WorldWideScience

Sample records for americium perchlorates

  1. Anomalous aryl strengthening of americium and europium complexes during extraction by alkylenediphosphine dioxides from perchloric acid media

    International Nuclear Information System (INIS)

    Extraction of americium and europium from perchlorate environments by solutions of three types of methylenediphosphine dioxides, namely (C6H5)P(O)(CH2)sub(n)(O)P(C6H5)2, (C6H5)2P(O)CH2(O)P(C8H17)2 and (C8H17)2P(O)(CH2)sub(n)(O)P(C8H17)2 has been studied (n is 1 or 2 ) The diluents used have been dichlorethane and chloroform. In perchlorate environments the distribuiton coefficients of americium and europium have proved to be by about 3 orders of magnitude higher than in nitric acid environments, i.e. in perchlorate media the complexes are far more stable. Separation coefficients of americium and REE in perchloric acid soutions are much higher than in nitrate environments. The average value of Am/Eu separation coeffecient at 1-5 M acidity was about 6 (with dichlorethane as diluent) or about 7 (with chloroform as diluent). The complexes essentially exist as trisolvated. Americium complexes display anomalous stability increase upon being diluted: by about 2 orders of magnitude with dichlorethane and by up to 3 orders of magnitude with chloroform used as diluent

  2. Anomalous aryl strengthening of complexes at americium and europium extraction with alkylenediphospine dioxide from perchloric media

    International Nuclear Information System (INIS)

    Studied was the extraction of americium(3) and europium(3) from perchlorate solutions(0.001 M) with dioxides of alkylenediphosphines of three types: aryl Ph2P(O)CH2(O)PPh2(briefly 4P), and Ph2P(O)(CH2)2(O)PPh2, mixed Ph2P(O)CH2(O)P(C8H17)2 (or 2Ph2Oct) and alkyl (C8H17)2P(O)CH2(O)P(C8H17)2 (or 4 Oct). Trisolvates of MeS3x(ClO4)3 are predominantly formed but americium disolvates are also present upon dilution with dichloroethane. For 4Ph,2Ph2Oct and 4 Oct the concentration is, respectively, 1015, 2x1014, and 1013; for disolvates by 4 orders of magnitude lower which is, nevertheless, by 2 orders of magnitude higher than for nitric acid solutions. The separation coefficient of β Am/Eu for 4Ph attains 6-8. As in the case of nitrate solutions, an anomalous aryl strengthening of the complexes is observed: an increase in the distribution coefficients and extraction constants in the series of 4 Oct - 2Ph 2 Oct - 4Ph, in spite of the introduction of electronegative aryl substituents into the dioxide molecule, which reduce electron density on oxygen atoms and basicity of dioxides. In contrast to nitric acid solutions, observed is a nonlinear effect of a change in basicity on extraction properties upon dilution with dichloroethane (dioxide of 2Ph2 Oct does not occupy an intermediate position but is close to 4Ph). Upon dilution with chloroform the dependence is linear and anomalous effect rises due to a different nature of interactions of dioxides with chloroform. When the bridge increases up to ethylene, an anomalous strengthening of the complexes disappears. However, the distribution coefficients upon extraction with alkyl dioxide are considerably lower, which can be explained by a stronger extraction of perchloric acid

  3. 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,...

  4. Preparation of americium amalgam

    International Nuclear Information System (INIS)

    The authors describe a method for the electrochemical preparation of an americium amalgam from americium dioxide and americium 241 and 243 for use in determining the physicochemical properties of the alloy. Moessbauer spectra were made using neptunium dioxide, in the neptunium 237 form, as an absorber. Results show that electrolysis produces a homogeneous amalgam that gives an unoxidized product on vacuum distillation at 200 degrees C

  5. Preparation of americium amalgam

    International Nuclear Information System (INIS)

    Using the method of NGR-spectroscopy with the aid of 241Am isotope chemical state of transuranium elements in the volume and on the surface of amalgams is studied. Amalgam preparation was realized in a simplified electrolytic cell. It is shown that in the process of amalgam preparation the first order of reaction as to actinide is observed; americium is distributed gradually over the volume and it is partially sorbed by the surface of glass capillary. NGR spectrum of dry residue after mercury distillation at 200 deg C points to the presence of americium-mercury intermetal compounds

  6. 1976 Hanford americium accident

    Energy Technology Data Exchange (ETDEWEB)

    Heid, K R; Breitenstein, B D; Palmer, H E; McMurray, B J; Wald, N

    1979-01-01

    This report presents the 2.5-year medical course of a 64-year-old Hanford nuclear chemical operator who was involved in an accident in an americium recovery facility in August 1976. He was heavily externally contaminated with americium, sustained a substantial internal deposition of this isotope, and was burned with concentrated nitric acid and injured by flying debris about the face and neck. The medical care given the patient, including the decontamination efforts and clinical laboratory studies, are discussed. In-vivo measurements were used to estimate the dose rates and the accumulated doses to body organs. Urinary and fecal excreta were collected and analyzed for americium content. Interpretation of these data was complicated by the fact that the intake resulted both from inhalation and from solubilization of the americium embedded in facial tissues. A total of 1100 ..mu..Ci was excreted in urine and feces during the first 2 years following the accident. The long-term use of diethylenetriaminepentate (DTPA), used principally as the zinc salt, is discussed including the method, route of administration, and effectiveness. To date, the patient has apparently experienced no complications attributable to this extensive course of therapy, even though he has been given approximately 560 grams of DTPA. 4 figures, 1 table.

  7. Chemistry of americium

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, W.W.

    1976-01-01

    Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

  8. 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.

  9. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  10. The Biokinetic Model of Americium

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    To improve in vivo measurements for detecting internal exposure from transuranium radio nuclides, such as neptunium, plutonium, americium, the bioknetic model was studied. According to ICRP report (1993, 1995, 1997) and other research, the

  11. Americium product solidification and disposal

    International Nuclear Information System (INIS)

    The americium product from the TRUEX processing plant needs to be converted into a form suitable for ultimate disposal. An evaluation of the disposal based on safety, number of process steps, demonstrated operability of the processes, production of low-level alpha waste streams, and simplicity of maintenance with low radiation exposures to personnel during maintenance, has been made. The best process is to load the americium on a cation exchange resin followed by calcination or oxidation of the resin after loading

  12. Perchlorate in seawater

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-05-10

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

  13. 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

  14. 2-(Benzenesulfonamidopyridinium perchlorate

    Directory of Open Access Journals (Sweden)

    Xun Li

    2009-06-01

    Full Text Available In the title compound, C11H11N2O2S+·ClO4−, the dihedral angle between the benzene and pyridinium rings is 87.33 (10°. An intramolecular N—H...O interaction, with an S=O-bonded O atom as receptor, occurs in the cation. In the crystal structure, ion pairs occur, being linked by strong N—H...O hydrogen bonds. The perchlorate anion plays a further role in the molecular packing by accepting several weak C—H...O interactions.

  15. Spectrochemical analysis of curium and americium samples

    International Nuclear Information System (INIS)

    Spectrochemical procedures have been developed to determine impurities in americium and curium samples. The simultaneous separation of many impurity elements from the base material (americium and curium) is carried out with extraction and extraction-chromatographic methods using di-2-ethylhexylphosphoric acid. It is shown that part of the elements are separated with extraction or sorption of americium and curium; the other part with the Talspeak process. Two fractions in the extraction chromatography and three fractions in the extraction separation of americium and curium, containing impurities, are analyzed separately by a.c. or d.c. arc spectrography. To increase the sensitivity of the spectrographic analysis and accelerate the burn-up of impurities from the crater of the carbon electrode bismuth fluoride and sodium chloride were used as chemically active substances. The extraction of impurities from weighed quantities of americium and curium samples of 5 to 10 mg permits the lower limit of determined impurity concentrations to be extended to 1 x 10-4 to 5 x 10-3% m/m. (author)

  16. Pyrochemical technology of plutonium and americium preparation and purification

    International Nuclear Information System (INIS)

    Pyrochemical tecnology of metallic plutonium and americium preparation and purification is considered. Investigations into plutonium dioxide reduction up to metal; plutonium electrolytic refining in molten salts; plutonium extraction from the molten salts and preparation of americium dioxide and metallic americium from its tetrafluoride are described

  17. Aqueous Chloride Operations Overview: Plutonium and Americium Purification/Recovery

    Energy Technology Data Exchange (ETDEWEB)

    Kimball, David Bryan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Skidmore, Bradley Evan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-06-22

    Acqueous Chloride mission is to recover plutonium and americium from pyrochemical residues (undesirable form for utilization and storage) and generate plutonium oxide and americium oxide. Plutonium oxide is recycled into Pu metal production flowsheet. It is suitable for storage. Americium oxide is a valuable product, sold through the DOE-OS isotope sales program.

  18. 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.

  19. 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...

  20. 1976 Hanford americium exposure incident: psychological aspects

    International Nuclear Information System (INIS)

    Accidents involving exposure to radiation or radioactive materials may involve an unusual degree of emotional trauma. Methods that may be employed in dealing with such trauma are discussed in relation to a specific accident in which a radiation worker was injured and seriously contaminated with americium-241

  1. Organic carbon biostimulates rapid rhizodegradation of perchlorate.

    Science.gov (United States)

    Yifru, Dawit D; Nzengung, Valentine A

    2008-12-01

    Previous hydroponics and field studies identified phytodegradation and rhizodegradation as the two main mechanisms by which plants metabolize perchlorate. Plant uptake and phytodegradation of perchlorate is a slower and undesired process that poses ecological risks resulting from phytoaccumulation of some fraction of the perchlorate. Meanwhile, rhizodegradation is a more rapid and favored process involving perchlorate-degrading bacteria utilizing dissolved organic carbon (DOC) as a carbon and energy (electron) source to rapidly degrade perchlorate to innocuous chloride. In the present study, rhizodegradation of perchlorate by willow trees (Salix nigra) was biostimulated using electron sources obtained from natural and artificial carbon sources. In bioreactors provided with carbon sources as 500 mg/L DOC, 25 to 40 mg/L of initial perchlorate concentrations were removed to below the ion chromatography method detection limit of 2 microg/L in approximately 9 d. For planted controls provided with no electron donors, the time required for the complete removal of the same doses of perchlorate was up to 70 d. Enhancement of rhizodegradation by organic carbon reduced the phytoaccumulated fraction of perchlorate by an order of magnitude from approximately 430 to 20 mg/kg. The implication of the present study is that the high fraction uptake and phytoaccumulation of perchlorate in agricultural products and the recycling of perchlorate into the ecosystem can be significantly curtailed by supplying electron donors derived from organic carbon sources to the root zone of plants. PMID:18593217

  2. PERCHLORATE PHYTOREMEDIATION USING HARDWOOD TREES AND VASCULAR PLANTS

    Science.gov (United States)

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

  3. 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.

  4. 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.

  5. Incentives for transmutation of americium in thermal reactors

    International Nuclear Information System (INIS)

    This report describes possible benefits when americium is irradiated in a thermal reactor. If all plutonium is partitioned from spent fuel, americium is the main contributor to the radiotoxicity of spent fuel upto several thousands of years of storage. It is shown that americium can be transmuted to other nuclides upon irradiation in a thermal reactor, leading to a 50% reduction of the radiotoxicity of neptunium, which can be an important contributor to the dose due to leakage of nuclides after one million years of storage. The radiotoxicity of americium can be reduced considerably after irradiation for 3 to 6 years in a thermal reactor with thermal neutron flux of 1014 cm-2s-1. The strongly α and neutron emitting transmutation products can most probably not be recycled again, so a transmutation process is suggested in which americium is irradiated for 3 to 6 years and then put to final storage. It is shown that the radiotoxicity of the transmuation products after a storage time of about one hundred years can be considerably reduced compared to the radiotoxicity of the initial americium. The same holds for the α activity and heat emission of the transmutation products. Because plutonium in spent fuel contributes for about 80% to the radiotoxicity upto 105 years of storage, recycling and transmutation of plutonium has first priority. Transmutation of americium is only meaningful when the radiotoxicity of plutonium is reduced far below the radiotoxicity of americium. (orig.)

  6. Surface complexation modeling of americium sorption onto volcanic tuff.

    Science.gov (United States)

    Ding, M; Kelkar, S; Meijer, A

    2014-10-01

    Results of a surface complexation model (SCM) for americium sorption on volcanic rocks (devitrified and zeolitic tuff) are presented. The model was developed using PHREEQC and based on laboratory data for americium sorption on quartz. Available data for sorption of americium on quartz as a function of pH in dilute groundwater can be modeled with two surface reactions involving an americium sulfate and an americium carbonate complex. It was assumed in applying the model to volcanic rocks from Yucca Mountain, that the surface properties of volcanic rocks can be represented by a quartz surface. Using groundwaters compositionally representative of Yucca Mountain, americium sorption distribution coefficient (Kd, L/Kg) values were calculated as function of pH. These Kd values are close to the experimentally determined Kd values for americium sorption on volcanic rocks, decreasing with increasing pH in the pH range from 7 to 9. The surface complexation constants, derived in this study, allow prediction of sorption of americium in a natural complex system, taking into account the inherent uncertainty associated with geochemical conditions that occur along transport pathways.

  7. 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,...

  8. 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...

  9. 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

  10. Electrochemical oxidation of americium in nitric medium: study of reaction mechanisms; Oxydation de l'americium par voie electrochimique: etude des mecanismes

    Energy Technology Data Exchange (ETDEWEB)

    Picart, S.; Chartier, D.; Donnet, L.; Adnet, J.M. [CEA Valrho, (DCC/DRRV/SPHA), 30 - Marcoule (France)

    2000-07-01

    One alternative selected by the CEA for partitioning minor actinides from aqueous solutions containing fission products is the selective extraction of oxidized americium. This is the SESAME process (Selective Extraction and Separation of Americium by Means of Electrolysis) aimed to convert americium to oxidation state (VI) and then extract it with a specific extractant of high valences. This paper presents the study of the electrochemical oxidation of americium in nitric medium which represents an important stage of the process. The reaction can be divided into two main steps: oxidation of americium (III) to americium (IV), and then of americium (IV) to americium (VI). For the first oxidation step, a ligand L is needed to stabilize the intermediate species americium (IV) which disproportionates in its free form into americium (III) and (V). Phospho-tungstate or silico-tungstate are appropriate ligands because they are stable in concentrated nitric acid and show a great affinity for metallic cations at oxidation state (IV) (Table 1 lists the stability constants of americium (IV) complexes). The presence of the lacunary poly-anion lowers the potential of the americium (IV) / americium (Ill) redox pair (see Figure 5 for the diagram of the apparent formal potential of americium versus ligand concentration). This makes it thermodynamically possible to oxidize americium (III) into americium (IV) at the anode of an electrolyzer in nitric acid. For the second oxidation step, a strong oxidant redox mediator, like silver (II), is needed to convert complexed americium at oxidation state (IV) to oxidation state (V). The AmVL complex is then hydrolyzed to yield americyle (V) aqua ion. A spectroscopic Raman study with {sup 18}O labeled species showed that the oxygen atoms of the americyle moiety came from water. This indicates that water hydrolyzes the americium (V) complex to produce americyle (V) aqua ion, AmO{sub 2}{sup +}. This cation reacts with silver (Il) to give

  11. Higher Americium Oxidation State Research Roadmap

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-12-18

    The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

  12. Plutonium and Americium Geochemistry at Hanford: A Site Wide Review

    Energy Technology Data Exchange (ETDEWEB)

    Cantrell, Kirk J.; Felmy, Andrew R.

    2012-08-23

    This report was produced to provide a systematic review of the state-of-knowledge of plutonium and americium geochemistry at the Hanford Site. The report integrates existing knowledge of the subsurface migration behavior of plutonium and americium at the Hanford Site with available information in the scientific literature regarding the geochemistry of plutonium and americium in systems that are environmentally relevant to the Hanford Site. As a part of the report, key research needs are identified and prioritized, with the ultimate goal of developing a science-based capability to quantitatively assess risk at sites contaminated with plutonium and americium at the Hanford Site and the impact of remediation technologies and closure strategies.

  13. Mixed chelation therapy for removal of plutonium and americium

    International Nuclear Information System (INIS)

    Iron-binding compounds, 2,3-dihydroxybenzoic acid (DHBA), 2-hydroxybenzoic acid (HBA), and 2-(acetyloxy)benzoic acid (ABA), were tested for their ability to remove americium and plutonium from rats following intraperitioneal injection of the radionuclides as citrates (pH 5). Treatments, 2 mmol/kg, were given on days 3, 6, 10, 12 and 14 following the actinide injection. DHBA and HBA caused about a 20% decrease in liver retention of americium compared to the control value, and DHB caused a similar effect for plutonium. The above agents, co-administered with 0.5 mmol polyaminopolycarboxylic acid (PAPCA)-type chelons, did not change tissue retention of americium and plutonium from that due to the PAPCAs alone. Administration of americium and plutonium to the same rats is useful for studying removal agents since the two actinides behave independently in their biological disposition and response to removal

  14. Gamma-sources on the basis of metallic americium-241

    International Nuclear Information System (INIS)

    A batch of gamma-radiation sources has been manufactured from metallic americium-241 of isotopic purity, its activity varying from 0.08 to 0.93 GBq. The cores of the sources are high-purity americium metal condensate on a tantalum or stainless steel substrate prepared by thermal decomposition of 241Pu-241Am alloy in a high vacuum. 7 refs., 1 tab

  15. Aqueous Chloride Operations Overview: Plutonium and Americium Purification/Recovery

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, Kyle Shelton [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Kimball, David Bryan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Skidmore, Bradley Evan [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-09-28

    These are a set of slides intended for an information session as part of recruiting activities at Brigham Young University. It gives an overview of aqueous chloride operations, specifically on plutonium and americium purification/recovery. This presentation details the steps taken perform these processes, from plutonium size reduction, dissolution, solvent extraction, oxalate precipitation, to calcination. For Americium recovery, it details the CLEAR (chloride extraction and actinide recovery) Line, oxalate precipitation and calcination.

  16. Pyrochemical investigations into recovering plutonium from americium extraction salt residues

    International Nuclear Information System (INIS)

    Progress into developing a pyrochemical technique for separating and recovering plutonium from spent americium extraction waste salts has concentrated on selective chemical reduction with lanthanum metal and calcium metal and on the solvent extraction of americium with calcium metal. Both techniques are effective for recovering plutonium from the waste salt, although neither appears suitable as a separation technique for recycling a plutonium stream back to mainline purification processes. 17 refs., 13 figs., 2 tabs

  17. 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

  18. Electrochemical oxidation of americium in nitric medium: study of reaction mechanisms

    International Nuclear Information System (INIS)

    One alternative selected by the CEA for partitioning minor actinides from aqueous solutions containing fission products is the selective extraction of oxidized americium. This is the SESAME process (Selective Extraction and Separation of Americium by Means of Electrolysis) aimed to convert americium to oxidation state (VI) and then extract it with a specific extractant of high valences. This paper presents the study of the electrochemical oxidation of americium in nitric medium which represents an important stage of the process. The reaction can be divided into two main steps: oxidation of americium (III) to americium (IV), and then of americium (IV) to americium (VI). For the first oxidation step, a ligand L is needed to stabilize the intermediate species americium (IV) which disproportionates in its free form into americium (III) and (V). Phospho-tungstate or silico-tungstate are appropriate ligands because they are stable in concentrated nitric acid and show a great affinity for metallic cations at oxidation state (IV) (Table 1 lists the stability constants of americium (IV) complexes). The presence of the lacunary poly-anion lowers the potential of the americium (IV) / americium (Ill) redox pair (see Figure 5 for the diagram of the apparent formal potential of americium versus ligand concentration). This makes it thermodynamically possible to oxidize americium (III) into americium (IV) at the anode of an electrolyzer in nitric acid. For the second oxidation step, a strong oxidant redox mediator, like silver (II), is needed to convert complexed americium at oxidation state (IV) to oxidation state (V). The AmVL complex is then hydrolyzed to yield americyle (V) aqua ion. A spectroscopic Raman study with 18O labeled species showed that the oxygen atoms of the americyle moiety came from water. This indicates that water hydrolyzes the americium (V) complex to produce americyle (V) aqua ion, AmO2+. This cation reacts with silver (Il) to give americyle (VI) ion. Figure

  19. Perchlorate in The Great Lakes: Isotopic Composition and Origin

    OpenAIRE

    Poghosyan, Armen; Sturchio, Neil C.; Morrison, Candice G.; Beloso, Abelardo D., Jr.; Guan, Yunbin; Eiler, John M.; Jackson, W. Andrew; Hatzinger, Paul B.

    2014-01-01

    Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ^(18)O, Δ^(17)O) and chlorine (δ^(37)Cl) along with the abundance of the radioactive isotope ^(36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0....

  20. 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

  1. Applicability of insoluble tannin to treatment of waste containing americium

    International Nuclear Information System (INIS)

    The applicability of insoluble tannin adsorbent to the treatment of aqueous waste contaminated with americium has been investigated. Insoluble tannin is considered highly applicable because it consists of only carbon, hydrogen and oxygen and so its volume can be easily reduced by incineration. This report describes measurements of the americium distribution coefficient in low concentration nitric acid. The americium distribution coefficients were found to decrease with increasing concentration of nitric acid and sodium nitrate, and with increasing temperature. At 25 C in 2.0 x 10-3 M HNO3, the distribution coefficient was found to be 2000 ml g-1. The adsorption capacity was determined by column experiments using europium as a simulant of americium, and found to be 7 x 10-3 mmol g-1-dried tannin in 0.01 M HNO3 at 25 C, which corresponds to approximately 1.7 mg-241Am/g-adsorbent(dried). The prospect of applying the adsorbent to the treatment of aqueous waste contaminated with americium appears promising. (orig.)

  2. Salvage of plutonium-and americium-contaminated metals

    International Nuclear Information System (INIS)

    Melt-slagging techniques were evaluated as a decontamination and consolidation step for metals contaminated with oxides of plutonium and americium. Experiments were performed in which mild steel, stainless steel, and nickel metals contaminated with oxides of plutonium and americium were melted in the presence of silicate slags of various compositions. The metal products were low in contamination, with the plutonium and americium strongly fractionated to the slags. Partition coefficients (plutonium in slag/plutonium in steel) of 7*10/sup 6/ with borosilicate slag and 3*10/sup 6/ for calcium, magnesium silicate slag were measured. Decontamination of metals containing as much as 14,000 p.p.m. plutonium appears to be as efficient as that of metals with plutonium levels of 400 p.p.m. Staged extraction, that is, a remelting of processed metal with clean slag, results in further decontamination of the metal. 10 refs

  3. 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...

  4. 1976 Hanford americium exposure incident: overview and perspective

    International Nuclear Information System (INIS)

    Salient features of the 1976 Hanford americium exposure incident are discussed. Comparisons are made with previous human and animal exposure data, and conclusions drawn relative to the injured workman, to health physics practices, and to the adequacy of current exposure limits

  5. 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.

  6. Synthesis and characterization of uranium-americium mixed oxides

    International Nuclear Information System (INIS)

    Americium isotopes represent a significant part of high-level and long-lived nuclear waste in spent fuels. Among the envisaged reprocessing scenarios, their transmutation in fast neutron reactors using uranium-americium mixed-oxide pellets (U1-xAmxO2±δ) is a promising option which would help decrease the ecological footprint of ultimate waste repository sites. In this context, this thesis is dedicated to the study of such compounds over a wide range of americium contents (7.5 at.% ≤ Am/(U+Am) ≤ 70 at.%), with an emphasis on their fabrication from single-oxide precursors and the assessment of their structural and thermodynamic stabilities, also taking self-irradiation effects into account. Results highlight the main influence of americium reduction to Am(+III), not only on the mechanisms of solid-state formation of the U1-xAmxO2±δ solid solution, but also on the stabilization of oxidized uranium cations and the formation of defects in the oxygen sublattice such as vacancies and cub-octahedral clusters. In addition, the data acquired concerning the stability of U1-xAmxO2±δ compounds (existence of a miscibility gap, vaporization behavior) were compared to calculations based on new thermodynamic modelling of the U-Am-O ternary system. Finally, α-self-irradiation-induced structural effects on U1-xAmxO2±δ compounds were analyzed using XRD, XAS and TEM, allowing the influence of americium content on the structural swelling to be studied as well as the description of the evolution of radiation-induced structural defects. (author)

  7. 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.

  8. 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...

  9. Extraction of Perchlorate Using Porous Organosilicate Materials

    Directory of Open Access Journals (Sweden)

    Jenna R. Taft

    2013-04-01

    Full Text Available Sorbent materials were developed utilizing two morphological structures, comprising either hexagonally packed pores (HX or a disordered pore arrangement (CF. The sorbents were functionalized with combinations of two types of alkylammonium groups. When capture of perchlorate by the sorbents was compared, widely varying performance was noted as a result of differing morphology and/or functional group loading. A material providing improved selectivity for perchlorate over perrhenate was synthesized with a CF material using N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride. Materials were applied in batch and column formats. Binding isotherms followed the behavior expected for a system in which univalent ligands of varying affinity compete for immobilized sites. Performance of the sorbents was also compared to that of commercial Purolite materials.

  10. Different Strategies for Biological Remediation of Perchlorate Contaminated Groundwater

    OpenAIRE

    Wang, Yue

    2012-01-01

    Perchlorate (ClO4-) has gained attention recently due to its interference with thyroid gland function. In infants and unborn children, inadequate thyroid hormone production can cause mental retardation and thyroid tumors. Since new perchlorate standards will be proposed in 2013, and if a stricter standard is imposed, cost effective technologies will be in high demand. The overall objective of this research was to evaluate two perchlorate bioremediation strategies using indigenous soil bact...

