 1-3 have been investigated, displaying weak out-of-phase AC signals under a zero-DC field. With an applied DC field of 1200 Oe, the quantum tunnelling of the magnetization was suppressed in 1-3 with the pre-exponential factor τ0 = 5.3 × 10(-7) s and the effective barrier ΔE/kB = 83 K for 1 as well as the pre-exponential factor τ0 = 3.09 × 10(-7) s and the effective barrier ΔE/kB = 39 K for 3. Interestingly, for the frequency dependence of the out-of-phase (χ'') of the AC susceptibility of 2, two slow relaxation of the magnetization processes occurred under the applied magnetic field of 1200 Oe, corresponding to the fast relaxation (FR) phase and slow relaxation (SR) phase, respectively. Arrhenius analysis gave the effective energy barrier (ΔE/kB) of 55 K and the pre-exponential factor (τ0) of 8.23 × 10(-12) for the SR. It is thus very likely that the FR process in complex 2 results from QTM enhanced by dipolar interactions between the Dy ions or the presence of the applied field. The structure-property relationship of some Dy(III) based mononuclear SMMs with the SAP configuration was further discussed.

  2. Magnetic Phase Transition of Nanocrystalline Bulk Metal Gadolinium and Dysprosium%纳米块体金属钆和镝的磁性相变分析

    Institute of Scientific and Technical Information of China (English)

    刘凤艳; 侯碧辉; 岳明; 王克军

    2011-01-01

    The magnetic properties of bulk nanocrystalline metal gadolinium (Gd) and dysprosium (Dy)samples were studied.The magnetization and Curie temperature TC of nanocrystalline Gd and Dy decreased usually as compared with the polycrystal.However,when the mean grain size was 10 nm, the Curie temperature Tc of nanocrystalline Dy increased to 100 K instead and there was an antiferromagnetic phase in nanocrystalline Gd.According to the calculation based on Ruderman-Kittel-Kasuya-Yosida exchange interaction, the exchange integral of the grain boundary atoms and crystalline surface atoms had its sign changed from plus to minus or vice versa, and there were three orderly phases in the steady state with the lowest energy, ferromagnetic phase, antiferromagnetic phase and fan phase.For the nanocrystals with mean grain size of 10 nm, the proportion of grain boundary to crystalline surface atoms was high, and as the result of superposition of the three phases, and there appeared a peak near the phase transition temperature for the nanocrystalline Gd.While for the Dy, the magnetization decreased gently with temperature, and showing a higher Curie temperature than in the case of the polycrystal.%对纳米晶钆(Gd)和镝(Dy)块体材料的磁性进行了研究.与多晶比较,通常纳米晶的磁化强度减小,居里温度TC降低,但平均粒径为10 nm的纳米晶Dy的居里温度TC反而升高到100 K,平均粒径为10 nm的纳米晶Gd中还存在明显的反铁磁相.通过RKKY交换作用的计算知道,晶面晶界处原子的交换积分会发生正负号的变化,能量最低的稳定状态对应三种有序相:铁磁相、反铁磁相和扇相,晶粒中在一定条件下出现三相共存.对于平均粒径为10 nm的纳米晶,晶面晶界处原子所占比例很大,三相叠加的结果,对于Gd,即是在相变点附近出现磁化强度尖峰;对于Dy,则是磁化强度随温度升高下降缓慢,表现为居里温度TC比多晶升高.

  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.

    Science.gov (United States)

    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. Effects of the anti-thyroidal compound potassium-perchlorate on the thyroid system of the zebrafish

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Perchlorate and Volatiles of the Brine of Lake Vida (Antarctica): Implication for the in Situ Analysis of Mars Sediments

    Science.gov (United States)

    Kenig, Fabien; Chou, Luoth; McKay, Christopher P.; Jackson, W. Andrew; Doran, Peter T.; Murray, Alison E.; Fritsen, Christian H.

    2016-01-01

    The cold (-13.4 C), cryoencapsulated, anoxic, interstitial brine of the 27 m-thick ice of Lake Vida (Victoria Valley, Antarctica) contains 49 microgram L-1 of perchlorate and 11 microgram L-1 of chlorate. Lake Vida brine (LVBr) may provide an analog for potential oxychlorine-rich subsurface brine on Mars. LVBr volatiles were analyzed by solid-phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS) with two different SPME fibers. With the exception of volatile organic sulfur compounds, most other volatiles observed were artifacts produced in the GC injector when the thermal decomposition products of oxychlorines reacted with reduced carbon derived from LVBr and the SPME fiber phases. Analysis of MilliQ water with perchlorate (40 microgram L-1) showed low level of organic artifacts, reflecting carbon limitation. In order to observe sample-derived organic compounds, both in analog samples and on Mars, the molar abundance of reduced carbon in a sample must exceed those of O2 and Cl2 produced during decomposition of oxychlorines. This suggests that the abundance of compounds observed by the Sample Analysis at Mars (SAM) instruments in Sheepbed samples (CB-3, CB5, and CB6) may be controlled by an increase in the reduced-carbon/oxychlorine ratio of these samples. To increase chances of in situ detection of Martian organics during pyrolysis-GC-MS, we propose that the derivatization agents stored on SAM may be used as an external source of reduced carbon, increasing artificially the reduced-carbon to perchlorate ratio during pyrolysis, allowing the expression of more abundant and perhaps more diverse Martian organic matter.

  6. Perchlorate and volatiles of the brine of Lake Vida (Antarctica): Implication for the in situ analysis of Mars sediments

    Science.gov (United States)

    Kenig, Fabien; Chou, Luoth; McKay, Christopher P.; Jackson, W. Andrew; Doran, Peter T.; Murray, Alison E.; Fritsen, Christian H.

    2016-07-01

    The cold (-13.4°C), cryoencapsulated, anoxic, interstitial brine of the >27 m thick ice of Lake Vida (Victoria Valley, Antarctica) contains 49 µg · L-1 of perchlorate and 11 µg · L-1 of chlorate. Lake Vida brine (LVBr) may provide an analog for potential oxychlorine-rich subsurface brine on Mars. LVBr volatiles were analyzed by solid-phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS) with two different SPME fibers. With the exception of volatile organic sulfur compounds, most other volatiles observed were artifacts produced in the GC injector when the thermal decomposition products of oxychlorines reacted with reduced carbon derived from LVBr and the SPME fiber phases. Analysis of MilliQ water with perchlorate (40 µg · L-1) showed low level of organic artifacts, reflecting carbon limitation. In order to observe sample-derived organic compounds, both in analog samples and on Mars, the molar abundance of reduced carbon in a sample must exceed those of O2 and Cl2 produced during decomposition of oxychlorines. This suggests that the abundance of compounds observed by the Sample Analysis at Mars (SAM) instruments in Sheepbed samples (CB-3, CB5, and CB6) may be controlled by an increase in the reduced-carbon/oxychlorine ratio of these samples. To increase chances of in situ detection of Martian organics during pyrolysis-GC-MS, we propose that the derivatization agents stored on SAM may be used as an external source of reduced carbon, increasing artificially the reduced-carbon to perchlorate ratio during pyrolysis, allowing the expression of more abundant and perhaps more diverse Martian organic matter.

  7. Systematic evaluation of nitrate and perchlorate bioreduction kinetics in groundwater using a hydrogen-based membrane biofilm reactor.

    Science.gov (United States)

    Ziv-El, Michal C; Rittmann, Bruce E

    2009-01-01

    To evaluate the simultaneous reduction kinetics of the oxidized compounds, we treated nitrate-contaminated groundwater (approximately 9.4 mg-N/L) containing low concentrations of perchlorate (approximately 12.5 microg/L) and saturated with dissolved oxygen (approximately 8 mg/L) in a hydrogen-based membrane biofilm reactor (MBfR). We systematically increased the hydrogen availability and simultaneously varied the surface loading of the oxidized compounds on the biofilm in order to provide a comprehensive, quantitative data set with which to evaluate the relationship between electron donor (H(2)) availability, surface loading of the electron acceptors (oxidized compounds), and simultaneous bioreduction of the electron acceptors. Increasing the H(2) pressure delivered more H(2) gas, and the total H(2) flux increased linearly from approximately 0.04 mg/cm(2)-d for 0.5 psig (0.034 atm) to 0.13 mg/cm(2)-d for 9.5 psig (0.65 atm). This increased rate of H(2) delivery allowed for continued reduction of the acceptors as their surface loading increased. The electron acceptors had a clear hydrogen-utilization order when the availability of hydrogen was limited: oxygen, nitrate, nitrite, and then perchlorate. Spiking the influent with perchlorate or nitrate allowed us to identify the maximum surface loadings that still achieved more than 99.5% reduction of both oxidized contaminants: 0.21 mg NO(3)-N/cm(2)-d and 3.4 microg ClO(4)/cm(2)-d. Both maximum values appear to be controlled by factors other than hydrogen availability.

  8. catena-Poly[[[(dimethyl-malonato-κO:O')(perchlorato-κO)copper(II)]-μ-bis-(3-pyridylmeth-yl)piperazinediium-κN:N] perchlorate dihydrate].

    Science.gov (United States)

    Farnum, Gregory A; Laduca, Robert L

    2008-11-13

    In the title compound, {[Cu(C(5)H(6)O(4))(ClO(4))(C(16)H(22)N(4))]ClO(4)·2H(2)O}(n), square-pyramidally coordinated Cu atoms with perchlorate and dimethyl-malonate ligands are connected into cationic sinusoidal coordination polymer chains by doubly protonated bis-(3-pyridylmeth-yl)piperazine (3-bpmp) ligands. The chains aggregate into pseudo-layers parallel to the (101) crystal planes by N-H⋯O hydrogen bonding. Unligated perchlorate anions and water mol-ecules of crystallization provide additional hydrogen bonding between pseudo-layers.

  9. The Preparation and Structure of [(2,4-Dimethyl-8-ethyl-5,8-diazadec-4-ene-2-aminechlorocopper(II] Perchlorate

    Directory of Open Access Journals (Sweden)

    Neil F. Curtis

    2013-01-01

    Full Text Available Copper(II chloride and perchlorate, N,N-diethylethane-1,2-diamine, react in (methanol with acetone and ammonia to form [(2,4-dimethyl-8-ethyl-5,8-diazadec-4-ene-2-aminechlorocopper(II] perchlorate, C12H27Cl2CuN3O4, , monoclinic, C2/c, (Hall-C2/c; a, 26.418(1, b, 9.7385(4; c, 14.0993(5 Å; β, 91.134(3°. This has copper(II in tetrahedrally distorted square-planar coordination by one primary, one tertiary, and one imine nitrogen atom and the chloride ion.

  10. Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex in perchloric acid medium

    Indian Academy of Sciences (India)

    T V N Partha Sarathi; A Kalyan Kumar; K Krishna Kishore; P Vani

    2005-07-01

    Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex has been studied in perchloric acid medium. The reaction is first order with respect to iron(III) and glycine. An increase in (phenanthroline) increases the rate, while increase in [H+] decreases the rate. Hence it can be inferred that the reactive species of the substrate is the zwitterionic form and that of the oxidant is [Fe(phen)2(H2O)2]3+. The proposed mechanism leads to the rate law as elucidated.

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

    Directory of Open Access Journals (Sweden)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Dracorhodin Perchlorate Induced Human Breast Cancer MCF-7 Apoptosis through Mitochondrial Pathways

    Science.gov (United States)

    Yu, Jing-hua; Zheng, Gui-bin; Liu, Chun-yu; Zhang, Li-ying; Gao, Hong-mei; Zhang, Ya-hong; Dai, Chun-yan; Huang, Lin; Meng, Xian-ying; Zhang, Wen-yan; Yu, Xiao-fang

    2013-01-01

    Objective: Dracorhodin perchlorate (DP) was a synthetic analogue of the antimicrobial anthocyanin red pigment dracorhodin. It was reported that DP could induce apoptosis in human prostate cancer, human gastric tumor cells and human melanoma, but the cytotoxic effect of DP on human breast cancer was not investigated. This study would investigate whether DP was a candidate chemical of anti-human breast cancer. Methods: The MTT assay reflected the number of viable cells through measuring the activity of cellular enzymes. Phase contrast microscopy visualized cell morphology. Fluorescence microscopy detected nuclear fragmentation after Hoechst 33258 staining. Flowcytometric analysis of Annexin V-PI staining and Rodamine 123 staining was used to detect cell apoptosis and mitochondrial membrane potential (MMP). Real time PCR detected mRNA level. Western blot examined protein expression. Results: DP dose and time-dependently inhibited the growth of MCF-7 cells. DP inhibited MCF-7 cell growth through apoptosis. DP regulated the expression of Bcl-2 and Bax, which were mitochondrial pathway proteins, to decrease MMP, and DP promoted the transcription of Bax and inhibited Bcl-2. Apoptosis-inducing factor (AIF) and cytochrome c which localized in mitochondrial in physiological condition were released into cytoplasm when MMP was decreased. DP activated caspase-9, which was the downstream of mitochondrial pathway. Therefore DP decreased MMP to release AIF and cytochrome c into cytoplasm, further activating caspase 9, lastly led to apoptosis. Conclusion: Therefore DP was a candidate for anti-breast cancer, DP induced apoptosis of MCF-7 through mitochondrial pathway. PMID:23869191

  14. Solution-reaction Calorimetric Study of Coordination Compounds of Rare Earth Perchlorates with Alanine and Imidazole

    Institute of Scientific and Technical Information of China (English)

    ZHAO, Yan-Ru(赵艳茹); HOU, An-Xin(侯安新); DONG, Jia-Xin(董家新); ZHAO, Shun-Sheng(赵顺省); LIU, Yi(刘义); QU, Song-Sheng(屈松生)

    2004-01-01

    Two coordination compounds of rare earth perchlorates with alanine and imidazole, [RE(Ala)n(Im)(H2O)](ClO4)3(s) (RE=La, n=3; RE=Nd, n=2), have been prepared and characterized. The standard molar enthalpies of reaction for the following two reactions, LaCL·7H2O(s)+3Ala(s)+Im(s)+3NaClO4(s)=[La(Ala).(Im)(H2O)]-(ClO4)3(s)+3NaCl(s)+6H2O(I)(1)and NdCl3·6H2O(s)+2Ala(s)+2Ala(s)+Im(s)+3NaClO4(s)=[Nd(Ala)2(Im)(H2O)]-(ClO4)3(s)+3NaCl(s)+5H2O(l) (2), were determined by solution-reaction calorimetry, at T=298.15 K, as 36.168 ±0.642kJ·mol-1 and 48.590±0.934kJ·mol-1 respectively. From the results and other auxiliary quantities, the standard molar enthalpies of formation of [La(Ala)3(Im)(H2O)](ClO4)3(s) and [Nd(Ala)2(Im)(H2O)] (ClO4)3(s) were derived,△fH(-)m{[La(Ala).(Im)(H2O)](ClO4)3,s}=(-2984.8±1.0)kJ·mol-1 and △fH(-)m{[Nd(Ala).(Im)(H2O)]-(ClO4)3,s}=(-2387.8±0.8)kJ·mol-1, respectively.

  15. Widespread presence of naturally occurring perchlorate in high plains of Texas and New Mexico.

    Science.gov (United States)

    Rajagopalan, Srinath; Anderson, Todd A; Fahlquist, Lynne; Rainwater, Ken A; Ridley, Moira; Jackson, W Andrew

    2006-05-15

    Perchlorate (CLO4-) occurrence in groundwater has previously been linked to industrial releases and the historic use of Chilean nitrate fertilizers. However, recently a number of occurrences have been identified for which there is no obvious anthropogenic source. Groundwater from an area of 155,000 km2 in 56 counties in northwest Texas and eastern New Mexico is impacted bythe presence of ClO4-. Concentrations were generally low (areas are impacted by concentrations up to 200 ppb. ClO4- distribution is not related to well type (public water system, domestic, agricultural, or water-table monitoring) or aquifer (Ogallala, Edward Trinity High Plains, Edwards Trinity Plateau, Seymour, or Cenozoic). Results from vertically nested wells strongly indicate a surface source. The source of ClO4- appears to most likely be atmospheric deposition. Evidence supporting this hypothesis primarily relates to the presence of ClO4- in tritium-free older water, the lack of relation between land use and concentration distribution, the inability of potential anthropogenic sources to account for the estimated mass of ClO4-, and the positive relationship between conserved anions (e.g., IO3-, Cl-, SO4(-2)) and ClO4-. The ClO4- distribution appears to be mainly related to evaporative concentration and unsaturated transport. This process has led to higher ClO4- and other ion concentrations in groundwater where the water table is relatively shallow, and in areas with lower saturated thickness. Irrigation may have accelerated this process in some areas by increasing the transport of accumulated salts and by increasing the number of evaporative cycles. Results from this study highlight the potential for ClO4- to impact groundwater in arid and semi-arid areas through long-term atmospheric deposition.

  16. Evidence for perchlorates and the origin of chlorinated hydrocarbons detected by SAM at the Rocknest aeolian deposit in Gale Crater

    Science.gov (United States)

    Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas; Atreya, Sushil K.; Brinckerhoff, William B.; Cabane, Michel; Coll, Patrice; Conrad, Pamela G.; Coscia, David; Dworkin, Jason P.; Franz, Heather B.; Grotzinger, John P.; Leshin, Laurie A.; Martin, Mildred G.; McKay, Christopher; Ming, Douglas W.; Navarro-González, Rafael; Pavlov, Alexander; Steele, Andrew; Summons, Roger E.; Szopa, Cyril; Teinturier, Samuel; Mahaffy, Paul R.

    2013-10-01

    A single scoop of the Rocknest aeolian deposit was sieved (trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of ~0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.

  17. Synthesis of polycrystalline Co{sub 3}O{sub 4} nanowires with excellent ammonium perchlorate catalytic decomposition property

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. Inducing porosity and growing carbon nanofibers in ferroin perchlorate: An example of morphological transitions in coordination complexes

    Science.gov (United States)

    Avraham, Efrat Shawat; Fleker, Ohad; Benisvy, Laurent; Oakes, Landon; Pint, Cary L.; Nessim, Gilbert D.

    2017-09-01

    Inducing porosity in solid coordination complex crystals, which are an important class of catalysts, is critical for many applications where a high surface area is required. However, unlike metal organic frameworks (MOFs), fabrication of porous coordination crystals remains a significant challenge. Here we demonstrate a simple method to produce and modulate porosity in coordination complex crystals using ferroin perchlorate, a model system that combines a common ionic complex with a very reactive counter-ion. Using thermal chemical vapor deposition (CVD), we show that by annealing ferroin perchlorate crystals at 350 °C under a flow of ethylene, hydrogen, argon, and oxygen, we induced pores in the crystal. We demonstrate that small amounts of oxygen, which may combine with hydrogen to form water, are essential for pore formation. We also demonstrate that pore size and density can be easily controlled by varying the ethylene flow. Upon raising the annealing temperature to 500 °C, we observed a second transition in which carbon nanofibers (CNFs) grew from the porous crystal. This approach represents a simple and effective method for the synthesis of porous materials with good control over pore size and density. It also enables the synthesis of complex networks of nanostructures (in our case CNFs) by simply varying process parameters such as temperature and gas flows. This represents an important advance for the fabrication of porous coordination complex crystals.

  19. Preparation of Nano-MnFe2O4 and Its Catalytic Performance of Thermal Decomposition of Ammonium Perchlorate

    Institute of Scientific and Technical Information of China (English)

    韩爱军; 廖娟娟; 叶明泉; 李燕; 彭新华

    2011-01-01

    Nano-MnFe2O4 particles were synthesized by co-precipitation phase inversion method and low-temperature combustion method respectively, using MnCl2, FeCl3, Mn(NO3)2, Fe(NO3)3, NaOH and C6H8O7. X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravim-etry-differential thermal analysis (TG-DTA) and differential scanning calorimetry (DSC) were used to characterize the structure, morphology, thermal stability of MnFe2O4 and its catalytic performance to ammonium perchlorate. Results showed that single-phased and uniform spinel MnFe2O4 was obtained. The average particle size was about 30 and 20 nm. The infrared absorption peaks appeared at about 420 and 574 cm-1, and the particles were stable below 524 ℃. Using the two prepared catalysts, the higher thermal decomposition temperature of ammonium perchlorate was decreased by 77.3 and 84.9 ℃ respectively, while the apparent decomposition heat was increased by 482.5 and 574.3 J?g?1. The catalytic mechanism could be explained by the favorable electron transfer space provided by outer d orbit of transition metal ions and the high specific surface absorption effect of MnFe2O4 particles.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  1. Crystal structure of barium perchlorate anhydrate, Ba(ClO42, from laboratory X-ray powder data

    Directory of Open Access Journals (Sweden)

    Jeonghoo H. Lee

    2015-06-01

    Full Text Available The previously unknown crystal structure of barium perchlorate anhydrate, determined and refined from laboratory X-ray powder diffraction data, represents a new structure type. The title compound was obtained by heating hydrated barium perchlorate [Ba(ClO42·xH2O] at 423 K in vacuo for 6 h. It crystallizes in the orthorhombic space group Fddd. The asymmetric unit contains one Ba (site symmetry 222 on special position 8a, one Cl (site symmetry 2 on special position 16f and two O sites (on general positions 32h. The structure can be described as a three-dimensional polyhedral network resulting from the corner- and edge-sharing of BaO12 polyhedra and ClO4 tetrahedra. Each BaO12 polyhedron shares corners with eight ClO4 tetrahedra, and edges with two ClO4 tetrahedra. Each ClO4 tetrahedron shares corners with four BaO12 polyhedra, and an edge with the other BaO12 polyhedron.

  2. Extension of the energy range of the experimental activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium up to 65 MeV

    CERN Document Server

    Tárkányi, F; Takács, S; Hermanne, A; Ignatyuk, A V

    2016-01-01

    Activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium were extended up to 65 MeV by using stacked foil irradiation and gamma spectrometry experimental methods. Experimental cross-sections data for the formation of the radionuclides $^{159}$Dy, $^{157}$Dy, $^{155}$Dy, $^{161}$Tb, $^{160}$Tb, $^{156}$Tb, $^{155}$Tb, $^{154m2}$Tb, $^{154m1}$Tb, $^{154g}$Tb, $^{153}$Tb, $^{152}$Tb and $^{151}$Tb are reported in the 36-65 MeV energy range, and compared with an old dataset from 1964. The experimental data were also compared with the results of cross section calculations of the ALICE and EMPIRE nuclear model codes and of the TALYS nuclear reaction model code as listed in the latest on-line libraries TENDL 2013.

  3. Extension of the energy range of the experimental activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium up to 65MeV.

    Science.gov (United States)

    Tárkányi, F; Ditrói, F; Takács, S; Hermanne, A; Ignatyuk, A V

    2015-04-01

    Activation cross-sections data of longer-lived products of proton induced nuclear reactions on dysprosium were extended up to 65MeV by using stacked foil irradiation and gamma spectrometry experimental methods. Experimental cross-sections data for the formation of the radionuclides (159)Dy, (157)Dy, (155)Dy, (161)Tb, (160)Tb, (156)Tb, (155)Tb, (154m2)Tb, (154m1)Tb, (154g)Tb, (153)Tb, (152)Tb and (151)Tb are reported in the 36-65MeV energy range, and compared with an old dataset from 1964. The experimental data were also compared with the results of cross section calculations of the ALICE and EMPIRE nuclear model codes and of the TALYS nuclear reaction model code as listed in the latest on-line libraries TENDL 2013. Copyright © 2015. Published by Elsevier Ltd.

  4. Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate

    Science.gov (United States)

    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

  5. Comparing the removal of perchlorate when using single-walled carbon nanotubes (SWCNTs) or granular activated carbon: adsorption kinetics and thermodynamics.

    Science.gov (United States)

    Lou, Jie C; Hsu, Yung S; Hsu, Kai L; Chou, Ming S; Han, Jia Y

    2014-01-01

    This study aims to remove perchlorate using single-walled carbon nanotubes (SWCNTs) or granular activated carbon (GAC). Dynamic and equilibrium adsorption experiments were performed to evaluate the thermodynamic behavior of perchlorate on SWCNTs and GAC. Key parameters affecting the adsorption, such as pH, ionic strength, and temperature were studied. The experimental results showed that the dynamic adsorption experiment achieved equilibrium in approximately eight hours. The adsorption capacity increased as the concentration of perchlorate increased or as the ionic strength decreased. The selected adsorption models were the modified Freundlich, the pseudo-1st-order, and the pseudo-2nd-order equations. The results showed that the modified Freundlich equation best described the kinetic adsorption processes. The maximal adsorption capacities of GAC and SWCNTs were 33.87-28.21 mg/g and 13.64 - 10.03 mg/g, respectively, at a constant temperature between 5°C and 45°C. The thermodynamic parameters, such as the equilibrium constant (K0 ), the standard free energy changes (ΔG°), the standard enthalpy change (ΔH°) and the standard entropy change (ΔS°), were obtained. The results of the isothermal equilibrium adsorption experiment showed that low pH levels, low ionic strength, and low-temperature conditions facilitated the perchlorate adsorption, indicating that GAC and SWCNTs are potential absorbents for water treatment.

  6. A copper(II) perchlorate-promoted tandem reaction of internal alkynol and salicyl N-tosylhydrazone: direct access to isochromeno[3,4-b]chromene.

    Science.gov (United States)

    Siyang, Hai Xiao; Wu, Xu Rui; Ji, Xiao Yue; Wu, Xin Yan; Liu, Pei Nian

    2014-08-11

    A copper(ii) perchlorate-promoted tandem reaction of internal alkynol and salicyl N-tosylhydrazone provides a novel, concise method for constructing isochromeno[3,4-b]chromene in 35-94% yields. The tandem reaction involves cycloisomerization, formal [4+2] cycloaddition and an elimination process.

  7. Comparison of Pumped and Diffusion Sampling Methods to Monitor Concentrations of Perchlorate and Explosive Compounds in Ground Water, Camp Edwards, Cape Cod, Massachusetts, 2004-05

    Science.gov (United States)

    LeBlanc, Denis R.; Vroblesky, Don A.

    2008-01-01

    Laboratory and field tests were conducted at Camp Edwards on the Massachusetts Military Reservation on Cape Cod to examine the utility of passive diffusion sampling for long-term monitoring of concentrations of perchlorate and explosive compounds in ground water. The diffusion samplers were constructed of 1-inch-diameter rigid, porous polyethylene tubing. The results of laboratory tests in which diffusion samplers were submerged in containers filled with ground water containing perchlorate, RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) indicate that concentrations inside the diffusion samplers equilibrated with concentrations in the containers within the 19-day-long test period. Field tests of the diffusion samplers were conducted in 15 wells constructed of 2- or 2.5-inch-diameter polyvinyl chloride pipe with 10-foot-long slotted screens. Concentrations of perchlorate, RDX, and HMX in the diffusion samplers placed in the wells for 42 to 52 days were compared to concentrations in samples collected by low-flow pumped sampling from 53 days before to 109 days after retrieval of the diffusion samples. The results of the field tests indicate generally good agreement between the pumped and diffusion samples for concentrations of perchlorate, RDX, and HMX. The concentration differences indicate no systematic bias related to contaminant type or concentration levels.

  8. Ferric Perchlorate Catalyzed One-pot Synthesis of 1,2,3,4-Tetrahydro-2-pyrimidinones and -thiones:an Expedient Protocol for the Biginelli Reaction

    Institute of Scientific and Technical Information of China (English)

    HERAVI,Majid Momahed; BEHBAHANI,Farahnaz Kargar OSKOOIE; Hossien Abdi

    2008-01-01

    An efficient synthesis of 1,2,3,4-tetrahydro-2-pyrimidinones and -thiones using ferric perchlorate as the catalyst from an aldehyde, ethyl acetoacetate, and urea or thiourea in acetonitrile was described. Compared to the classical Biginelli reaction conditions, this new method consistently has the advantage of full catalysis, good yields and short reaction time.

  9. ANALYSIS OF THE KINETICS OF SOLVOLYSIS OF P-NITROPHENYLSULFONYLMETHYL PERCHLORATE IN BINARY ALCOHOLIC MIXTURES IN TERMS OF THE THERMODYNAMIC PROPERTIES OF THE SOLVENT MIXTURES

    NARCIS (Netherlands)

    WIJNEN, JW; ENGBERTS, JBFN; BLANDAMER, MJ

    1993-01-01

    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 fracti

  10. EFFECTS OF LOW DOSE MIXTURES OF PCB126 AND PERCHLORATE ON THE HYPTHALAMIC-PITUITARY-THYROID (HPT) AXIS IN THE MALE RAT.

    Science.gov (United States)

    Perchlorate (ClO4) and 3,3',4,4',5-pentachlorobiphenyl (PCB126) are environmental contaminants known to disturb thyroid hormone homeostasis by well defined modes of action that lead to hypothyroidism in the rat. PCB126 increases phase II conjugation of T4 (T4-glucuronide) by indu...

  11. Hexanuclear, heterometallic, Ni₃Ln₃ complexes possessing O-capped homo- and heterometallic structural subunits: SMM behavior of the dysprosium analogue.

    Science.gov (United States)

    Goura, Joydeb; Guillaume, Rogez; Rivière, Eric; Chandrasekhar, Vadapalli

    2014-08-04

    The reaction of hetero donor chelating mannich base ligand 6,6'-{(2-(dimethylamino)ethylazanediyl)bis(methylene)}bis(2-methoxy-4-methylphenol) with Ni(ClO4)2·6H2O and lanthanide(III) salts [Dy(III) (1); Tb(III) (2); Gd (III) (3); Ho(III) (4); and Er(III) (5)] in the presence of triethylamine and pivalic acid afforded a series of heterometallic hexanuclear Ni(II)-Ln(III) coordination compounds, [Ni3Ln3(μ3-O)(μ3-OH)3(L)3(μ-OOCCMe3)3]·(ClO4)·wCH3CN·xCH2Cl2·yCH3OH·zH2O [for 1, w = 8, x = 3, y = 0, z = 5.5; for 2, w = 0, x = 5, y = 0, z = 6.5; for 3, w = 15, x = 18, y = 3, z = 7.5; for 4, w = 15, x = 20, y = 6, z = 9.5; and for 5, w = 0, x = 3, y = 2, z = 3]. The molecular structure of these complexes reveals the presence of a monocationic hexanuclear derivative containing one perchlorate counteranion. The asymmetric unit of each of the hexanuclear derivatives comprises the dinuclear motif [NiLn(L)(μ3-O)(μ3-OH)(μ-Piv)]. The cation contains three interlinked O-capped clusters: one Ln(III)3O and three Ni(II)Ln(III)2O. Each of the lanthanide centers is eight- coordinated (distorted trigonal-dodecahedron), while the nickel centers are hexacoordinate (distorted octahedral). The study of the magnetic properties of all compounds are reported and suggests single molecule magnet behavior for the Dy(III) derivative (1).

  12. Experimental evidence for supercooled brines, viscous liquids, and low temperature perchlorate glasses on Mars

    Science.gov (United States)

    Toner, J.; Catling, D. C.; Light, B.

    2013-12-01

    The presence of liquid water on the cold and dry surface of Mars is possible where concentrated salt solutions lower the freezing point of water. The eutectic temperature is the maximum equilibrium freezing point depression possible for a given salt solution, which ranges from near 0°C for carbonates and sulfates, to as low as -75°C for perchlorates. Although eutectic temperatures suggest a lower temperature limit for liquid water on Mars, salt solutions will typically supercool below their eutectic before crystallization occurs. We report on results investigating the magnitude of supercooling and its variation with salt composition and concentration for pure salt solutions and saturated soil solutions of MgSO4, MgCl2, NaCl, NaClO4, Mg(ClO4)2, and Ca(ClO4)2. We measured supercooling by monitoring solution temperatures during slow cooling and warming experiments. Our results indicate that supercooling is pervasive. Slowly cooled MgSO4, MgCl2, NaCl, and NaClO4 solutions typically supercool 5-15°C below their eutectic temperature before crystallizing. The addition of soil to these salt solutions has a variable effect on supercooling. Relative to the pure salt solutions, supercooling decreases in MgSO4 soil solutions, increases in MgCl2 soil solutions, and is similar in NaCl and NaClO4 soil solutions. Supercooling in MgSO4, MgCl2, NaCl, and NaClO4 solutions could marginally extend the duration of liquid water during relatively warm daytime temperatures in the Martian summer. Remarkably, we found that Mg(ClO4)2 and Ca(ClO4)2 solutions never crystallize during slow cooling, but remain in a supercooled, liquid state until forming an amorphous glass near -120°C. Even if soil is added to the solutions, which will induce crystallization in most salt solutions, a glass still forms during cooling. The large supercooling effect in Mg(ClO4)2 and Ca(ClO4)2 solutions has the potential to prevent water from freezing over diurnal and possibly annual cycles on Mars. Glasses are

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

    Science.gov (United States)

    Estrada, Nubia Luz; Böhlke, John Karl; 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

    2017-01-01

    Natural perchlorate (ClO4−) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ37Cl, δ18O, and Δ17O), indicating that ClO4− may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO4−, but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO4− in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO4− was transported from solutions into plants similarly to NO3− but preferentially to Cl− (4-fold). The ClO4− isotopic compositions of initial ClO4− reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO4− uptake or accumulation. The ClO4− isotopic composition of field-grown snap beans was also consistent with that of ClO4− in varying proportions from irrigation water and precipitation. NO3− uptake had little or no effect on NO3− isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε (15N/18O) ratio of 1.05 was observed between NO3− in hydroponic solutions and leaf extracts, consistent with partial NO3− reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO4− in commercial produce, as illustrated by spinach, for which the ClO4− isotopic composition was similar to that of indigenous natural ClO4−. Our results indicate that some types of plants can accumulate and (presumably) release ClO4− to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO4−and NO3− in plants may be useful for determining sources of fertilizers and sources of ClO4− in their growth environments and

  14. Studies on composite solid propellant with tri-modal ammonium perchlorate containing an ultrafine fraction

    Directory of Open Access Journals (Sweden)

    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

  15. Selective Anion Exchange Resins for the Removal of Perchlorate [(CIO{sub 4}{sup -})] from Groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Gu, B.

    1999-05-20

    The primary objective of this project was to evaluate a novel bifunctional anion exchange resin for the cost-effective, in situ treatment of groundwater contaminated with perchlorate (ClO{sub 4}{sup -}). Both laboratory and field studies were performed to determine the selectivity and capacity of the bifunctional synthetic resins to sorb ClO{sub 4}{sup -} from simulated or actual contaminated groundwater. A number of synthetic bifunctional resins, including two commercial versions made by Purolite International and three commercially available, mono-functional resins, were tested. Initial laboratory batch and column breakthrough studies determined the best synthetic resins and the optimal conditions for the field experiment. Laboratory results indicated that the bifunctional synthetic resins, D-3696 and RO-02-119 were highly selective toward ClO{sub 4}{sup -} and performed {approx}5 times better than the best commercial nitrate resin (Purolite{reg_sign} A-520E) and more than an order of magnitude better than some nonselective commercial resins (e.g. Amberlite{reg_sign} IRA-900). The bifunctional resins were particularly effective in removing trace quantities of ClO{sub 4}{sup -} in groundwater to below the detection limit ({approx} 3 {micro}g/L). A field trial demonstrated that the bifunctional resin (D-3696) was able to treat {approx} 110,000 bed volumes of groundwater before a 10% breakthrough of ClO{sub 4}{sup -} occurred under the column flow-through conditions (running at {approx} 2 bed volumes per minute). On the other hand, the Purolite{reg_sign} A-520E resin was able to treat {approx} 23,000 bed volumes of groundwater under the same experimental conditions. No pretreatment was needed to remove either dissolved organic matter or other competing anions (such as SO{sub 4}{sup 2-} or NO{sub 3}{sup -}) in the groundwater, and the treatment process did not alter the water quality by removing or adding secondary by-products because of the high selectivity of the

  16. Soil, plant, and terrain effects on natural perchlorate distribution in a desert landscape

    Science.gov (United States)

    Andraski, Brian J.; Jackson, W.A.; Welborn, Toby L.; Böhlke, John Karl; Sevanthi, Ritesh; Stonestrom, David A.