  11. 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).

  12. 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.

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

    Science.gov (United States)

    Wen, Li-Lian; Yang, Qiang; Zhang, Zhao-Xin; Yi, Yang-Yi; Tang, Youneng; Zhao, He-Ping

    2016-11-15

    This work evaluated the interaction of perchlorate and trichloroethene (TCE), two common co-contaminants in groundwater, during bioreduction in serum bottles containing synthetic mineral salts media and microbial consortia. TCE at concentrations up to 0.3mM did not significantly affect perchlorate reduction; however, perchlorate concentrations higher than 0.1mM made the reduction of TCE significantly slower. Perchlorate primarily inhibited the reduction of vinyl chloride (VC, a daughter product of TCE) to ethene. Mechanistic analysis showed that the inhibition was mainly because perchlorate reduction is thermodynamically more favorable than reduction of TCE and its daughter products and not because of toxicity due to accumulation of dissolved oxygen produced during perchlorate reduction. As the initial perchlorate concentration increased from 0 to 600mg/L in a set of serum bottles, the relative abundance of Rhodocyclaceae (a putatively perchlorate-reducing genus) increased from 6.3 to 80.6%, while the relative abundance of Dehalococcoides, the only known genus that is able to reduce TCE all the way to ethene, significantly decreased. Similarly, the relative abundance of Proteobacteria (a phylum to which most known perchlorate-reducing bacteria belong) increased from 22% to almost 80%. PMID:27449607

  14. Neptunium and americium control for international non-proliferation regime

    International Nuclear Information System (INIS)

    It was decided in the IAEA Board of Governors Meeting held in Sept. 1999 that Neptunium and Americium could be diverted for manufacturing nuclear weapon or explosives, so that appropriate measures should be taken for the prevention of proliferation of these materials. It is expected to take relatively long time for settling down the aligned system dealing with the above materials because the present regulatory statement was prepared on the basis of voluntary offers from the States concerned. The necessity of preventive measures is being convinced among Member States, but it would not be easy to take voluntary participation in detail because of their respective interests. It is expected that this paper could contribute to the effective response as to the international commitments as well as for protecting the domestic nuclear industry and R and D area through analysis on the IAEA's approach on Neptunium and Americium

  15. Thermophysical properties of americium-containing barium plutonate

    International Nuclear Information System (INIS)

    Polycrystalline specimens of americium-containing barium plutonate have been prepared by mixing the appropriate amounts of (Pu0.91Am0.09)O2 and BaCO3 powders followed by reacting and sintering at 1600 K under the flowing gas atmosphere of dry-air. The sintered specimens had a single phase of orthorhombic perovskite structure and were crack-free. Elastic moduli were determined from longitudinal and shear sound velocities. Debye temperature was also determined from sound velocities and lattice parameter measurements. Thermal conductivity was calculated from measured density at room temperature, literature values of heat capacity and thermal diffusivity measured by laser flash method in vacuum. Thermal conductivity of americium-containing barium plutonate was roughly independent of temperature and registered almost the same magnitude as that of BaPuO3 and BaUO3. (author)

  16. Perchlorate in the Great Lakes: isotopic composition and origin.

    Science.gov (United States)

    Poghosyan, Armen; Sturchio, Neil C; Morrison, Candice G; Beloso, Abelardo D; Guan, Yunbin; Eiler, John M; Jackson, W Andrew; Hatzinger, Paul B

    2014-10-01

    Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean. PMID:25171443

  17. 1976 Hanford americium-exposure incident: decontamination and treatment facility

    International Nuclear Information System (INIS)

    An injured worker, contaminated with over 6 mCi of americium-241, required special treatment and housing for 4 months. This paper is a description of the design and management of the facility in which most of the treatment and housing occurred. The problems associated with contamination control, waste handling, supplies, and radiological concerns during the two-stage transfer of the patient from a controlled situation to his normal living environment are discussed in detail

  18. Ingestion Pathway Transfer Factors for Plutonium and Americium

    Energy Technology Data Exchange (ETDEWEB)

    Blanchard, A.

    1999-07-28

    Overall transfer factors for major ingestion pathways are derived for plutonium and americium. These transfer factors relate the radionuclide concentration in a given foodstuff to deposition on the soil. Equations describing basic relationships consistent with Regulatory Guide 1.109 are followed. Updated values and coefficients from IAEA Technical Reports Series No. 364 are used when a available. Preference is given to using factors specific to the Savannah River Site.

  19. Method for removal of plutonium impurity from americium oxides and fluorides

    Science.gov (United States)

    FitzPatrick, John R.; Dunn, Jerry G.; Avens, Larry R.

    1987-01-01

    Method for removal of plutonium impurity from americium oxides and fluorides. AmF.sub.4 is not further oxidized to AmF.sub.6 by the application of O.sub.2 F at room temperature, while plutonium compounds present in the americium sample are fluorinated to volatile PuF.sub.6, which can readily be separated therefrom, leaving the purified americium oxides and/or fluorides as the solid tetrafluoride.

  20. Gut uptake factors for plutonium, americium and curium

    International Nuclear Information System (INIS)

    Data on estimates of the absorption of plutonium, americium and curium from the human gut based on measurements of uptake in other mammalian species are reviewed. It is proposed that for all adult members of the public ingesting low concentrations of plutonium in food and water, 0.05% would be an appropriate value of absorption except when the conditions of exposure are known and a lower value can be justified. For dietary intakes of americium and curium, the available data do not warrant a change from the ICRP value of 0.05%. For newborn children ingesting americium, curium and soluble forms of plutonium, a value of 1% absorption is proposed for the first 3 months of life during which the infant is maintained on a milk diet. It is proposed that a value of 0.5% should be used for the first year of life to take account of the gradual maturation of the gut. In considering the ingestion of insoluble oxides of plutonium by infants, it is proposed that absorption is taken as 0.1% for the first 3 months and 0.05% for the first year. (author)

  1. High ozone increases soil perchlorate but does not affect foliar perchlorate content

    Science.gov (United States)

    Ozone (O3) is implicated in the natural source inventory of perchlorate (ClO4-), a hydrophilic salt that migrates to ground water and interferes with uptake of iodide in mammals, including humans. Tropospheric O3 is elevated in many areas. We previously showed (Grantz et al., 2013; Environmental Pol...

  2. 76 FR 7762 - Drinking Water: Regulatory Determination on Perchlorate

    Science.gov (United States)

    2011-02-11

    ... Storage in the Thyroid Gland of Human Neonates. J. Pediatric Endocrinology & Metabolism. Vol. 16. p. 521... AGENCY 40 CFR Part 141 RIN 2040-AF08 Drinking Water: Regulatory Determination on Perchlorate AGENCY... the Agency's) regulatory determination for perchlorate in accordance with the Safe Drinking Water...

  3. PERCHLORATE IDENTIFICATION IN FERTILIZERS AND ACCUMULATION IN LETTUCE SEEDLINGS

    Science.gov (United States)

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

  4. Bioremediation Potential of Perchlorate Contaminated Deep Vadose Zone

    Science.gov (United States)

    Gal, H.; Ronen, Z.; Weisbrod, N.; Dahan, O.; Nativ, R.

    2007-12-01

    Widespread perchlorate contamination was found in the vadose zone near a plant that manufactures ammonium perchlorate above the coastal aquifer of Israel in Ramat Hasharon. As part of the plant's operations, untreated industrial wastewater was disposed of for over 30 years in unlined wastewater ponds and nearby washes, causing contamination of the unsaturated zone (up to 2200 mg kg-1 sediment at a depth of 20 m) and the groundwater below it (up to 300 mg L-1). In this study, we examined the potential for microbial metabolism of perchlorate reduction in the contaminated deep vadose zone profile by native microbial communities. Microbial reduction of perchlorate was found in three of the four sediment samples taken from different depths. The sediments taken from 1 m (shallowest) and 35 m (deepest- close to the water table) showed the fastest degradation rates, while the sediment taken from 15 m showed the slowest rate. No perchlorate reduction was observed in the sediment taken from 20 m, where perchlorate concentrations were highest. These results were correlated to the viable microorganism counts in the profile. In experiments in which the effect of nitrate was examined, the lag time for perchlorate degradation was found to be inversely correlated to the initial nitrate concentration, while the perchlorate-reduction rates were faster in treatments with higher initial nitrate concentrations. We found no perchlorate degradation as long as nitrate was present in the system: perchlorate reduction was initiated only after all of the nitrate had been reduced. Nitrate-reduction rates were correlated to the initial nitrate concentrations and no lag period was observed. Nitrite was temporarily accumulated during nitrate reduction and was totally reduced, like nitrate, after 4 days. Count of viable microbial communities as well as PCR analysis of the chlorite dismutase gene in the native microbial population exposed to high concentrations of perchlorate (10,000-20,000 mg L-1

  5. Airborne plutonium-239 and americium-241 concentrations measured from the 125-meter Hanford Meteorological Tower

    International Nuclear Information System (INIS)

    Airborne plutonium-239 and americium-241 concentrations and fluxes were measured at six heights from 1.9 to 122 m on the Hanford meteorological tower. The data show that plutonium-239 was transported on nonrespirable and small particles at all heights. Airborne americium-241 concentrations on small particles were maximum at the 91 m height

  6. 10 CFR 31.8 - Americium-241 and radium-226 in the form of calibration or reference sources.

    Science.gov (United States)

    2010-01-01

    ... 10 Energy 1 2010-01-01 2010-01-01 false Americium-241 and radium-226 in the form of calibration or... BYPRODUCT MATERIAL § 31.8 Americium-241 and radium-226 in the form of calibration or reference sources. (a..., americium-241 or radium-226 in the form of calibration or reference sources: (1) Any person in a...

  7. Uncertainty analysis of doses from ingestion of plutonium and americium.

    Science.gov (United States)

    Puncher, M; Harrison, J D

    2012-02-01

    Uncertainty analyses have been performed on the biokinetic model for americium currently used by the International Commission on Radiological Protection (ICRP), and the model for plutonium recently derived by Leggett, considering acute intakes by ingestion by adult members of the public. The analyses calculated distributions of doses per unit intake. Those parameters having the greatest impact on prospective doses were identified by sensitivity analysis; the most important were the fraction absorbed from the alimentary tract, f(1), and rates of uptake from blood to bone surfaces. Probability distributions were selected based on the observed distribution of plutonium and americium in human subjects where possible; the distributions for f(1) reflected uncertainty on the average value of this parameter for non-specified plutonium and americium compounds ingested by adult members of the public. The calculated distributions of effective doses for ingested (239)Pu and (241)Am were well described by log-normal distributions, with doses varying by around a factor of 3 above and below the central values; the distributions contain the current ICRP Publication 67 dose coefficients for ingestion of (239)Pu and (241)Am by adult members of the public. Uncertainty on f(1) values had the greatest impact on doses, particularly effective dose. It is concluded that: (1) more precise data on f(1) values would have a greater effect in reducing uncertainties on doses from ingested (239)Pu and (241)Am, than reducing uncertainty on other model parameter values and (2) the results support the dose coefficients (Sv Bq(-1) intake) derived by ICRP for ingestion of (239)Pu and (241)Am by adult members of the public.

  8. Recovery of americium-241 from aged plutonium metal

    International Nuclear Information System (INIS)

    After separation and purification, both actinides were precipitated as oxalates and calcined. A large-scale process was developed using dissolution, separation, purification, precipitation, and calcination. Efforts were made to control corrosion, to avoid product contamination, to keep the volume of process and waste solutions manageable, and to denitrate solutions with formic acid. The Multipurpose Processing Facility (MPPF), designed for recovery of transplutonium isotopes, was used for the first time for the precipitation and calcination of americium. Also, for the first time,, large-scale formic acid denitration was performed in a canyon vessel at SRP

  9. Effect of 241-americium on bone marrow stroma

    International Nuclear Information System (INIS)

    The regulation of haemopoiesis occurs via complex interactions between the stroma and the haemopoietic cells. An attempt to further clarifying the mechanisms and the exact role of the stroma in the regulation was made in a study. Results revealed that the murine bone marrow stromal cells are highly radiosensitive after injection with 241-americium and can thus be considered as a target population after internal contamination. In addition, observations are made which may be important for risk estimation for the developing animal and during pregnancy. Contamination in utero and by lactation shows persistent damage up to 1 year after contamination at an average annual dose of 5 cGy. (author)

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

    Science.gov (United States)

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

    2014-12-01

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

  11. 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.

  12. Preferential decorporation of americium by pulmonary administration of DTPA dry powder after inhalation of aged PuO2 containing americium in rats

    International Nuclear Information System (INIS)

    After inhalation of plutonium oxides containing various percentages of americium in rats, we identified an acellular transient pulmonary compartment, the epithelial lining fluid (ELF), in which a fraction of actinide oxides dissolve prior to absorption and subsequent extrapulmonary deposit. Chelation therapy is usually considered to be poorly efficient after inhalation of actinide oxides. However, in the present study, prompt pulmonary administration of diethylenetriaminepentaacetic acid (DTPA) as a dry powder led to a decrease in actinide content in ELF together with a limitation of bone and liver deposits. Because americium is more soluble than plutonium, higher amounts of americium were found in ELF, extrapulmonary tissues and urine. Our results also demonstrated that the higher efficacy of DTPA on americium compared to plutonium in ELF induced a preferential inhibition of extrapulmonary deposit and a greater urinary excretion of americium compared to plutonium. All together, our data justify the use of an early and local DTPA treatment after inhalation of plutonium oxide aerosols in which americium can be in high proportion such as in aged compounds. (authors)

  13. 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.

  14. Kilogram-scale purification of americium by ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Wheelwright, E. J.

    1979-01-01

    Sequential anion and cation exchange processes have been used for the final purification of /sup 241/Am recovered during the reprocessing of aged plutonium metallurgical scrap. Plutonium was removed by absorption of Dowex 1, X-3.5 (30 to 50 mesh) anion exchange resin from 6.5 to 7.5 M HNO/sub 3/ feed solution. Following a water dilution to 0.75 to 1.0 M HNO/sub 3/, americium was absorbed on Dowex 50W, X-8 (50 to 100 mesh) cation exchange resion. Final purification was accomplished by elution of the absorbed band down 3 to 4 successive beds of the same resin, preloaded with Zn/sup 2 +/, with an NH/sub 4/OH buffered chelating agent. The recovery of mixed /sup 241/Am-/sup 243/Am from power reactor reprocessing waste has been demonstrated. Solvent extraction was used to recover a HNO/sub 3/ solution of mixed lanthanides and actinides from waste generated by the reprocessng of 13.5 tons of Shippingport Power Reactor blanket fuel. Sequential cation exchange band-displacement processes were then used to separate americium and curium from the lanthanides and then to separate approx. 60 g of /sup 244/Cm from 1000 g of mixed /sup 241/Am-/sup 243/Am.

  15. Analytical performance of radiochemical method for americium determination in urine

    International Nuclear Information System (INIS)

    This paper presents an analytical method developed and adapted for separation and analysis of Plutonium (Pu) isotopes and Americium (Am) in urine samples. The proposed method will attend the demand of internal exposure monitoring program for workers involved mainly with dismantling rods and radioactive smoke detectors. In this experimental procedure four steps are involved as preparation of samples, sequential radiochemical separation, preparation of the source for electroplating and quantification by alpha spectrometry. In the first stage of radiochemical separation, plutonium is conventionally isolated employing the anion exchange technique. Americium isolation is achieved sequentially by chromatographic extraction (Tru.spec column) from the load and rinse solutions coming from the anion exchange column. The 243Am tracer is added into the sample as chemical yield monitors and to correct the results improving the precision and accuracy. The mean recovery obtained is 60%, and the detection limit for 24h urine sample is 1.0 mBq L-1 in accordance with the literature. Based in the preliminary results, the method is appropriate to be used in monitoring programme of workers with a potential risk of internal contamination. (author)

  16. Development of separation techniques of americium from reprocessing solution

    International Nuclear Information System (INIS)

    Americium(Am) and neptunium(Np) finally transfer to the waste stream in the current PUREX reprocessing process. As an option, some methods have been developed to recover Am and Np from the waste stream to decrease long-term toxicity of the high level waste. The most stable valence state of Am is III, but TBP (tri-n-butyl phosphate) which is an extractant used in the PUREX reprocessing does not extract Am(III). Therefore, some special extractants have been developed to recover Am(III). However, they also extract rare-earth elements(REs), which necessitates the separation process for Am from REs. We have been developing a separation process which consists of valence control of Am to the VI state and its extraction with TBP. This process allows Am recovery from reprocessing solution and Am separation from REs simultaneously. Americium(III) is oxidized to Am(VI) by electrochemical oxidation and chemical oxidation using peroxodisulfate ammonium and silver nitrate. The latter was adopted here because the chemical oxidation reaction proceeds faster than the electrochemical method. Reaction mechanisms of oxidation and extraction were investigated. Based on the mechanisms, we found that extraction efficiency could be improved and waste generation could be minimized. (author)

  17. The NAS Perchlorate Review: Adverse Effects?

    Energy Technology Data Exchange (ETDEWEB)

    Johnston, Richard B.; Corley, Richard; Cowan, Linda; Utiger, Robert D.

    2005-11-01

    To the editor: Drs. Ginsberg and Rice argue that the reference dose for perchlorate of 0.0007 mg/kg per day recommended by the National Academies’ Committee to Assess the Health Implications of Perchlorate Ingestion is not adequately protective. As members of the committee, we disagree. Ginsberg and Rice base their conclusion on three points. The first involves the designation of the point of departure as a NOEL (no-observed-effect level) versus a LOAEL (lowest-observed-adverse- effect level). The committee chose as its point of departure a dose of perchlorate (0.007 mg/kg per day) that when given for 14 days to 7 normal subjects did not cause a significant decrease in the group mean thyroid iodide uptake (Greer et al. 2002). Accordingly, the committee considered it a NOEL. Ginsberg and Rice focus on the fact that only 7 subjects were given that dose, and they 1seem to say that attention should be paid only to the results in those subjects in whom there was a 1fall in thyroid iodide uptake, and that the results in those in whom there was no fall or an increase should be ignored. They consider the dose to be a LOAEL because of the fall in uptake in those few subjects. It is important to note that a statistically significant decrease of, for example, 5% or even 10%, would not be biologically important and, more important, would not be sustained. For example, in another study (Braverman et al. 2004), administration of 0.04 mg/kg per day to normal subjects for 6 months had no effect on thyroid iodide uptake when measured at 3 and 6 months, and no effect on serum thyroid hormone or thyrotropin concentrations measured monthly (inspection of Figure 5A in the paper by Greer et al. suggests that this dose would inhibit thyroid iodide uptake by about 25% if measured at 2 weeks). The second issue involves database uncertainty. In clinical studies, perchlorate has been administered prospectively to 68 normal subjects for 2 weeks to 6 months. In one study (Brabant et al. 1992

  18. 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.

  19. 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.

  20. 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.

  1. Selective leaching studies of deep-sea sediments loaded with americium, neptunium and plutonium

    International Nuclear Information System (INIS)

    A series of selective leaching experiments were undertaken to investigate the solid phase speciation and distribution of americium, neptunium and plutonium which had been experimentally loaded onto different marine sediment types. The chemical leaches employed showed rather poor selectivity but certain trends were evident. Adsorption was not by ion exchange. Americium showed a preferential affinity for carbonate and plutonium for organic matter. Neptunium appeared to have no preferential affinities. Americium was sorbed by acetic acid residues (CaCO3 removed) and by unleached carbonate-rich sediments with equal efficiency. This indicates that it is able to diversify its solid phase affinity/distribution depending upon which solid phases are available. (author)

  2. 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

  3. Pretreatment of americium/curium solutions for vitrification

    International Nuclear Information System (INIS)

    Vitrification will be used to stabilize an americium/curium (Am/Cm) solution presently stored in F-Canyon for eventual transport to the heavy isotope programs at Oak Ridge National Laboratory. Prior to vitrification, an in-tank oxalate precipitation and a series of oxalic/nitric acid washes will be used to separate these elements and lanthanide fission products from the bulk of the uranium and metal impurities present in the solution. Pretreatment development experiments were performed to understand the behavior of the lanthanides and the metal impurities during the oxalate precipitation and properties of the precipitate slurry. The results of these experiments will be used to refine the target glass composition allowing optimization of the primary processing parameters and design of the solution transfer equipment

  4. Oxidation of some disubstituted anisole derivatives with ceric perchlorate in perchloric acid solution

    International Nuclear Information System (INIS)

    The influence of concentration of particular reagents on the kinetics of Ce(IV) reduction by 2,6-dimethyl and 3,5-dimethyl-anisole as well as 2-methoxy-5-methyl- and 4-methoxy-2-methyl-aniline in perchloric acid solution was investigated, establishing the stoichiometry of these processes. Some intermediate products - macromolecular, derivatives of p-benzoquinone and 4,4'-diphenoquinone - were separated and identified. The effects of substituents and the conditions of performed oxidation processes on the kind and yields of the resultant products were considered. (author). 22 refs, 1 fig., 1 tab

  5. Plutonium and americium in sediments of Lithuanian lakes

    International Nuclear Information System (INIS)

    The assessment of contribution of the global and the Chernobyl NPP (Nuclear Power Plant) accident plutonium and americium to plutonium pollution in sediments of Lithuanian lakes is presented. Theoretical evaluation of activity ratios of 238Pu/239+240Pu and 241Pu/239+240Pu in the reactor of unit 4 of the Chernobyl NPP before the accident was performed by means of the ORIGEN-ARP code from the SCALE 4.4A program package. Non-uniform distribution of radionuclides in depositions on the Lithuanian territory after nuclear weapon tests and the Chernobyl NPP accident is experimentally observed by measuring the lake sediment pollution with actinides. The activity concentration of sediments polluted with plutonium ranges from 2.0 ± 0.5 Bq/kg d.w. (dry weight) in Lake Asavelis to 14 ± 2 Bq/kg d.w. in Lake Juodis. The ratio of activity concentrations of plutonium isotopes 238Pu/239+240Pu measured by α-spectrometry in the 10-cm-thick upper layer of bottom sediment varies from 0.03 in Lake Juodis to 0.3 in Lake Zuvintas. The analysis of the ratio values shows that the deposition of the Chernobyl origin plutonium is prevailing in southern and south-western regions of Lithuania. Plutonium of nuclear weapon tests origin in sediments of lakes is observed on the whole territory of Lithuania, and it is especially distinct in central Lithuania. The americium activity due to 241Pu decay after the Chernobyl NPP accident and global depositions in bottom sediments of Lithuanian lakes has been evaluated to be from 0.9 to 5.7 Bq/kg. (author)

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

    International Nuclear Information System (INIS)

    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 ∼ 150 μg 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: ► Estimated infant exposures to perchlorate were, on a μg/kg basis, ∼ 5 × higher than those of mothers. ► Daily supplements are less effective than iodized salt in providing iodine to lactating women. ► Low iodine and high perchlorate in milk may place infants at risk of iodine deficiency.

  7. 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.

  8. Kinetic parameters of transformation of americium and plutonium physicochemical forms in podsol soils

    International Nuclear Information System (INIS)

    Kinetic parameters of transformation of americium and plutonium physicochemical forms have been estimated and the prognosis of fixing and remobilization of these nuclides in podsol soils have been made on that basis in the work. (authors)

  9. Calibration procedures for in vivo sodium iodide spectrometry of plutonium and americium in the human lung

    International Nuclear Information System (INIS)

    This paper describes the calibration techniques and associated error analysis for the in vivo measurement by NaI spectrometry of heavy elements in the lung, specifically plutonium and americium. A very brief description of the instrumentation system is included

  10. Relativistic density functional theory modeling of plutonium and americium higher oxide molecules

    Science.gov (United States)

    Zaitsevskii, Andréi; Mosyagin, Nikolai S.; Titov, Anatoly V.; Kiselev, Yuri M.

    2013-07-01

    The results of electronic structure modeling of plutonium and americium higher oxide molecules (actinide oxidation states VI through VIII) by two-component relativistic density functional theory are presented. Ground-state equilibrium molecular structures, main features of charge distributions, and energetics of AnO3, AnO4, An2On (An=Pu, Am), and PuAmOn, n = 6-8, are determined. In all cases, molecular geometries of americium and mixed plutonium-americium oxides are similar to those of the corresponding plutonium compounds, though chemical bonding in americium oxides is markedly weaker. Relatively high stability of the mixed heptoxide PuAmO7 is noticed; the Pu(VIII) and especially Am(VIII) oxides are expected to be unstable.