    2014-01-01

    Perchlorate (ClO4−) is a contaminant that occurs naturally throughout the world, but little is known about its distribution and interactions in terrestrial ecosystems. The objectives of this Amargosa Desert, Nevada study were to determine (i) the local-scale distribution of shallow-soil (0–30 cm) ClO4− with respect to shrub proximity (far and near) in three geomorphic settings (shoulder slope, footslope, and valley floor); (ii) the importance of soil, plant, and terrain variables on the hillslope-distribution of shallow-soil and creosote bush [Larrea tridentata (Sessé & Moc. ex DC.) Coville] ClO4−; and (iii) atmospheric (wet plus dry, including dust) deposition of ClO4− in relation to soil and plant reservoirs and cycling. Soil ClO4− ranged from 0.3 to 5.0 μg kg−1. Within settings, valley floor ClO4− was 17× less near shrubs due in part to enhanced leaching, whereas shoulder and footslope values were ∼2× greater near shrubs. Hillslope regression models (soil, R2 = 0.42; leaf, R2 = 0.74) identified topographic and soil effects on ClO4− deposition, transport, and cycling. Selective plant uptake, bioaccumulation, and soil enrichment were evidenced by leaf ClO4− concentrations and Cl−/ClO4− molar ratios that were ∼8000× greater and 40× less, respectively, than soil values. Atmospheric deposition ClO4− flux was 343 mg ha−1 yr−1, ∼10× that for published southwestern wet-deposition fluxes. Creosote bush canopy ClO4− (1310 mg ha−1) was identified as a previously unrecognized but important and active reservoir. Nitrate δ18O analyses of atmospheric deposition and soil supported the leaf-cycled–ClO4− input hypothesis. This study provides basic data on ClO4− distribution and cycling that are pertinent to the assessment of environmental impacts in desert ecosystems and broadly transferable to anthropogenically contaminated systems.

  17. Changes in gastric sodium-iodide symporter (NIS) activity are associated with differences in thyroid gland sensitivity to perchlorate during metamorphosis.

    Science.gov (United States)

    Carr, James A; Murali, Sharanya; Hu, Fang; Goleman, Wanda L; Carr, Deborah L; Smith, Ernest E; Wages, Mike

    2015-08-01

    We investigated stage-dependent changes in sensitivity of the thyroid gland to perchlorate during development of African clawed frog tadpoles (Xenopus laevis) in relation to non-thyroidal iodide transporting tissues. Perchlorate-induced increases in thyroid follicle cell size and colloid depletion were blunted when exposures began at Nieuwkoop-Faber (NF) stage 55 compared to when exposures began at NF stages 49 or 1-10. To determine if the development of other iodide transporting tissues may contribute to this difference we first examined which tissues expressed transcripts for the sodium dependent iodide symporter (NIS). RT-PCR analysis revealed that NIS was expressed in stomach and small intestine in addition to the thyroid gland of X. laevis tadpoles. NIS mRNA was not detected in lung, kidney, skin, gill, muscle, heart or liver. Perchlorate sensitive (125)I uptake was found in stomach, lung, kidney, gill, and small intestine but not muscle, liver, or heart. Perchlorate-sensitive (125)I uptake by stomach was 6-10 times greater than in any other non-thyroidal tissue in tadpoles. While NF stage 49 tadpoles exhibited perchlorate-sensitive uptake in stomach it was roughly 4-fold less than that observed in NF stage 55 tadpoles. Although abundance of NIS gene transcripts was greater in stomachs from NF stage 55 compared to NF stage 49 tadpoles this difference was not statistically significant. We conclude that gastric iodide uptake increases between NF stages 49 and 55, possibly due to post-translational changes in NIS glycosylation or trafficking within gastric mucosal cells. These developmental changes in gastric NIS gene expression may affect iodide availability to the thyroid gland.

  18. Theoretical Study of Energetic Complexes (Ⅲ): Bis-(5-nitro-2Htetrazolato-N2)tetraammine Cobalt(Ⅲ) Perchlorate (BNCP) and Its Transition Metal (Ni/Fe/Cu/Zn) Perchlorate Analogues

    Institute of Scientific and Technical Information of China (English)

    尚静; 张建国; 张同来; 黄辉胜; 张绍文; 舒远杰

    2012-01-01

    The geometric conformation and electronic structure of bis-(5-nitro-2H-tetrazolato-N2)tetraammine cobalt(Ⅲ) perchlorate and its Ni/Fe/Cu/Zn analogues are studied under the TPSS (Tao-Perdew-Staroverov-Scuseria) levels of density functional theory in order to throw light on the relationship between their energy gaps and impact sensitivity While the perchlorate ions are coordinated with the copper cation, which is different from the other four compounds NBO (Natural bond orbital) analyses indicated that the metal-ligand interaction in the Co complex is covalent, while the others are ionic. The analysis of the electrostatic potential demonstrated that the O atoms from the nitro-tetrazole ring and perchlorate were primarily negative, while the other atoms were positive. The study was also conducted to gain a better understanding of the correlation of the energy gap and impact sensitivity.

  19. Dysprosium selective potentiometric membrane sensor

    Energy Technology Data Exchange (ETDEWEB)

    Zamani, Hassan Ali, E-mail: haszamani@yahoo.com [Department of Applied Chemistry, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of); Faridbod, Farnoush; Ganjali, Mohammad Reza [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of)

    2013-03-01

    A novel Dy(III) ion-selective PVC membrane sensor was made using a new synthesized organic compound, 3,4-diamino-N Prime -((pyridin-2-yl)methylene)benzohydrazide (L) as an excellent sensing element. The electrode showed a Nernstian slope of 19.8 {+-} 0.6 mV per decade in a wide concentration range of 1.0 Multiplication-Sign 10{sup -6}-1.0 Multiplication-Sign 10{sup -2} mol L{sup -1}, a detection limit of 5.5 Multiplication-Sign 10{sup -7} mol L{sup -1}, a short conditioning time, a fast response time (< 10 s), and high selectivity towards Dy(III) ion in contrast to other cations. The proposed sensor was successfully used as an indicator electrode in the potentiometric titration of Dy(III) ions with EDTA. The membrane sensor was also applied to the F{sup -} ion indirect determination of some mouth washing solutions and to the Dy{sup 3+} determination in binary mixtures. Highlights: Black-Right-Pointing-Pointer The novelty of this work is based on the high affinity of the ionophore toward the Dy{sup 3+} ions. Black-Right-Pointing-Pointer This technique is very simple, fast and inexpensive and it is not necessary to use sophisticated equipment. Black-Right-Pointing-Pointer The newly developed sensor is superior to the formerly reported Dy{sup 3+} sensors in terms of selectivity.

  20. The magnetocaloric effect in dysprosium

    Science.gov (United States)

    Benford, S. M.

    1979-01-01

    The magnetocaloric effect in polycrystalline Dy was measured in the 84-280-K range in measuring fields from 1 to 7 T. These adiabatic temperature changes reflect structural changes in Dy with applied field and temperature, and include the first magnetocaloric data for a helical antiferromagnet. Above the Neel point (179 K) a field increase always caused heating; below the Neel point fields less than about 2 T cause cooling for some values of initial temperature. The largest temperature increase with a 7 T field occurs at the Neel point and at fields below 2 T near the Curie point. For refrigeration purposes the optimal working region for a Dy cooling element is field dependent.

  1. Diastereoisomeric β-ethyl aspartate-cobalt(III) complexes: Λ(+)578- and Δ(-)578-bis(ethane-1,2-diamine)[β-ethyl (S)-aspartato]cobalt(III) bis(perchlorate) monohydrate.

    Science.gov (United States)

    Hammershøi, Anders; Schau-Magnussen, Magnus; Bendix, Jesper; Mølgaard, Anne

    2010-11-01

    The structures of the diastereoisomers Λ(+)(578)-, (I), and Δ(-)(578)-bis(ethane-1,2-diamine)[β-ethyl (S)-aspartato-κ(2)N,O(1)]cobalt(III) bis(perchlorate) monohydrate, (II), both [Co(C(6)H(10)N(2)O(4))(C(2)H(8)N(2))(2)](ClO(4))(2)·H(2)O, are compared. In both structures, the ester group of the amino acid side chain is engaged only in intramolecular hydrogen bonding to coordinated amine groups. This interaction is stronger in (I) and correlates with previously observed diastereoisomeric equilibrium ratios for related metal complex systems in aqueous media. The two perchlorate anions of (II) are located on twofold axes. Both perchlorates in (I) and one of the perchlorates in (II) are affected by disorder. Both structures exhibit extensive three-dimensional hydrogen-bonding networks.

  2. Quantitative determination of perchlorate in bottled water and tea with online solid phase extraction high-performance liquid chromatography coupled to tandem mass spectrometry.

    Science.gov (United States)

    Lin, Shu-Ling; Lo, Chih-Yu; Fuh, Ming-Ren

    2012-07-13

    Due to the similarity in ionic radius, perchlorate has been reported to inhibit the iodide intake in the thyroid gland, which may lead to low heart rate, weight gain, and fatigue. In recent years, the presence of perchlorate in drinking water, surface water, soil, and food supplies in the United States has raised a great concern on establishing the maximum residue limit (MRL) for perchlorate to reduce its possible adverse influence on human health. US EPA currently puts perchlorate on the final third Contamination Candidate List (CCL3) and suggests a health reference level at 4.9 μg L⁻¹. The MRL of perchlorate was therefore set at 5.0 μg L⁻¹ by the authors for method validation. In this study, large volume injection (up to 1-mL) and online solid phase extraction (SPE) were utilized for pre-concentrating perchlorate ions and removing unretained matrix components prior to reversed-phase HPLC analysis using ESI-tandem MS under the negative mode. After eluting perchlorate from online SPE, 0.1% formic acid solution was utilized for isocratic HPLC analysis without any organic solvent. Multiple reaction monitoring (MRM) and the internal standard, Cl₁₈O₄⁻, were utilized for quantitatively determining perchlorate in bottled water and bottled tea samples. Two linear ranges, 0.05-0.50 μg L⁻¹ and 0.50-10.00 μg L⁻¹, were established to better estimate the residual amounts of perchlorate in bottled water samples with a method detection limit (MDL, signal-to-noise ratio of 3) of 0.01 μg L⁻¹. The linear range was 1.50-10.00 μg L⁻¹ for bottled tea samples with a MDL of 0.5 μg L⁻¹. In addition, the proposed method was further validated based on the EU Commission Decision 2002/657/EC, including within-laboratory reproducibility, decision limit (CCα), and detection capability (CCβ) for bottled water and bottled tea samples. The intra-day/inter-day precision and accuracy as well as within-laboratory reproducibility were determined by calculating

  3. Boron nitride encapsulated copper nanoparticles: a facile one-step synthesis and their effect on thermal decomposition of ammonium perchlorate

    Science.gov (United States)

    Huang, Caijin; Liu, Qiuwen; Fan, Wenjie; Qiu, Xiaoqing

    2015-11-01

    Reactivity is of great importance for metal nanoparticles used as catalysts, biomaterials and advanced sensors, but seeking for high reactivity seems to be conflict with high chemical stability required for metal nanoparticles. There is a subtle balance between reactivity and stability. This could be reached for colloidal metal nanoparticles using organic capping reagents, whereas it is challenging for powder metal nanoparticles. Here, we developed an alternative approach to encapsulate copper nanoparticles with a chemical inertness material—hexagonal boron nitride. The wrapped copper nanoparticles not only exhibit high oxidation resistance under air atmosphere, but also keep excellent promoting effect on thermal decomposition of ammonium perchlorate. This approach opens the way to design metal nanoparticles with both high stability and reactivity for nanocatalysts and their technological application.

  4. Synthesis of CNTs/CuO and its catalytic performance on the thermal decomposition of ammonium perchlorate

    Directory of Open Access Journals (Sweden)

    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.

  5. Bis[(2-methylbenzylbis(pyridin-2-ylmethyl-κNamine-κN]manganese(II bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Ray J. Butcher

    2014-03-01

    Full Text Available In the title complex, [Mn(C20H21N32](ClO42, two tridentate (2-methylbenzylbis(pyridin-2-ylmethylamine (L ligands form the MnII complex [MnL2](ClO42. The MnII ion lies on a twofold axis and the complex cation is significantly distorted from regular octahedral geometry. The packing is stabilized by weak C—H...O interactions between the cations and anions, which link them into a zigzag ribbon along [101]. The perchlorate anion is disordered and was constrained to be tetrahedral with two orientations having occupancies of 0.768 (4 and 0.232 (4. The 2-methylbenzyl moiety is also disordered over two sets of sites, with occupancies of 0.508 (15 and 0.492 (15.

  6. Structure effect of molybdenum (5) complexes on its activity in appearance of catalytic polarographic currents of chlorate- and perchlorate ions

    Energy Technology Data Exchange (ETDEWEB)

    Zajtsev, P.M.; Zhdanov, S.I.; Dergacheva, E.N.; Savchenko, E.N.; Nikolaeva, T.D. (Vsesoyuznyj Nauchno-Issledovatel' skij Inst. Khimicheskikh Reaktivov i Osobo Chistykh Veshchestv, Moscow (USSR))

    1982-08-01

    Polarographic behaviour and reactivity of synthesized molybdenum (5) in reactions, conditioning catalytic currents of ClO/sub 3//sup -/ and ClO/sub 4//sup -/ have been studied. Their comparison with similar characteristics for molybdenum (5) appearing in the process of Mo (6) solution polarography is made. For the purpose a salt of molybdenum (5) in H/sub 2/SO/sub 4/, HCl and HClO/sub 4/ solutions have been synthesized by electrochemical and chemical ways. It has been established that in reactions conditioning catalytic currents of chlorate- and perchlorate-ions the preservation of structure of Mo (6) complex in the Mo (5) complex formed, i.e. processes of Mo (5) complex ageing, plays a very significant role.

  7. Optimized geometry, vibration (IR and Raman spectra and nonlinear optical activity of p-nitroanilinium perchlorate molecule: A theoretical study

    Directory of Open Access Journals (Sweden)

    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.

  8. Synthesis of chrysalis-like CuO nanocrystals and their catalytic activity in the thermal decomposition of ammonium perchlorate

    Indian Academy of Sciences (India)

    Jun Wang; Shanshan He; Zhanshuang Li; Xiaoyan Jing; Milin Zhang; Zhaohua Jiang

    2009-11-01

    Chrysalis-like morphologies of CuO have been synthesized in large-quantity via a simple chemical deposition method without the use of any complex instruments and reagents. CuO nanocrystals showed a different morphology at three different temperatures, 25, 60 and 100°C. The particle size, morphology and crystal structure of the samples were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectra. The catalytic effect of CuO nanoparticles on the decomposition of ammonium perchlorate (AP) was investigated by STA 409 PC thermal analyzer at a heating rate of 10°C min-1 from 35 to 500°C. Compared with the thermal decomposition of pure AP, the addition of CuO nanoparticles decreased the decomposition temperature of AP by about 85°C.

  9. Concentration of zinc ions in perchlorate medium by a menbrane-gel using an acid extractant (DEHPA

    Directory of Open Access Journals (Sweden)

    Belhadji L.

    2013-07-01

    Full Text Available Recent decades, it is an awareness of the importance of ecological balance in the environment, balances threatened by industrial pollution. A new spirit presides we seek to minimize pollution of receiving waters. The present work is to study the liquid-gel-extraction of zinc ions in perchlorate medium by an acid extractant: the di (ethyl-2 hexyl phosphorique acid, or DEHPA. Two types of polymers were used as supports of solvent extraction: a polybutadiene rubber cross-linked respectively with 0.1% dicumyl peroxide and 0.4% dicumyl peroxide, vulcanized at 160°C, one is most cross-linked than the other. The liquid-gel extraction is based on the principles of the liquid-liquid extraction.

  10. Kinetic studies on the formation of nitrosamines I. Formation of dimethylnitrosamine in aqeous solution of perchloric acid.

    Science.gov (United States)

    Cachaza, J M; Casado, J; Castro, A; López Quintela, M A

    1978-01-01

    The kinetics of nitrosation of dimethylamine (DMA) in aqueous perchloric acid solution have been studied using a differential spectrophotometric technique. The rate law is Initial rate = e[DMA]0 [nitrite]2 0 [H+]/(f + [H+])2 where [DMA]0 and [nitrite]0 represent initial stoichiometric concentrations. At 310.0 K and mu = 2.0 M, e = (2.2 +/- 0.2) X 10(-5) M-1 s-1 and f = (1.28 +/- 0.02) X 10(-3) M. The associated activation energy is 56 +/- 3 kJ mol-1. A clear inhibition of the nitrosation rate by ionic strength has been observed in which only the kinetic parameter (f) has an effective change. It is concluded that under the experimental conditions of this work only the dinitrogen trioxid is the effective carrier for the nitrosation.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  12. Bis(acetonitrile-κN(1,10-phenanthroline-κ2N,N′platinum(II bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Kwang Ha

    2010-04-01

    Full Text Available The asymmetric unit of the title compound, [Pt(CH3CN2(C12H8N2](ClO42, contains one half of a cationic PtII complex and pair of half perchlorate anions, one of which is disordered over two sites in a 0.53 (3:0.47 (3 ratio. The complex and anions are disposed about a crystallographic mirror plane parallel to the ac plane passing through the Pt and Cl atoms. In the complex, the PtII ion lies in a distorted square-planar environment defined by four N atoms of the chelating 1,10-phenanthroline ligand and two distinct acetonitrile molecules. The component ions interact by means of intermolecular C—H...O hydrogen bonds.

  13. The perchlorate discharge test with {sup 123}I for the diagnosis of the Pendred syndrome in children; Der Depletionstest mit {sup 123}Iod zur Diagnose des Pendred-Syndroms bei Kindern

    Energy Technology Data Exchange (ETDEWEB)

    Hahn, K.; Fischer, S. [Klinik und Poliklinik fuer Nuklearmedizin, Klinikum der Ludwig-Maximilians-Univ. Muenchen (Germany)

    2009-03-15

    The method for the diagnosis of the Pendred Syndrome in children by the Perchlorate discharge test using {sup 123}I is described. The older child, who has the Pendred Syndrome and the obligatory hearing deficit, frequently has neither a goitre nor hypothyroidism, but other investigations (bone growth, scars and function tests) can also show changes. However a more certain diagnosis of this disorder in children is possible by the perchlorate discharge test using {sup 123}I. (orig.)

  14. Distribution of Natural Perchlorate in a Desert Landscape-Amargosa Desert Research Site, Nevada

    Science.gov (United States)

    Andraski, B. J.; Jackson, A.; Welborn, T.; Stonestrom, D. A.; Bohlke, J. K.

    2011-12-01

    Knowledge of perchlorate (ClO4-) occurrence is important due to health concerns, evolving groundwater-protection regulations, and for forensic investigations. The distribution of natural ClO4- is being studied at the U.S. Geological Survey's Amargosa Desert Research Site to improve understanding of factors that influence its accumulation and cycling in a desert landscape. The first part of the study evaluated the effect of plants on shallow (0-30 cm) soil concentrations in three settings-shoulder slope, footslope, and valley floor; samples were collected adjacent to plants and in interspaces 2.5-5 m from plants. For the valley-floor, there was a 17-fold decrease between interspace (5.0 μg/kg) and plant-adjacent (0.3 μg/kg) ClO4- concentrations. Chloride (Cl-) concentrations also showed large differences and indicated salt accumulation beneath the interspace desert pavement, but localized leaching adjacent to plants. For the shoulder and footslope, differences between interspace and plant-adjacent ClO4- concentrations were smaller (two fold on average) and inverted (interspace 2.0 μg/kg; plant-adjacent 3.8 μg/kg), and differences between interspace and plant-adjacent Cl- were negligible. Shoulder and footslope indications of a localized increase in ClO4- adjacent to plants suggest a cyclic mechanism of plant uptake, bioaccumulation, and leaf drop. The second part of the study examined ClO4- variability across a 9-ha hillslope. Data first were analyzed by assigning each sampling point to one of three elevation bands-upper, middle, or lower. Soil and plant data both showed trends of increasing ClO4- with decreasing elevation. Concentrations were, for soil (μg/kg): upper (1.6) middle (3.9) > lower (3.6). Multiple-linear regression analyses also were used to explore the relative importance of soil, plant, and terrain variables that influenced ClO4- concentrations across the hillslope. Important explanatory variables for soil ClO4- are land-surface elevation and

  15. Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

    Science.gov (United States)

    Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.; Cabane, Michel; Coll, Patrice; Conrad, Pamela G.; Coscia, David; Dworkin, Jason P.; Franz, Heather B.; Grotzinger, John P.; Leshin, Laurie A.; Martin, Mildred G.; McKay, Christopher; Ming, Douglas W.; Navarro-Gonzalez, Rafael; Pavlov, Alexander; Steele, Andrew; Summons, Roger E.; Szopa, Cyril; Teinturier, Samuel; Mahaffy, Paul R.

    2013-01-01

    A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the

  16. 生物修复高氯酸盐污染的研究进展%Research advance in bioremediation technology of perchlorate contamination

    Institute of Scientific and Technical Information of China (English)

    高海硕; 陈桂葵; 黎华寿

    2012-01-01

    生物修复技术是目前高氯酸盐污染环境整治的最具潜力的修复技术之一,具有成本低、无二次污染的特点,是国内外一个新的研究热点,亦是仅见的污染控制及修复的环境友好技术.介绍了环境中高氯酸盐污染的来源与分布,阐述了生物修复(主要包括植物修复和微生物修复)的特点及作用机制,认识到2种类型修复技术各有其优劣势;重点综述了生物修复高氯酸盐污染的国内外研究现状,得出植物根际降解对植物修复高氯酸盐起着十分重要作用,而微生物修复是目前最有希望获得大规模应用的高氯酸盐污染修复技术;最后提出了植物微生物联合强化修复高氯酸盐污染的技术将更具应用前景.%Bioremediation is the most potential technologies in perchlorate contamination remediation. As the only environmentally friendly remediation technologies so far, bioremediation technology had the advantage of low cost and no secondary pollution,it become a new research hotspot at home and abroad. This paper introduced the source and distribution of perchlorate contamination,described the characteristics and mechanism of bioremediation technology (mainly included phytoremediation and microbial remediation) in perchlorate contamination remediation; the advantages and disadvantages of these two bioremediation techniques was summarized and compared. The research status of perchlorate contamination bioremediation was reviewed. It was found that plant rhizosphere degradation played an important role in phytoremediation;microbial remediation was the most hopeful technology for large-scale application in perchlorate pollution remediation. The phyto-microbial strengthen remediation technology was put forward; it would had more application prospects in perchlorate contamination remeditation.

  17. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    Science.gov (United States)

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated.

  18. Control of Sulfidogenesis Through Bio-oxidation of H2S Coupled to (per)chlorate Reduction

    Energy Technology Data Exchange (ETDEWEB)

    Gregoire, Patrick [Univ. of California, Berkeley, CA (United States); Engelbrektson, Anna [Univ. of California, Berkeley, CA (United States); Hubbard, Christopher G. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Metlagel, Zoltan [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Csencsits, Roseann [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Auer, Manfred [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Conrad, Mark E. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Thieme, Jurgen [Brookhaven National Lab. (BNL), Upton, NY (United States); Northrup, Paul [Brookhaven National Lab. (BNL), Upton, NY (United States); Coates, John D. [Univ. of California, Berkeley, CA (United States)

    2014-04-04

    Here, we investigate H2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H2S coupled to (per)chlorate reduction without sustaining growth. H2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. We also propose a novel hybrid enzymatic-abiotic mechanism for H2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

  19. The Investigation of Magnesium Perchlorate/Iron Phase-mineral Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

    Science.gov (United States)

    Sutter, B.; Heil, E.; Archer, P. D.; Ming, D. W.; Eigenbrode, J. L.; Franz, H. B.; Glavin, D. P.; McAdam, A. C.; Mahaffy, P. R.; Niles, P. B.; Stern, J. C.; Navarro-Gonzalez, R.; McKay, C. P.

    2014-01-01

    The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumber-land (CB) drill hole materials in Gale Crater (Fig. 1) [1,2]. Chlorinated hydrocarbons have also been detect-ed by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS) [1,2,3,4]. These detections along with the detection of perchlorate (ClO4(-)) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) [5] suggesting perchlo-rate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal tempera-ture match to the SAM O2 and HCl release data [1,2]. Catalytic reactions of Fe phases in the Gale Crater ma-terial with perchlorates can potentially reduce the de-composition temperatures of these otherwise pure per-chlorate/chlorate phases [e.g., 6,7]. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate was found to cause O2 release temperatures to be closer match to the SAM O2 release data and enhance HCl gas releases. Exact matches to the SAM data has unfortnunately not been achieved with Ca-perchlorate-Fe-phase mixtures [8]. The effects of Fe-phases on magnesium perchlorate thermal decomposi-tion release of O2 and HCl have not been evaluated and may provide improved matches to the SAM O2 and HCl release data. This work will evaluate the thermal decomposition of magnesium perchlorate mixed with fayalite/magnetite phase and a Mauna Kea palagonite (HWMK 919). The objectives are to 1) summarize O2 and HCl releases from the Gale Crater materials, and 2) evaluate the O2 and HCl releases from the Mg-perchlorate + Fe phase mixtures to determine if Mg-perchlorate mixed with Fe-phases can explain the Gale Crater O2 and HCl releases.

  20. Contrasting coordination behavior of Group 12 perchlorate salts with an acyclic N3O2 donor ligand by X-ray crystallography and (1)H NMR.

    Science.gov (United States)

    Tice, Daniel B; Pike, Robert D; Bebout, Deborah C

    2016-08-09

    An unbranched N3O2 ligand 2,6-bis[((2-pyridinylmethyl)oxy)methyl]pyridine (L1) was used to prepare new mononuclear heteroleptic Group 12 perchlorate complexes characterized by IR, (1)H NMR and X-ray crystallography. Racemic complexes with pentadentate L1 and one to four oxygens from either water or perchlorate bound to a metal ion were structurally characterized. Octahedral [Zn(L1)(OH2)](ClO4)2 (1) and pentagonal bipyramidal [Cd(L1)(OH2)(OClO3)]ClO4 (2) structures were found with lighter congeners. The polymorphic forms of [Hg(L1)(ClO4)2] characterized (3 in P1[combining macron] and 4 in P21/c) had a mix of monodentate, anisobidentate and bidentate perchlorates, providing the first examples of a tricapped trigonal prismatic Hg(ii) coordination geometry, as well as additional examples of a rare square antiprismatic Hg(ii) coordination geometry. Solution state (1)H NMR characterization of the Group 12 complexes in CD3CN indicated intramolecular reorganization remained rapid under conditions where intermolecular M-L1 exchange was slow on the chemical shift time scale for Zn(ii) and on the J(M(1)H) time scale for Cd(ii) and Hg(ii). Solution studies with more than one equivalent of ligand also suggested that a complex with a 1 : 2 ratio of M : L1 contributed significantly to solution equilibria with Hg(ii) but not the other metal ions. The behavior of related linear pentadentate ligands with Group 12 perchlorate salts is discussed.

  1. Limited overshooting of NH{sub 4}{sup +} ions in ammonium perchlorate; Ograniczene przeskoki jonow NH{sub 4}{sup +} w nadchloranie amonowym

    Energy Technology Data Exchange (ETDEWEB)

    Birczynski, A.; Lalowicz, Z.T. [Inst. of Nuclear Physics, Cracow (Poland); Ingman, L.P.; Punkkinen, M.; Ylinen, E.E. [Wihuri Physical Lab., Turku Univ., Turku (Finland)

    1995-12-31

    The interpretation of NMR spectra for polycrystalline sample of ammonium perchlorate in helium temperature assumes the tunneling of NH{sub 4}{sup +}. Such interpretation does not agree with experimental data. The hypothesis of additional motion (fast rotation around one of C3 axis) has been checked and discussed on the base of NMR spectra of NH{sub 4}ClO{sub 4} monocrystal for the temperature range 2.1-25 K. 9 refs, 1 fig.

  2. Comparative Demonstration of Active and Semi-Passive In Situ Bioremediation Approaches for Perchlorate Impacted Groundwater: Active In Situ Bioremediation Demonstration

    Science.gov (United States)

    2013-04-01

    4% chlorine), which was passed through a cylinder of sodium chlorite (NaClO2) within the unit housing, generating 8% chlorine dioxide gas (ClO2...mediated redox reactions, whereby perchlorate serves as an electron acceptor, and is reduced via chlorate to chlorite . Chlorite then undergoes a...injection and extraction wells to achieve the desired electron donor coverage. Soluble electron donors such as sodium lactate, citric acid, or

  3. Preparation and Application of Perchloric Acid Supported on Alumina (Al2O3-HCIO4) to the Synthesis of α-(α-Amidobenzyl)-β-naphthols

    Institute of Scientific and Technical Information of China (English)

    SHATERIAN,Hamid Reza; KHORAMI,Fahimeh; AMIRZADEH,Azita; GHASHANG,Majid

    2009-01-01

    Preparation of perchloric acid supported on alumina and its primary application as a solid supported heterogeneous catalyst to the synthesis of α-(α-amidobenzyl)-β-naphthols by a one-pot,three-component condensation of benzaldehydes,β-naphthol and acetamide or benzamide under thermal solvent-free conditions were described.The present methodology offers several advantages such as simple procedure,shorter reaction time,and excellent yields.

  4. Field Demonstration and Validation of a New Device for Measuring Groundwater and Perchlorate Fluxes at IHDIV-NSWC, Indian Head, MD

    Science.gov (United States)

    2006-07-01

    potential hazard associated with this activity is exposure to perchlorate present in the ground water through skin contact. Waterproof , chemical... Waterproof , chemical resistant gloves shall be worn by site personnel when sub-sampling the PFMs and transferring to sample vials. 1.4.4 Site...water or disinfectant moist towelettes before eating, drinking, smoking, or applying cosmetics . These activities will be restricted to the designated

  5. Ion-selective electrodes using multi-walled carbon nanotubes as ion-to-electron transducers for the detection of perchlorate.

    Science.gov (United States)

    Parra, Enrique J; Crespo, Gastón A; Riu, Jordi; Ruiz, Aurora; Rius, F Xavier

    2009-09-01

    A solid contact ion-selective electrode using for the first time multi-walled carbon nanotubes (MWCNT) for the transducer material was developed for detecting perchlorate in water. To demonstrate the excellent ion-to electron transducer ability of the MWCNTs, a 15 microm thick layer of carboxylated MWCNT was deposited between an acrylic membrane selective to perchlorate ions and a glassy carbon rod used as the substrate and electrical conductor. The electrodes showed a Nernstian response of 57 mV decade(-1) (standard deviation of 3 mV decade(-1) over time and different electrodes) across a wide linear range of 10(-6) to 10(-2) M. The limit of detection was 10(-7.4) M of perchlorate. The response time was less than 10 s for activities higher than 10(-6) M and the intermediate-term potential stability shows a small drift of 0.22 mV h(-1) recorded over 5 hours. The electrode displays a selectivity comparable to liquid-contacted ISEs containing the same membrane.

  6. Determination of low levels of perchlorate in lettuce and spinach using ion chromatography-electrospray ionization mass spectrometry (IC-ESI-MS).

    Science.gov (United States)

    Seyfferth, Angelia L; Parker, David R

    2006-03-22

    A sample preparation method was developed to quantify environmentally relevant (low micrograms per liter) concentrations of perchlorate (ClO4(-)) in leafy vegetables using IC-ESI-MS. Lettuce and spinach were macerated, centrifuged, and filtered, and the aqueous extracts were rendered water-clear using a one-step solid-phase extraction method. Total time for extraction and sample preparation was 6 h. Ion suppression was demonstrated and was likely due to unknown organics still present in the extract solution after cleanup. However, this interference was readily eliminated using a Cl(18)O4(-) internal standard at 1 microg/L in all standards and samples. Hydroponically grown perchlorate-free butterhead lettuce was spiked to either 10.3 or 37.7 microg/kg of fresh weight (FW), and recoveries were between 91 and 98% and between 93 and 101%, respectively. Five types of lettuce and spinach from a local grocery store were then analyzed; they contained from 0.6 to 6.4 microg/kg of FW. Spike recoveries using the store-bought samples ranged from 89 to 100%. The method detection limit for perchlorate in plant extracts is 40 ng/L, and the corresponding minimum reporting limit is 200 ng/L or 0.8 microg/kg of FW.

  7. 高氯酸盐的环境毒理学效应及其机制的研究进展%Environmental toxicological effect and mechanism of perchlorate

    Institute of Scientific and Technical Information of China (English)

    吴春笃; 李顺; 许小红; 张波

    2013-01-01

    Perchlorate is a persistent toxic contaminant in the environment and the environmental problems caused have drawn the extensive attention of human beings. The perchlorate rarely exists in natural environment and mainly exists in the soil, furthermore, the atmosphere also produces a certain amount of perchlorate in some conditions. The pollution is mainly caused by the mass production and use of ammonium perchlorate and potassium perchlorate. Perchlorate is quite soluble,it can be rapidly transported and diffused in aqueous systems and achieve enrichment in plants and animals, then enters into human body through ingestion behavior. By competing with the sodium-iodide symporter (NIS) for transporting iodide into thyroid, perchlorate inhibits iodide uptake,influences the thyroid and pituitary hormone level and then inhibits the normal metabolism and growth of organisms. Based on the perchlorate toxicology data of potential adverse effects on thyroid function,growth, development,reproduction and neurodevelopment, this paper reviewed the perchlorate toxicity mechanism and the future research prospect was presented.%高氯酸盐是一种具有持久性的有毒污染物质,其环境污染问题引起了人类的广泛关注.天然环境中的高氯酸盐比例很少,主要存在于土壤中;此外,在某些环境条件下,大气中也能产生一定量的高氯酸盐;其人为污染主要来源于大量生产和使用的高氯酸铵和高氯酸钾.高氯酸盐易溶于水,可以在水环境中快速迁移扩散,在动植物体内富集并通过人类摄食作用进入人体.高氯酸根能够竞争性利用钠/碘转运体(NIS),抑制甲状腺吸收碘离子,进而影响甲状腺和脑垂体的激素水平,阻碍生物体正常的新陈代谢和生长发育.笔者基于高氯酸盐对甲状腺、生长发育、生殖行为及神经系统等潜在危害的毒理学研究,综述了高氯酸盐对生物体的毒性作用机制,并对其研究前景进行了展望.

  8. US Environmental Protection Agency Method 314.1, an automated sample preconcentration/matrix elimination suppressed conductivity method for the analysis of trace levels (0.50 microg/L) of perchlorate in drinking water.