  11. Distribution of uranium, americium and plutonium in the biomass of freshwater macrophytes

    Energy Technology Data Exchange (ETDEWEB)

    Zotina, T.A.; Kalacheva, G.S.; Bolsunovsky, A.YA. [Institute of Biophysics SB RAS, Akademgorodok, Krasnoyarsk (Russian Federation)

    2010-07-01

    Accumulation of uranium ({sup 238}U), americium ({sup 241}Am) and plutonium ({sup 242}Pu) and their distribution in cell compartments and biochemical components of the biomass of aquatic plants Elodea canadensis, Ceratophyllum demersum, Myrioplyllum spicatum and aquatic moss Fontinalis antipyretica have been investigated in laboratory batch experiments. Isotopes of uranium, americium and plutonium taken up from the water by Elodea canadensis apical shoots were mainly absorbed by cell walls, plasmalemma and organelles. A small portion of isotopes (about 6-13 %) could be dissolved in cytoplasm. The major portion (76-92 %) of americium was bound to cell wall cellulose-like polysaccharides of Elodea canadensis, Myriophyllum spicatum, Ceratophyllum demersum and Fontinalis antipyretica, 8-23 % of americium activity was registered in the fraction of proteins and carbohydrates, and just a small portion (< 1%) in lipid fraction. The distribution of plutonium in the biomass fraction of Elodea was similar to that of americium. Hence, americium and plutonium had the highest affinity to cellulose-like polysaccharides in Elodea biomass. Distribution of uranium in the biomass of Elodea differed essentially from that of transuranium elements: a considerable portion of uranium was recorded in the fraction of protein and carbohydrates (51 %). From our data we can assume that uranium has higher affinity to carbohydrates than proteins. (authors)

  12. Aluminum-based drinking-water treatment residuals: A novel sorbent for perchlorate removal

    International Nuclear Information System (INIS)

    Perchlorate contamination of aquifers and drinking-water supplies has led to stringent regulations in several states to reduce perchlorate concentrations in water at acceptable levels for human consumption. Several perchlorate treatment technologies exist, but there is significant cost associated with their use, and the majority of them are unable to degrade perchlorate to innocuous chloride. We propose the use of a novel sorbent for perchlorate, i.e. an aluminum-based drinking-water treatment residual (Al-WTR), which is a by-product of the drinking-water treatment process. Perchlorate sorption isotherms (23 ± 1 oC) showed that the greatest amount (65%) of perchlorate removed by the Al-WTR was observed with the lowest initial perchlorate load (10 mg L-1) after only 2 h of contact time. Increasing the contact time to 24 h, perchlorate removal increased from 65 to 76%. A significant correlation was observed between the amounts of perchlorate removed with evolved chloride in solution, suggesting degradation of perchlorate to chloride. - Drinking-water treatment residuals are a low-cost sorbent for perchlorate

  13. 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...

  14. Effect of americium-241 on luminous bacteria. Role of peroxides

    Energy Technology Data Exchange (ETDEWEB)

    Alexandrova, M., E-mail: maka-alexandrova@rambler.r [Siberian Federal University, Svobodny 79, 660041 Krasnoyarsk (Russian Federation); Rozhko, T. [Siberian Federal University, Svobodny 79, 660041 Krasnoyarsk (Russian Federation); Vydryakova, G. [Institute of Biophysics SB RAS, Akademgorodok 50, 660036 Krasnoyarsk (Russian Federation); Kudryasheva, N. [Siberian Federal University, Svobodny 79, 660041 Krasnoyarsk (Russian Federation); Institute of Biophysics SB RAS, Akademgorodok 50, 660036 Krasnoyarsk (Russian Federation)

    2011-04-15

    The effect of americium-241 ({sup 241}Am), an alpha-emitting radionuclide of high specific activity, on luminous bacteria Photobacterium phosphoreum was studied. Traces of {sup 241}Am in nutrient media (0.16-6.67 kBq/L) suppressed the growth of bacteria, but enhanced luminescence intensity and quantum yield at room temperature. Lower temperature (4 {sup o}C) increased the time of bacterial luminescence and revealed a stage of bioluminescence inhibition after 150 h of bioluminescence registration start. The role of conditions of exposure the bacterial cells to the {sup 241}Am is discussed. The effect of {sup 241}Am on luminous bacteria was attributed to peroxide compounds generated in water solutions as secondary products of radioactive decay. Increase of peroxide concentration in {sup 241}Am solutions was demonstrated; and the similarity of {sup 241}Am and hydrogen peroxide effects on bacterial luminescence was revealed. The study provides a scientific basis for elaboration of bioluminescence-based assay to monitor radiotoxicity of alpha-emitting radionuclides in aquatic solutions. - Highlights: {yields} Am-241 in water solutions (A = 0.16-6.7 kBq/L) suppresses bacterial growth.{yields} Am-241 (A = 0.16-6.7 kBq/L) stimulate bacterial luminescence. {yields} Peroxides, secondary radiolysis products, cause increase of bacterial luminescence.

  15. 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.

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

    International Nuclear Information System (INIS)

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

  17. 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.

  18. 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

  19. 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...

  20. 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...

  1. Nitrate and Perchlorate removal from groundwater by ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Burge, S; Halden, R

    1999-09-15

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

  2. 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.

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

    International Nuclear Information System (INIS)

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

  4. 10 CFR 32.57 - Calibration or reference sources containing americium-241 or radium-226: Requirements for license...

    Science.gov (United States)

    2010-01-01

    ... or radium-226: Requirements for license to manufacture or initially transfer. 32.57 Section 32.57... americium-241 or radium-226: Requirements for license to manufacture or initially transfer. An application... containing americium-241 or radium-226, for distribution to persons generally licensed under § 31.8 of...

  5. Separation and determination of americium in low-level alkaline waste of NPP origin

    Science.gov (United States)

    Todorov, B.; Djingova, R.; Nikiforova, A.

    2006-01-01

    The aim of this work is to develop a short and cost-saving procedure for the determination of 241Am in sludge sample of the alkaline low-level radioactive waste (LL LRAW) collected from Nuclear Power Plant “Kozloduy”. The determination of americium was a part of a complex analytical approach, where group actinide separation was achieved. An anion exchange was used for separation of americium from uranium, plutonium and iron. For the separation of americium extraction with diethylhexyl phosphoric acid (DEHPA) was studied. The final radioactive samples were prepared by micro co-precipitation with NdF3, counted by alpha and gamma spectrometry. The procedure takes 2 hours. The recovery yield of the procedure amounts to (95 ± 1.5)% and the detection limit is 53 mBq/kg 241Am (t=150 000 s). The analytical procedure was applied for actual liquid wastes and results were compared to standard procedure.

  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. 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

  8. Detection of Perchlorate Anion on Functionalized Silver Colloids Using Surface-Enhanced Raman Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Tio, J.; Wang, W.; Gu, B.

    2005-01-01

    Perchlorate anion interferes with the uptake of iodide by the human thyroid gland and consequently disrupts the regulation of metabolism. Chronic exposure to high levels of perchlorate may lead to the formation of thyroid gland tumors. Although the Environmental Protection Agency (EPA) has not set a maximum contaminant level (MCL) for perchlorate, a draft drinking water range of 4-18 ppb based on 2 liter daily consumption of water has been established. The current EPA approved method for detecting perchlorate uses ion chromatography which has a detection limit of ~1ppb and involves lengthy analytical time in the laboratory. A unique combination of the surface-enhanced Raman scattering (SERS) effect and the bifunctional anion exchange resin’s high selectivity may provide an alternative way to detect perchlorate at such low concentrations and with high specificity. SERS, which uses laser excitation of adsorbed perchlorate anions on silver nanoparticles, has been shown to detect perchlorate anions at concentrations as low as 50 ppb. Normal micro-Raman analysis of perchlorate sorbed onto the resin beads has detected an even lower concentration of 10 ppb. In an effort to integrate these two effects, silver nanoparticles were coated with N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, a functional group similar to that found on the resin bead, and subsequently inserted into different perchlorate concentration environments. This method has resulted in perchlorate detection down to ~10 ppb and a more consistent detection of perchlorate anion at ~50 ppb than that of earlier methods. As suggested by the direct insertion of functionalized silver colloids into perchlorate samples, this technique may potentially allow for the development of a probe using on-site Raman spectrometry to detect significantly low concentrations of perchlorate in situ rather than in the laboratory.

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

    International Nuclear Information System (INIS)

    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

  10. Isotopic and elemental composition of plutonium/americium oxides influence pulmonary and extra-pulmonary distribution after inhalation in rats

    International Nuclear Information System (INIS)

    The biodistribution of plutonium and americium has been studied in a rat model after inhalation of two PuO2 powders in lungs and extra-pulmonary organs from 3 d to 3 mo. The main difference between the two powders was the content of americium (approximately 46% and 4.5% of total alpha activity). The PuO2 with a higher proportion of americium shows an accelerated transfer of activity from lungs to blood as compared to PuO2 with the lower americium content, illustrated by increased urinary excretion and higher bone and liver actinide retention. The total alpha activity measured reflects mostly the americium biological behavior. The activity contained in epithelial lining fluid, recovered in the acellular phase of broncho-alveolar lavages, mainly contains americium, whereas plutonium remains trapped in macrophages. Epithelial lining fluid could represent a transitional pulmonary compartment prior to translocation of actinides to the blood and subsequent deposition in extra-pulmonary retention organs. In addition, differential behaviors of plutonium and americium are also observed between the PuO2 powders with a higher dissolution rate for both plutonium and americium being obtained for the PuO2 with the highest americium content. Our results indicate that the biological behavior of plutonium and americium after translocation into blood differ two-fold: (1) for the two actinides for the same PuO2 aerosol, and (2) for the same actinide from the two different aerosols. These results highlight the importance of considering the specific behavior of each contaminant after accidental pulmonary intake when assessing extra-pulmonary deposits from the level of activity excreted in urine or for therapeutic strategy decisions. (authors)

  11. Isotopic and elemental composition of plutonium/americium oxides influence pulmonary and extra-pulmonary distribution after inhalation in rats.

    Science.gov (United States)

    Van der Meeren, A; Grémy, O

    2010-09-01

    The biodistribution of plutonium and americium has been studied in a rat model after inhalation of two PuO(2) powders in lungs and extra-pulmonary organs from 3 d to 3 mo. The main difference between the two powders was the content of americium (approximately 46% and 4.5% of total alpha activity). The PuO(2) with a higher proportion of americium shows an accelerated transfer of activity from lungs to blood as compared to PuO(2) with the lower americium content, illustrated by increased urinary excretion and higher bone and liver actinide retention. The total alpha activity measured reflects mostly the americium biological behavior. The activity contained in epithelial lining fluid, recovered in the acellular phase of broncho-alveolar lavages, mainly contains americium, whereas plutonium remains trapped in macrophages. Epithelial lining fluid could represent a transitional pulmonary compartment prior to translocation of actinides to the blood and subsequent deposition in extra-pulmonary retention organs. In addition, differential behaviors of plutonium and americium are also observed between the PuO(2) powders with a higher dissolution rate for both plutonium and americium being obtained for the PuO(2) with the highest americium content. Our results indicate that the biological behavior of plutonium and americium after translocation into blood differ two-fold: (1) for the two actinides for the same PuO(2) aerosol, and (2) for the same actinide from the two different aerosols. These results highlight the importance of considering the specific behavior of each contaminant after accidental pulmonary intake when assessing extra-pulmonary deposits from the level of activity excreted in urine or for therapeutic strategy decisions.

  12. 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.

  13. Adsorption-desorption characteristics of plutonium and americium with sediment particles in the estuarine environment: studies using plutonium-237 and americium-241

    International Nuclear Information System (INIS)

    The particle formation of plutonium and americium, their adsorption onto fresh water sediments and the desorption from the sediments in sea water were studied in the Laboratory under simulated river-estuary conditions, using γ-emitting plutonium-237 and americium-241. The results of the experiments show that the particle formation of plutonium depends on its valence states, on pH and on the salinity of the medium. For river water at pH4, some 25%, 20% and 30% of the added 237Pu was in particulate form, larger than 0.45 μm, for Pu (III), Pu (IV) and Pu (VI), respectively, while 65%, 90% and 50% of the respective valence states was associated with particles at pH 8. In sea water the general pattern remains similar, although Pu (VI) is more soluble in sea water owing to higher ligand concentrations for carbonate and bicarbonate complexes. The pH-dependency of particle formation of Am (III) is more steep than that of plutonium and seems to be influenced by colloidal substances occurring in the experimental media. The adsorption-desorption characteristics of plutonium and americium with the sediment in river water as well as sea water reflect the characteristics of their particle formation, being dependent upon such properties as valence states, the pH and salinity of the medium. A sewage effluent added to the media has small but measurable effects on the adsorption-desorption processes of plutonium. (author)

  14. 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.

  15. 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.

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

    International Nuclear Information System (INIS)

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

  17. Cesium-137 and americium-241 distribution by granulometric fractions of soil at Azgir test site grounds

    International Nuclear Information System (INIS)

    In measurements of radionuclide specific content in surface soil layer of contaminated territories it is important to determine in what agglomerations of soil particles there is the highest radionuclide concentration. For this purpose granulometric composition of soil at Azgir test site was studied and cesium-137 and americium-241 distribution by soil fractions was researched. (author)

  18. Apparatus for fabrication of americium- beryllium neutron sources prevents capsule contamination

    Science.gov (United States)

    Mohr, W. C.; Van Loom, J. A.

    1967-01-01

    Modified gloved enclosure is used to fill a capsule with a mixture of americium and beryllium radioactive powders to seal weld the opening, and to test it for leaks. It contains a horizontal partition, vortex mixer, mounting press, welder, test vessel, and radiation shielding to prevent surface contamination.

  19. Evaluation of the readsorption of plutonium and americium in dynamic fractionations of environmental solid samples

    DEFF Research Database (Denmark)

    Petersen, Roongrat; Hou, Xiaolin; Hansen, Elo Harald

    2008-01-01

    extractions. The degree of readsorption in dynamic and conventional batch extraction systems are compared and evaluated by using a double-spiking technique. A high degree of readsorption of plutonium and americium (>75%) was observed in both systems, and they also exhibited similar distribution patterns...

  20. 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.

  1. Effect of bone-status on retention and distribution of americium-241 in bones of small rodents

    International Nuclear Information System (INIS)

    Forced physical exercise before and after application of americium-241 resulted in only small changes in bone-structure and behaviour of the radionuclide in bone. Feeding of a low phosphorus or low calcium diet resulted in an increased excretion of americium from bone, whereby Zn-DTPA as chelating agent removed an additional fraction of the radionuclide from bone. Low calcium diet and simultaneous continuous infusion of pharmacological doses of vitamin D-hormones didn't increase the excretion of americium more than the low calcium diet alone. (orig.)

  2. 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

  3. Interaction and diffusion transport of americium in soils

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez-Guinart, Oriol; Rigol, Anna; Vidal, Miquel [Analytical Chemistry department, Faculty of Chemistry, University of Barcelona, Marti i Franques 1-11, 08028, Barcelona (Spain)

    2014-07-01

    The final disposal of High Level Radioactive Wastes (HLRW) is based on its long-term storage in underground facilities located in geological stable sites with a multi-barrier system, the so called Deep Geological Repositories (DGR), that will keep HLRW confined for >10.000 years. After this period of time, leachates rich in long-live radioisotopes might escape from DGR and start to transport towards the biosphere. There is still a lack of information concerning the interaction and transport in soils of some radionuclides present in HLRW, especially for radionuclides that present a high sorption, such as americium (Am). Having reliable information about the mobility of radionuclides in soils is crucial in order to develop risk assessment models and to take proper decisions in case of soil contamination. The aim of the present work was, by means of laboratory scale experiments, to study the interaction and, for first time, to evaluate the diffusion transport of {sup 241}Am in soils. The {sup 241}Am interaction in soils was assessed by applying sorption batch assays to 20 soil samples with contrasted edaphic properties which allowed us to quantify the solid-liquid distribution coefficient (K{sub d}) and desorption percentage. K{sub d} (Am) values ranged from 10{sup 3} to 10{sup 5} L kg{sup -1} and desorption percentages were always less than 2% which denoted a high capacity of the soil to incorporate the Am and a low reversibility of the sorption process. The influence of soil properties in {sup 241}Am interaction was studied by means of multiple linear and multivariate regressions. Although a single correlation between K{sub d} (Am) values and a soil property was not found, the main properties affecting {sup 241}Am interaction in soils were soil pH, carbonate and organic matter contents in the soil. Finally, additional batch assays at different controlled pH were done to study Am sorption as a function of the contact solution pH. A variation of the Am sorption

  4. 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

  5. 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.

  6. SKIN DOSIMETRY IN CONDITIONS OF ITS CONSTANT SURFACE CONTAMINATION WITH SOLUTIONS OF PLUTONIUM-239 AND AMERICIUM-241

    Directory of Open Access Journals (Sweden)

    E. B. Ershov

    2012-01-01

    Full Text Available The article considers, on the basis of experimental data, the issue of assessing dose burdens to the skin basal layer in conditions of its permanent contamination with solutions of plutonium-239 and americium-241 and subsequent decontamination.

  7. 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.

  8. Archaeal (Per)Chlorate Reduction at High Temperature: An Interplay of Biotic and Abiotic Reactions

    NARCIS (Netherlands)

    Liebensteiner, M.; Pinkse, M.W.H.; Schaap, P.J.; Stams, A.J.M.; Lomans, B.P.

    2013-01-01

    Perchlorate and chlorate anions [(per)chlorate] exist in the environment from natural and anthropogenic sources, where they can serve as electron acceptors for bacteria. We performed growth experiments combined with genomic and proteomic analyses of the hyperthermophile Archaeoglobus fulgidus that s

  9. 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.

  10. 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.

  11. 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.

  12. Influence of biofilms on migration of uranium, americium and europium in the environment; Einfluss von Biofilmen auf das Migrationsverhalten von Uran, Americium und Europium in der Umwelt

    Energy Technology Data Exchange (ETDEWEB)

    Baumann, Nils; Zirnstein, Isabel; Arnold, Thuro

    2015-07-01

    The report on the influence of biofilms on migration of uranium, americium and europium in the environment deals with the contamination problems of uranium mines such as SDAG WISMUT in Saxonia and Thuringia. In mine waters microorganisms form a complex microbiological biocoenosis in spite of low pH values and high heavy metal concentrations including high uranium concentrations. The analyses used microbiological methods like confocal laser scanning microscopy and molecular-biological techniques. The interactions of microorganism with fluorescent radioactive heavy metal ions were performed with TRLFS (time resolved laser-induced fluorescence spectroscopy).

  13. (Dicyanamido)[tris(2-pyridylmethyl)amine]zinc(II) perchlorate

    OpenAIRE

    Shi Guo Zhang; Hong Yan Zhao; Hong Li

    2008-01-01

    In the title complex, [Zn(C2N3)(C18H18N4)]ClO4, the ZnII ion has a slightly distorted trigonal–bipyramidal ZnN5 coordination geometry. The crystal structure is stabilized by weak intermolecular C—H...O and C—H...N hydrogen bonds. In addition, there are relatively close contacts between the O atoms of the perchlorate anion and symmetry-related pyridine rings [O...Cg = 3.179 (3) and 3.236 (3) Å, where Cg is the centroid of a pyridine ring], and between t...

  14. Prediction of Particle Size of Ammonium Perchlorate during Pulverisation

    Directory of Open Access Journals (Sweden)

    Sunil Jain

    2006-07-01

    Full Text Available Ammonium perchlorate has been pulverised by an impact mill (air classifier mill to studythe influence of different operating parameters, viz., effect of mill speed, classifier speed, feedrate, and damper opening (suction rate on the particle size. Further based on the differentgrinding parameters, an empirical equation has been developed and used for the prediction ofparticle size. The experimental results indicate that the values are very close to the predictedones. In addition, particle size distribution has also been studied by applying different modelequations and it has been found that Rosin-Rammler model is the most suitable model for thisoperation.

  15. Comparative DFT study of crystalline ammonium perchlorate and ammonium dinitramide.

    Science.gov (United States)

    Zhu, Weihua; Wei, Tao; Zhu, Wei; Xiao, Heming

    2008-05-22

    The electronic structure, vibrational properties, absorption spectra, and thermodynamic properties of crystalline ammonium perchlorate (AP) and ammonium dinitramide (ADN) have been comparatively studied using density functional theory in the local density approximation. The results shows that the p states for the two solids play a very important role in their chemical reaction. From the low frequency to high frequency region, ADN has more motion modes for the vibrational frequencies than AP. The absorption spectra of AP and ADN display a few, strong bands in the fundamental absorption region. The thermodynamic properties show that ADN is easier to decompose than AP as the temperature increases. PMID:18396853

  16. Liquid-liquid extraction separation and sequential determination of plutonium and americium in environmental samples by alpha-spectrometry

    International Nuclear Information System (INIS)

    A procedure is described by which plutonium and americium can be determined in environmental samples. The sample is leached with nitric acid and hydrogen peroxide, and the two elements are co-precipitated with ferric hydroxide and calcium oxalate. The calcium oxalate is incinerated at 4500 and the ash is dissolved in nitric acid. Plutonium is extracted with tri-n-octylamine solution in xylene from 4M nitric acid and stripped with ammonium iodide/hydrochloric acid. Americium is extracted with thenoyltrifluoroacetone solution in xylene at pH 4 together with rare-earth elements and stripped with 1M nitric acid. Americium and the rare-earth elements thus separated are sorbed on Dowex 1 x 4 resin from 1M nitric acid in 93% methanol, the rare-earth elements are eluted with 0.1M hydrochloric acid/0.5M ammonium thiocyanate/80% methanol and the americium is finally eluted with 1.5M hydrochloric acid in 86% methanol. Plutonium and americium in each fraction are electro-deposited and determined by alpha-spectrometry. Overall average recoveries are 81% for plutonium and 59% for americium. (author)

  17. 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

  18. Influence of environmental factors on the gastrointestinal absorption of plutonium and americium

    International Nuclear Information System (INIS)

    The absorption of plutonium and americium from the gastrointestinal tract was studied, using adult hamsters and rabbits. Both actinides were administered as inorganic compounds, as organic complexes with naturally occurring chelating agents, and in a biologically incorporated form in liver tissues. The absorption of the tetravalent and hexavalent forms of plutonium were compared and the effect of protracted administration at very low concentrations was investigated. In addition, plutonium uptake from contaminated sediments and grass, collected near a nuclear-fuel reprocessing plant, was measured. The results of these studies suggest that chronic exposure of man to plutonium and americium in food and water will not lead to any substantial increase in their gastrointestinal absorption above the values currently recommended by the International Commission on Radiological Protection to define the occupational exposure of workers

  19. Electrodeposition of americium on a liquid cadmium cathode from a molten salt bath

    International Nuclear Information System (INIS)

    A high-activity experiment involving the electrode position of americium on a liquid cadmium cathode from a LiCl-KCl eutectic with about 3 g of AmO2 was conducted in a shielded cell in the ATALANTE complex. After describing the electrolyzer and the experimental conditions, the authors discuss the preparation of the LiCl-KCl-AmCl3 solution and briefly review its electrochemical properties. It was clearly confirmed that Am(III) reduction on an inert solid cathode occurs in two steps forming Am(II) before Am(0), whereas only one reduction step was observed on liquid cadmium. The main results of this study concern americium electrode position on the liquid cadmium cathode (recovery yields, current densities, problems encountered). The solvent properties of cadmium for actinide/lanthanide separation are discussed. (authors)

  20. Analysis of americium-beryllium neutron source composition using the FRAM code

    Energy Technology Data Exchange (ETDEWEB)

    Hypes, P. A. (Philip A.); Bracken, D. S. (David S.); Sampson, Thomas E.; Taylor, W. A. (Wayne A.)

    2002-01-01

    The FRAM code was originally developed to analyze high-resolution gamma spectra from plutonium items. Its capabilities have since been expanded to include analysis of uranium spectra. The flexibility of the software also enables a capable spectroscopist to use FRAM to analyze spectra in which neither plutonium nor uranium is present in significant amounts. This paper documents the use of FRAM to determine the {sup 239}Pu/{sup 241}Am, {sup 243}Am/{sup 241}Am, {sup 237}Np/{sup 241}Am, and {sup 239}Np/{sup 241}Am ratios in americium-beryllium neutron sources. The effective specific power of each neutron source was calculated from the ratios determined by FRAM in order to determine the americium mass of each of these neutron sources using calorimetric assay. We will also discuss the use of FRAM for the general case of isotopic analysis of nonplutonium, nonuranium items.

  1. Experimental Insight into the Radiation Resistance of Zirconia-Based Americium Ceramics

    International Nuclear Information System (INIS)

    Our works shows that the americium pyrochlore 241Am2Zr2O7 undergoes a phase transition to a defect-fluorite structure along with an unusual volume contraction when subjected to internal radiation from α-emitting actinides. Disorder relaxation proceeds through the simultaneous formation of cation anti sites and oxygen Frenkel pairs. X-ray absorption spectroscopy at the Am-LII and the Zr-K edges reveals that Am-O polyhedra show an increasing disorder with increasing exposure. In contrast, the Zr-O polyhedral units remain highly ordered, while rotating along edges and corners, thereby reducing the structural strain imposed by the growing disorder around americium. We believe it is this particular property of the compound that provides the remarkable resistance to radiation (≥9.4 * 1018) α-decay events g-1 or 0.80 dpa). (authors)

  2. Standard test method for quantitative determination of americium 241 in plutonium by Gamma-Ray spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    1994-01-01

    1.1 This test method covers the quantitative determination of americium 241 by gamma-ray spectrometry in plutonium nitrate solution samples that do not contain significant amounts of radioactive fission products or other high specific activity gamma-ray emitters. 1.2 This test method can be used to determine the americium 241 in samples of plutonium metal, oxide and other solid forms, when the solid is appropriately sampled and dissolved. 1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  3. Calcium and zinc DTPA administration for internal contamination with plutonium-238 and americium-241.