    Science.gov (United States)

    Wagner, Herbert P; Pepich, B V; Pohl, C; Later, D; Joyce, R; Srinivasan, K; Thomas, D; Woodruff, A; Deborba, B; Munch, D J

    2006-06-16

    Since 1997 there has been increasing interest in the development of analytical methods for the analysis of perchlorate. The US Environmental Protection Agency (EPA) Method 314.0, which was used during the first Unregulated Contaminant Monitoring Regulation (UCMR) cycle, supports a method reporting limit (MRL) of 4.0 microg/L. The non-selective nature of conductivity detection, combined with very high ionic strength matrices, can create conditions that make the determination of perchlorate difficult. The objective of this work was to develop an automated, suppressed conductivity method with improved sensitivity for use in the second UCMR cycle. The new method, EPA Method 314.1, uses a 35 mm x 4 mm cryptand concentrator column in the sample loop position to concentrate perchlorate from a 2 mL sample volume, which is subsequently rinsed with 10 mM NaOH to remove interfering anions. The cryptand concentrator column is combined with a primary AS16 analytical column and a confirmation AS20 analytical column. Unique characteristics of the cryptand column allow perchlorate to be desorbed from the cryptand trap and refocused on the head of the guard column for subsequent separation and analysis. EPA Method 314.1 has a perchlorate lowest concentration minimum reporting level (LCMRL) of 0.13 microg/L in both drinking water and laboratory synthetic sample matrices (LSSM) containing up to 1,000 microg/L each of chloride, bicarbonate and sulfate.

  9. Vibrational spectroscopic, optical and thermal properties of a hybride pyridazine perchlorate complex-An experimental and theoretical study

    Science.gov (United States)

    Podsiadła, D.; Czupiński, O.; Rospenk, M.; Czapla, Z.

    2016-12-01

    Various methods of experiment: differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermogravimetric analysis (TGA) and infrared (IR) spectroscopy have been used to investigate the phase transitions in pyridazine perchlorate crystal. DSC showed the existence of phase transition at T = 341 K. The vibrational IR spectra in Nujol and Perfluorolube mulls were studied in a wide temperature range, from room temperature to 380 K. Special attention was put on the temperatures near the phase transition temperature. The temperature changes of wavenumbers, gravity center and band intensities were analyzed to clarify the phase transition molecular mechanism. Information about hydrogen bonds was obtained. For more detailed band assignment and overall spectral presentation Raman and far infrared (FT-FIR) spectra at room temperature have been carried out. The experimental data interpretation was supported by theoretical calculations based on density functional theory, with the B3LYP method and 6-311++G(d,p) basic set. Some theoretical conformations were analyzed. Calculated normal vibrational modes of the molecule, their frequencies and intensities were compared with these recorded in experiment.

  10. Synthesis and Crystal Structure of the Perchlorate Salt of Diprotonated 2,3-Di-2-pyridyl-5-nitroquinoxaline

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The diprotonated perchlorate salt of 2,3-di-2-pyridyl-5-nitroquinoxaline [C18H13N5O2](ClO4)2((CH3OH)((C2H5OH) has been synthesized and characterized by elemental analysis, IR and NMR spectra. X-ray diffraction analysis at room temperature indicates that the title compound (C21H23N5O12Cl2, Mr = 608.34) crystallizes in triclinic, space group P ī with a = 7.992(8), b = 12.82(1), c = 13.42(1) (A), α= 104.77(2), β = 97.84(2), γ = 95.48(2), V = 1305(2) (A)3, Z = 2, Dc = 1.549 g/cm3, F(000) = 628 and ((MoK() = 0.317 mm-1. The final R and wR factors are 0.0566 and 0.1016, respectively with 4325 independent reflections. The quinoxaline ring makes the dihedral angles of 44.2(2) and 33.9(5)( with two protonated pyridine rings whose dihedral angle is 48.1(6)(. The favored orientation of two protonated pyridine rings is that their N atoms are opposite to each other. There exist intra- and inter-molecular N-H…O hydrogen bonds and π…π interactions which stabilize the structure further.

  11. Phase Behavior and Dynamics of the ABA Triblock Copolymer Poly(Ethylene Glycol) Distearate Doped with Lithium Perchlorate

    Science.gov (United States)

    Giotto, Marcus V.; Sangiorge, Clausymara L.; Harris, Douglas J.; de Oliveira, Armando L.; Schmidt-Rohr, Klaus; Bonagamba, Tito J.

    2002-03-01

    Poly(ethylene glycol) distearate (PEGD) complexed with lithium perchlorate has been studied by NMR, SAXS, DSC, and Polarized-Light Optical Microscopy (PLOM). Unlike other polymer electrolytes, highly Lithium-doped PEGD samples exhibit sharp Li-7 NMR quadrupolar powder patterns even at temperatures well above the melting point, indicating that this copolymer is microphase separated and the dynamics in the poly(ethylene glycol) (PEG) phase are anisotropic. Measurements of the Li-7 central transition linewidth in highly doped samples show three distinct line narrowings, due to the PEG glass transition ( 20°C), the stearate melting point of the polymer ( 35°C), and an order-disorder transition ( 72°C). SAXS, DSC, and PLOM confirm the presence of a microphase-separated state up to 72 °C. C-13 and H-1 NMR show that the segmental mobility in the ordered state is reduced compared to the isotropic melt. The results confirm the previously proposed order-disorder model to explain the dependence of the ionic conductivity on the lithium concentration for Lithium-doped PEGD samples.

  12. Highly Selective Liquid Membrane Sensor Based on 1,3,5-Triphenylpyrylium Perchlorate for Quick Monitoring of Sulfate Ions

    Energy Technology Data Exchange (ETDEWEB)

    Ganjali, Mohammad Reza; Ghorbani, Maryam; Daftari, Azadeh; Norouzi, Parviz; Pirelahi, Hooshang; Dargahani, Hossein Daryanavard [Tehran University, Tehran (Iran, Islamic Republic of)

    2004-02-15

    A highly selective membrane electrode based on 1,3,5-triphenylpyrylium perchlorate (TPPP) is presented. The proposed electrode shows very good selectivity for sulfate ions over a wide variety of common inorganic and organic anions. The sensor displays a nice Nernstian slope of -29.7 mV per decade. The working concentration ranges of the electrode is 1.0 x 10{sup -1} . 6.3 x 10{sup -6} M with a detection limit of 4.0 x 10{sup -6} M (480 ng per mL). The response time of the sensor in whole concentration ranges is very short (< 6 s). The response of the sensor is independent on the pH range of 2.5-9.5. The best performance was obtained with a membrane composition of 32% PVC, 59% benzyl acetate, 5% TPPP and 4% hexadecyltrimethylammonium bromide. It was successfully used as an indicator electrode for titration of sulfate ions with barium ions. The electrode was also applied for determination of salbutamol sulfate and paramomycine sulfate

  13. ATR-FTIR studies on ion interaction of lithium perchlorate in polyacrylate/poly(ethylene oxide) blends

    Science.gov (United States)

    Sim, L. H.; Gan, S. N.; Chan, C. H.; Yahya, R.

    2010-08-01

    The interaction behaviours between components of polyacrylate (PAc)/poly(ethylene oxide) (PEO) and lithium perchlorate (LiClO 4) were investigated in detail by Attenuated Total Reflectance (ATR)-Fourier Transformed Infrared (FTIR) spectroscopy. Solution cast films of the PAc/PEO and PAc/PEO/LiClO 4 were examined. No obvious shifting of the characteristic ether and ester group stretching modes of PEO and PAc was observed, indicating incompatibility of the binary PAc/PEO blend. The spectroscopic studies on the PAc/PEO/LiClO 4 blends reveal that Li + ions coordinate individually to the polymer components at the ether oxygen of PEO and the C-O of the ester group of PAc. Frequency changes observed on the ν(C-O-C) and ω(CH 2) of PEO confirm the coordination between PEO and Li + ions resulting in crystallinity suppression of PEO. The absence of experimental evidence on the formation of PEO-Li +-PAc complexes suggests that LiClO 4 does not enhance the compatibility of PAc/PEO blend.

  14. Specific interactions of functionalised gold surfaces with ammonium perchlorate or starch; towards a chemical cartography of their mixture

    Energy Technology Data Exchange (ETDEWEB)

    Mercier, D. [CNRS, UMR CNRS 7609, Laboratoire de Reactivite de Surface, Paris (France); Universite Pierre et Marie Curie - UPMC Paris VI, Laboratoire de Reactivite de Surface, 4 place Jussieu, 75252 Paris Cedex 05 (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France); Mercader, C.; Quere, S.; Hairault, L. [CEA, DAM, Le Ripault, F-37260 Monts (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France); Methivier, C. [CNRS, UMR CNRS 7609, Laboratoire de Reactivite de Surface, Paris (France); Universite Pierre et Marie Curie - UPMC Paris VI, Laboratoire de Reactivite de Surface, 4 place Jussieu, 75252 Paris Cedex 05 (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France); Pradier, C.M., E-mail: claire-Marie.pradier@upmc.fr [CNRS, UMR CNRS 7609, Laboratoire de Reactivite de Surface, Paris (France); Universite Pierre et Marie Curie - UPMC Paris VI, Laboratoire de Reactivite de Surface, 4 place Jussieu, 75252 Paris Cedex 05 (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer Measurements of interactions by Quartz Crystal Microbalance. Black-Right-Pointing-Pointer AFM and CFM measurements, tip functionalisation. Black-Right-Pointing-Pointer Surface nano-imaging. - Abstract: By functionalising gold samples, planar wafers or AFM tips, with an acid- or an amino acid-terminated thiols, mercaptoundecanoic acid (MUA) and homocystein (H-Cyst) respectively, we were able to differentiate the interactions with ammonium perchlorate (AP) and starch (S), two components of a nanocomposition mixture. To do so, the interaction between gold functionalized surfaces and the two targeted compounds have been characterized and quantified by several complementary techniques. Polarisation modulation-infrared spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS), providing chemical analyses of gold surfaces after contacting S or AP, proved that both compounds were retained on MUA or H-Cyst-modified surfaces, but to various extents. Quartz crystal microbalance on-line measurements enabled to monitor the kinetics of interaction and showed distinct differences in the behaviour of MUA and H-Cyst-surfaces towards the two compounds. Having observed that only H-Cyst-modified surfaces enables to get a contrast on the chemical force microscopy (CFM) images, this new result could be well explained by examining the data obtained by combining the above-mentioned surface characterisation techniques.

  15. Indirect Determination of Perchloric Ion in Diethydiprydine Perchlorate by ICP-AES with Tetraphenylphosphonium Chloride as Precipitation Reagent%ICP-AES 法间接测定高氯酸二乙基联吡啶中的高氯酸根

    Institute of Scientific and Technical Information of China (English)

    刘永明; 李桂芝

    2001-01-01

    A method for indirect determination of perchloric ion by ICP-AESwas studied and optimal conditions were selected. The perchloric ion in insoluble diethydiprydine perchlorate sample was reacted with excessive tetraphenylphosphonium chloride(TTPC) and converted to TPPClO4 in filtrate and was then detected by ICP-AES. This method was used for analysis of ClO4- in diethydiprydine perchlorate with RSD of 0.74% and recovery of 97.3%~100.6%. The obtained results were consistent with those by gravimetric method.%研究了ICP-AES法间接测定高氯酸二乙基联吡啶中高氯酸根含量的方法。选择了氯化四苯(TPPCl)与高氯酸根发生沉淀的条件及ICP-AES测定氯化四苯的最佳条件。在氯化四苯过量的情况下,在水中难溶的高氯酸二乙基联吡啶可以定量转化成TPPClO4晶形沉淀。通过测定反应剩余的TPPCl,可计算得到样品中高氯酸根的含量。方法的相对标准偏差0.74%,回收率99.5%~100.6%。同时以TPPCl为沉淀剂,用重量法测定了样品中高氯酸根含量,结果与ICP-AES法一致。

  16. Microstructure and dielectric properties of dysprosium-doped barium titanate ceramics Microestrutura e propriedades dielétricas de cerâmicas de titanato de bário dopado com disprósio

    Directory of Open Access Journals (Sweden)

    Y. Pu

    2005-09-01

    Full Text Available The substitution behavior and lattice parameter of barium titanate between solid_solubility with a dopant concentration in the range of 0.25 to 1.5 mol% are studied. The influences of dysprosium-doped fraction on the grain size and dielectric properties of barium titanate ceramic, including dielectric constant and breakdown electric field strength, are investigated via scanning electronic microscopy, X-ray diffraction and electric property tester. The results show that, at a dysprosium concentration of 0.75 mol%, the abnormal grain growth is inhibited and the lattice parameters of grain rise up to the maximum because of the lowest vacancy concentration. In addition, the finegrain and high density of barium titanate ceramic result in its excellent dielectric properties. The relative dielectric constant (25 °C reaches to 4100. The temperature coefficient of the capacitance varies from -10 to 10% within the temperature range of -15 °C -100 °C, and the breakdown electric field strength (alternating current achieves 3.2 kV/mm. These data suggest that our barium titanate could be used in the manufacture of high voltage ceramic capacitors.Foram estudados o comportamento da substituição e o parâmetro de rede de titanato de bário da solubilidade sólida com uma concentração de dopante na faixa 0,25-1,5 mol%. As influências da fração do dopante disprósio no tamanho de grão e nas propriedades dielétricas da cerâmica de titanato de bário, incluindo constante dielétrica e rigidez dielétrica foram investigadas por meio de microscopia eletrônica de varredura, difração de raios X e teste de propriedades elétricas. Os resultados mostram que a uma concentração de disprósio de 0,75 mol% o crescimento anormal de grão é inibido e os parâmetros de rede aumentam até um máximo devido a menor concentração de vacâncias. Além disso, as cerâmicas de grãos pequenos e alta densidade resultam em excelentes propriedades dielétricas. A

  17. Neodymium Dysprosium Modified Starch- coated Magnetic Fluid Preparation of Ferrite%淀粉包覆镝钕改性铁氧体磁性液体的制备

    Institute of Scientific and Technical Information of China (English)

    林穗云; 周育辉

    2011-01-01

    In this paper, in order to obtain the ferrite magnetic fluids of higher saturation magnetic intensity with simple technology, nanometer magnetite ( Fe3O4 ) particles ware prepared by chemical co - precipitation. And to a certain proportion of Dysprosium Neodymium ferrite magnetic fluids on the modification, we selected starch prepara- tion for the relief of water - based coating of rare earth iron oxide magnetic fluid composites. We also investigated the amount of Nd - Dy, the amount of coating agent, reaction temperature, coating temperature on the performance of the products and the effects of particle size, and its preliminary characterization was also performed . Through experiment,we summed up, under n (Fe) : [ n ( Nd3+ ) + n ( Dy3+ ) ] = 30:1 and n ( Fe3 + ) : n ( Fe2 + ) = 1.70 ~ 1. 75, the ratio for use of dysprosium and neodymium is n(Dy3+ ) : n(Nd3+ ) =4:1, 25%NH3 · H2O(A. R. ) as precipitating agent and pH value conditioner; the reacting system temperature was controlled in 35 ℃, and the pH value was adjusted to 9 ~ 11 ; the best dosage of starch as the relief is O. 0050g each 6OraL magnetic fluids, the temperature of surfactant was controlled in 50℃ and the pH value was adjusted to 2 ~ 3. In such system under the conditions of a water - based rare - earth compound Nd Dy Fe Magnetic, fluid magnetic oxygen was higher than or- dinary water- based ferrite.%为制备工艺简单且饱和磁化强度高的磁流体,本文采用化学共沉淀法制得了纳米磁性Fe304粒子.然后以一定比例的镝钕对铁氧体磁流体改性,选择淀粉为包覆剂制备水基稀土复合铁氧磁流体.考察了镝钕的用量、包覆剂的用量、反应温度、包覆温度等因素对产物粒径及性能的影响,并对其进行了初步的性能表征.实验总结出适宜的条件:在n(Fe):[n(Nd3+)+n(Dy3+)]=30:1,n(Fe3+):n(Fe2+)=1.70~1.75

  18. Degradation of Adenine on the Martian Surface in the Presence of Perchlorates and Ionizing Radiation: A Reflectron Time-of-flight Mass Spectrometric Study

    Science.gov (United States)

    Góbi, Sándor; Bergantini, Alexandre; Kaiser, Ralf I.

    2017-04-01

    The aim of the present work is to unravel the radiolytic decomposition of adenine (C5H5N5) under conditions relevant to the Martian surface. Being the fundamental building block of (deoxy)ribonucleic acids, the possibility of survival of this biomolecule on the Martian surface is of primary importance to the astrobiology community. Here, neat adenine and adenine–magnesium perchlorate mixtures were prepared and irradiated with energetic electrons that simulate the secondary electrons originating from the interaction of the galactic cosmic rays with the Martian surface. Perchlorates were added to the samples since they are abundant—and therefore relevant oxidizers on the surface of Mars—and they have been previously shown to facilitate the radiolysis of organics such as glycine. The degradation of the samples were monitored in situ via Fourier transformation infrared spectroscopy and the electron ionization quadruple mass spectrometric method; temperature-programmed desorption profiles were then collected by means of the state-of-the-art single photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), allowing for the detection of the species subliming from the sample. The results showed that perchlorates do increase the destruction rate of adenine by opening alternative reaction channels, including the concurrent radiolysis/oxidation of the sample. This new pathway provides a plethora of different radiolysis products that were identified for the first time. These are carbon dioxide (CO2), isocyanic acid (HNCO), isocyanate (OCN‑), carbon monoxide (CO), and nitrogen monoxide (NO); an oxidation product containing carbonyl groups (R1R2–C=O) with a constrained five-membered cyclic structure could also be observed. Cyanamide (H2N–C≡N) was detected in both irradiated samples as well.

  19. 水合羟基高氯酸镍(Ⅱ)的晶体结构%Crystal Structure of the [nickel(Ⅱ)-(μ3-hydroxide)-(μ3-perchlorate)-aqua]n Complex

    Institute of Scientific and Technical Information of China (English)

    吴倩; 宋玉梅; 袁荣鑫; 熊仁根

    2004-01-01

    Green single crystal of the title compound was accidentally obtained by the reaction of N,N′-bis(pyridylcarbonyl)-4,4′-diaminodiphenyl ether (L) with nickel perchlorate. In the structure of [Ni(μ3-OH)(μ3-ClO4)(H2O)]n, the local coordinating geometry around Ni center displays a distorted octahedron in which one coordination site of each metal atom was occupied by a water molecule. Each perchlorate anion and hydroxyl group acts as a tridentate bridging spacer to bind three Ni atoms, thus resulting in the formation of two-dimensional layered network.

  20. catena-Poly[[[(dimethyl­malonato-κ2 O:O′)(perchlorato-κO)copper(II)]-μ-bis­(3-pyridylmeth­yl)piperazinediium-κ2 N 1′:N 4′] perchlorate dihydrate

    Science.gov (United States)

    Farnum, Gregory A.; LaDuca, Robert L.

    2008-01-01

    In the title compound, {[Cu(C5H6O4)(ClO4)(C16H22N4)]ClO4·2H2O}n, square-pyramidally coordinated Cu atoms with perchlorate and dimethyl­malonate ligands are connected into cationic sinusoidal coordination polymer chains by doubly protonated bis­(3-pyridylmeth­yl)piperazine (3-bpmp) ligands. The chains aggregate into pseudo-layers parallel to the (101) crystal planes by N—H⋯O hydrogen bonding. Unligated perchlorate anions and water mol­ecules of crystallization provide additional hydrogen bonding between pseudo-layers. PMID:21581141

  1. Establishment of the conditions for the determination of the concentration of the uranyl ion in perchloric media by Fluorescence; Establecimiento de las condiciones para la determinacion de la concentracion del ion uranilo en medio perclorico por Fluorescencia

    Energy Technology Data Exchange (ETDEWEB)

    Contreras R, A.; Ordonez R, E.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)]. e-mail: contraida@yahoo.com.mx

    2004-07-01

    The influence of the p H is reported in the spectra of luminescence of the ion uranyl in sodium perchlorate 2M. The best spectra were observed to ph <3 that to neutral and basic p Hs this is explained by the present species. They were carried out four calibration curves for the uranyl in perchloric acid media, taking into account the area under the curve, the maximum height of two characteristic peaks of this ion, in those that one observes a better correlation with the maximum height of the peak located to 486.7 nm. (Author)

  2. Combustion of Organic Molecules by the Thermal Decomposition of Perchlorate Salts: Implications for Organics at the Mars Phoenix Scout Landing Site

    Science.gov (United States)

    Ming, D.W.; Morris, R.V.; Niles, B.; Lauer, H.V.; Archer, P.D.; Sutter, B.; Boynton, W.V.; Golden, D.C.

    2009-01-01

    The Mars 2007 Phoenix Scout Mission successfully landed on May 25, 2008 and operated on the northern plains of Mars for 150 sols. The primary mission objective was to study the history of water and evaluate the potential for past and present habitability in Martian arctic ice-rich soil [1]. Phoenix landed near 68 N latitude on polygonal terrain created by ice layers that are a few centimeters under loose soil materials. The Phoenix Mission is assessing the potential for habitability by searching for organic molecules in the ice or icy soils at the landing site. Organic molecules are necessary building blocks for life, although their presence in the ice or soil does not indicate life itself. Phoenix searched for organic molecules by heating soil/ice samples in the Thermal and Evolved-Gas Analyzer (TEGA, [2]). TEGA consists of 8 differential scanning calorimeter (DSC) ovens integrated with a magnetic-sector mass spectrometer with a mass range of 2-140 daltons [2]. Endothermic and exothermic reactions are recorded by the TEGA DSC as samples are heated from ambient to 1000 C. Evolved gases, including any organic molecules and their fragments, are simultaneously measured by the mass spectrometer during heating. Phoenix TEGA data are still under analysis; however, no organic fragments have been identified to date in the evolved gas analysis (EGA). The MECA Wet Chemistry Lab (WCL) discovered a perchlorate salt in the Phoenix soils and a mass 32 peak evolved between 325 and 625 C for one surface sample dubbed Baby Bear [3]. The mass 32 peak is attributed to evolved O2 generated during the thermal decomposition of the perchlorate salt. Perchlorates are very strong oxidizers when heated, so it is possible that organic fragments evolved in the temperature range of 300-600 C were combusted by the O2 released during the thermal decomposition of the perchlorate salt. The byproduct of the combustion of organic molecules is CO2. There is a prominent release of CO2 between 200

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

    DEFF Research Database (Denmark)

    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 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....

  4. Poly(4-vinylpyridinium) perchlorate as an efficient solid acid catalyst for the chemoselective preparation of 1,1-diacetates from aldehydes under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    Nader Ghaffari Khaligh

    2014-01-01

    Poly(4-vinylpyridinium) perchlorate has been used as a supported, recyclable, environmental-ly-benign catalyst for the formation of acylals from aliphatic and aromatic aldehydes in good to excellent yields under solvent-free conditions. Notably, the reaction conditions were tolerant of ketones. This methodology offers several distinct advantages, including its operational simplicity and high product yield, as well as being green in terms of avoiding the use of toxic catalysts and solvents. Furthermore, the catalyst can be recovered and reused several times without any loss in its activity.

  5. [1,3-Bis(diphenylphosphanylpropane-κ2P,P′](1,10-phenanthroline-κ2N,N′copper(I perchlorate

    Directory of Open Access Journals (Sweden)

    Ye-Lan Xiao

    2011-12-01

    Full Text Available The title compound, [Cu(C12H8N2(C27H26P2]ClO4, crystallizes with two CuI complex cations and two perchlorate anions in the asymmetric unit. Each CuI cation is four-coordinated by two P atoms of a 1,3-bis(diphenylphosphanylpropane molecule and two N atoms of a 1,10-phenanthroline ligand, with a coordination geometry that can be considered as distorted tetrahedral. The crystal studied was twinned with a twin ratio of 0.786 (2:0.214 (2.

  6. Thermodynamic properties of actinide complexes. II. Thorium(IV)--acetate system. [Formation of thorium(IV)-acetate complexes in aqueous perchlorate medium

    Energy Technology Data Exchange (ETDEWEB)

    Portanova, R.; Di Bernardo, P.; Traverso, O.; Mazzocchin, G.A.; Magon, L.

    1975-10-01

    The changes in free energy, enthalpy and entropy for the formation of thorium(IV)--acetate complexes have been determined at 25/sup 0/C and in 1.00 M aqueous perchlorate-medium. All five complexes formed, are found to be stabilized by a large gain of entropy. The marked increase in the values of ..delta..H/sub j/ and ..delta..S/sub j/, relative to the third step of complexation has been explained in terms of a coordination change.

  7. Copper(II) bromide, nitrate and perchlorate complexes with sterically demanding N-(6-methylpyridin-2-yl)acetamide ligands.

    Science.gov (United States)

    Smolentsev, Anton I

    2017-08-01

    Functionalized acid amides are widely used in biology, medicine, environmental chemistry and many other areas. Among them, pyridine-substituted amides, in particular N-(pyridin-2-yl)acetamide and its derivatives, play an important role due to their excellent chelating properties. The donor properties of these ligands can be effectively modified by introducing electron-donating substituents (e.g. alkyl groups) into the heterocycle. On the other hand, substituents in the α-position of the pyridine ring can create steric hindrance, which significantly influences the coordination number and geometry. To achieve a better understanding of these effects, copper(II) complexes with sterically demanding N-(6-methylpyridin-2-yl)acetamide ligands (L) and monoanions of different size, shape and coordination ability have been chosen as model compounds. The crystal structures of three new compounds, bromidobis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bromide, [CuBr(C8H10N2O)]Br, (I), aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) dinitrate, [Cu(C8H10N2O)(H2O)](NO3)2, (II), and aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bis(perchlorate), [Cu(C8H10N2O)(H2O)](ClO4)2, (III), have been determined by single-crystal X-ray diffraction analysis. It has been shown that the presence of the 6-methyl group results in either a distorted square-pyramidal or a distorted trigonal-bipyramidal coordination geometry around the Cu(II) centres instead of the typical octahedral geometry observed when the methyl substituent is absent or occupies any other position on the pyridine ring. Moreover, due to the steric hindrance provided by the L ligands, only the bromide ligand, the smallest of the series, enters into the first coordination sphere of the Cu(II) ion in (I). In (II) and (III), the vacant coordination site of the Cu(II) ion is occupied by a water molecule, while the nitrate and perchlorate anions are not involved in coordination to the metal centre

  8. Effects of salinity on simultaneous reduction of perchlorate and nitrate in a methane-based membrane biofilm reactor.

    Science.gov (United States)

    Zhang, Yin; Chen, Jia-Xian; Wen, Li-Lian; Tang, Youneng; Zhao, He-Ping

    2016-12-01

    This study builds upon prior work showing that methane (CH4) could be utilized as the sole electron donor and carbon source in a membrane biofilm reactor (MBfR) for complete perchlorate (ClO4(-)) and nitrate (NO3(-)) removal. Here, we further investigated the effects of salinity on the simultaneous removal of the two contaminants in the reactor. By testing ClO4(-) and NO3(-) at different salinities, we found that the reactor performance was very sensitive to salinity. While 0.2 % salinity did not significantly affect the hydrogen-based MBfR for ClO4(-) and NO3(-) removals, 1 % salinity completely inhibited ClO4(-) reduction and significantly lowered NO3(-) reduction in the CH4-based MBfR. In salinity-free conditions, NO3(-) and ClO4(-) removal fluxes were 0.171 g N/m(2)-day and 0.091 g/m(2)-day, respectively, but NO3(-) removal fluxes dropped to 0.0085 g N/m(2)-day and ClO4(-) reduction was completely inhibited when the medium changed to 1 % salinity. Scanning electron microscopy (SEM) showed that the salinity dramatically changed the microbial morphology, which led to the development of wire-like cell structures. Quantitative real-time PCR (qPCR) indicated that the total number of microorganisms and abundances of functional genes significantly declined in the presence of NaCl. The relative abundances of Methylomonas (methanogens) decreased from 31.3 to 5.9 % and Denitratisoma (denitrifiers) decreased from 10.6 to 4.4 % when 1 % salinity was introduced.

  9. Surface-enhanced Raman scattering of perchlorate on cationic-modified silver nanofilms - Effect of inorganic anions

    Science.gov (United States)

    Hao, Jumin; Han, Mei-Juan; Meng, Xiaoguang; Weimer, Wayne; Wang, Qingwu K.

    2015-02-01

    Surface-enhanced Raman scattering (SERS) has emerged as one of the most sensitive spectroscopic analysis methods for the detection of environmental contaminants in water, including perchlorate (ClO4-). However, as with other commonly used analytical techniques, analysis of realistic environmental samples by SERS presents a challenge due to complex chemical components coexisting in the samples. In this work, we investigated the influence of inorganic anions (particularly oxyanions) on SERS spectra of ClO4- using a cationic thiol modified silver nanofilm substrate (Cys-Ag/rCu). The results show that the anions present in the samples did not shift the ClO4- characteristic band positions, but did decrease signal intensities due to their competitive binding with the -NH3+ groups of cationic thiol molecules immobilized on the substrates. The pH changes caused by both the dissociation of H2PO4- and the hydrolysis of HCO3- may also play a non-negligible role. The selectivity of the Cys-Ag/rCu substrate towards these anions was determined to be in the following order: ClO4- > SO42- > HCO3-, NO3- > Cl- > H2PO4-, indicating preferential adsorption of ClO4- ions. In the solutions with multiple anions present, the ClO4- SERS spectra were affected simultaneously by all the coexisting anions. Calibration curves with very good linear relationships were successfully obtained, demonstrating the great potential of quantitative detection of aqueous ClO4- in the matrix.

  10. Extraction and separation of titanium(IV with D2EHPA and PC-88A from aqueous perchloric acid solutions

    Directory of Open Access Journals (Sweden)

    PURSHOTTAM M. DHADKE

    2002-07-01

    Full Text Available The liquid-liquid extraction of Ti(IV from perchlorate media using, di(2-ethylhexyl phosphoric acid (D2EHPA and 2-ethylhexyl prosphonic acid mono-2-ethylhexyl ester (PC-88A in toluene as the extractant was studied. Quantitative extraction of Ti(IV was observed in the lower acidity range of 0.01 to 0.1 mol dm-3 with 0.003 mol dm-3 D2EHPA and 0.01 mol dm-3 PC-88A in toluene, respectively, and in the higher acidity range of 9.0 to 10.0 mol dm-3 with 0.1 mol dm-3 D2EHPA and PC-88A in toluene. Ti(IV was completely stripped from the metal loaded organic phase of both the extractants with 3 % H2O2 in 1 M H2SO4 and determined spectrophotometrically. The stoichiometry of the extracted species was determined on the basis of slope analysis. The extraction in the lower acidity range was found to proceed by a cation-exchange mechanism with the extracted species being TiOR2·2HR, while in the higher acidity range it was by solvation with the extracted species being Ti(OH3ClO4·4HR. Separation of Ti(IV was also carried out from some associated metals like Fe(III, Al(III, V(V, Ce(IV, Mg(II and Mn(II. The developed methods were extended for the determination of Ti(IV in real samples like ilmenite, magnetite and red mud in order to show the practical utility of the extractants.

  11. Application of a Re-Pd bimetallic catalyst for treatment of perchlorate in waste ion-exchange regenerant brine.

    Science.gov (United States)

    Liu, Jinyong; Choe, Jong Kwon; Sasnow, Zachary; Werth, Charles J; Strathmann, Timothy J

    2013-01-01

    Concentrated sodium chloride (NaCl) brines are often used to regenerate ion-exchange (IX) resins applied to treat drinking water sources contaminated with perchlorate (ClO(4)(-)), generating large volumes of contaminated waste brine. Chemical and biological processes for ClO(4)(-) reduction are often inhibited severely by high salt levels, making it difficult to recycle waste brines. Recent work demonstrated that novel rhenium-palladium bimetallic catalysts on activated carbon support (Re-Pd/C) can efficiently reduce ClO(4)(-) to chloride (Cl(-)) under acidic conditions, and here the applicability of the process for treating waste IX brines was examined. Experiments conducted in synthetic NaCl-only brine (6-12 wt%) showed higher Re-Pd/C catalyst activity than in comparable freshwater solutions, but the rate constant for ClO(4)(-) reduction measured in a real IX waste brine was found to be 65 times lower than in the synthetic NaCl brine. Through a series of experiments, co-contamination of the IX waste brine by excess NO(3)(-) (which the catalyst reduces principally to NH(4)(+)) was found to be the primary cause for deactivation of the Re-Pd/C catalyst, most likely by altering the immobilized Re component. Pre-treatment of NO(3)(-) using a different bimetallic catalyst (In-Pd/Al(2)O(3)) improved selectivity for N(2) over NH(4)(+) and enabled facile ClO(4)(-) reduction by the Re-Pd/C catalyst. Thus, sequential catalytic treatment may be a promising strategy for enabling reuse of waste IX brine containing NO(3)(-) and ClO(4)(-).

  12. Investigation of heat transfer in zirconium potassium perchlorate at low temperature: A study of the failure mechanism of the NASA standard initiator

    Science.gov (United States)

    Varghese, Philip L.

    1989-01-01

    The objective of this work was to study the reasons for the failure of pyrotechnic initiators at very low temperatures (10 to 100 K). A two-dimensional model of the NASA standard initiator was constructed to model heat transfer from the electrically heated stainless steel bridgewire to the zirconium potassium perchlorate explosive charge and the alumina charge cup. Temperature dependent properties were used in the model to simulate initiator performance over a wide range of initial temperatures (10 to 500 K). A search of the thermophysical property data base showed that pure alumina has a very high thermal conductivity at low temperatures. It had been assumed to act as a thermal insulator in all previous analyses. Rapid heat transfer from the bridgewire to the alumina at low initial temperatures was shown to cause failure of the initiators if the wire did not also make good contact with the zirconium potassium perchlorate charge. The mode is able to reproduce the results of the tests that had been conducted to investigate the cause for failure. It also provides an explanation for previously puzzling results and suggests simple design changes that will increase reliability at very low initial temperatures.

  13. Cocrystallization of photosensitive energetic copper(II) perchlorate complexes with the nitrogen-rich ligand 1,2-Di(1H-tetrazol-5-yl)ethane.

    Science.gov (United States)

    Evers, Jürgen; Gospodinov, Ivan; Joas, Manuel; Klapötke, Thomas M; Stierstorfer, Jörg

    2014-11-01

    Two recently introduced concepts in the design of new energetic materials, namely complexation and cocrystallization, have been applied in the synthesis and characterization of the energetic copper(II) compound "[Cu(dt-5-e)2(H2O)](ClO4)2," which consists of two different complex cations and can be described as a model energetic ionic cocrystal. The presence of both the N-rich 1,2-di(1H-tetrazol-5-yl)ethane ligand and oxidizing perchlorate counterion results in a new type of energetic material. The ionic complex cocrystal consists of a mononuclear and a trinuclear complex unit. It can be obtained by precipitation from perchloric acid or by dehydration of the related mononuclear coordination compound [Cu(dt-5-e)2(H2O)2](ClO4)2·2H2O at 70 °C in the solid state. The transformation starting at 60 °C was monitored by X-ray powder diffraction and thermal analysis. The energetic ionic cocrystal was shown to be a new primary explosive suitable for laser ignition. The different coordination spheres within the ionic cocrystal (octahedral and square pyramidal) were shown by UV/vis/NIR spectroscopy to result in excellent light absorption.