    Science.gov (United States)

    Kazzi, Ziad N; Heyl, Alexander; Ruprecht, Johann

    2012-08-01

    The accidental or intentional release of plutonium or americium can cause acute and long term adverse health effects if they enter the human body by ingestion, inhalation, or injection. These effects can be prevented by rapid removal of these radionuclides by chelators such as calcium or zinc diethylenetriaminepentaacetate (calcium or zinc DTPA). These compounds have been shown to be efficacious in enhancing the elimination of members of the actinide family particularly plutonium and americium when administered intravenously or by nebulizer. The efficacy and adverse effects profile depend on several factors that include the route of internalization of the actinide, the type, and route time of administration of the chelator, and whether the calcium or zinc salt of DTPA is used. Current and future research efforts should be directed at overcoming limitations associated with the use of these complex drugs by using innovative methods that can enhance their structural and therapeutic properties.

  4. Final Radiological Assessment of External Exposure for CLEAR-Line Americium Recovery Operations

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Adam C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Belooussova, Olga N. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hetrick, Lucas Duane [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2014-11-12

    Los Alamos National Laboratory is currently planning to implement an americium recovery program. The americium, ordinarily isotopically pure 241Am, would be extracted from existing Pu materials, converted to an oxide and shipped to support fabrication of americium oxide-beryllium neutron sources. These operations would occur in the currently proposed Chloride Extraction and Actinide Recovery (CLEAR) line of glove boxes. This glove box line would be collocated with the currently-operational Experimental Chloride Extraction Line (EXCEL). The focus of this document is to provide an in-depth assessment of the currently planned radiation protection measures and to determine whether or not further design work is required to satisfy design-goal and ALARA requirements. Further, this document presents a history of americium recovery operations in the Department of Energy and high-level descriptions of the CLEAR line operations to provide a basis of comparison. Under the working assumptions adopted by this study, it was found that the evaluated design appears to mitigate doses to a level that satisfies the ALARA-in-design requirements of 10 CFR 835 as implemented by the Los Alamos National Laboratory procedure P121. The analyses indicate that extremity doses would also meet design requirements. Dose-rate calculations were performed using the radiation transport code MCNP5 and doses were estimated using a time-motion study developed in consort with the subject matter expert. A copy of this report and all supporting documentation are located on the Radiological Engineering server at Y:\\Rad Engineering\\2013 PROJECTS\\TA-55 Clear Line.

  5. Bidentate organophosphorus extraction of americium and plutonium from Hanford Plutonium Reclamation Facility waste

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, W.W.

    1974-09-01

    Applicability of bidentate organiphosphorus reagents to recovery of americium and plutonium from Hanford's Plutonium Reclamation Facility acid (approx. 2M HNO/sub 3/) waste stream (CAW solution) was studied. A solvent extraction process which employs a 30% DHDECMP (dihexyl-N, N-diethylcarbamylmethylene phosphonate)-CCl/sub 4/ extractant was devised and successfully tested in mixer-settler runs with actual CAW solution. Substitution of DHDECMP for DBBP eliminates the need to perform careful neutralization of unbuffered CAW soluton and increases overall americium recovery from the present 60 to 80% level to greater than or equal to 90%. Disadvantages to such substitution include the high cost (approx. $50/liter) of DHDECMP and the need to purify it (by acid (6M HCl) hydrolysis and alkaline washing) from small amounts of an unidentified impurity which prevents stripping of americium with dilute HNO/sub 3/. Distribution data obtained in this study confirm Siddall's earlier contention that bidentate organophosphorus regents can be used to remove actinides from concentrated high-level Purex process acid waste; a conceptual flowsheet for such an extraction process is given.

  6. 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.

  7. 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. PMID:27383240

  8. 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. PMID:27383240

  9. 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.

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

    International Nuclear Information System (INIS)

    Highlights: → Ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. → DNAN is identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. → 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 (ClO4-) 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

  11. 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.

  12. 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.

  13. 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 ...

  14. 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...

  15. A rapid and simple method for the separation of TBP-dodecane by perchloric acid

    International Nuclear Information System (INIS)

    Organic solvents, including TBP etc., are widely used as an extractant, and treated and disposed by storage, incineration, and absorption into absorbent after they were used. Any of those methods does not aim at recycling of solvents, treating concurrently the extractant and the diluent without separating them. In this paper, a test is reported on the TBP-dodecane separation by perchloric acid for a separation test of the diluent from the extractant as a first step toward recycling. Basically this separation method is already reported by P. Mark et al. as a method for the analysis of TBP, but it requires a large amount of perchloric acid. With a further detailed study of the perchloric acid effects on the TBP-dodecane separation, it was made clear that the separation is possible by adding a fixed amount of TBP contacted with perchloric acid to the TBP-dodecane solvent. In this paper, its outline is presented. (author)

  16. 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.

  17. 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. PMID:25828411

  18. 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.

  19. Americium(3) coordination chemistry: An unexplored diversity of structure and bonding

    Energy Technology Data Exchange (ETDEWEB)

    Fedosseev, A.M.; Grigoriev, M.S.; Budantseva, N.A. [A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation); Guillaumont, D.; Den Auwer, Ch.; Moisy, Ph. [CEA Marcoule, Nuclear Energy Division, RadioChemistry and Processes Department, 30 (France); Le Naour, C.; Simoni, E. [CNRS, University Paris-11 Orsay, IPN, 91 - Orsay (France)

    2010-06-15

    The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic groups, namely the amino-tri-acetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH{sub 3}){sub 6}][M(NTA){sub 2}(H{sub 2}O)].8H{sub 2}O with M Nd, Yb and Am, and [Co(NH{sub 3}){sub 6}]{sub 2}K[M{sub 3}(Cit){sub 4}(H{sub 2}O){sub 3}].18H{sub 2}O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents. (authors)

  20. Americium(3) coordination chemistry: An unexplored diversity of structure and bonding

    International Nuclear Information System (INIS)

    The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic groups, namely the amino-tri-acetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH3)6][M(NTA)2(H2O)].8H2O with M Nd, Yb and Am, and [Co(NH3)6]2K[M3(Cit)4(H2O)3].18H2O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents. (authors)

  1. MARIOS: Irradiation of UO{sub 2} containing 15% americium at well defined temperature

    Energy Technology Data Exchange (ETDEWEB)

    D' Agata, E., E-mail: elio.dagata@ec.europa.eu [European Commission, Joint Research Centre, Institute for Energy - P.O. Box 2, 1755 ZG Petten (Netherlands); Hania, P.R. [Nuclear Research and Consultancy Group, P.O. Box 25, 1755 ZG Petten (Netherlands); Bejaoui, S. [Commissariat a l' Energie Atomique, DEC CEA-Cadarache, 13108 St. Paul lez Durance Cedex (France); Sciolla, C.; Wyatt, T.; Hannink, M.H.C. [Nuclear Research and Consultancy Group, P.O. Box 25, 1755 ZG Petten (Netherlands); Herlet, N.; Jankowiak, A. [Commissariat a l' Energie Atomique DTEC CEA Marcoule, 30207 Bagnols sur Ceze Cedex (France); Klaassen, F.C. [Nuclear Research and Consultancy Group, P.O. Box 25, 1755 ZG Petten (Netherlands); Bonnerot, J.-M. [Commissariat a l' Energie Atomique, DEC CEA-Cadarache, 13108 St. Paul lez Durance Cedex (France)

    2012-01-15

    Highlights: Black-Right-Pointing-Pointer MARIOS is designed to check the behaviour of Minor Actinide Blanket Module concept. Black-Right-Pointing-Pointer Main requirement of the experiment is an accurate control of the temperature. Black-Right-Pointing-Pointer The swelling and the helium release will be the main output of the experiment. Black-Right-Pointing-Pointer A complementary experiment (DIAMINO), will be performed in the next future. - Abstract: Americium is a strong contributor to the long term radiotoxicity of high activity nuclear waste. Transmutation by irradiation in nuclear reactors of long-lived nuclides like {sup 241}Am is, therefore, an option for the reduction of radiotoxicity and residual power packages as well as the repository area. The MARIOS irradiation experiment is the latest of a series of experiments on americium transmutation (e.g. EFTTRA-T4, EFTTRA-T4bis, HELIOS). MARIOS experiment is carried out in the framework of the 4-year project FAIRFUELS of the EURATOM 7th Framework Programme (FP7). During the past years of experimental work in the field of transmutation and tests of innovative nuclear fuel containing americium, the release or trapping of helium as well as swelling has shown to be the key issue for the design of such kinds of target. Therefore, the main objective of the MARIOS experiment is to study the in-pile behaviour of UO{sub 2} containing minor actinides (MAs) in order to gain knowledge on the role of the microstructure and of the temperature on the gas release and on fuel swelling. The MARIOS experiment will be conducted in the HFR (high flux reactor) in Petten (The Netherlands) and will start in the beginning of 2011. It has been planned that the experiment will last 11 cycles, corresponding to 11 months. This paper covers the description of the objective of the experiment, as well as a general description of the design of the experiment.

  2. Speciation of americium in seawater and accumulation in the marine sponge Aplysina cavernicola.

    Science.gov (United States)

    Maloubier, Melody; Michel, Hervé; Solari, Pier Lorenzo; Moisy, Philippe; Tribalat, Marie-Aude; Oberhaensli, François R; Dechraoui Bottein, Marie Yasmine; Thomas, Olivier P; Monfort, Marguerite; Moulin, Christophe; Den Auwer, Christophe

    2015-12-21

    The fate of radionuclides in the environment is a cause of great concern for modern society, seen especially in 2011 after the Fukushima accident. Among the environmental compartments, seawater covers most of the earth's surface and may be directly or indirectly impacted. The interaction between radionuclides and the marine compartment is therefore essential for better understanding the transfer mechanisms from the hydrosphere to the biosphere. This information allows for the evaluation of the impact on humans via our interaction with the biotope that has been largely undocumented up to now. In this report, we attempt to make a link between the speciation of heavy elements in natural seawater and their uptake by a model marine organism. More specifically, because the interaction of actinides with marine invertebrates has been poorly studied, the accumulation in a representative member of the Mediterranean coralligenous habitat, the sponge Aplysina cavernicola, was investigated and its uptake curve exposed to a radiotracer (241)Am was estimated using a high-purity Ge gamma spectrometer. But in order to go beyond the phenomenological accumulation rate, the speciation of americium(III) in seawater must be assessed. The speciation of (241)Am (and natural europium as its chemically stable surrogate) in seawater was determined using a combination of different techniques: Time-Resolved Laser-Induced Fluorescence (TRLIF), Extended X-ray Absorption Fine Structure (EXAFS) at the LIII edge, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and Scanning Electron Microscopy (SEM) and the resulting data were compared with the speciation modeling. In seawater, the americium(III) complex (as well as the corresponding europium complex, although with conformational differences) was identified as a ternary sodium biscarbonato complex, whose formula can be tentatively written as NaAm(CO3)2·nH2O. It is therefore this chemical form of americium that is

  3. Speciation of americium in seawater and accumulation in the marine sponge Aplysina cavernicola.

    Science.gov (United States)

    Maloubier, Melody; Michel, Hervé; Solari, Pier Lorenzo; Moisy, Philippe; Tribalat, Marie-Aude; Oberhaensli, François R; Dechraoui Bottein, Marie Yasmine; Thomas, Olivier P; Monfort, Marguerite; Moulin, Christophe; Den Auwer, Christophe

    2015-12-21

    The fate of radionuclides in the environment is a cause of great concern for modern society, seen especially in 2011 after the Fukushima accident. Among the environmental compartments, seawater covers most of the earth's surface and may be directly or indirectly impacted. The interaction between radionuclides and the marine compartment is therefore essential for better understanding the transfer mechanisms from the hydrosphere to the biosphere. This information allows for the evaluation of the impact on humans via our interaction with the biotope that has been largely undocumented up to now. In this report, we attempt to make a link between the speciation of heavy elements in natural seawater and their uptake by a model marine organism. More specifically, because the interaction of actinides with marine invertebrates has been poorly studied, the accumulation in a representative member of the Mediterranean coralligenous habitat, the sponge Aplysina cavernicola, was investigated and its uptake curve exposed to a radiotracer (241)Am was estimated using a high-purity Ge gamma spectrometer. But in order to go beyond the phenomenological accumulation rate, the speciation of americium(III) in seawater must be assessed. The speciation of (241)Am (and natural europium as its chemically stable surrogate) in seawater was determined using a combination of different techniques: Time-Resolved Laser-Induced Fluorescence (TRLIF), Extended X-ray Absorption Fine Structure (EXAFS) at the LIII edge, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and Scanning Electron Microscopy (SEM) and the resulting data were compared with the speciation modeling. In seawater, the americium(III) complex (as well as the corresponding europium complex, although with conformational differences) was identified as a ternary sodium biscarbonato complex, whose formula can be tentatively written as NaAm(CO3)2·nH2O. It is therefore this chemical form of americium that is

  4. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    International Nuclear Information System (INIS)

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg−1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (∼0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13− coordination environment (e.g. >90%) and no (III XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO2 matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am3+ face an AmO813− coordination environment in the (Pu,U)O2 matrix. • The americium dioxide is reduced by the uranium dioxide matrix

  5. Fabrication of uranium–americium mixed oxide pellet from microsphere precursors: Application of CRMP process

    Energy Technology Data Exchange (ETDEWEB)

    Remy, E. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Picart, S., E-mail: sebastien.picart@cea.fr [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Delahaye, T. [Fuel Cycle Technology Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Jobelin, I. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Lebreton, F.; Horlait, D. [Fuel Cycle Technology Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Bisel, I. [Radiochemistry and Processes Department, CEA, Nuclear Energy Division, F-30207 Bagnols-sur-Cèze (France); Blanchart, P. [Heterogeneous Materials Research Group, Centre Européen de la Céramique, F-87068 Limoges (France); Ayral, A. [Institut Européen des Membranes, CNRS-ENSCM-UM2, CC47, University Montpellier 2, F-34095 Montpellier cedex 5 (France)

    2014-10-15

    Highlights: • Dust free process for (U,Am)O{sub 2} transmutation target fabrication. • Synthesis of U{sub 0.9}Am{sub 0.1}O{sub 2} mixed oxide microspheres from ion exchange resin. • Fabrication of dense U{sub 0.9}Am{sub 0.1}O{sub 2} pellet with 95% TD from mixed oxide microspheres. - Abstract: Mixed uranium–americium oxides are one of the materials envisaged for Americium Bearing Blankets dedicated to transmutation in fast neutron reactors. Recently, several processes have been developed in order to validate fabrication flowchart in terms of material specifications such as density and homogeneity but also to suggest simplifications for lowering industrial costs and hazards linked to dust generation of highly contaminating and irradiating compounds. This study deals with the application of an innovative route using mixed oxide microspheres obtained from metal loaded resin bead calcination, called Calcined Resin Microsphere Pelletization (CRMP). The synthesis of mixed oxide microsphere precursor of U{sub 0.9}Am{sub 0.1}O{sub 2±δ} is described as well as its characterisation. The use of this free-flowing precursor allows the pressing and sintering of one pellet of U{sub 0.9}Am{sub 0.1}O{sub 2±δ}. The ceramic obtained was characterised and results showed that its microstructure is dense and homogeneous and its density attains 95% of the theoretical density. This study validates the scientific feasibility of the CRMP process applied to the fabrication of uranium and americium-containing materials.

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

    International Nuclear Information System (INIS)

    Graphical abstract: The molecular geometry, electronic structure, infrared spectra, and heats of reaction and formation of cobalt and nickel tris(carbohydrazide) perchlorates as well as copper bis(carbohydrazide) perchlorate are investigated using the HSE screened hybrid density functional. The metal-ligand interaction, thermal stability, and red-shift of the amino stretching vibrations of these complexes are also discussed. Moreover, it is found there is a relationship between the energy gap and impact sensitivity. - Abstract: 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 σN-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.

  7. 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.

  8. Impacts of natural organic matter on perchlorate removal by an advanced reduction process.

    Science.gov (United States)

    Duan, Yuhang; Batchelor, Bill

    2014-01-01

    Perchlorate can be destroyed by Advanced Reduction Processes (ARPs) that combine chemical reductants (e.g., sulfite) with activating methods (e.g., UV light) in order to produce highly reactive reducing free radicals that are capable of rapid and effective perchlorate reduction. However, natural organic matter (NOM) exists widely in the environment and has the potential to influence perchlorate reduction by ARPs that use UV light as the activating method. Batch experiments were conducted to obtain data on the impacts of NOM and wavelength of light on destruction of perchlorate by the ARPs that use sulfite activated by UV light produced by low-pressure mercury lamps (UV-L) or by KrCl excimer lamps (UV-KrCl). The results indicate that NOM strongly inhibits perchlorate removal by both ARP, because it competes with sulfite for UV light. Even though the absorbance of sulfite is much higher at 222 nm than that at 254 nm, the results indicate that a smaller amount of perchlorate was removed with the UV-KrCl lamp (222 nm) than with the UV-L lamp (254 nm). The results of this study will help to develop the proper way to apply the ARPs as practical water treatment processes. PMID:24521418

  9. Preliminary analyses for perchlorate in selected natural materials and their derivative products

    Science.gov (United States)

    Orris, G.J.; Harvey, G.J.; Tsui, D.T.; Eldrige, J.E.

    2003-01-01

    Increasing concern about sources of perchlorate contamination in ground and surface waters has led to interest in identifying potential sources of natural perchlorate and products derived from these natural sources. To date, most perchlorate found in ground and surface waters has been attributed to its major uses as an oxidizer in solid propellants for rockets, in fireworks and other explosives, and a variety of other uses of man-made perchlorate salts. However, perchlorate found in the soils, surface water, and ground water of some locations cannot be linked to an anthropogenic source. This paper contains preliminary data on the detection and non-detection of perchlorate in a variety of natural materials and their products, including some fertilizer materials. These data were previously presented at two conferences; once in poster session and once orally (Harvey and others, 1999; Orris and others, 2000). Although the results presented here are included in a journal article awaiting publication, the lack of public information on this topic has led to repeated requests for the data used as the basis for our presentations in 1999 and 2000.

  10. 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.

  11. Influence of biofilms on migration of uranium, americium and europium in the environment

    International Nuclear Information System (INIS)

    The report on the influence of biofilms on migration of uranium, americium and europium in the environment deals with the contamination problems of uranium mines such as SDAG WISMUT in Saxonia and Thuringia. In mine waters microorganisms form a complex microbiological biocoenosis in spite of low pH values and high heavy metal concentrations including high uranium concentrations. The analyses used microbiological methods like confocal laser scanning microscopy and molecular-biological techniques. The interactions of microorganism with fluorescent radioactive heavy metal ions were performed with TRLFS (time resolved laser-induced fluorescence spectroscopy).

  12. Plutonium and americium in arctic waters, the North Sea and Scottish and Irish coastal zones

    DEFF Research Database (Denmark)

    Hallstadius, L.; Aarkrog, Asker; Dahlgaard, Henning;

    1986-01-01

    Plutonium and americium have been measured in surface waters of the Greenland and Barents Seas and in the northern North Sea from 1980 through 1984. Measurements in water and biota, Fucus, Mytilus and Patella, were carried out in North-English and Scottish waters in 1982 and Fucus samples were...... plutonium from the latter to Spitsbergen waters. Fallout plutonium in Arctic waters has a residence time of the order of several years, while for Pu from Sellafield we estimate mean residence times of 11–15 months in Scottish waters and, tentatively, 1·5-3 y during transport from the North Channel (north...

  13. Comparison of acid leachate and fusion methods to determine plutonium and americium in environmental samples

    International Nuclear Information System (INIS)

    The Analytical Chemistry Laboratory at Argonne National Laboratory performs radiochemical analyses for a wide variety of sites within the Department of Energy complex. Since the chemical history of the samples may vary drastically from site to site, the effectiveness of any analytical technique may also vary. This study compares a potassium fluoride-pyrosulfate fusion technique with an acid leachate method. Both normal and high-fired soils and vegetation samples were analyzed for both americium and plutonium. Results show both methods work well, except for plutonium in high-fired soils. Here the fusion method provides higher accuracy

  14. Purification of used scintillation liquids containing the alpha emitters americium and plutonium

    International Nuclear Information System (INIS)

    In Sweden, alpha radioactive waste liquids with an activity over some kBq per waste container cannot be sent for final storage. Therefore, in this work, a method for a purification of alpha active scintillation cocktails was developed. Until today (March, 2013) more than 20 L of scintillation liquids have successfully been purified from americium and plutonium. The products of the process are a solid fraction that can be sent to final storage and a practically non-radioactive liquid fraction that can be sent to municipal incineration. (author)

  15. Study of the extraction and the purification of americium and trivalent actinides contained in effluents with supported liquid membranes

    International Nuclear Information System (INIS)

    The supported liquid membrane technique is studied and developed for americium recovery from uranium or plutonium matrices and decontamination of liquid radioactive wastes. First tests on uranium-nickel solutions with a flat membrane showed the easiness of the operation and the efficiency of the process. Acid-resistant (10 N), interchangeable elements with hollow fibers, are developed and also a computerized automatic device. The different tests on americium solutions demonstrate the feasibility and the reliability of the system. Influence of various parameters on transfer kinetics is investigated

  16. Inhibition of microbial sulfate reduction in a flow-through column system by (per)chlorate treatment

    OpenAIRE

    Anna eEngelbrektson; Christopher eHubbard; Lauren eTom; Aaron eBOUSSINA; Yong Tae eJin; Hayden eWong; Yvette Marisa Piceno; Hans Karl Carlson; Mark eConrad; Andersen, Gary L.; Coates, John D.

    2014-01-01

    Microbial sulfate reduction is a primary cause of oil reservoir souring. Here we show that amendment with chlorate or perchlorate [collectively (per)chlorate] potentially resolves this issue. Triplicate packed columns inoculated with marine sediment were flushed with coastal water amended with yeast extract and one of nitrate, chlorate, or perchlorate. Results showed that although sulfide production was dramatically reduced by all treatments, effluent sulfide was observed in the nitrate (10 m...

  17. 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.

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

    International Nuclear Information System (INIS)

    Graphical abstract: Schemes of perchlorate reduction in ClO4−/ClO3−–NO3− e−acceptor systems. - Highlights: • We created a multiple electron acceptor/donor system for ClO4− reduction. • Nitrate reduction was inhibited when using perchlorate-grown Azospira sp. KJ. • Reduction proceeded as an order of ClO3−, ClO4−and NO3−. • 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 ClO4−–ClO3−, ClO4−–ClO3−–NO3−,and ClO4−–NO3− acceptor systems, while being completely inhibited by the additional O2 in the ClO4−–O2 acceptor system. The reduction proceeded as an order of ClO3−, ClO4−, and NO3− in the ClO4−–ClO3−–NO3− system. KS,vmax, and qmax obtained at different e− 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

  19. 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 <0.1 percent perchlorate and ppm levels of organic carbon at landing site 1 and 2 [2]. The suggestion of perchlorate in the Viking sites [2] has been challenged on the grounds that the detected compounds (CH3Cl and CH2Cl2) were carried from Earth [4]. Recently the Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory (MSL) ran four samples from an aeolian bedform named Rocknest. The samples analyzed were portioned from the fifth scoop at this location. The samples were heated to 835C at 35C/min with a He flow. The SAM QMS detected a major oxygen release (300-500C) [5], coupled with the release of chlorinated hydrocarbons (chloromethane, dichloromethane, trichloromethane, and chloromethylpropene) detected both by SAM QMS and GC-MS derived from known Earth organic contaminants in the instrument [6]. Calcium perchlorate appears to be the best candidate for evolved O2 in the Rocknest samples at this time but other Cl species (e.g., chlorates) are possible and must be evaluated. The potential detection of perchlorates in Rocknest material adds weight to the argument that both Viking Landers measured signatures of

  20. Particle size distribution and perchlorate levels in settled dust from urban roads, parks, and roofs in Chengdu, China.

    Science.gov (United States)

    Li, Yiwen; Shen, Yang; Pi, Lu; Hu, Wenli; Chen, Mengqin; Luo, Yan; Li, Zhi; Su, Shijun; Ding, Sanglan; Gan, Zhiwei

    2016-01-01

    A total of 27 settled dust samples were collected from urban roads, parks, and roofs in Chengdu, China to investigate particle size distribution and perchlorate levels in different size fractions. Briefly, fine particle size fractions (intake is safe to both children and adults in Chengdu, China. However, due to perchlorate mainly existing in fine particles, there is a potential for perchlorate to transfer into surface water and the atmosphere by runoff and wind erosion or traffic emission, and this could act as an important perchlorate pollution source for the indoor environment, and merits further study. PMID:26608047

  1. Contribution to the prediction of americium, plutonium and neptunium behaviour in the geosphere: chemical data

    International Nuclear Information System (INIS)

    An exhaustive bibliographic review on hydrolysis of americium gives the stability constants, at zero ionic strength. No evidence of Am(OH)4- formation was found by solubility studies up to pH 2 (CO3)3 characterised by its X-ray diffraction pattern is studied at a high ionic strength. All the published results on Am in carbonate media are reinterpreted using these stability constants (Am-OH-CO3 complexes are not needed). No evidence of Am(CO3)45- formation was found by spectrophotometry up to 3M. Literature results are used to determine the formal redox potentials at pH = 9.4 and to calculate the formation constants, at zero ionic strength. The formation of complexes between americium and humic materials (purified fulvic and humic acids) has been studied by a spectrophotometric technique. The results are interpreted by the formation of a 1:1 complexe. Solubility of the solid PuO2(CO3) is measured in bicarbonate media at high ionic strength, to obtain the solubility product and formation constants of the PuO2(CO3)i2-2i complexes

  2. Inhibition of microbial sulfate reduction in a flow-through column system by (perchlorate treatment

    Directory of Open Access Journals (Sweden)

    Anna eEngelbrektson

    2014-06-01

    Full Text Available Microbial sulfate reduction is a primary cause of oil reservoir souring. Here we show that amendment with chlorate or perchlorate [collectively (perchlorate] potentially resolves this issue. Triplicate packed columns inoculated with marine sediment were flushed with coastal water amended with yeast extract and one of nitrate, chlorate, or perchlorate. Results showed that although sulfide production was dramatically reduced by all treatments, effluent sulfide was observed in the nitrate (10 mM treatment after an initial inhibition period. In contrast, no effluent sulfide was observed with (perchlorate (10 mM. Microbial community analyses indicated temporal community shifts and phylogenetic clustering by treatment. Nitrate addition stimulated Xanthomonadaceae and Rhizobiaceae growth, supporting their role in nitrate metabolism. (Perchlorate showed distinct effects on microbial community structure compared with nitrate and resulted in a general suppression of the community relative to the untreated control combined with a significant decrease in sulfate reducing species abundance indicating specific toxicity. Furthermore, chlorate stimulated Pseudomonadaceae and Pseudoalteromonadaceae, members of which are known chlorate respirers, suggesting that chlorate may also control sulfidogenesis by biocompetitive exclusion of sulfate-reduction. Perchlorate addition stimulated Desulfobulbaceae and Desulfomonadaceae, which contain sulfide oxidizing and elemental sulfur-reducing species respectively, suggesting that effluent sulfide concentrations may be controlled through sulfur redox cycling in addition to toxicity and biocompetitive exclusion. Sulfur isotope analyses further support sulfur cycling in the columns, even when sulfide is not detected. This study indicates that (perchlorate show great promise as inhibitors of sulfidogenesis in natural communities and provides insight into which organisms and respiratory processes are involved.

  3. 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)

  4. 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.

  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. The distribution of plutonium-239 and americium-241 in the Syrian hamster following its intravenous administration as citrate

    International Nuclear Information System (INIS)

    Actinide distribution in various tissues and the skeleton of hamsters by liquid scintillation counting or isotope dilution. For plutonium 57% of activity was concentrated in the skeleton and more than 90% in the liver and skeleton after seven days. For americium the liver retained more than 50% of total activity and 25% was excreted in urine within seven days. (U.K.)

  7. EURADOS intercomparison on measurements and Monte Carlo modelling for the assessment of Americium in a USTUR leg phantom

    International Nuclear Information System (INIS)

    A collaboration of the EURADOS working group on 'Internal Dosimetry' and the United States Transuranium and Uranium Registries (USTUR) has taken place to carry out an intercomparison on measurements and Monte Carlo modelling determining americium deposited in the bone of a USTUR leg phantom. Preliminary results and conclusions of this intercomparison exercise are presented here. (authors)

  8. Investigations of neutron characteristics for salt blanket models; integral fission cross section measurements of neptunium, plutonium, americium and curium isotopes

    International Nuclear Information System (INIS)

    Neutron characteristics of salt blanket micromodels containing eutectic mixtures of sodium, zirconium, and uranium fluorides were measured on FKBN-2M, BIGR and MAKET facilities. The effective fission cross sections of neptunium, plutonium, americium, and curium isotopes were measured on the neutron spectra formed by micromodels. (author)

  9. NOVEL ASSOCIATIONS BETWEEN URINARY PERCHLORATE AND POTENTIALLY RELEVANT EFFECTS ON RISK FACTORS FOR HEART DISEASE BASED ON NHANES 2001-2002

    Science.gov (United States)

    Perchlorate is a widespread environmental pollutant, and is a thyroid hormone disruptor. A previous population study based on the National Health and Nutrition Examination Survey (NHANES) 2001-2002 database showed that urinary perchlorate concentrations were associated with signi...

  10. Adaptive evolution of Desulfovibrio alaskensis G20 for developing resistance to perchlorate

    Science.gov (United States)

    Mehta-Kolte, M. G.; Youngblut, M.; Redford, S.; Gregoire, P.; Carlson, H. K.; Coates, J. D.

    2015-12-01

    Due to its toxic, explosive, and corrosive nature, inadvertent biological H2S production by sulfate reducing microorganisms (SRM) poses significant health and industrial operational risks. Anthropogenic sources are dominated by the oil industry where H2S in reservoir gases and fluids has an associated annual cost estimated at $90 billion globally. Our previous studies have identified perchlorate (ClO4-) as a selective and potent inhibitor of SRM in pure culture and complex microbial ecosystems. However, constant addition of inhibitors like perchlorate to natural ecosystems may result in a new adaptive selective pressure on SRM populations. With this in mind we investigated the ability of Desulfovibrio alaskensis G20, a model oil reservoir SRM, to adapt to perchlorate and develop a resistance. Serial transfers of three parallel cultures with increasing concentrations of perchlorate up to 100 mM were generated and compared to wild-type strains that were transferred for same number of generations in absence of perchlorate. Genome sequencing revealed that all three adapted strains had single non-synonymous single-nucleotide polymorphisms in the same gene, Dde_2265, the sulfate adenylytransferase (ATP sulfurylase (ATPS)) (EC 2.7.7.4). ATPS catalyzes the first committed step in sulfate reduction and is essential in all SRM. IC50s against growth for these evolved strains demonstrated a three-fold increased resistance to perchlorate compared to wild-type controls. These evolved strains also had 5x higher transcriptional abundance of Dde_2265 compared to the wild-type strain. Biochemical characterization of the purified ATPS enzyme from both wild-type and the evolved strain showed that the mutant ATPS from the evolved strain was resistant to perchlorate inhibition of ATP turnover with a KI for perchlorate that was 3x greater relative to the wild-type ATPS. These results demonstrate that a single-base pair mutation in ATPS can have a significant impact on developing

  11. 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.

  12. Developmental timing of sodium perchlorate exposure alters angiogenesis, thyroid follicle proliferation and sexual maturation in stickleback.

    Science.gov (United States)

    Furin, Christoff G; von Hippel, Frank A; Postlethwait, John H; Buck, C Loren; Cresko, William A; O'Hara, Todd M

    2015-08-01

    Perchlorate, a common aquatic contaminant, is well known to disrupt homeostasis of the hypothalamus-pituitary-thyroid axis. This study utilizes the threespine stickleback (Gasterosteus aculeatus) fish to determine if perchlorate exposure during certain windows of development has morphological effects on thyroid and gonads. Fish were moved from untreated water to perchlorate-contaminated water (30 and 100mg/L) starting at 0, 3, 7, 14, 21, 42, 154 and 305 days post fertilization until approximately one year old. A reciprocal treatment (fish in contaminated water switched to untreated water) was conducted on the same schedule. Perchlorate exposure increased angiogenesis and follicle proliferation in thyroid tissue, delayed gonadal maturity, and skewed sex ratios toward males; effects depended on concentration and timing of exposure. This study demonstrates that perchlorate exposure beginning during the first 42 days of development has profound effects on stickleback reproductive and thyroid tissues, and by implication can impact population dynamics. Long-term exposure studies that assess contaminant effects at various stages of development provide novel information to characterize risk to aquatic organisms, to facilitate management of resources, and to determine sensitive developmental windows for further study of underlying mechanisms. PMID:25865142

  13. 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.

  14. [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%.

  15. Effectiveness of removal of aqueous perchlorate by Cuprilig, a copper(II) derivative of Octolig.

    Science.gov (United States)

    Martin, Dean F; Kondis, Nicholas P; Alldredge, Robert L

    2009-02-01

    The present study describes the effectiveness of removal of perchlorate ion by Octolig a commercially available immobilized ligand, IMLIG, and by Cuprilig, the cupric ion derivative of this material. Octolig consists of polyethylenediamine moieties covalently bound to a high-surface area silica gel (CAS Registry number = 404899-06-5). Perchlorate in drinking water is a nuisance anion that escapes from firms that produce rocket fuel, batteries, and fireworks and becomes a contaminant of groundwater. It may also be a natural component of the environment. Perchlorate ion can interfere with thyroid function and may also cause birth defects. Perchlorate contamination of water supplies is serious because of the difficulty in removing it, especially in the western United States where a combination of drought and water shortages exacerbate the problems of supplying safe drinking water to an increasing population. In this study, aqueous solutions were passed over a chromatography column containing samples of Cuprilig. Test water contained 70 microg perchlorate/L and effluent was below detection level (water and in well water. Analyses were performed by a commercial laboratory. Mechanisms of interaction are proposed. PMID:19123099

  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. Purification of scintillation cocktails containing the alpha emitters americium and plutonium

    International Nuclear Information System (INIS)

    One efficient way of measuring alpha emitters is by the usage of liquid scintillation counting (LSC). A liquid sample is placed in a vial containing a scintillation cocktail. The alpha particles excite electrons in the surrounding liquid, and when they are de-excited photons are emitted. The photons are detected and the activity can be quantified. LSC has a high efficiency for alpha radiation and is therefore a fast and easy way for measuring alpha emitting samples. One drawback is that it does not differentiate very well between alpha energies; measurements of for example curium and plutonium simultaneously are impossible and demand other techniques. Another drawback is the production of a liquid alpha active waste. In Sweden alpha radioactive waste liquids with an activity over some kBq per waste container cannot be sent for final storage. If, however, the activity of the liquids could be reduced by precipitation of the actinides, it would be possible to send away the liquid samples to municipal incineration. In this work a method for a purification of alpha active scintillation cocktails was developed. The method was first tried on a lab scale, and then scaled up. Until today (March, 2013) more than 20 liters of scintillation liquids have successfully been purified from americium and plutonium at Chalmers University of Technology in Sweden. The four scintillation cocktails used were Emulsifier Safe®, Hionic-Fluor®, Ultima Gold AB® and Ultima Gold XR®. The scintillation cocktails could all be purified from americium with higher yield than 95%. The yield was kept when the liquids were mixed. Also plutonium could be precipitated with a yield over 95% in all cocktails except in Hionic-Fluor® (>55%). However, that liquid in particular could be purified (>95%) by mixing it with the three other cocktails. Up-scaling was performed to a batch size of 6-8 L of scintillation cocktail. In neither the americium nor the plutonium system, adverse effects of increasing the

  18. 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 ...

  19. Martian Chlorine Chemistry: A Study of Perchlorate on the Martian Surface, Evidence of an Ongoing Formation Mechanism and Implications of a Complex Chlorine Cycle

    Science.gov (United States)

    Carrier, Brandi L.

    2015-10-01

    The research presented herein addresses the detection of perchlorate on Mars, evidence of perchlorate in Mars meteorite EETA 79001, determination of the perchlorate parent salts at the Phoenix landing site, and the ongoing formation of perchlorate from chloride minerals as well as from other oxychlorine species. The detection of perchlorate in three samples by the Phoenix Wet Chemistry Laboratory and the implication of these results are discussed. The further detection of perchlorate in Mars meteorite EETA 79001 by ion chromatography and the determination of the parent salts of the perchlorate detected at the Phoenix landing site by electrochemical analyses and ion chromatography are detailed and the implications of the identity of the parent salts are discussed. The possible formation pathways for martian perchlorate are then explored and a possible mechanism for ongoing perchlorate formation on the martian surface is detailed. Perchlorate is shown to be formed upon exposure of chloride minerals, as well as of chlorite and chlorate salts, to current Mars relevant conditions including temperature, pressure, ultraviolet radiation and atmospheric composition. The implications of this ongoing perchlorate formation for the survival and detection of organics, the oxidizing nature of the soil, formation of liquid brines and recurring slope lineae are discussed. Further preliminary experiments have been conducted to investigate the effects of perchlorate formation on the survival and degradation of organic compounds.

  20. A thermodynamic study of actinide oxide targets/fuels for americium transmutation

    International Nuclear Information System (INIS)

    A thermodynamic study was performed on the systems Am-O, AmOx-MgO, AmOx-MgAl2O4, Pu-Mg-O and U-Mg-O. Both experimental work (X-ray analyses, oxygen potential measurements etc.) and calculations on the phase diagrams involved were made. The reaction between americium oxide and spinel is expected to form the compound AmAlO3. Isothermal sections have been calculated for AmOx-(MgO, Al2O3), Pu-Mg-O and U-Mg-O at 2000 K using the software package ''Thermo-Calc''. Thermodynamic equilibrium data were used to predict the behaviour of actinide oxides in a reactor. The implication of the results for the technological application is discussed, with emphasis on the effects of the high oxygen potential of AmO2 as compared to the conventional fuel, i.e. UO2. (author)

  1. The uptake of plutonium-239, 240, americium-241, strontium-90 into plants

    International Nuclear Information System (INIS)

    This report describes the results of measurements on the uptake of plutonium, americium, strontium-90 and caesium-137 into peas, beet, oats, sweet corn, tomatoes and vegetable marrow grown in tubs containing radioactively-contaminated silts. The silts had been taken from an area of West Cumbria commonly referred to as the Ravenglass estuary. The experiments are categorised as being carried out under non-standard conditions because of the manner in which the radioactivity came to be incorporated into the growth medium. The growth medium was representative of conditions which could arise when the estuarine silt moves inland under the influence of wind and tide and mixes with the adjacent farm land. The silt had been contaminated by radioactive effluents from the nuclear fuels reprocessing plant at Sellafield and this contamination had been brought about by natural means. (Auth.)

  2. Complex formation of trivalent americium with salicylic acid at very low concentrations

    International Nuclear Information System (INIS)

    For the first time, the complexation of americium(III) with salicylic acid was studied at trace metal concentrations using a 2.0 m Long Path Flow Cell for UV-vis spectroscopy. The detection limit of Am(III) in aqueous solution at pH 3.0 was found to be 5 x 10-9 M. Two Am(III)-salicylate complexes were formed at pH 5.0 in 0.1 M NaClO4, indicated by a clear red shift of the absorption maximum. The absorption spectra obtained from spectrophotometric titration were analyzed by means of factor analysis and complex stabilities were calculated to be log β110 = 2.56 ± 0.08 and log β120 = 3.93 ± 0.19. (author)

  3. Standard practice for The separation of americium from plutonium by ion exchange

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2001-01-01

    1.1 This practice describes the use of an ion exchange technique to separate plutonium from solutions containing low concentrations of americium prior to measurement of the 241Am by gamma counting. 1.2 This practice covers the removal of plutonium, but not all the other radioactive isotopes that may interfere in the determination of 241Am. 1.3 This practice can be used when 241Am is to be determined in samples in which the plutonium is in the form of metal, oxide, or other solid provided that the solid is appropriately sampled and dissolved (See Test Methods C758, C759, and C1168). 1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  4. Transportability Class of Americium in K Basin Sludge under Ambient and Hydrothermal Processing Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Delegard, Calvin H.; Schmitt, Bruce E.; Schmidt, Andrew J.

    2006-08-01

    This report establishes the technical bases for using a ''slow uptake'' instead of a ''moderate uptake'' transportability class for americium-241 (241Am) for the K Basin Sludge Treatment Project (STP) dose consequence analysis. Slow uptake classes are used for most uranium and plutonium oxides. A moderate uptake class has been used in prior STP analyses for 241Am based on the properties of separated 241Am and its associated oxide. However, when 241Am exists as an ingrown progeny (and as a small mass fraction) within plutonium mixtures, it is appropriate to assign transportability factors of the predominant plutonium mixtures (typically slow) to the Am241. It is argued that the transportability factor for 241Am in sludge likewise should be slow because it exists as a small mass fraction as the ingrown progeny within the uranium oxide in sludge. In this report, the transportability class assignment for 241Am is underpinned with radiochemical characterization data on K Basin sludge and with studies conducted with other irradiated fuel exposed to elevated temperatures and conditions similar to the STP. Key findings and conclusions from evaluation of the characterization data and published literature are summarized here. Plutonium and 241Am make up very small fractions of the uranium within the K Basin sludge matrix. Plutonium is present at about 1 atom per 500 atoms of uranium and 241Am at about 1 atom per 19000 of uranium. Plutonium and americium are found to remain with uranium in the solid phase in all of the {approx}60 samples taken and analyzed from various sources of K Basin sludge. The uranium-specific concentrations of plutonium and americium also remain approximately constant over a uranium concentration range (in the dry sludge solids) from 0.2 to 94 wt%, a factor of {approx}460. This invariability demonstrates that 241Am does not partition from the uranium or plutonium fraction for any characterized sludge matrix. Most

  5. 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

    2015-07-01

    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.

  6. 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.

  7. 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.

  8. 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.

  9. A low cost igniter utilizing an SCB and titanium sub-hydride potassium perchlorate pyrotechnic

    Science.gov (United States)

    Bickes, R. W., Jr.; Grubelich, M. C.; Hartman, J. K.; McCampbell, C. B.; Churchill, J. K.

    1994-01-01

    A conventional NSI (NASA Standard Initiator) normally employs a hot-wire ignition element to ignite ZPP (zirconium potassium perchlorate). With minor modifications to the interior of a header similar to an NSI device to accommodate an SCB (semiconductor bridge), a low cost initiator was obtained. In addition, the ZPP was replaced with THKP (titanium sub-hydride potassium perchlorate) to obtain increased overall gas production and reduced static-charge sensitivity. This paper reports on the all-fire and no-fire levels obtained and on a dual mix device that uses THKP as the igniter mix and a thermite as the output mix.

  10. 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.

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

    Science.gov (United States)

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

    2000-01-01

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

  12. 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

  13. 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.

  14. 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.

  15. (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.

  16. 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...

  17. 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...

  18. 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.

  19. 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 ...

  20. Preparation and Analysis of Solid Solutions in the Potassium Perchlorate-Permanganate System.

    Science.gov (United States)

    Johnson, Garrett K.

    1979-01-01

    Describes an experiment, designed for and tested in an advanced inorganic laboratory methods course for college seniors and graduate students, that prepares and analyzes several samples in the nearly ideal potassium perchlorate-permanganate solid solution series. The results are accounted for by a theoretical treatment based upon aqueous…

  1. 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…

  2. Reactive Transport Model of Sulfur Cycling as Impacted by Perchlorate and Nitrate Treatments.

    Science.gov (United States)

    Cheng, Yiwei; Hubbard, Christopher G; Li, Li; Bouskill, Nicholas; Molins, Sergi; Zheng, Liange; Sonnenthal, Eric; Conrad, Mark E; Engelbrektson, Anna; Coates, John D; Ajo-Franklin, Jonathan B

    2016-07-01

    Microbial souring in oil reservoirs produces toxic, corrosive hydrogen sulfide through microbial sulfate reduction, often accompanying (sea)water flooding during secondary oil recovery. With data from column experiments as constraints, we developed the first reactive-transport model of a new candidate inhibitor, perchlorate, and compared it with the commonly used inhibitor, nitrate. Our model provided a good fit to the data, which suggest that perchlorate is more effective than nitrate on a per mole of inhibitor basis. Critically, we used our model to gain insight into the underlying competing mechanisms controlling the action of each inhibitor. This analysis suggested that competition by heterotrophic perchlorate reducers and direct inhibition by nitrite produced from heterotrophic nitrate reduction were the most important mechanisms for the perchlorate and nitrate treatments, respectively, in the modeled column experiments. This work demonstrates modeling to be a powerful tool for increasing and testing our understanding of reservoir-souring generation, prevention, and remediation processes, allowing us to incorporate insights derived from laboratory experiments into a framework that can potentially be used to assess risk and design optimal treatment schemes. PMID:27267666

  3. DISTRIBUTION OF PERCHLORATE IN SAMPLES OF SODIUM NITRATE (CHILE SALTPETER) FERTILIZER DERIVED FROM NATURAL CALICHE

    Science.gov (United States)

    Two lots of sodium nitrate fertilizer derived from Chilean caliche were analyzed to determine the distribution of perchlorate throughout the material. Although our samples represent a limited amount, we found that distribution was essentially homogeneous in any 100-g portion. Whe...

  4. 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.

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

    Science.gov (United States)

    Hatzinger, P.B.; Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Heraty, L.J.; Borden, R.C.

    2009-01-01

    Environmental context. Perchlorate (ClO4-) and nitrate (NO3-) are common co-contaminants in groundwater, with both natural and anthropogenic sources. Each of these compounds is biodegradable, so in situ enhanced bioremediation is one alternative for treating them in groundwater. Because bacteria typically fractionate isotopes during biodegradation, stable isotope analysis is increasingly used to distinguish this process from transport or mixing-related decreases in contaminant concentrations. However, for this technique to be useful in the field to monitor bioremediation progress, isotope fractionation must be quantified under relevant environmental conditions. In the present study, we quantify the apparent in situ fractionation effects for stable isotopes in ClO4- (Cl and O) and NO3- (N and O) resulting from biodegradation in an aquifer. Abstract. 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 (18O/37Cl) 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 (18O/15N), which is within the range of values

  6. The behaviour under irradiation of molybdenum matrix for inert matrix fuel containing americium oxide (CerMet concept)

    Science.gov (United States)

    D'Agata, E.; Knol, S.; Fedorov, A. V.; Fernandez, A.; Somers, J.; Klaassen, F.

    2015-10-01

    Americium is a strong contributor to the long term radiotoxicity of high activity nuclear waste. Transmutation by irradiation in nuclear reactors or Accelerator Driven System (ADS, subcritical reactors dedicated to transmutation) of long-lived nuclides like 241Am is therefore an option for the reduction of radiotoxicity of waste packages to be stored in a repository. In order to safely burn americium in a fast reactor or ADS, it must be incorporated in a matrix that could be metallic (CerMet target) or ceramic (CerCer target). One of the most promising matrix to incorporate Am is molybdenum. In order to address the issues (swelling, stability under irradiation, gas retention and release) of using Mo as matrix to transmute Am, two irradiation experiments have been conducted recently at the High Flux Reactor (HFR) in Petten (The Netherland) namely HELIOS and BODEX. The BODEX experiment is a separate effect test, where the molybdenum behaviour is studied without the presence of fission products using 10B to "produce" helium, the HELIOS experiment included a more representative fuel target with the presence of Am and fission product. This paper covers the results of Post Irradiation Examination (PIE) of the two irradiation experiments mentioned above where molybdenum behaviour has been deeply investigated as possible matrix to transmute americium (CerMet fuel target). The behaviour of molybdenum looks satisfying at operating temperature but at high temperature (above 1000 °C) more investigation should be performed.

  7. Consideration of the effect of lymph-node deposition upon the measurement of plutonium and americium in the lungs

    International Nuclear Information System (INIS)

    Measurement of an inhaled radionuclide by external photon counting includes quantities which may be contained in lymph nodes, as well as quantities in the lungs. An overestimate of the lung burden can result, if a portion of the radionuclide were present in the lymph nodes. This problem is analyzed with respect to the measurement of inhaled plutonium containing plutonium-241 and americium-241, when americium-241 has been used as a tracer for the plutonium. Equations are derived which yield the amounts of americium and of plutonium in the lungs and in the lymph nodes as a function of time after exposure and for various translocation and retention parameters. Count histories (count profiles) of actual exposure cases are compared with calculated count profiles in order to gain insight into possible values of the translocation and retention parameters. Comparison is also made with calculated count profiles using values of translocation and retention parameters recommended by the International Commission on Radiological Protection (ICRP) for use with the Task Group Lung Model. The magnitude of the possible overestimate (error factor) was calculated for combinations o

  8. HELIOS: the new design of the irradiation of U-free fuels for americium transmutation

    Energy Technology Data Exchange (ETDEWEB)

    D' Agata, E. [European Commission, Joint Research Centre, Institute for Energy, P.O. Box 2, 1755 ZG Petten (Netherlands); Klaassen, F.; Sciolla, C. [Nuclear Research and Consultancy Group, Dept. Life Cycle and Innovations, P.O. Box 25 1755 ZG Petten (Netherlands); Fernandez-Carretero, A. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, 76125 Karlsruhe (Germany); Bonnerot, J.M. [Commissariat a l' Energie Atomique, DEC/SESC/LC2I CEA-Cadarache, 13108 St. Paul lez Durance Cedex (France)

    2009-06-15

    Americium is one of the radioactive elements that mostly contribute to the radiotoxicity of the nuclear spent fuel. Transmutation of long-lived nuclides like Americium is an option for the reduction of the mass, the radiotoxicity and the decay heat of nuclear waste. The HELIOS irradiation experiment is the last evolution in a series of experiments on americium transmutation. The previous experiments, EFTTRA-T4 and T4bis, have shown that the release or trapping of helium is the key issue for the design of such kind of target. In fact, the production of helium, which is characteristic of {sup 241}Am transmutation, is quite significant. The experiment is carried out in the framework of the 4-year project EUROTRANS of the EURATOM 6. Framework Programme (FP6). Therefore, the main objective of the HELIOS experiment is to study the in-pile behaviour of U-free fuels such as CerCer (Pu, Am, Zr)O{sub 2} and Am{sub 2}Zr{sub 2}O{sub 7}+MgO or CerMet (Pu, Am)O{sub 2}+Mo in order to gain knowledge on the role of the fuel microstructure and of the temperature on the gas release and on the fuel swelling. The experiment was planned to be conducted in the HFR (High Flux Reactor) in Petten (The Netherlands) starting the first quarter of 2007. Because of the innovative aspects of the fuel, the fabrication has had some delays as well as the final safety analyses of the original design showed some unexpected deviation. Besides, the HFR reactor has been unavailable since August 2008. Due to the reasons described above, the experiment has been postponed. HELIOS should start in the first quarter of 2009 and will last 300 full power days. The paper will cover the description of the new design of the irradiation experiment HELIOS. The experiment has been split in two parts (HELIOS1 and HELIOS2) which will be irradiated together. Moreover, due to the high temperature achieved in cladding and to the high amount of helium produced during transmutation the experiment previously designed for a

  9. 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.