  14. Ex situ synthesis of G/$\\alpha$-Fe$_2$O$_3$ nanocomposite and its catalytic effect on the thermal decomposition of ammonium perchlorate

    Indian Academy of Sciences (India)

    MERIEM AMINA FERTASSI; QI LIU; RUNZE LI; PINGAN LIU; JINGYUAN LIU; RONG-RONG CHEN; LIANHE LIU; JUN WANG

    2017-08-01

    $\\alpha$-Fe$_2$O$_3$ nanoparticles were prepared by a facile hydrothermal method using ferric chloride hexahydrate(FeCl$_3$·6H$_2$O) as a precursor. Graphene oxide (GO) was synthesized using a modified Hummers method and graphenenanosheets (G) were successfully obtained by thermal reduction of GO. G/$\\alpha$-Fe$_2$O$_3$ nanocomposite was prepared using ex situ synthesis in the presence of $\\alpha$-Fe$_2$O$_3$ nanoparticles and GO solution. The characterization of the as-prepared materialswas performed using X-ray diffraction analyses and Fourier transform infrared spectroscopy; their morphology wasinvestigated by scanning electron microscopy and transmission electron microscopy; the specific surface area (SBET) wasdetermined by nitrogen adsorption; their catalytic activity on the thermal decomposition of ammonium perchlorate (AP) wasinvestigated by differential thermal analysis (DTA). The results of DTA indicated that the obtained nanomaterials contributein ameliorating the thermal decomposition of AP; specifically, the high decomposition temperature of AP decreases from432 to 380$^{\\circ}$C. A significant decrease in the activation energy was also achieved in the presence of these nanomaterials, and the mixture of ammonium perchlorate with G/$\\alpha$-Fe$_2$O$_3$ showed the lowest value (from 129 to 80.33 kJ mol$^{−1}$).

  15. Geochemical Trends and Natural Attenuation of RDX, Nitrate, and Perchlorate in the Hazardous Test Area Fractured-Granite Aquifer, White Sands Missile Range, New Mexico, 1996-2006

    Science.gov (United States)

    Langman, Jeff B.; Robertson, Andrew J.; Bynum, Jamar; Gebhardt, Fredrick E.

    2008-01-01

    A fractured-granite aquifer at White Sands Missile Range is contaminated with the explosive compound RDX, nitrate, and perchlorate (oxidizer associated with rocket propellant) from the previous use of the Open Burn/Open Detonation site at the Hazardous Test Area. RDX, nitrate, and perchlorate ground-water concentrations were analyzed to examine source characteristics, spatial and temporal variability, and the influence of the natural attenuation processes of dilution and degradation in the Hazardous Test Area fractured-granite aquifer. Two transects of ground-water wells from the existing monitoring-site network - one perpendicular to ground-water flow (transect A-A') and another parallel to ground-water flow (transect B-B') - were selected to examine source characteristics and the spatial and temporal variability of the contaminant concentrations. Ground-water samples collected in 2005 from a larger sampling of monitoring sites than the two transects were analyzed for various tracers including major ions, trace elements, RDX degradates, dissolved gases, water isotopes, nitrate isotopes, and sulfate isotopes to examine the natural attenuation processes of dilution and degradation. Recharge entrains contaminants at the site and transports them downgradient towards the Tularosa Basin floor through a poorly connected fracture system(s). From 1996 to 2006, RDX, nitrate, and perchlorate concentrations in ground water downgradient from the Open Burn/Open Detonation site have been relatively stable. RDX, nitrate, and perchlorate in ground water from wells near the site indicate dispersed contaminant sources in and near the Open Burn/Open Detonation pits. The sources of RDX and nitrate in the pit area have shifted with time, and the shift correlates with the regrading of the south and east berms of each pit in 2002 and 2003 following closure of the site. The largest RDX concentrations were in ground water about 0.1 mile downgradient from the pits, the largest perchlorate

  16. (2,2'-Bipyridine-4,4'-dicarboxylic acid-κ2N,N')chlorido(2,2':6',2''-terpyridyl-κ3N,N',N'')ruthenium(II) perchlorate ethanol monosolvate monohydrate

    DEFF Research Database (Denmark)

    Nielsen, Anne; McKenzie, Christine Joy; Bond, Andrew David

    2012-01-01

    ,4 '-dicarboxylic acid ligands, with interplanar separations of 3.65 (1) and 3.72 (1) angstrom. Three O atoms of the perchlorate ion are each disordered equally over two positions. The hydroxy group of the ethanol molecule is also disordered over two sites with refined occupancies of 0.794 (9) and 0.206 (9)....

  17. Treatment of Perchlorate-Contaminated Groundwater Using Highly-Selective, Regenerable Anion-Exchange Resins at Edwards Air Force Base

    Energy Technology Data Exchange (ETDEWEB)

    Gu, B.

    2003-05-30

    Selective ion exchange is one of the most effective treatment technologies for removing low levels of perchlorate (ClO{sub 4}{sup -}) from contaminated water because of its high efficiency without adverse impacts on the water quality caused by adding or removing any chemicals or nutrients. This report summarizes both the laboratory and a field pilot-scale studies to determine the ability and efficiency of the bifunctional synthetic resins to remove ClO{sub 4}{sup -} from the contaminated groundwater at the Edwards Air Force Base in California. Regeneration of the resins after groundwater treatment was also evaluated using the FeCl{sub 3}-HCl regeneration technique recently developed at Oak Ridge National Laboratory. On the basis of this study, the bifunctional resin, D-3696 was found to be highly selective toward ClO{sub 4}{sup -} and performed much better than one of the best commercial nitrate-selective resins (Purolite A-520E) and more than an order of magnitude better than the Purolite A-500 resin (with a relatively low selectivity). At an influent concentration of {approx} 450 {micro}g/L ClO{sub 4}{sup -} in groundwater, the bifunctional resin bed treated {approx} 40,000 empty bed volumes of groundwater before a significant breakthrough of ClO{sub 4}{sup -} occurred. The presence of relatively high concentrations of chloride and sulfate in site groundwater did not appear to affect the ability of the bifunctional resin to remove ClO{sub 4}{sup -}. However, the presence of high iron or iron oxyhydroxides and/or biomass in groundwater caused a significant fouling of the resin beds and greatly influenced the effectiveness in regenerating the resins sorbed with ClO{sub 4}{sup -}. Under such circumstances, a prefilter ({approx} 0.5-1 {micro}m) was found to be necessary to remove these particulates and to reduce the risk of fouling of the resin beds. Without significant fouling, the resin bed could be effectively regenerated by the FeCl{sub 3} displacement technique

  18. Atacama perchlorate as an agricultural contaminant in groundwater: isotopic and chronologic evidence from Long Island, New York.

    Science.gov (United States)

    Böhlke, John Karl; Hatzinger, Paul B; Sturchio, Neil C; Gu, Baohua; Abbene, Irene; Mroczkowski, Stanley J

    2009-08-01

    Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4(-)-bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this has been largely circumstantial. Here we report ClO4- stable isotope data (delta37Cl, delta18O, and delta17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4 contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages > 20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased with groundwater age, possibly because of decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO3- fertilizers in recent years. Because ClO4-/NO3- ratios of Atacama NO3- fertilizers imported in the past (approximately 2 x 10(-3) mol mol(-1)) were much higher than the CO4-/NO3- ratio of recommended drinking-water limits (7 x 10(-5) mol mol(-1) in New York), ClO4- could exceed drinking-water limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century.

  19. 表面修饰对镝铁氧体纳米磁粒子的合成及其磁性能的影响%Effect of Surface Modification on Formation and Magnetic Property of Dysprosium Ferrite Nanomagnetic Particles

    Institute of Scientific and Technical Information of China (English)

    陈静; 张茂润; 邓真娟

    2011-01-01

    利用湿化学法制备镝铁氧体纳米磁粒子时,用适量的阴离子表面活性剂进行表面修饰,能够有效地控制磁粒子的粒径,同时避免干燥时产生硬团聚.文章介绍了用月桂酸、月桂酸钠、正十二烷基硫酸钠对磁粒子进行表面修饰的研究结果,探讨了三者及其用量对磁粒子的形成及磁性能的影响.借助X射线衍射仪(XRD)、透射电镜(TEM)、振动样品磁强计(VSM)、红外光谱仪(IR)对产物的性能进行了表征.结果表明,用月桂酸修饰后的产物具有Fe3O4磁粒子的晶型结构且结晶度高、磁性能优异、平均粒径约16nm;用月桂酸钠、正十二烷基硫酸钠修饰后的产物不具有Fe3O4磁粒子的晶型结构,结晶度低且磁性能差.%When wet chemical method are use to prepare dysprosium-doped ferrite magnetic nanoparticles, right a-mount of anionic surfactant were doped as surface modification, which can effectively control the size of magnetic particles, and avoid producing hard reunion when dry out. This paper introduces the research results of magnetic particle surface modification by using lauric acid, laurel acid sodium and lauryl sodium sulfate, discusses the effect of lauric acid, laurel acid sodium and lauryl sodium sulfate and their dosages on the formation of magnetic and its magnetic property. The properties of the product can be characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), infrared spectrometer (IR). The results showed that the product modified with lauric acid have a crystalline structure of Fe3O4 magnetic particles and high crystallin-ity, excellent magnetic properties. The average particle size is about 16 nm; the product modified with laurel acid sodium and lauryl sodium sulfate does not have the crystalline structure of Fe3O4 magnetic particles, with low crystal-linity and low magnetic property.

  20. Heterometallic octanuclear RE(III)3Ni(II)5 (RE = Dy(III), Gd(III) and Y(III)) clusters with slow magnetic relaxation for the dysprosium derivative.

    Science.gov (United States)

    Wang, Huiyu; Ke, Hongshan; Lin, Shuang-Yan; Guo, Yang; Zhao, Lang; Tang, Jinkui; Li, Yun-Hui

    2013-04-21

    Reactions of rare earth benzoate and nickel perchlorate with a Schiff-base ligand, 2-([(2-hydroxyphenyl)imino]methyl) phenol (H2L), in the presence of triethylamine yielded three heterobimetallic octanuclear clusters of general formula [RE3Ni5L5(PhCOO)3(μ3-OH)5(μ3-OCH3)(CH3OH)4(H2O)]·xCH3OH·yH2O (RE = Dy(III), x = 4, y = 4 (1), RE = Gd(III), x = 5, y = 4 (2), RE = Y(III), x = 5, y = 3 (3)). Single-crystal X-ray diffraction reveals that the metal core of each cluster consists of two distorted [RE2Ni2O4] cubane-like moieties and a heterobimetallic triangular [RE2NiO2] unit, with RE ions arranged in a typical triangular fashion. Variable-temperature solid state magnetic susceptibilities of these complexes were measured in the temperature range 2-300 K and the results indicate that an overall ferromagnetic interaction among the metal ions is operative for compounds 2 and 3. Under zero external field, the Dy3Ni5 compound shows a frequency dependence of the out-of-phase (χ'') signals, which indicates slow relaxation of the magnetization.

  1. Effect of the presence of chlorates and perchlorates on the pyrolysis of organic compounds: implications for measurements done with the SAM experiment onboard the Curiosity rover

    Science.gov (United States)

    Millan, Maeva; Szopa, Cyril; Buch, Arnaud; Belmahdi, Imène; Coll, Patrice; Glavin, Daniel P.; Freissinet, Caroline; Archer, Doug; Sutter, Brad; Summons, Roger E.; Navarro-Gonzalez, Rafael; Cabane, Michel; Mahaffy, Paul

    2016-04-01

    The Sample Analysis at Mars (SAM) experiment onboard the Curiosity rover of the Mars Science Laboratory mission is partly devoted to the in situ molecular analysis of gases evolving from solid samples collected on Mars surface/sub-surface. SAM has a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to the separation and identification of organic and inorganic material [1]. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. As the Viking landers in 1976 [2], SAM detected chlorohydrocarbons with the pyrolysis GC-QMS experiment [3,4]. The detection of perchlorates salts in soil at the Phoenix Landing site [6] suggests that these chlorohydrocarbons could come from the reaction of organics with oxychlorines. Oxychlorines indeed decomposed into molecular oxygen and volatile chlorine when heated and react with the organic matter in the samples by oxidation and/or chlorination processes. [3,5,7,8]. During SAM pyrolysis, samples are heated to 850°C. SAM detected C1 to C3 chloroalkanes, entirely attributed to reaction products occurring during the pyrolysis experiment between oxychlorines and organic carbon from instrument background [3] and chlorobenzene and C2 to C4 dichloroalkanes produced by reaction between Mars endogenous organics with oxychlorines [4]. To help understanding the influence of perchlorate and chlorate salts on organic matter during SAM pyrolysis, we systemically study the reaction products formed during pyrolysis of various organic compounds mixed with various perchlorates and chlorates. We selected organics from simple molecule forms as for instance PAHs and amino acids to complex material (>30 carbon atoms) such as kerogen. The perchlorate and chlorate salts are prepared at 1 wt % concentration in silica and mixed with the organics to study the potential qualitative and

  2. Sol–gel method to prepare graphene/Fe{sub 2}O{sub 3} aerogel and its catalytic application for the thermal decomposition of ammonium perchlorate

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Yuanfei; Li, Xiaoyu; Li, Guoping; Luo, Yunjun, E-mail: yjluo@bit.edu.cn [Beijing Institute of Technology, School of Materials Science and Engineering (China)

    2015-10-15

    Graphene/Fe{sub 2}O{sub 3} (Gr/Fe{sub 2}O{sub 3}) aerogel was synthesized by a simple sol–gel method and supercritical carbon dioxide drying technique. In this study, the morphology and structure were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and nitrogen sorption tests. The catalytic performance of the as-synthesized Gr/Fe{sub 2}O{sub 3} aerogel on the thermal decomposition of ammonium perchlorate (AP) was investigated by thermogravimetric and differential scanning calorimeter. The experimental results showed that Fe{sub 2}O{sub 3} with particle sizes in the nanometer range was anchored on the Gr sheets and Gr/Fe{sub 2}O{sub 3} aerogel exhibits promising catalytic effects for the thermal decomposition of AP. The decomposition temperature of AP was obviously decreased and the total heat release increased as well.

  3. Preparation of CoFeO Nanocrystallites by Solvothermal Process and Its Catalytic Activity on the Thermal Decomposition of Ammonium Perchlorate

    Directory of Open Access Journals (Sweden)

    Shusen Zhao

    2010-01-01

    Full Text Available Nanometer cobalt ferrite (CoFe2O4 was synthesized by polyol-medium solvothermal method and characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, and selected area electron diffraction (SAED. Further, the catalytic activity and kinetic parameters of CoFe2O4 nanocrystallites on the thermal decomposition behavior of ammonium perchlorate (AP have been investigated by thermogravimetry and differential scanning calorimetry analysis (TG-DSC. The results imply that the catalytic performance of CoFe2O4 nanocrystallites is significant and the decrease in the activation energy and the increase in the rate constant for AP further confirm the enhancement in catalytic activity of CoFe2O4 nanocrystallites. A mechanism based on an proton transfer process has also been proposed for AP in the presence of CoFe2O4 nanocrystallites.

  4. Titanium subhydride potassium perchlorate (TiH1.65/KClO4) burn rates from hybrid closed bomb-strand burner experiments.

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, Marcia A. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Oliver, Michael S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2012-08-01

    A hybrid closed bomb-strand burner is used to measure the burning behavior of the titanium subhydride potassium perchlorate pyrotechnic with an equivalent hydrogen concentration of 1.65. This experimental facility allows for simultaneous measurement of the closed bomb pressure rise and pyrotechnic burn rate as detected by electrical break wires over a range of pressures. Strands were formed by pressing the pyrotechnic powders to bulk densities between 60% and 90% theoretical maximum density. The burn rate dependance on initial density and vessel pressure are measured. At all initial strand densities, the burn is observed to transition from conductive to convective burning within the strand. The measured vessel pressure history is further analyzed following the closed bomb analysis methods developed for solid propellants.

  5. Palladium(II)-catalyzed oxidation of L-tryptophan by hexacyanoferrate(III) in perchloric acid medium: a kinetic and mechanistic approach

    Indian Academy of Sciences (India)

    Ahmed Fawzy

    2016-02-01

    The catalytic effect of palladium(II) on the oxidation of L-tryptophan by potassium hexacyanoferrate( III) has been investigated spectrophotometrically in aqueous perchloric acid medium. A first order dependence in [hexacyanoferrate(III)] and fractional-first order dependences in both [L-tryptophan] and [palladium(II)] were obtained. The reaction exhibits fractional-second order kinetics with respect to [H+]. Reaction rate increased with increase in ionic strength and dielectric constant of the medium. The effect of temperature on the reaction rate has also been studied and activation parameters have been evaluated and discussed. Initial addition of the reaction product, hexacyanoferrate(II), does not affect the rate significantly. A plausible mechanistic scheme explaining all the observed kinetic results has been proposed. The final oxidation products are identified as indole-3-acetaldehyde, ammonium ion and carbon dioxide. The rate law associated with the reaction mechanism is derived.

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

    Science.gov (United States)

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

    2011-12-15

    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.

  7. Stabilisation of tetravalent cerium in perchloric acid medium and measurement of the stability constants of its fluoride complexes using ion selective potentiometry.

    Science.gov (United States)

    Sawant, R M; Rastogi, R K; Mahajan, M A; Chaudhuri, N K

    1996-01-01

    The stability constants of the fluoride complexes of cerium(IV) in 1 M (HClO(4), NaClO(4)) medium have been measured potentiometrically using a fluoride ion-selective electrode. Quantitative oxidation of cerium to its tetravalent state and its stabilisation in the perchlorate medium were accomplished by oxidation with AgO followed by quick addition of a known amount of fluoride ion. This procedure ensures stability of the oxidation state and prevents hydrolysis and polymerisation of Ce(IV). Logarithms of the average values of beta(1), beta(2), beta(3) and beta(4) were estimated to be 7.57+/-0.04, 14.50+/-0.03, 20.13+/-0.37 and 24.14+/-0.10 respectively.