  10. 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

  11. Americium-based oxides: Dense pellet fabrication from co-converted oxalates

    Energy Technology Data Exchange (ETDEWEB)

    Horlait, Denis; Lebreton, Florent [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze (France); Gauthé, Aurélie [CEA, DEN, DRCP/SERA/LCAR, 30207 Bagnols-sur-Cèze (France); Caisso, Marie [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze (France); Arab-Chapelet, Bénédicte; Picart, Sébastien [CEA, DEN, DRCP/SERA/LCAR, 30207 Bagnols-sur-Cèze (France); Delahaye, Thibaud, E-mail: thibaud.delahaye@cea.fr [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze (France)

    2014-01-15

    Mixed oxides are used as nuclear fuels and are notably envisaged for future fuel cycles including plutonium and minor actinide recycling. In this context, processes are being developed for the fabrication of uranium–americium mixed-oxide compounds for transmutation. The purpose of these processes is not only the compliance with fuel specifications in terms of density and homogeneity, but also the simplification of the process for its industrialization as well as lowering dust generation. In this paper, the use of a U{sub 0.85}Am{sub 0.15}O{sub 2±δ} powder synthesized by oxalate co-conversion as a precursor for dense fuel fabrications is assessed. This study notably focuses on sintering, which yielded pellets up to 96% of the theoretical density, taking advantage of the high reactivity and homogeneity of the powder. As-obtained pellets were further characterized to be compared to those obtained via processes based on the UMACS (Uranium Minor Actinide Conventional Sintering) process. This comparison highlights several advantages of co-converted powder as a precursor for simplified processes that generate little dust.

  12. Study of biosorbents application on the treatment of radioactive liquid wastes with americium-241

    International Nuclear Information System (INIS)

    The use of nuclear energy for many different purposes has been intensified and highlighted by the benefits that it provides. Medical diagnosis and therapy, agriculture, industry and electricity generation are examples of its application. However, nuclear energy generates radioactive wastes that require suitable treatment ensuring life and environmental safety. Biosorption and bioaccumulation represent an emergent alternative for the treatment of radioactive liquid wastes, providing volume reduction and physical state change. This work aimed to study biosorbents for the treatment of radioactive liquid wastes contaminated with americium-241 in order to reduce the volume and change the physical state from liquid to solid. The biosorbents evaluated were Saccharomyces cerevisiae immobilized in calcium alginate beads, inactivated and free cells of Saccharomyces cerevisiae, calcium alginate beads, Bacillus subtilis, Cupriavidus metallidurans and Ochrobactrum anthropi. The results were quite satisfactory, achieving 100% in some cases. The technique presented in this work may be useful and viable for implementing at the Waste Management Laboratory of IPEN - CNEN/SP in short term, since it is an easy and low cost method. (author)

  13. Mutual separation of americium(III) and europium(III) using glycolamic acid and thioglycolamic acid

    Energy Technology Data Exchange (ETDEWEB)

    Suneesh, A.S.; Venkatesan, K.A.; Syamala, K.V.; Antony, M.P.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Fuel Chemistry Div.

    2012-07-01

    The extractants, bis(2-ethylhexyl)diglycolamicacid (HDEHDGA) and bis(2-ethylhexy)thiodiglycolamic acid (HDEHSDGA) were synthesized and characterized by {sup 1}H and {sup 13}C NMR, mass and IR spectroscopy. The extraction behaviour of {sup (152+154})Eu(III) and {sup 241}Am(III) from nitric acid medium by a solution of HDEHDGA (or HDEHSDGA) in n-dodecane (n-DD) was studied for the mutual separation of actinides and lanthanides. The effect of various parameters such as the pH, concentrations of HDEHDGA, HDEHSDGA, sodium nitrate, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) and diethylenetriaminepentaacetic acid (DTPA) on the separation factor (SF) of americium(III) over europium(III) and vice versa was studied, and the conditions needed for the preferential separation were optimised. The results show that HDEHDGA exhibits higher extraction for {sup (152+154)}Eu(III) and HDEHSDGA shows the superior selectivity for {sup 241}Am(III). (orig.)

  14. Determination of plutonium americium and curium in soil samples by solvent extraction with trioctylphosphine oxide

    International Nuclear Information System (INIS)

    A method of Pu, Am and Cm determination in soil samples, which was developed for analyzing samples from territories subjected to radioactive contamination as a result of the Chernobyl accident is described. After preliminary treatment the samples were leached by solution of 7 mol/l HNO23+0.3 mol/l KBrO3 during heating. Pu was isolated by extraction with 0.05 mol TOPO from 7 mol/l HNO3. 144Ce and partially remaining in water phase isotopes of Zr, U and Th were isolated in an extraction-chromatographic column with TOPO and PbO2. Then Am and Cm were extracted by 0.2 mol/l TOPO from solution 1 mol/l HLact+0.07 mol/l DTPA+1 mol/l Al(NO3)3. Alpha-activity of both extracted products was determined in liquid scintillation counter. Chemical yield of plutonium counted to 85±10%, that of americium and curium -75±10%. 17 refs

  15. Development and Testing of an Americium/Lanthanide Separation Flowsheet Using Sodium Bismuthate

    Energy Technology Data Exchange (ETDEWEB)

    Jack Law; Bruce Mincher; Troy Garn; Mitchell Greenhalgh; Nicholas Schmitt; Veronica Rutledge

    2014-04-01

    The separation of Am from the lanthanides and curium is a key step in proposed advanced fuel cycle scenarios. The partitioning and transmutation of Am is desirable to minimize the long-term heat load of material interred in a future high-level waste repository. A separation process amenable to process scale-up remains elusive. Given only subtle chemistry differences within and between the ions of the trivalent actinide and lanthanide series this separation is challenging ; however, higher oxidation states of americium can be prepared using sodium bismuthate and separated via solvent extraction using diamylamylphosphonate (DAAP) extraction. Among the other trivalent metals only Ce is also oxidized and extracted. Due to the long-term instability of Am(VI) , the loaded organic phase is readily selectively stripped to partition the actinide to a new acidic aqueous phase. Batch extraction distribution ratio measurements were used to design a flowsheet to accomplish this separation. Additionally, crossflow filtration was investigated as a method to filter the bismuthate solids from the feed solution prior to extraction. Results of the filtration studies, flowsheet development work and flowsheet performance testing using a centrifugal contactor are detailed.

  16. Speciation and bioavailability of Americium-241 in the fresh water environment

    International Nuclear Information System (INIS)

    Due to its anthropogenic origin, the transuranic americium 241 confronts physiologists with the intriguing question, which mechanisms are involved in the incorporation or elimination of such artificial elements in biological cycles. The investigations on the speciation and bioavailability of 241Am in the freshwater environment aim to establish a relation between the behavior of 241Am in freshwater ecosystems and its availability for biota. In the limnic environment, most often characterized by a high organic load and a low conductivity, the effect of complexation of 241Am with humic acids and competition with trivalent cations such as A1 and Fe, were proven to be significant on the speciation of 241Am. Based on the registration of the 241Am uptake by a large number of freshwater organisms, the crayfish Astacus leptodactylus Eschscholtz was chosen to study the whole-body uptake of 241Am, its corresponding organ distribution and its retention in the animal. The share of external fixation and ingestion in the global uptake, and the effect of speciation on it, were studied more carefully. Other aspects in this physiological part were: the kinetics of 241Am in the hemolymph and the hepatopancreas, and its subcellular distribution in the digestive gland. Finally, by comparing the physiology of 241Am with some other metals (240Pu, 64Cu, 198Au) with analogous or contradictional properties, we tried to find out whether the behavior of 241Am in organisms can be explained from its chemical characteristics

  17. Solution speciation of plutonium and Americium at an Australian legacy radioactive waste disposal site.

    Science.gov (United States)

    Ikeda-Ohno, Atsushi; Harrison, Jennifer J; Thiruvoth, Sangeeth; Wilsher, Kerry; Wong, Henri K Y; Johansen, Mathew P; Waite, T David; Payne, Timothy E

    2014-09-01

    During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed. PMID:25126837

  18. Solution speciation of plutonium and Americium at an Australian legacy radioactive waste disposal site.

    Science.gov (United States)

    Ikeda-Ohno, Atsushi; Harrison, Jennifer J; Thiruvoth, Sangeeth; Wilsher, Kerry; Wong, Henri K Y; Johansen, Mathew P; Waite, T David; Payne, Timothy E

    2014-09-01

    During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed.

  19. Reaction of Elemol with Acetic acid –Perchloric acid: Characterization of a novel oxide and (+)-β-cyperone

    Digital Repository Service at National Institute of Oceanography (India)

    Wahidullah, S.; Govenkar, M.B.; Paknikar, S.K.

    The minor unidentified compounds of acetic acid- perchloric acid dehydration of elemol (1) have been fully characterized. The structure and relative stereochemistry as shown in (2) of the less polar fragrant compound named as elemoxide was deduced...

  20. 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.

  1. 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

  2. Perchlorate content of plant foliage reflects a wide range of species-dependent accumulation but not ozone-induced biosynthesis

    International Nuclear Information System (INIS)

    Perchlorate (ClO4−) interferes with uptake of iodide in humans. Emission inventories do not explain observed distributions. Ozone (O3) is implicated in the natural origin of ClO4−, and has increased since pre-industrial times. O3 produces ClO4−in vitro from Cl−, and plant tissues contain Cl− and redox reactions. We hypothesize that O3 exposure may induce plant synthesis of ClO4−. We exposed contrasting crop species to environmentally relevant O3 concentrations. In the absence of O3 exposure, species exhibited a large range of ClO4− accumulation but there was no relationship between leaf ClO4− and O3, whether expressed as exposure or cumulative flux (dose). Older, senescing leaves accumulated more ClO4− than younger leaves. O3 exposed vegetation is not a source of environmental ClO4−. There was evidence of enhanced ClO4− content in the soil surface at the highest O3 exposure, which could be a significant contributor to environmental ClO4−. -- Highlights: • Exposure to ozone in crop species does not induce accumulation nor biosynthesis of perchlorate. • Older leaves accumulate more perchlorate than younger leaves. • Soil surface may accumulate perchlorate following exposure to ozone. • Species differ greatly in accumulation of perchlorate from the rhizosphere, independent of ozone. • Ozone exposed vegetation is not a candidate source of environmental perchlorate. -- Exposure of crop species to ozone did not lead to biosynthesis or greater accumulation of foliar perchlorate. Older leaves accumulated more perchlorate than younger leaves

  3. 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.

  4. A Reservoir of Natural Perchlorate in Unsaturated Zones of Arid and Semi-Arid Regions, Southwestern USA

    Science.gov (United States)

    Rao, B. A.; Stonestrom, D. A.; Anderson, T. A.; Orris, G. J.; Rajagapolan, S.; Sandvig, R. M.; Scanlon, B. R.; Walvoord, M. A.; Jackson, W.

    2006-12-01

    Natural perchlorate (ClO4-) is generally present in unsaturated zones of steppe-to-desert regions of the arid and semi-arid southwestern United States. The perchlorate is associated with atmospherically deposited chloride that has accumulated throughout the Holocene. To assess this natural reservoir, we analyzed unsaturated-zone profiles from ten sites across Nevada, New Mexico, Texas, and Utah for perchlorate and other anions. The sampled sites represent a wide range of precipitation (0.1 0.5 m yr-1), dominant vegetation, soil type, underlying geology, and include five distinct ecological regions: Chihuahuan, Mojave, and southern Great Basin deserts; Arizona-New Mexico semi-desert; and Texas High Plains dry steppe. Concentrations of perchlorate correlated closely with chloride and bromide. The perchlorate reservoir (up to 1 kg ha-1) is sufficiently large to impact groundwater when natural recharge during pluvial periods or induced recharge after conversion to agriculture flushes accumulated salts from the unsaturated zone. This little explored source can explain perchlorate in milk and other agricultural products far from anthropogenic contamination, and should be considered when evaluating overall exposure risk.

  5. 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.

  6. Secondary transformation mechanism of paramagnetic centers in irradiated alkali metal perchlorates

    International Nuclear Information System (INIS)

    The EPR method has been used to study thermal transformations of paramagnetic centres (PC) in X-ray irradiated potassium, rubidium and cesium perchlorates. Experimental data make it possible to suppose that diffusion coefficient of O- ion a rather high and this ion is freely diffused already at 262 K. Colliding with [MeClO4]+ centres it is transformed in a molecule of oxygen. Another part of O- is transformed in stable ozonide-ion at 300 K. About room temperature hole centres dissociate with formation of ClO2 radical. It is supposed that part of electron and hole centres is not stabilized but at 77 K it is transformed in stable radiolysis products. This process most effective proceeds in dislocations and on the surface of microcrystals. The suggested model of thermal transformations of primary PC in irradiated perchlorates of alkali metals explains formation of all the finite ion and paramagnetic radiolysis products

  7. 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.

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

    Science.gov (United States)

    Sutter, B.; Heil, E.; Morris, R. V.; Archer, P. D.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Freissinet C.; Glavin, D. P.; McAdam, A. C.; Mahaffy, P.; Martin-Torres, F. Javier; Navarro-Gonzalez, R.; Paz-Zorzano, Maria; Stern, J. C.; McKay, C. P.

    2015-01-01

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

  9. 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.

  10. Sweet and Sour: Attenuating Sulfidogenesis in an Advective Flow Column System with Perchlorate or Nitrate Treatment

    Science.gov (United States)

    Engelbrektson, A. L.; Hubbard, C. G.; Piceno, Y.; Boussina, A.; Jin, Y.; Dubinsky, E. A.; Tom, L.; Hu, P.; Conrad, M. E.; Anderson, G. L.; Coates, J. D.

    2013-12-01

    Hydrogen sulfide (H2S) biogenesis in oil reservoirs is a primary cause of souring and of associated costs in reservoir and pipeline maintenance. In addition to the corrosive effects of the H2S itself, abiotic and biological oxidation also generates sulfuric acid, further degrading metallic surfaces. Amending these environments with perchlorate (ClO4-) resolves these problems by inhibition of biological sulfate reduction and re-oxidation of H2S to elemental sulfur by dissimilatory (per)chlorate reducing bacteria (DPRB). Triplicate flow through columns packed with San Francisco bay sediment were flushed with bay water ([SO4=] = 25-30 mM) containing yeast extract with 50 mM inhibitor concentrations (NO3-or ClO4-) decreasing to 25 mM and finally 12.5 mM. Influent and effluent geochemistry was monitored and DNA was prepared from the sediment bed for microbial community analysis. Souring was reversed by both treatments (at 50 mM) compared to the control columns that had no ion addition. Nitrate began to re-sour when treatment concentration was decreased to 25 mM but treatment had to be decreased to 12.5 mM before the perchlorate treated columns began to re-sour. However, the treated columns re-soured to a lesser extent than the control columns. Phylochip microbial community analyses indicated microbial community shifts and phylogenetic clustering by treatment. Isotopic analysis of sulfate showed trends that broadly agreed with the geochemistry but also suggested further sulfur cycling was occurring. This study indicates that perchlorate shows great promise as an inhibitor of sulfidogenesis in natural communities and provides insight into which organisms are involved in this process.

  11. Electrochromic iridium oxide films: Compatibility with propionic acid, potassium hydroxide, and lithium perchlorate in propylene carbonate

    OpenAIRE

    Wen, Rui-Tao; Niklasson, Gunnar A.; Granqvist, Claes G.

    2013-01-01

    Porous thin films of It oxide were prepared by reactive dc magnetron sputtering onto unheated substrates. The crystallite size was similar to 5 nm, and a small amount of unoxidized Ir was present. The electrochromic performance was studied by optical transmittance measurements and cyclic voltammetry applied to films in aqueous and non-aqueous electrolytes, specifically being 1 M propionic acid, 1 M potassium hydroxide (KOH), and 1 M lithium perchlorate in propylene carbonate (Li-PC). Cyclic v...

  12. Disproportionation of plutonium IV in concentrated solutions of plutonium in perchloric acid

    International Nuclear Information System (INIS)

    This work was carried out to study the dependence of the PuIV disproportionation reaction in perchloric acid solution on the plutonium concentration up to 20 g/l. Solutions of such high plutonium concentration have not previously been studied. It was found that the bimolecular rate constant and the equilibrium constant of the disproportionation reaction were not appreciably different from their values at lower concentrations. (author)

  13. 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.

  14. The use of chlorate, nitrate, and perchlorate to promote crude oil mineralization in salt marsh sediments.

    Science.gov (United States)

    Brundrett, Maeghan; Horita, Juske; Anderson, Todd; Pardue, John; Reible, Danny; Jackson, W Andrew

    2015-10-01

    Due to the high volume of crude oil released by the Deepwater Horizon oil spill, the salt marshes along the gulf coast were contaminated with crude oil. Biodegradation of crude oil in salt marshes is primarily limited by oxygen availability due to the high organic carbon content of the soil, high flux rate of S(2-), and saturated conditions. Chlorate, nitrate, and perchlorate were evaluated for use as electron acceptors in comparison to oxygen by comparing oil transformation and mineralization in mesocosms consisting of oiled salt marsh sediment from an area impacted by the BP Horizon oil spill. Mineralization rates were determined by measuring CO2 production and δ (13)C of the produced CO2 and compared to transformation evaluated by measuring the alkane/hopane ratios over a 4-month period. Total alkane/hopane ratios decreased (~55-70 %) for all treatments in the following relative order: aerated ≈ chlorate > nitrate > perchlorate. Total CO2 produced was similar between treatments ranging from 550-700 mg CO2-C. The δ (13)C-CO2 values generally ranged between the indigenous carbon and oil values (-17 and -27‰, respectively). Oil mineralization was greatest for the aerated treatments and least for the perchlorate amended. Our results indicate that chlorate has a similar potential as oxygen to support oil mineralization in contaminated salt marshes, but nitrate and perchlorate were less effective. The use of chlorate as a means to promote oil mineralization in situ may be a promising means to remediate contaminated salt marshes while preventing unwanted secondary impacts related to nutrient management as in the case of nitrate amendments. PMID:25854211

  15. 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). PMID:27248576

  16. Temporal and spatial variation of perchlorate in streambed sediments: results from in-situ dialysis samplers

    International Nuclear Information System (INIS)

    The fate of perchlorate (ClO4-) in streambed sediments is becoming a concern due to the increasing number of groundwater and surface water contamination sites in the United States. Dialysis samplers were deployed at three sites over a period of 1 year to determine the vertical distribution of ClO4-in sediment pore water. Results indicated that the spatial and temporal ClO4-penetration into sediments could be affected by numerous factors, such as temperature, microbial degradation, ClO4-surface water concentration, and sediment physico-geological properties. In general, maximum ClO4-penetration into sediments at the studied sites was 30 cm below the sediment-water surface. The vertical sequential depletion of electron acceptors in sediments suggested that microbial reduction was responsible for ClO4-depletion in stream sediments. Biodegradation of ClO4-occurred over a seasonally variable active depth zone of 1-10 cm. Results implied that there was a rapid natural attenuation potential of perchlorate in saturated near-surface sediments. -Perchlorate may be rapidly attenuated in saturated near-surface sediments

  17. A study of plutonium and americium concentrations in seaspray on the southern Scottish coast

    International Nuclear Information System (INIS)

    Seaspray and seawater have been collected from the southern Scottish coast and, for comparison, Cumbria in northwest England during 1989 and 1991. The occurrence of sea-to-land transfer of the actinides plutonium and americium in seaspray was observed on these coasts using muslin screens (a semi-quantitative technique most efficient for collecting large spray droplets) and high volume conventional air samplers. The actinides and fine particulate in the spray were present in relatively higher concentrations than measured in the adjacent seawater, i.e. the spray was enriched in particulate actinides. The net efficiency of the muslim screens in collecting airborne plutonium isotopes and 241Am generally appeared to be about 20%. A review of earlier published concentrations of 239+240Pu and 241Am measured in aerosol and deposition for over a year several tens of metres inland was carried out. This suggested that airborne activities are up to a factor of 5 times higher in Cumbria than southern Scotland. However, neither the new data collected in 1989 and 1991 nor this older data suggests any enhancement of seaspray actinide enrichment in southern Scotland compared to Cumbria. This finding contrasts with earlier, more limited, comparisons that have been carried out which suggested such a difference. There is clear evidence of considerable localised spatial and temporal variability in aerosol actinide enrichment over the beaches in both areas. Enrichments varies between 20 and 500 relative to the adjacent surf zone waters. However, the average enrichment in spray based on the continuous measurements made further inland is likely to be at the lower end of this range. (author)

  18. Biosorption of Americium-242 by saccharomyces cerevisiae: preliminary evaluation and mechanism

    International Nuclear Information System (INIS)

    As an important radioisotope in nuclear industry and other fields, americium-241 is one of the most serious contamination concerns duo to its high radiation toxicity and long half-life. In this experiment, the biosorption of 241Am from solution by a fungus, Saccharomyces cerevisiae (S. cerevisiae), and the effects of various experimental conditions on the biosorption and the mechanism were explored. The preliminary results showed that S. cerevisiae is a very efficient biosorbent. An average of more than 99% of the total 241Am could be removed by S. cerevisiae of 2.1g/L (dry weight) from 241Am solutions of 2.22MBq/L -555 MBq/L (Co). The adsorption equilibrium was achieved within 1 hour and the optimum pH ranged 1-3. The culture times of more than 16 hours were suitable and the efficient adsorption of 241Am by the S. cerevisiae could be noted. The biosorption of 241Am by the decomposed cell wall, protoplasm or cell membrane of S. cerevisiae was same efficient as by the intact fungus, but the some components of S. cerevisiae, such as protein and acylation group had obvious effect on adsorption. When the concentrations of coexistent Eu3+, Nd3+ were 100 times more than that of 241Am, the adsorption rates would drop to 65%. However, most of the investigated acidic ions have no significant influence on the 241Am adsorption but minute change of pH value, while the saturated EDTA can strong inhibit the biosorption of 241Am.. (authors)

  19. Transport of plutonium, americium, and curium from soils into plants by roots

    International Nuclear Information System (INIS)

    For assessing the dose from radionuclides in agricultural products by ingestion it is necessary to know the soil to plant transfer factors. The literature was entirely investigated, in order to judge the size of the soil to plant transfer factors. In total, 92 publications - from 1948 to 1978 -have been evaluated. As result, transfer factors from 10-9 to 10-3 have been found for Plutonium, and from 10-6 to 1 for Americium. For Curium only few data are available in literature. The considerable variation of the measured transfer factors is based on the dependence of these transfer factors from the ion exchange capacity of soils, from the amount of organic materials, from the pH-value, and from the mode of contamination. There are, in any case, contradictory data, although there has been detected a dependence of the transfer factors from these parameters. Chelating agenst increase the transfer factors to approximately 1300. As well, fertilizers have an influence on the size of the transfer factors - however, the relationships have been scarcely investigated. The distribution of actinides within the individual parts of plants has been investigated. The highest concentrations are in the roots; in the plant parts above ground the concentration of actinides decreases considerably. The most inferior transfer factors were measured for the respective seed or fruits. The soil to plant transfer factors of actinides are more dependend on the age of the plants within one growing period. At the beginning of the period, the transfer factor is considerably higher than at the end of this period. With respect to plants with a growing period of several years, correlations are unknown. (orig.)

  20. The treatment of liquid radioactive waste containing Americium by using a cation exchange method

    International Nuclear Information System (INIS)

    A research in the treatment of a liquid radioactive waste containing americium has been done. The liquid radioactive waste used in this research was standard solution of U dan Ce with the initial activity of 100 ppm. The experimental investigation is aimed at a study of the effects of the waste pH, the column dimension of IR-120 cation exchanger which is expressed as L/D, the flow rate of a liquid waste and the influence of thiocyanate as a complex agent against the efficiency of a decontamination for uranium and cerium element. The experiment was done by passing downward the feed of uranium and cerium solution into an IR-120 type of cation exchanger with the L/D of 11.37. From the experimental parameters done in this research where the influence of waste pH was varied from 3 - 8, the geometric column (L/D) 11.37, the liquid flow rate was from 2.5 - 10 ml/m and the thiocyanate concentration was between 100 ppm-500 ppm can be concluded that the optimum operational condition for the ion exchange achieved were the waste pH for uranium = 4 and the waste pH for cerium = 6, the flow rate = 2.5 ml/men. From the given maximum value of DF for uranium = 24 (DE = 95.83%) and of DF for cerium = 40 (DE = 97.5%), it can also be concluded that this investigation is to be continued in order that the greater value of DF/DE can be achieved

  1. 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.