  8. Synthesis and Crystal Structure of an Ion-pair Supramolecular Associate 2,9-Diformyl- 1,10-phenanthrolinebis (2,6-dimethylanil)cobalt(Ⅱ) Perchlorate

    Institute of Scientific and Technical Information of China (English)

    LI Gang; JIE Su-Yun; TANG Ning; SUN Wen-Hua

    2006-01-01

    2,9-Diformyl-1,10-phenanthrolinebis(2,6-dimethylanil)cobalt(Ⅱ) perchlorate was synthesized and demonstrated to be [CoL2][ClO4]2 by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group C2/c with a = 22.294(4), b = 15.122(3), c = 20.640(4) (A), β =119.618(4)°, V = 6048.9(19) (A)3, C63H52Cl2CoN9O9, Mr= 1208.97, F(000) = 2504, Dc= 1.328g/cm3,Z = 4, μ = 0.436, the final R = 0.0712 and wR = 0.1718 for 1734 observed reflections (1> 2σ(Ⅰ)). In its solid state the helical polymeric chains are supramolecularly associated through intermolecular and inter- ionic hydrogen bonding interactions.

  9. STUDIES ON THE RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN Ⅳ. COPOLYMERIZATION OF TETRAHYDROFURAN AND PROPYLENE OXIDE INITIATED BY FUMING SULFURIC ACID AND PERCHLORIC ACID CATALYST SYSTEM

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hongzhi; GAO Guozhen; WANG Yin; FENG Xinde(S. T. Voong)

    1983-01-01

    The yield of copolymerization of tetrahydrofuran and propylene oxide (THF: PO = 100: 5-15, by wt) using a binary catalyst of fuming sulfuric acid (21% or 28%) and perchloric acid is around 50-60%, and the loss of THF in the reaction is below 10-15%. The average molecular weight of the product can be controlled in the range of 1000-2000 by varying the binary catalyst system.The present method, which is different from the usual copolymerization initiated by BF3-diol or SbCl5-diol system, shows the pecularities i.e. the yield of copolymerization with the low PO feed is not decreased, the hydroxyl functionality is equal to 2, and the end-groups are predominantly primary hydroxyls (around 65-70%).

  10. Structural Peculiarities of Ion-Conductive Organic-Inorganic Polymer Composites Based on Aliphatic Epoxy Resin and Salt of Lithium Perchlorate

    Science.gov (United States)

    Matkovska, Liubov; Iurzhenko, Maksym; Mamunya, Yevgen; Tkachenko, Igor; Demchenko, Valeriy; Synyuk, Volodymyr; Shadrin, Andriy; Boiteux, Gisele

    2017-06-01

    The article is concerned with hybrid amorphous polymers synthesized basing on epoxy oligomer of diglycide aliphatic ester of polyethylene glycol that was cured by polyethylene polyamine and lithium perchlorate salt. Structural peculiarities of organic-inorganic polymer composites were studied by differential scanning calorimetry, wide-angle X-ray spectra, infrared spectroscopic, scanning electron microscopy, elemental analysis, and transmission and reflective optical microscopy. On the one hand, the results showed that the introduction of LiClO4 salt into epoxy polymer leads to formation of the coordinative metal-polymer complexes of donor-acceptor type between central Li+ ion and ligand. On the other hand, the appearance of amorphous microinclusions, probably of inorganic nature, was also found.

  11. Ion-molecule interactions in solutions of lithium perchlorate in propylene carbonate + diethyl carbonate mixtures: an IR and molecular orbital study.

    Science.gov (United States)

    Wang, Jianji; Wu, Yanping; Xuan, Xiaopeng; Wang, Hanqing

    2002-08-01

    FTIR spectra have been recorded and analyzed for solutions of lithium perchlorate in propylene carbonate (PC), diethyl carbonate (DEC), and PC + DEC mixtures. It has been shown that the carbonyl stretch bands for PC and DEC are very sensitive to the interaction between Li+ and the solvent molecules. They split with addition of LiClO4, indicating a strong interaction of Li+ with PC and DEC through the oxygen group of PC and both oxygen and ether oxygen atoms of DEC. In conjunction with molecular orbital calculation, the optimized geometries of solvation are given. In addition, solvent separated ion pairs and contact ion pairs were observed in LiClO4/DEC solutions, and no preferential solvation of Li+ in LiClO4/PC + DEC solutions were detected.

  12. Isotopic composition and origin of indigenous natural perchlorate and co-occurring nitrate in the southwestern United States

    Science.gov (United States)

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

    2010-01-01

    Perchlorate (ClO4−) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO4− appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO4− indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO4− (δ18O, Δ17O, δ37Cl) and associated NO3− (δ18O, Δ17O, δ15N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO3−-rich surface caliche deposits near Death Valley, California. The data indicate natural ClO4− in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO4− from the Atacama Desert of Chile as well as all known synthetic ClO4−. ClO4− in Death Valley caliche has a range of high Δ17O values (+8.6 to +18.4 ‰), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O3). However, the Death Valley δ37Cl values (−3.1 to −0.8 ‰) and δ18O values (+2.9 to +26.1‰) are higher than those of Atacama ClO4−. In contrast, ClO4− from western Texas and New Mexico has much lower Δ17O (+0.3 to +1.3‰), with relatively high δ37Cl (+3.4 to +5.1 ‰) and δ18O (+0.5 to +4.8 ‰), indicating either that this material was not primarily generated with O3 as a reactant or that the ClO4− was affected by postdepositional O isotope exchange. High Δ17O values in ClO4− (Atacama and Death Valley) are associated with high Δ17O values in NO3−, indicating that both compounds preserve characteristics of O3-related atmospheric production in hyper-arid settings, whereas both compounds have low Δ17O values in less arid settings. Although Δ17O variations in terrestrial NO3− can be attributed to mixing of atmospheric

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

    Science.gov (United States)

    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

  14. Isotopic composition and origin of indigenous natural perchlorate and co-occurring nitrate in the southwestern United States.

    Science.gov (United States)

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

    2010-07-01

    Perchlorate (ClO(4)(-)) has been detected widely in groundwater and soils of the southwestern United States. Much of this ClO(4)(-) appears to be natural, and it may have accumulated largely through wet and dry atmospheric deposition. This study evaluates the isotopic composition of natural ClO(4)(-) indigenous to the southwestern U.S. Stable isotope ratios were measured in ClO(4)(-) (delta(18)O, Delta(17)O, delta(37)Cl) and associated NO(3)(-) (delta(18)O, Delta(17)O, delta(15)N) in groundwater from the southern High Plains (SHP) of Texas and New Mexico and the Middle Rio Grande Basin (MRGB) in New Mexico, from unsaturated subsoil in the SHP, and from NO(3)(-)-rich surface caliche deposits near Death Valley, California. The data indicate natural ClO(4)(-) in the southwestern U.S. has a wide range of isotopic compositions that are distinct from those reported previously for natural ClO(4)(-) from the Atacama Desert of Chile as well as all known synthetic ClO(4)(-). ClO(4)(-) in Death Valley caliche has a range of high Delta(17)O values (+8.6 to +18.4 per thousand), overlapping and extending the Atacama range, indicating at least partial atmospheric formation via reaction with ozone (O(3)). However, the Death Valley delta(37)Cl values (-3.1 to -0.8 per thousand) and delta(18)O values (+2.9 to +26.1 per thousand) are higher than those of Atacama ClO(4)(-). In contrast, ClO(4)(-) from western Texas and New Mexico has much lower Delta(17)O (+0.3 to +1.3 per thousand), with relatively high delta(37)Cl (+3.4 to +5.1 per thousand) and delta(18)O (+0.5 to +4.8 per thousand), indicating either that this material was not primarily generated with O(3) as a reactant or that the ClO(4)(-) was affected by postdepositional O isotope exchange. High Delta(17)O values in ClO(4)(-) (Atacama and Death Valley) are associated with high Delta(17)O values in NO(3)(-), indicating that both compounds preserve characteristics of O(3)-related atmospheric production in hyper-arid settings

  15. Radioactive iodide (131 I-) excretion profiles in response to potassium iodide (KI) and ammonium perchlorate (NH4ClO4) prophylaxis.

    Science.gov (United States)

    Harris, Curtis; Dallas, Cham; Rollor, Edward; White, Catherine; Blount, Benjamin; Valentin-Blasini, Liza; Fisher, Jeffrey

    2012-08-01

    Radioactive iodide ((131)I-) protection studies have focused primarily on the thyroid gland and disturbances in the hypothalamic-pituitary-thyroid axis. The objective of the current study was to establish (131)I- urinary excretion profiles for saline, and the thyroid protectants, potassium iodide (KI) and ammonium perchlorate over a 75 hour time-course. Rats were administered (131)I- and 3 hours later dosed with either saline, 30 mg/kg of NH(4)ClO(4) or 30 mg/kg of KI. Urinalysis of the first 36 hours of the time-course revealed that NH(4)ClO(4) treated animals excreted significantly more (131)I- compared with KI and saline treatments. A second study followed the same protocol, but thyroxine (T(4)) was administered daily over a 3 day period. During the first 6-12 hour after (131)I- dosing, rats administered NH(4)ClO(4) excreted significantly more (131)I- than the other treatment groups. T(4) treatment resulted in increased retention of radioiodide in the thyroid gland 75 hour after (131)I- administration. We speculate that the T(4) treatment related reduction in serum TSH caused a decrease synthesis and secretion of thyroid hormones resulting in greater residual radioiodide in the thyroid gland. Our findings suggest that ammonium perchlorate treatment accelerates the elimination rate of radioiodide within the first 24 to 36 hours and thus may be more effective at reducing harmful exposure to (131)I- compared to KI treatment for repeated dosing situations. Repeated dosing studies are needed to compare the effectiveness of these treatments to reduce the radioactive iodide burden of the thyroid gland.

  16. Investigation of the Structure, Optical and Electrical Properties of Lithium Perchlorate Doped Polyaniline Composite: Aloe Vera Used as a Bio-Plasticizer

    Science.gov (United States)

    Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vijeth, H.; Sharanappa, Chapi; Raghu, S.; Devendrappa, H.

    2017-08-01

    Bio-plasticizer based polyaniline (PANI)/lithium perchlorate (LiClO4) composites were synthesized by the facile in situ method. The composites were characterized using the Fourier transform infrared spectroscopy (FT-IR) to identify the chemical interactions. A band appeared at 1502 cm-1 due to the presence of the -H2CO- group and CH2 scissor mode vibration for the PAL15% composite. This considerable change in the morphology of LiClO4 homogeneous dispersion in a PANI matrix was investigated by scanning electron microscopy (SEM). The UV-Visible absorption (UV-Vis) showed 300-400 nm attributed to the π-π* transition and exhibited a red shift from 535 nm to 617 nm in the visible region, indicating a decrease in band gap. The variations in dielectric constant with the addition of lithium perchlorate (LiClO4) at different temperatures and in the frequency range of 20 Hz-1 MHz were assessed through impedance analysis. The temperature dependent electrical conductivity increased with increasing temperature as well as dopant concentration. High conductivity of 1.41 × 10-3 S/cm corresponding to activation energy of 0.02 eV and 2.95 eV optical band gap for 15 wt.% of LiClO4 concentration was observed. The cyclic voltammetry measurement revealed a typical rectangular shape of the integral area, suggesting that the composite has strong electrochemical strength and is a possible candidate for electrochemical super capacitor and solar cell applications.

  17. Thyroid scintigraphy and perchlorate test after recombinant human TSH: a new tool for the differential diagnosis of congenital hypothyroidism during infancy

    Energy Technology Data Exchange (ETDEWEB)

    Fugazzola, Laura; Vannucchi, Guia; Mannavola, Deborah; Beck-Peccoz, Paolo [University of Milan and Fondazione Policlinico IRCCS, Department of Medical Sciences, Milan (Italy); Persani, Luca [University of Milan and Istituto Auxologico Italiano, Department of Medical Sciences, Via Zucchi, Cusano, Milan (Italy); Carletto, Marco; Longari, Virgilio [Fondazione Policlinico IRCCS, Department of Nuclear Medicine, Milan (Italy); Vigone, Maria C.; Cortinovis, Francesca; Weber, Giovanna [Universita Vita-Salute S. Raffaele, Centro di Endocrinologia dell' Infanzia e dell' Adolescenza, Milan (Italy); Beccaria, Luciano [A. Manzoni Hospital, Paediatric Unit, Lecco (Italy)

    2007-09-15

    Prompt initiation of l-thyroxine therapy in neonates with congenital hypothyroidism (CH) often prevents the performance of functional studies. Aetiological diagnosis is thus postponed until after infancy, when the required investigations are performed after l-thyroxine withdrawal. The aim of this study was to verify the efficacy and safety of new protocols for rhTSH (Thyrogen) testing during l-thyroxine replacement in the differential diagnosis of CH. Ten CH patients (15-144 months old) were studied. Seven had neonatal evidence of gland in situ at the ultrasound examination performed at enrolment and received two rhTSH injections (4 {mu}g/kg daily, i.m.) with {sup 123}I scintigraphy and perchlorate test on day 3. Three patients with an ultrasound diagnosis of thyroid dysgenesis received three rhTSH injections with {sup 123}I scintigraphy on days 3 and 4. TSH and thyroglobulin (Tg) determinations were performed on days 1, 3 and 4, and neck ultrasound on day 1. rhTSH stimulation caused Tg levels to increase in eight cases. Blunted Tg responses were seen in two patients with ectopia and hypoplasia. Interestingly, in two cases the association of different developmental defects was demonstrated. Perchlorate test revealed a total iodide organification defect in two patients, including one with a neonatal diagnosis of Pendred's syndrome, who were subsequently found to harbour TPO mutations. rhTSH did not cause notable side-effects. These new rhTSH protocols always resulted in accurate disease characterisation, allowing specific management and targeted genetic analyses. Thus, rhTSH represents a valid and safe alternative to l-thyroxine withdrawal in the differential diagnosis of CH in paediatric patients. (orig.)

  18. 纳米级金属和金属复合物粉末对高氯酸铵和高氯酸铵/聚合丁二烯复合固体推进剂热分解特性的影响%Effects of Metal and Composite Metal Nanopowders on the Thermal Decomposition of Ammonium Perchlorate (AP) and the Ammonium Perchlorate/Hydroxyterminated Polybutadiene (AP/HTPB) Composite Solid Propellant

    Institute of Scientific and Technical Information of China (English)

    刘磊力; 李凤生; 谈玲华; 李敏; 杨毅

    2004-01-01

    Effects of metal (Ni, Cu, Al) and composite metal (NiB, NiCu, NiCuB) nanopowders on the thermal decomposition of ammonium perchlorate (AP) and composite solid propellant ammonium perchlorate/hydroxyterminated polybutadiene (AP/HTPB) were studied by thermal analysis (DTA). The results show that metal and composite metal nanopowders all have good catalytic effects on the thermal decomposition of AP and AP/HTPB composite solid propellant. The effects of metal nanopowders on the thermal decomposition of AP are less than those of the composite metal nanopowders. The effects of metal and composite metal nanopowders on the thermal decomposition of AP are different from those on the thermal decomposition of the AP/HTPB composite solid propellant.

  19. 2-Amino-4-methyl-6-oxo-3,6-dihydro-pyrimidin-1-ium perchlorate-2-amino-6-methyl-pyrimidin-4(1H)-one-water (1/1/1).

    Science.gov (United States)

    Kaabi, Kamel; El Glaoui, Maher; Ferretti, Valeria; Zeller, Matthias; Ben Nasr, Cherif

    2011-09-01

    In the title compound, C(5)H(8)N(3)O(+)·ClO(4) (-)·C(5)H(7)N(3)O·H(2)O, each perchlorate anion is paired with a protonated cationic 2-amino-6-methyl-pyrimidin-4(1H)-one and another non-protonated entity of the same organic pyrimidinone. The crystal structure is stabilized by N-H⋯O(org), N-H⋯O(water), N-H⋯O(ClO4), O-H⋯O(ClO4), N-H⋯N and C-H⋯O(ClO4) hydrogen bonds between the anions, organic entities and water mol-ecules. Inter-molecular π-π stacking inter-actions between neighbouring organic rings are observed with a face-to-face distance of 3.776 (2) Å, and O-H⋯O hydrogen bonds link the perchlorate anions and the water mol-ecules into chains along the b-axis direction. The perchlorate anion and the inter-stitial water mol-ecule are disordered over two mutually incompatible positions with a common occupancy ratio of 0.678 (16):0.322 (16).

  20. Carcinoembryonic antigen: assay following heat compared with perchloric acid extraction in patients with colon cancer, non-neoplastic gastrointestinal diseases, or chronic renal failure

    Energy Technology Data Exchange (ETDEWEB)

    Witherspoon, L.R.; Shuler, S.E.; Alyea, K.; Husserl, F.E.

    1983-10-01

    Heat inactivation has been proposed as an alternative to perchloric acid (PCA) precipitation for the extraction of carcinoembryonic antigen (CEA) from human plasma. A commercial RIA kit using heat inactivation was examined and results compared with those obtained with PCA precipitation. Adequate sensitivity (1.5 ..mu..g CEA/I plasma), satisfactory analytical recovery of CEA added to plasma, and dilutional linearity of samples found to have elevated CEA concentrations, were demonstrated for the heat-inactivation assay. Between-assay precision was better with the heat inactivation than with the PCA assay. Although the absolute concentration of CEA estimated after heat inactivation was consistently lower than that estimated after PCA extraction of plasma specimens, there was excellent correlation between results obtained with the two methods in colon cancer patients free of disease, colon cancer patients with residual or recurrent disease, patients with benign gastrointestinal disease, and in patients with chronic renal failure. The heat-inactivation assay is an excellent alternative to the PCA assay.