  2. Use of radioisotopes in the study of tetracycline analytical application. Extraction of compounds formed between tetracycline and neptunium and americium elements

    International Nuclear Information System (INIS)

    The behavior of tetracycline as complexing agent, in solvent extraction studies of neptunium and americium, using benzyl alcohol as the organic phase, is presented. By using radioactive tracers of 239Np and 241Am the extraction percent of these elements were determined as a function of pH in the absence and in the presence of several masking agents. The influence of shaking time and the use of different types of supporting eletrolytes upon the extraction behavior was also studied. The extraction curves obtained using EDTA as masking agent show that tetracycline can be used for neptunium and americium separation. In this condition neptunium is extracted into the organic phase and americium remains in the aqueous phase. (Author)

  3. Effect of a long-term release of plutonium and americium into an estuarine and coastal sea ecosystem

    International Nuclear Information System (INIS)

    This paper discusses the general problem of speciation of plutonium and americium in aquatic ecosystems and the implications relative to their fate in those systems. The following conclusions were reached: several oxidation states of plutonium coexist in the natural environment; the effect of environmental changes such as pH and Esub(h) values and complexes are probably the cause of these various oxidation states; a clearer definition of the 'concentration factor' should be given in view of the important role the sediments play in supplying plutonium for transfer through the food web. (author)

  4. EFFECT OF COMPOSITION OF SELECTED GROUNDWATERS FROM THE BASIN AND RANGE PROVINCE ON PLUTONIUM, NEPTUNIUM, AND AMERICIUM SPECIATION.

    Science.gov (United States)

    Rees, Terry F.; Cleveland, Jess M.; Nash, Kenneth L.

    1984-01-01

    The speciation of plutonium, neptunium, and americium was determined in groundwaters from four sources in the Basin and Range Province: the lower carbonate aquifer, Nevada Test Site (NTS) (Crystal Pool); alluvial fill, Frenchman Flat, NTS (well 5C); Hualapai Valley, Arizona (Red Lake south well); and Tularosa Basin, New Mexico (Rentfrow well). The results were interpreted to indicate that plutonium and, to a lesser extent, neptunium are least soluble in reducing groundwaters containing a large concentration of sulfate ion and a small concentration of strongly complexing anions. The results further emphasize the desirability of including studies such as this among the other site-selection criteria for nuclear waste repositories.

  5. Microstructure and elemental distribution of americium-containing MOX fuel under the short-term irradiation tests

    International Nuclear Information System (INIS)

    In order to investigate the effect of americium addition to MOX fuels on the irradiation behavior, the 'Am-1' program is being conducted in JAEA. The Am-1 program consists of two short-term irradiation tests of 10-minute and 24-hour irradiations and a steady-state irradiation test. The short-term irradiation tests were successfully completed and the post irradiation examinations (PIEs) are in progress. The PIEs for Am-containing MOX fuels focused on the microstructural evolution and redistribution behavior of Am at the initial stage of irradiation and the results to date are reported. (author)

  6. Inhibition of microbial sulfate reduction in a flow-through column system by (per)chlorate treatment.

    Science.gov (United States)

    Engelbrektson, Anna; Hubbard, Christopher G; Tom, Lauren M; Boussina, Aaron; Jin, Yong T; Wong, Hayden; Piceno, Yvette M; Carlson, Hans K; Conrad, Mark E; Anderson, Gary; Coates, John D

    2014-01-01

    Microbial sulfate reduction is a primary cause of oil reservoir souring. Here we show that amendment with chlorate or perchlorate [collectively (per)chlorate] potentially resolves this issue. Triplicate packed columns inoculated with marine sediment were flushed with coastal water amended with yeast extract and one of nitrate, chlorate, or perchlorate. Results showed that although sulfide production was dramatically reduced by all treatments, effluent sulfide was observed in the nitrate (10 mM) treatment after an initial inhibition period. In contrast, no effluent sulfide was observed with (per)chlorate (10 mM). Microbial community analyses indicated temporal community shifts and phylogenetic clustering by treatment. Nitrate addition stimulated Xanthomonadaceae and Rhizobiaceae growth, supporting their role in nitrate metabolism. (Per)chlorate showed distinct effects on microbial community structure compared with nitrate and resulted in a general suppression of the community relative to the untreated control combined with a significant decrease in sulfate reducing species abundance indicating specific toxicity. Furthermore, chlorate stimulated Pseudomonadaceae and Pseudoalteromonadaceae, members of which are known chlorate respirers, suggesting that chlorate may also control sulfidogenesis by biocompetitive exclusion of sulfate-reduction. Perchlorate addition stimulated Desulfobulbaceae and Desulfomonadaceae, which contain sulfide oxidizing and elemental sulfur-reducing species respectively, suggesting that effluent sulfide concentrations may be controlled through sulfur redox cycling in addition to toxicity and biocompetitive exclusion. Sulfur isotope analyses further support sulfur cycling in the columns, even when sulfide is not detected. This study indicates that (per)chlorate show great promise as inhibitors of sulfidogenesis in natural communities and provides insight into which organisms and respiratory processes are involved. PMID:25071731

  7. Development of a methodology for the determination of americium and thorium by ICP-AES and their inter-element effect

    International Nuclear Information System (INIS)

    Due to the scarcity of good quality uranium resources, the growth of nuclear technology in India is dependent on the utilization of the vast thorium resources. Therefore, Advance Heavy Water Reactor is going to acquire significant role in the scenario of Indian nuclear technology, where (Th, Pu)O2 will be utilized as fuel in the outermost ring of the reactor core. This will lead to a complex matrix containing thorium as well as americium, which is formed due to β-decay of plutonium. The amount of americium is dependent on the burn up and the storage time of the Pu based fuels. In the present case, attempt was made to develop a method for the determination of americium as well as thorium by ICP-AES. Two emission lines of americium were identified and calibration curves were established for determination of americium. Though the detection limit of 283.236 nm line (5 ng mL-1) of americium was found to be better than that of 408.930 nm (11 ng mL-1), the former line is significantly interfered by large amount of thorium. Three analytical lines (i.e. 283.242, 283.730 and 401.913 nm) of thorium were identified and calibration curves were established along with their detection limits. It was observed that 283.242 and 401.913 nm line are having similar detection limits (18 and 13 ng mL-1, respectively) which are better than that of 283.730 nm (60 ng mL-1). This can be attributed to the high background of 283.273 nm channel of thorium. The spectral interference study revealed that even small amount of americium has significant contribution on 283.242 nm channel of thorium while the other two channels remain practically unaffected. Considering both these facts, spectral interference and analytical performance (detection limits and sensitivity), it was concluded that 401.913 nm line is the best analytical line out of the three lines for determination of thorium in presence of americium. (author)

  8. 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. PMID:26297465

  9. Effect of radiolysis on leachability of plutonium and americium from 76-101 glass. [Glass containing 2 mole % plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L.; Fried, S.; Friedman, A.M.; Susak, N.; Rickert, P.; Sullivan, J.C.; Karim, D.P.; Lam, D.J.

    1982-01-01

    One aspect of the leachability of actinide-bearing glass which has not been adequately addressed is the effect of radiolysis of the system (glass-water) on the amount of actinides liberated from the glass. In the present study, we have investigated the leaching of plutonium and americium from 76-101 glass samples (containing 2 mole % plutonium) in the presence of a one megaRad/hour gamma-radiation field. The presence of the radiation field was found to increase the leaching rate of both plutonium and americium by a factor of five. Speciation studies of the plutonium in the leachate indicate that the plutonium is present predominantly in the higher oxidation states, Pu(V) and Pu(VI) and that it is significantly associated with colloidal particles. Examination of the glass surfaces with x-ray photoemission spectroscopy, XPS, both before and after leaching was carried out; these studies showed lower surface concentrations of plutonium in the samples of glass leached in the radiation field. 1 figure, 3 tables.

  10. Osteosarcoma induction by plutonium-239, americium-241 and neptunium-237 : the problem of deriving risk estimates for man

    International Nuclear Information System (INIS)

    Spontaneous bone cancer (osteosarcoma) represents only about 0.3% of all human cancers, but is well known to be inducible in humans by internal contamination with radium-226 and radium-224. plutonium-239, americium-241 and neptunium-237 form, or will form, the principal long-lived alpha particle emitting components of high activity waste and burnt-up nuclear fuel elements. These three nuclides deposit extensively in human bone and although, fortunately, no case of a human osteosarcoma induced by any of these nuclides is known, evidence from animal studies suggests that all three are more effective than radium-226 in inducing osteosarcoma. The assumption that the ratio of the risk factors, the number of osteosarcoma expected per 10000 person/animal Gy, for radium-226 and any other bone-seeking alpha-emitter will be independent of animal species has formed the basis of all the important studies of the radiotoxicity of actinide nuclides in experimental animals. The aim of this communication is to review the risk factors which may be calculated from the various animal studies carried out over the last thirty years with plutonium-237, americium-241 and neptunium-237 and to consider the problems which may arise in extrapolating these risk factors to homo sapiens

  11. 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.

  12. Experimental Study on Behavior of Americium in Pyrochemical Process of Nitride Fuel Cycle

    International Nuclear Information System (INIS)

    R and D on the transmutation of long-lived minor actinides (MA) by the accelerator-driven system (ADS) using nitride fuels is underway at JAEA. In regard to reprocessing technology, pyrochemical process has several advantages in case of treating spent fuel with large decay heat and fast neutron emission, and recovering highly enriched N-15. In the pyrochemical reprocessing, plutonium and MA are dissolved in LiCl-KCl eutectic melts and selectively recovered into liquid cadmium (Cd) cathode by molten salt electrorefining. The electrochemical behavior in LiCl-KCl eutectic melts and the subsequent nitride formation behavior of plutonium and MA recovered in liquid Cd cathode are investigated. In this paper, recent results on electrochemical study of americium (Am) on electrolyses of AmN in LiCl-KCl eutectic melts and nitride formation of Am recovered in the liquid Cd cathode are presented. Electrochemical behavior of Am on anodic dissolution of AmN and recovery of Am into a liquid Cd cathode by electrolyses in LiCl-KCl eutectic melts was investigated by transient electrochemical techniques. The formal standard potential of Am(III)/Am(0) obtained with the liquid Cd electrode is more positive than that calculated for the solid metal electrode. The potential shift is considered to be attributed to the lowering of the activity of Am by the formation of the intermetallic compound with Cd. Potentiostatic electrolyses of AmN in LiCl-KCl eutectic melts containing AmCl3 at 773 K were carried out. Nitrogen gas generated by the anodic dissolution of AmN was observed, and the current efficiency was obtained from the ratio of the amount of released nitrogen gas and the passed electric charge to be 20 - 28 %. Am was recovered as Am-Cd alloy in the liquid Cd cathode, in which AmCd6 type phase was identified besides Cd phase. The recovered Am was converted to AmN by the nitridation-distillation combined method, in which the Am-Cd alloy was heated in nitrogen gas stream at 973 K. These

  13. LIBS Spectral Data for a Mixed Actinide Fuel Pellet Containing Uranium, Plutonium, Neptunium and Americium

    Energy Technology Data Exchange (ETDEWEB)

    Judge, Elizabeth J. [Los Alamos National Laboratory; Berg, John M. [Los Alamos National Laboratory; Le, Loan A. [Los Alamos National Laboratory; Lopez, Leon N. [Los Alamos National Laboratory; Barefield, James E. [Los Alamos National Laboratory

    2012-06-18

    Laser-induced breakdown spectroscopy (LIBS) was used to analyze a mixed actinide fuel pellet containing 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2}. The preliminary data shown here is the first report of LIBS analysis of a mixed actinide fuel pellet, to the authors knowledge. The LIBS spectral data was acquired in a plutonium facility at Los Alamos National Laboratory where the sample was contained within a glove box. The initial installation of the glove box was not intended for complete ultraviolet (UV), visible (VIS) and near infrared (NIR) transmission, therefore the LIBS spectrum is truncated in the UV and NIR regions due to the optical transmission of the window port and filters that were installed. The optical collection of the emission from the LIBS plasma will be optimized in the future. However, the preliminary LIBS data acquired is worth reporting due to the uniqueness of the sample and spectral data. The analysis of several actinides in the presence of each other is an important feature of this analysis since traditional methods must chemically separate uranium, plutonium, neptunium, and americium prior to analysis. Due to the historic nature of the sample fuel pellet analyzed, the provided sample composition of 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2} cannot be confirm without further analytical processing. Uranium, plutonium, and americium emission lines were abundant and easily assigned while neptunium was more difficult to identify. There may be several reasons for this observation, other than knowing the exact sample composition of the fuel pellet. First, the atomic emission wavelength resources for neptunium are limited and such techniques as hollow cathode discharge lamp have different dynamics than the plasma used in LIBS which results in different emission spectra. Secondly, due to the complex sample of four actinide elements, which all have very dense electronic energy levels, there may be reactions and

  14. Preconcentration of low levels of americium and plutonium from waste waters by synthetic water-soluble metal-binding polymers with ultrafiltration

    International Nuclear Information System (INIS)

    A preconcentration approach to assist in the measurement of low levels of americium and plutonium in waste waters has been developed based on the concept of using water-soluble metal-binding polymers in combination with ultrafiltration. The method has been optimized to give over 90% recovery and accountability from actual waste water. (author)

  15. Theoretical investigation of pressure-induced structural transitions in americium using GGA+U and hybrid density functional theory methods

    DEFF Research Database (Denmark)

    Verma, Ashok K.; Modak, P.; Sharma, Surinder M.;

    2013-01-01

    First-principles calculations have been performed for americium (Am) metal using the generalized gradient approximation + orbital-dependent onsite Coulomb repulsion via Hubbard interaction (GGA+U) and hybrid density functional theory (HYB-DFT) methods to investigate various ground state propertie...

  16. 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

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

    Science.gov (United States)

    Shcherbakova, Viktoria; Oshurkova, Viktoria; Yoshimura, Yoshitaka

    2015-01-01

    The terrestrial permafrost represents a range of possible cryogenic extraterrestrial ecosystems on Earth-like planets without obvious surface ice, such as Mars. The autotrophic and chemolithotrophic psychrotolerant methanogens are more likely than aerobes to function as a model for life forms that may exist in frozen subsurface environments on Mars, which has no free oxygen, inaccessible organic matter, and extremely low amounts of unfrozen water. Our research on the genesis of methane, its content and distribution in permafrost horizons of different ages and origin demonstrated the presence of methane in permanently frozen fine-grained sediments. Earlier, we isolated and described four strains of methanogenic archaea of Methanobacterium and Methanosarcina genera from samples of Pliocene and Holocene permafrost from Eastern Siberia. In this paper we study the effect of sodium and magnesium perchlorates on growth of permafrost and nonpermafrost methanogens, and present evidence that permafrost hydogenotrophic methanogens are more resistant to the chaotropic agent found in Martian soil. In this paper we study the effect of sodium and magnesium perchlorates on the growth of permafrost and nonpermafrost methanogens, and present evidence that permafrost hydogenotrophic methanogens are more resistant to the chaotropic agent found in Martian soil. Furthermore, as shown in the studies strain M2(T) M. arcticum, probably can use perchlorate anion as an electron acceptor in anaerobic methane oxidation. Earth's subzero subsurface environments are the best approximation of environments on Mars, which is most likely to harbor methanogens; thus, a biochemical understanding of these pathways is expected to provide a basis for designing experiments to detect autotrophic methane-producing life forms on Mars. PMID:27682103

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

    Science.gov (United States)

    Shcherbakova, Viktoria; Oshurkova, Viktoria; Yoshimura, Yoshitaka

    2015-01-01

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

  19. 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.

  20. 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.

  1. 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.

  2. Lanthanide perchlorate complexes of quinoline-1-oxide and isoquinoline-2-oxide

    OpenAIRE

    Kalyanasundaram, R; Navaneetham, NS; Soundararajan, S.

    1985-01-01

    Complexes of lanthanide perchlorates with quinoline-1-oxide and isoquinoline-2-oxide have been isolated for the first time characterised by analysis, conductance and IR, NMR and electronic spectoral studies. The complexes of quinoline-1-oxide have the composition $Ln(QNO)_8$$(ClO_4)_3$ where Ln = La, Pr or Nd and $Ln(QNO)_7$ where Ln = Gd, Dy, Ho, Er, Yb. The isoquinoline-2-oxide complexes analyse for the formula $Ln(IsoQNO)_7(ClO_4)_3$ where Ln = La-Yb.

  3. 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 tempe...... temperatures between 1.2 and 1.4 K. At 0.9 K, a perpendicular magnetic field of 25 mT nearly restores normal resistance. Below 0.1 K, this critical field exceeds 50 mT....

  4. 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.

  5. Reanalysis of the Viking results suggests perchlorate and organics at mid-latitudes on Mars

    Science.gov (United States)

    Navarro-Gonzalez, R.; Vargas, E.; de La Rosa, J.; Raga, A. C.; McKay, C.

    2010-12-01

    The most comprehensive search for organics in the Martian soil was performed by the Viking Landers. Martian soil was subjected to a thermal volatilization process in order to vaporize and break organic molecules, and the resultant gases and volatiles were analyzed by gas chromatography-mass spectrometry. Only water at 0.1-1.0 wt% was detected with traces of chloromethane at 15 ppb in the Viking Landing site 1, and water at 0.05-1.0 wt% and carbon dioxide at 50-700 ppm with traces of dichloromethane at 0.04-40 ppb in the Viking Landing site 2. The abundance ratio of the 35Cl and 37Cl isotopes in these chlorohydrocarbons was 3:1, corresponding to the terrestrial isotopic abundance. Therefore, these chlorohydrocarbons were considered to be terrestrial contaminants although they had not been detected at those levels in the blank runs. Recently, perchlorate was discovered in the Martian Arctic soil by the Phoenix Lander. Here we show that when Mars-like soils from the Atacama Desert with 32±6 ppm of organic carbon are mixed with 1 wt% magnesium perchlorate and heated nearly all the organics present are decomposed to water and carbon dioxide, but a small amount are chlorinated forming 1.6 ppm of chloromethane and 0.02 ppm of dichloromethane at 500○C. A chemical kinetics model was developed to predict the degree of oxidation and chlorination of organics in the Viking oven. The isotopic distribution of 35Cl and 37Cl for Mars is not known. Studies on Earth indicate that there is no isotopic fractionation of chlorine in the mantle or crust, despite the fact that it is significantly depleted on the planet as compare to solar abundances. The 37Cl/35Cl isotopic ratio in carbonaceous chondrites is similar to the Earth’s value, which suggests that the terrestrial planets, including Mars, were all formed from a similar reservoir of chlorine species in the presolar nebulae and that there was no further isotopic fractionation during the Earth’s differentiation or late

  6. 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].

  7. 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

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

    International Nuclear Information System (INIS)

    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

  9. 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.

  10. 123Iodine scintigraphy and perchlorate discharge test in the diagnosis of congenital hypothyroidism

    International Nuclear Information System (INIS)

    Aim: Thirty eight children suffering from congenital primary permanent hypothyroidism were studied to determine the diagnostic impact of 123I scintigraphy in comparison to laboratory findings and ultrasonography. Methods: In all patients 123I scintigraphy was performed after intravenous administration of 3,7 MBq 123I. If accumulation of the radiotracer in thyroid tissue occured a perchlorate discharge test was performed subsequently. Results: Scintigraphy revealed athyrosis in 7 children. In 9 children a lingual thyroid was observed. Deficiency in iodine organification was diagnosed by a significant discharge of 123I in 15 patients. In four of these children the diagnosis of Pendred's syndrome could be established. Ectopic thyroid tissue could be demonstrated only by scintigraphy where clinical examination and sonography failed in the diagnosis in all cases. Hypoplasia of the thyroid gland as it was diagnosed in 2 cases by ultrasonography appeared to be unlikely because of normal 123I uptake was seen in these patients. In 2 patients with scintigraphic proven athyrosis an orthotopic gland had been falsely considered by ultrasound. In 44% of our patients the final diagnosis could only be established if 123I scintigraphy and perchlorate discharge test were performed. Conclusion: This findings suggest that scintigraphy is indispensible in the correct diagnostic work up of congenital hypothyroidism. (orig.)

  11. 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.

  12. 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.

  13. 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.

  14. Reversible, Selective Trapping of Perchlorate from Water in Record Capacity by a Cationic Metal-Organic Framework.

    Science.gov (United States)

    Colinas, Ian R; Silva, Rachel C; Oliver, Scott R J

    2016-02-16

    We report the capture of ppm-level aqueous perchlorate in record capacity and kinetics via the complete anion exchange of a cationic metal-organic framework. Ambient conditions were used for both the synthesis of silver 4,4'-bipyridine nitrate (SBN) and the exchange, forming silver 4,4'-bipyridine perchlorate (SBP). The exchange was complete within 90 min, and the capacity was 354 mg/g, representing 99% removal. These values are greater than current anion exchangers such as the resins Amberlite IRA-400 (249 mg/g), Purolite A530E (104 mg/g), and layered double hydroxides (28 mg/g). Moreover, unlike resins and layered double hydroxides, SBN is fully reusable and displays 96% regeneration to SBN in nitrate solution, with new crystal formation allowing the indefinite cycling for perchlorate. We show seven cycles as proof of concept. Perchlorate contamination of water represents a serious health threat because it is a thyroid endocrine disruptor. This noncomplexing anionic pollutant is significantly mobile and environmentally persistent. Removal of other anionic pollutants from water such as chromate, pertechnetate, or arsenate may be possible by this methodology. PMID:26765213

  15. 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

  16. Stability of penta- and hexavalent americium in the solutions of sodium peroxydisulfate and sodium bromate at intensive internal α-irradiation

    International Nuclear Information System (INIS)

    The spectrometric method has been used for studying the dependence of the rates of radiolytic reduction of Am(5) and (6) on the initial concentration of sodium persulfate and bromate, Am(5) and (6), acidity, and the dose rate of inner alpha-irradiation of the solutions. The high dose rates of inner alpha-irradiation of solutions (up to 3.25x1021 eV/lxmin-250Ci/l) have been attained with the aid of curium isotopes. The stability of americium (6) ions towards the action of ionizing radiation in solutions of sodium persulfate and bromate has been shown to be considerable lower than that of americium (5). The chemical difference has been shown in radiolytic behaviour between Am(5) and Am(6) ions in solutions of sodium persulfate and bromate. The equations have been derived showing the dependence of the rates of Am(6) and Am(5) reduction of different variables

  17. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium-americium mixed oxides

    Science.gov (United States)

    Prieur, D.; Lebreton, F.; Martin, P. M.; Caisso, M.; Butzbach, R.; Somers, J.; Delahaye, T.

    2015-10-01

    Uranium-americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U1-xAmxO2±δ samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U1-xAmxO2±δ leads to the formation of similar fluorite solid solution indicating the presence of Am+III and U+V in equimolar proportions.

  18. THE FIRST ISOLATION OF AMERICIUM IN THE FORM OF PURE COMPOUNDS - THE SPECIFIC ALPHA-ACTIVITY AND HALF-LIFE OF Am241

    Energy Technology Data Exchange (ETDEWEB)

    Cunningham, B.B.; Asprey, L.B.

    1950-07-20

    The microgram scale isolation and preparation of pure compounds of americium is described. Data are presented to show that the alpha-half-life of the isotope Am{sup 241} is 490 {+-} 14 years. The absorption spectrum of Am(III) in 1M nitric acid in the range 3500-8000 mu is given. The wave lengths of 10 of the most prominent lines in the copper spark emission spectrum of americium are given to the nearest 0.01 {angstrom}. Evidence is presented to show that the potential for the Am(III)-Am(IV) couple in acid solution is more negative than -2v and that the potential for the Am(II)-Am(III) couple is more positive than +0.9v.

  19. A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorption on the Relaxed (0001) Surface of Double Hexagonal Close Packed Americium

    OpenAIRE

    Dholabhai, P. P.; Atta-Fynn, R.; A.K. Ray

    2009-01-01

    Ab initio total energy calculations within the framework of density functional theory have been performed for atomic hydrogen and oxygen chemisorption on the (0001) surface of double hexagonal packed americium using a full-potential all-electron linearized augmented plane wave plus local orbitals method. Chemisorption energies were optimized with respect to the distance of the adatom from the relaxed surface for three adsorption sites, namely top, bridge, and hollow hcp sites, the adlayer str...

  20. Experimental study of Americium-241 biokinetics in Homarus Gammarus lobster. Analysis of the accumulation and detoxication mechanisms at the sub-cellular level

    International Nuclear Information System (INIS)

    The Americium 241 radioelement accumulation and elimination rate and mechanisms in the lobster organism have been experimentally studied; incorporation and detoxification capacities of each organ are evaluated. The existence of various biological compartments is shown; the major role of the digestive gland in accumulation of the radioelement, its distribution towards the various organs, and its resorption is comprehensively described, with an analysis at the subcellular and molecular levels. 401 p., 65 fig., 43 tab., 428 ref

  1. Effect of Triethanolamine and Benzaldehyde on the Storage Stability of Polystyrene- Ammonium Perchlorate Propellant

    Directory of Open Access Journals (Sweden)

    K. Kishore

    1986-10-01

    Full Text Available The effect of triethanolamine and benzaldehyde on the stability of polystyrene has been studied by dynamic thermogravimetry (TG. Slower decomposition of polymer in the presence of these compounds indicates their inhibiting ability on the oxidation of the polymer. The burning rate measurements of polystyrene (PS/ammonium perchlorate (AP propellants at ambient temperature and pressure shows an increase with the storage time. The percentage change in the burning rate of the propellants containing aldehyde and amine is less during the ageing which indicates the increased stability of the propellants. The safe-life time of the propellants for the ballistic stability has been calculated from the activation energy for the ageing process using an Arrhenius type equation. The safe-life of the propellants containing triethanolamine and benzaldehyde is more than the neat propellant.

  2. Thyroid scintigraphy and perchlorate discharge test in the diagnosis of congenital hypothyroidism

    Energy Technology Data Exchange (ETDEWEB)

    El-Desouki, M. [Dept. of Medicine, King Saud Univ., Riyadh (Saudi Arabia); Al-Jurayyan, N. [Dept. of Paediatrics, King Saud Univ., Riyadh (Saudi Arabia); Al-Nuaim, A. [Div. of Endocrinology, King Saud Univ., Riyadh (Saudi Arabia); Al-Herbish, A. [Dept. of Paediatrics, King Saud Univ., Riyadh (Saudi Arabia); Abo-Bakr, A. [Dept. of Paediatrics, King Saud Univ., Riyadh (Saudi Arabia); Al-Mazrou, Y. [Ministry of Health, Riyadh (Saudi Arabia); Al-Swailem, A. [Ministry of Health, Riyadh (Saudi Arabia)

    1995-09-01

    Quantitative thyroid scanning using low doses of technetium-99m sodium pertechnetate was performed on 147 infants (55 males and 92 females) with congenital hypothyroidism detected through the national neonatal screening programme. Thirty-two (21.8%) were athyrotic, while 62 (42.2%) had an ectopic thyroid and 53 (36%) had a eutopic gland with increased {sup 99m}Tc uptake (mean 17%; range, 5%-38%). The perchlorate discharge test (PDT) was performed in nine of the infants with ectopic glands and 15 with eutopic glands; the findings were consistent with an organification defect in 22 cases (seven ectopic and 15 eutopic). Thyroid scintigraphy and PDT can add useful aetiological, genetic and prognostic information in the clinical evaluation of infants with congenital hypothyroidism detected by neonatal screening. (orig.). With 4 figs., 1 tab.

  3. 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.

  4. Effect of hydrogen storage alloy on combustion properties of ammonium perchlorate /glycidylazide polymer -based propellant

    Science.gov (United States)

    Li, G. P.; Dou, Y. M.; Chai, C. P.; Luo, Y. J.

    2015-12-01

    Hydrogen storage alloys can serve as good potential fuels for propellant design, by improving the energy and combustion properties. The influence of hydrogen storage alloy (A30) on the combustion properties of ammonium perchlorate/glycidylazide polymer (AP/GAP)-based on propellant were studied. The results showed that A30 could increase the burning rate of propellants by 29.75% and 74.78%, compared with B30 and Al. The combustion model of AP/GAP-based propellant containing different fuel was built. Firstly, A30 reduced the high decomposition temperature and promote condensed phase reaction heat of AP. Secondly, A30 deduced the burning surface temperature. Thirdly, A30 might prove the explosive heat of propellant. Therefore, A30 could greatly improve combustion properties of AP/GAP-based propellant.

  5. Effect of Microwave Heating on the Leaching of Lateritic Nickel Ore in Perchloric Acid

    International Nuclear Information System (INIS)

    In this study, the leaching conditions of Sivrihisar (Adatepe) limonite type lateritic ore in acidic medium were investigated. Leaching experiments were carried out using conventional and microwave-assisted method. The effects of stirring speed, leaching temperature, perchloric acid concentration, solid/liquid ratio and particle size on conventional leaching were determined. Microwave-assisted leaching was carried out by using the optimum results of the conventional leaching. The pre-heating process was applied on different microwave powers (0, 90, 180, 360 and 600 W) and pre-processing time (0, 1, 3, 5, 7, 10, 15 and 20 min). These experimental results demonstrated that acid leaching was a convenient method for Ni extraction from lateritic ore. The higher dissolution and the higher Ni recoveries in the microwave-assisted leaching process were obtained in less leach time. (author)

  6. Thyroid scintigraphy and perchlorate discharge test in the diagnosis of congenital hypothyroidism

    International Nuclear Information System (INIS)

    Quantitative thyroid scanning using low doses of technetium-99m sodium pertechnetate was performed on 147 infants (55 males and 92 females) with congenital hypothyroidism detected through the national neonatal screening programme. Thirty-two (21.8%) were athyrotic, while 62 (42.2%) had an ectopic thyroid and 53 (36%) had a eutopic gland with increased 99mTc uptake (mean 17%; range, 5%-38%). The perchlorate discharge test (PDT) was performed in nine of the infants with ectopic glands and 15 with eutopic glands; the findings were consistent with an organification defect in 22 cases (seven ectopic and 15 eutopic). Thyroid scintigraphy and PDT can add useful aetiological, genetic and prognostic information in the clinical evaluation of infants with congenital hypothyroidism detected by neonatal screening. (orig.). With 4 figs., 1 tab

  7. 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.

  8. Hydration of some trivalent metal ions extracted as perchlorates with trioctylphosphine oxide in hexane

    International Nuclear Information System (INIS)

    Perchlorates of Sc3+, Y3+, La3+, and Eu3+ have each been extracted from 0.1 mol x dem-3 aqueous solution of μ=1 with trioctylphosphine oxide (TOPO) in hexane. The hydration number of the extracted salts has been determined by Karl Fischer titration. Sc3+, Y3+, and Eu3+ are extracted as the tetra- and hexa-solvates of TOPO but the assumption of octa-solvate on addition to the tetra-solvate explains the extraction data of La3+ well. The hydration number of tetra-solvates is 2(Sc3+ and Eu3+), 3(Y3+) and probably 4 for La3+ ion. That of hexa-and octa-solvates is 4-5. (author)

  9. Hydration and Solvation of Metal Perchlorates Extracted with Trioctylphosphine Oxide in Hexane

    International Nuclear Information System (INIS)

    Perchlorates of Sc3+, Y3+, La3+, and Eu3+ have each been extracted from 0.1 mol dm-3 aqueous solution of μ=1 with trioctylphosphine oxide (TOPO) in hexane. The hydration number of the extracted salts has been determined by Karl Fischer titration. Sc3+, Y3+, and Eu3+ are extracted as the tetra- and hexa-solvates of TOPO but the assumption of octa-solvate on addition to the tetra-solvate explains the extraction data of La3+ well. The hydration number of tetra-solvates is 2 (Sc3+ and Eu3+), 3 (Y3+) and probably 4 for La3+ ion. That of hexa-and octa- solvates is 4-5. (author). 1 tabs

  10. A Consideration for Design of Ammonium Perchlorate/Hydroxyl Terminated Polybutadiene Composite Propellant

    Science.gov (United States)

    Kohga, Makoto

    Specific impulse and burning rate characteristics are the important properties for the propellant design. Because of the requirements for the preparation of ammonium perchlorate (AP)/hydroxyl-terminated polybutadiene (HTPB) composite propellant, there is an upper limit content, φ of AP contained propellant. Specific impulse and burning rate increase with increasing the AP content. The specific impulse, Ispφ and the burning rate, rφ of the propellant prepared at φ, rφ are the highest values of the propellant prepared with AP used as an oxidizer. It is necessary for the propellant design to estimate φ, Ispφ and rφ. The φ, Ispφ and rφ are closely associated with the specific surface area, Swp measured by air-permeability method. Therefore, these values are estimated with Swp. A process for the design of AP/HTPB composite propellant would be proposed in this study.

  11. Complexes of rare-earth perchlorates with ditbutyl amides of di, tri and tetraglycolic acids

    OpenAIRE

    Premlatha, C; Soundararajan, S

    1981-01-01

    New complexes of lanthanide perchlorates with di-t-butyl amides of di, tri and tetraglycolic acids have been synthesised. The complexes have the general formula Ln(DiGA)3(ClO4)3; Ln(TriGA)2 (ClO4)3 and Ln(TetGA)2 (C1O4)3, where Ln = La-Yb and Y and DiGA = N,N′, di-t-butyl diglycolamide, TriGA N,N′, di-t-butyl triglycolamide and TetGA = N,N′ di-t-butyl tetraglycolamide, respectively. The complexes have been characterized by analysis, electrolytic conductance, infrared,1H and13C nuclear magneti...

  12. Application of Probabilistic Risk Assessment in Establishing Perchlorate and Goitrogen Risk Mitigation Strategies.

    Science.gov (United States)

    Crawford-Brown, Douglas

    2015-09-01

    This paper applies probabilistic risk assessment in quantifying risks from cumulative and aggregate risk pathways for selected goitrogens in water and food. Results show that the percentages of individuals with a Hazard Index (HI) value above 1 ranges between 30% and 50% both with and without serum half-life correction when a traditional regulatory assessment approach based on establishment of a No Observed Effects Level (NOEL) is used. When an exposure-response curve is instead used and a threshold of 50% inhibition is assumed, 1.1% or less of the population exceeds an HI value of 1 with no serum half-life correction, rising to as high as 11% when serum half-life correction is applied. If 0% to 5% threshold for iodide uptake inhibition is assumed for production of adverse effects, the percentage of the population with an HI above 1 is 46.2% or less with no serum half-life correction, and 47.2% or less when serum half-life correction is applied. The probabilistic analysis shows that while there are exposed groups for whom perchlorate exposures are the primary cause of individuals having HI values above 1, these constitute significantly less than 1% of the population. Instead, the potential risk from exposure to goitrogens is dominated by nitrates without serum half-life correction and thiocyanates with serum half-life correction, suggesting public health protection is better accomplished by a focus on these and other goitrogens expect in highly limited cases where waterborne perchlorate is at unusually high concentrations. PMID:26322488

  13. A new method for the determination of plutonium and americium using high pressure microwave digestion and alpha-spectrometry or ICP-SMS

    International Nuclear Information System (INIS)

    Plutonium and americium are radionuclides particularly difficult to measure in environmental samples because they are a-emitters and therefore necessitate a careful separation before any measurement, either using radiometric methods or ICP-SMS. Recent developments in extraction chromatography resins such as EichromR TRU and TEVA have resolved many of the analytical problems but drawbacks such as low recovery and spectral interferences still occasionally occur. Here, we report on the use of the new EichromR DGA resin in association with TEVA resin and high pressure microwave acid leaching for the sequential determination of plutonium and americium in environmental samples. The method results in average recoveries of 83 ± 15% for plutonium and 73 ± 22% for americium (n = 60), and a less than 10% deviation from reference values of four IAEA reference materials and three samples from intercomparisons exercises. The method is also suitable for measuring 239Pu in water samples at the μBq/l level, if ICP-SMS is used for the measurement. (author)

  14. An experimental study of americium-241 biokinetics in the Lobster Homarus Gammarus. Analysis of the accumulation/storage and detoxification processes at the subcellular level

    International Nuclear Information System (INIS)

    An experimental study of americium-241 kinetics has been conducted in the lobster Homarus gammmarus. The investigations were conducted at all the levels from the whole body to the subcellular and molecular levels. The animals were contaminated by a single or chronic ingestion of 241 Am labelled mussels. Assessments of accumulation, elimination and distribution of the radionuclide were established on organisms kept in the laboratory; they made it possible to demonstrate the importance of the digestive gland in the radionuclide transfer pathways. The preliminary results led to structural then ultrastructural investigations of the digestive gland in association with radioautographic studies and cellular extractions methods. Four cellular types were demonstrated, only two of them being implied in the radionuclide retention, the former being responsible for americium intake and the latter for its long-term retention. By means of biochemical techniques, subcellular accumulation was studied and the organelles implied in the nuclide retention were specified. Finally, a method of cellular nuclei dissociation was developed; it made it possible to analyse the molecular nature of americium ligands and to demonstrate the function of the protein nuclear matrix in the nuclide retention

  15. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium–americium mixed oxides

    Energy Technology Data Exchange (ETDEWEB)

    Prieur, D., E-mail: dam.prieur@gmail.com [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); Lebreton, F. [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze cedex (France); Martin, P.M. [CEA, DEN, DEC/SESC/LLCC, 13108 Saint-Paul-Lez-Durance cedex (France); Caisso, M. [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze cedex (France); Butzbach, R. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Radiochemistry, P.O. Box 10119, 01314 Dresden (Germany); Somers, J. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, D-76125 Karlsruhe (Germany); Delahaye, T. [CEA, DEN, DTEC/SDTC/LEMA, 30207 Bagnols-sur-Cèze cedex (France)

    2015-10-15

    Uranium–americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U{sub 1−x}Am{sub x}O{sub 2±δ} samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U{sub 1−x}Am{sub x}O{sub 2±δ} leads to the formation of similar fluorite solid solution indicating the presence of Am{sup +III} and U{sup +V} in equimolar proportions. - Graphical abstract: Formation of (U{sup IV/V},Am{sup III})O{sup 2} solid solution by sol–gel and by powder metallurgy. - Highlights: • Uranium–americium mixed oxides were synthesized by sol–gel and powder metallurgy. • Fluorite solid solutions with similar local environment have been obtained. • U{sup V} and Am{sup III} are formed in equimolar proportions.

  16. 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)

  17. 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.

  18. 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.

  19. Acute and chronic activity of perchlorate and hexavalent chromium contamination on the survival and development of Culex quinquefasciatus Say (Diptera: Culicidae)

    Energy Technology Data Exchange (ETDEWEB)

    Sorensen, Mary A. [Department of Entomology, University of California, Riverside, CA 92521 (United States)]. E-mail: mary.sorensen@email.ucr.edu; Jensen, Peter D. [Department of Entomology, University of California, Riverside, CA 92521 (United States); Walton, William E. [Department of Entomology, University of California, Riverside, CA 92521 (United States); Trumble, John T. [Department of Entomology, University of California, Riverside, CA 92521 (United States)

    2006-12-15

    Effects of water contamination with perchlorate and hexavalent chromium [Cr (VI)] on the mosquito Culex quinquefasciatus were assessed. The chronic (10-day) LC{sub 5}s values for perchlorate and chromium were 74 {+-} 8.0 mg/L and 0.41 {+-} 0.15 mg/L, respectively. Relative Growth Index, a measure of growth and mortality rates in a population, was significantly reduced within 5 days for levels of perchlorate as low as 25 mg/L and for levels of chromium as low as 0.16 mg/L. Neither compound altered wing length of surviving adults. In combination, contaminants were synergistic, causing 14% more mortality than predicted. Acute (24-h) LC{sub 5} values for perchlorate and Cr (VI) were 17,000 {+-} 3200 and 38 {+-} 1.3 mg/L, respectively. Effects on mosquito larvae in contaminated environments are likely to be observed for Cr (VI) but not for perchlorate, which generally does not occur at levels as high as those shown here to affect larval mosquitoes. - While pollution with hexavalent chromium may adversely affect Culex quinquefasciatus larvae, levels of perchlorate currently in the environment will not impact these insects.

  20. 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

  1. Use of radioanalytical methods for determination of uranium, neptunium, plutonium, americium and curium isotopes in radioactive wastes

    International Nuclear Information System (INIS)

    Activated charcoal is a common type of radioactive waste that contains high concentrations of fission and activation products. The management of this waste includes its characterization aiming the determination and quantification of the specific radionuclides including those known as Difficult-to-Measure Radionuclides (RDM). The analysis of the RDM's generally involves complex radiochemical analysis for purification and separation of the radionuclides, which are expensive and time-consuming. The objective of this work was to define a methodology for sequential analysis of the isotopes of uranium, neptunium, plutonium, americium and curium present in a type of radioactive waste, evaluating chemical yield, analysis of time spent, amount of secondary waste generated and cost. Three methodologies were compared and validated that employ ion exchange (TI + EC), extraction chromatography (EC) and extraction with polymers (ECP). The waste chosen was the activated charcoal from the purification system of primary circuit water cooling the reactor IEA-R1. The charcoal samples were dissolved by acid digestion followed by purification and separation of isotopes with ion exchange resins, extraction and chromatographic extraction polymers. Isotopes were analyzed on an alpha spectrometer, equipped with surface barrier detectors. The chemical yields were satisfactory for the methods TI + EC and EC. ECP method was comparable with those methods only for uranium. Statistical analysis as well the analysis of time spent, amount of secondary waste generated and cost revealed that EC method is the most effective for identifying and quantifying U, Np, Pu, Am and Cm present in charcoal. (author)

  2. Intramolecular sensitization of americium luminescence in solution: shining light on short-lived forbidden 5f transitions.

    Science.gov (United States)

    Sturzbecher-Hoehne, M; Yang, P; D'Aléo, A; Abergel, R J

    2016-06-14

    The photophysical properties and solution thermodynamics of water soluble trivalent americium (Am(III)) complexes formed with multidentate chromophore-bearing ligands, 3,4,3-LI(1,2-HOPO), Enterobactin, and 5-LIO(Me-3,2-HOPO), were investigated. The three chelators were shown to act as antenna chromophores for Am(III), generating sensitized luminescence emission from the metal upon complexation, with very short lifetimes ranging from 33 to 42 ns and low luminescence quantum yields (10(-3) to 10(-2)%), characteristic of Near Infra-Red emitters in similar systems. The specific emission peak of Am(III) assigned to the (5)D1 → (7)F1 f-f transition was exploited to characterize the high proton-independent stability of the complex formed with the most efficient sensitizer 3,4,3-LI(1,2-HOPO), with a log β110 = 20.4 ± 0.2 value. In addition, the optical and solution thermodynamic features of these Am(III) complexes, combined with density functional theory calculations, were used to probe the influence of electronic structure on coordination properties across the f-element series and to gain insight into ligand field effects.

  3. Nano-cerium vanadate: a novel inorganic ion exchanger for removal of americium and uranium from simulated aqueous nuclear waste.

    Science.gov (United States)

    Banerjee, Chayan; Dudwadkar, Nilesh; Tripathi, Subhash Chandra; Gandhi, Pritam Maniklal; Grover, Vinita; Kaushik, Chetan Prakash; Tyagi, Avesh Kumar

    2014-09-15

    Cerium vanadate nanopowders were synthesized by a facile low temperature co-precipitation method. The product was characterized by X-ray diffraction and transmission electron microscopy and found to consist of ∼25 nm spherical nanoparticles. The efficiency of these nanopowders for uptake of alpha-emitting radionuclides (233)U (4.82 MeV α) and (241)Am (5.49 MeV α, 60 keV γ) has been investigated. Thermodynamically and kinetically favorable uptake of these radionuclides resulted in their complete removal within 3h from aqueous acidic feed solutions. The uptake capacity was observed to increase with increase in pH as the zeta potential value decreased with the increase in pH but effect of ionic strength was insignificant. Little influence of the ions like Sr(2+), Ru(3+), Fe(3+), etc., in the uptake process indicated CeVO4 nanopowders to be amenable for practical applications. The isotherms indicated predominant uptake of the radioactive metal ions in the solid phase of the exchanger at lower feed concentrations and linear Kielland plots with positive slopes indicated favorable exchange of the metal ions with the nanopowder. Performance comparison with the other sorbents reported indicated excellent potential of nano-cerium vanadate for removing americium and uranium from large volumes of aqueous acidic solutions.

  4. Distribution of plutonium, americium, and several rare earth fission product elements between liquid cadmium and LiCl-KCl eutectic

    International Nuclear Information System (INIS)

    Separation factors were measured that describe the partition between molten cadmium and molten LiCl-KCl eutectic of plutonium, americium, praseodymium, neodymium, cerium, lanthanum, gadolinium, dysprosium, and yttrium. The temperature range was 753-788 K, and the range of concentrations was that allowed by the sensitivity of the chemical analysis methods. Mean separation factors were derived for Am-Pu, Nd-Am, Nd-Pu, Nd-Pr, Gd-La, Dy-La, La-Ce, La-Nd, Y-La, and Y-Nd. Where previously published data were available, agreement was good. For convenience, the following series of separation factors relative to plutonium was derived by combining the measured separation factors: Pu, 1.00 (basis); Am, 1.54; Pr, 22.0; Nd, 23.4; Ce, 26; La, 70; Gd, 77; Dy, 270; Y, 3000. These data are used in calculating the distribution of the actinide and rare earth elements in the prochemical reprocessing of spent fuel from the Integral Fast Reactor. (orig.)

  5. Evaluation of synthetic water-soluble metal-binding polymers with ultrafiltration for selective concentration of americium and plutonium

    International Nuclear Information System (INIS)

    Routine counting methods and ICP-MS are unable to directly measure the new US Department of Energy (DOE) regulatory level for discharge waters containing alpha-emitting radionuclides of 30 pCi/L total alpha or the 0.05 pCi/L regulatory level for Pu or Am activity required for surface waters at the Rocky Flats site by the State of Colorado. This inability indicates the need to develop rapid, reliable, and robust analytical techniques for measuring actinide metal ions, particularly americium and plutonium. Selective separation or preconcentration techniques would aid in this effort. Water-soluble metal-binding polymers in combination with ultrafiltration are shown to be an effective method for selectively removing dilute actinide ions from acidic solutions of high ionic strength. The actinide-binding properties of commercially available water-soluble polymers and several polymers which have been reported in the literature were evaluated. The functional groups incorporated in the polymers were pyrrolidone, amine, oxime, and carboxylic, phosphonic, or sulfonic acid. The polymer containing phosphonic acid groups gave the best results with high distribution coefficients and concentration factors for 241Am(III) and 238Pu(III)/(IV) at pH 4 to 6 and ionic strengths of 0.1 to 4

  6. Characteristics of plutonium and americium contamination at the former U.K. atomic weapons test ranges at Maralinga and Emu

    International Nuclear Information System (INIS)

    Physico-chemical studies on environmental plutonium are described, which provide data integral to an assessment of dose for the inhalation of artificial actinides by Australian Aborigines living a semi-traditional lifestyle at Maralinga and Emu, sites of U.K. atomic weapons tests between 1953 and 1963. The most significant area, from a radiological perspective, is the area contaminated by plutonium in a series of ''one point'' safety trials in which large quantities of plutonium were dispersed explosively at a location known as Taranaki. The activity distribution of plutonium and americium with particle size is quite different from the mass distribution, as a considerably higher proportion of the activity is contained in the finer (inhalable) fraction than of the mass. Except in areas which were disturbed through ploughing during a cleanup in 1967, most the activity remains in the top 1 cm of the surface. Much of the activity is in particulate form, even at distances > 20 km from the firing sites, and discrete particles have been located even at distances beyond 100 km. Data are presented which permit the assessment of annual committed doses through the inhalation pathway, for Aborigines living a semi-traditional lifestyle in the areas affected by the Taranaki firings in particular. (author)

  7. 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].

  8. 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.

  9. 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.

  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. Concentration of zinc ions in perchlorate medium by a menbrane-gel using an acid extractant (DEHPA)

    OpenAIRE

    Belhadji L.; Belkacemi F.; Hadj-Boussaad D.E.

    2013-01-01

    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 wit...

  12. Reactions between cerium(IV) and methyl-6-x-derivatives of aniline in perchloric acid solutions

    International Nuclear Information System (INIS)

    The oxidation of 2,6-dimethyl-, 2-isopropyl-6-methyl, 2-chloro-6-methyl-and 2-methyl-6-nitro aniline with cerium(IV) in perchloric acid solutions has been examined. It has been found that the concentration of hydrogen ions and the basicity of nitrogen atom in the amine group decide about the resultant intermediate products. Some of these products can be practically prepared using cerium(IV) as an oxidizing agent. (author). 16 refs, 1 tab

  13. 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.

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

    International Nuclear Information System (INIS)

    Highlights: → The thermodynamics of the reactions of ciprofloxacin (CIP) with Ca(ClO4)2 and Mg(ClO4)2 were investigated by conductometric titration. → The reactions of CIP with each ion produce two ionic complexes with the formulas M(CIP)2+ and M(CIP)22+. → 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(ClO4)2) and magnesium perchlorate (Mg(ClO4)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)2+ and M(CIP)22+. The stability constants K1 and K2 at 25 oC for the complexes formed from the reaction with Ca(ClO4)2 were 8.84 x 104 and 3.62 x 104, respectively. For the reaction with Mg(ClO4)2K1 and K2 were 1.72 x 105 and 2.50 x 103, respectively. The enthalpy (ΔH1, ΔH2, ΔH12) and entropy (ΔS1, ΔS2, ΔS12) 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 (ΔS12 = -468.12 and -478.89 J/K mol for complexation with Ca(ClO4)2 and Mg(ClO4)2, respectively) and enthalpy (ΔH12 = -193.09 and -192.01 kJ/mol for complexation with Ca(ClO4)2 and Mg(ClO4)2, respectively), which indicate that the reactions are driven by the enthalpy change.

  15. 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.

  16. 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

  17. 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

  18. Immunological detection of small organic molecules in the presence of perchlorates: relevance to the life marker chip and life detection on Mars.

    Science.gov (United States)

    Rix, Catherine S; Sims, Mark R; Cullen, David C

    2011-11-01

    The proposed ExoMars mission, due to launch in 2018, aims to look for evidence of extant and extinct life in martian rocks and regolith. Previous attempts to detect organic molecules of biological or abiotic origin on Mars have been unsuccessful, which may be attributable to destruction of these molecules by perchlorate salts during pyrolysis sample extraction techniques. Organic molecules can also be extracted and measured with solvent-based systems. The ExoMars payload includes the Life Marker Chip (LMC) instrument, capable of detecting biomarker molecules of extant and extinct Earth-like life in liquid extracts of martian samples with an antibody microarray assay. The aim of the work reported here was to investigate whether the presence of perchlorate salts, at levels similar to those at the NASA Phoenix landing site, would compromise the LMC extraction and detection method. To test this, we implemented an LMC-representative sample extraction process with an LMC-representative antibody assay and used these to extract and analyze a model sample that consisted of a Mars analog sample matrix (JSC Mars-1) spiked with a representative organic molecular target (pyrene, an example of abiotic meteoritic infall targets) in the presence of perchlorate salts. We found no significant change in immunoassay function when using pyrene standards with added perchlorate salts. When model samples spiked with perchlorate salts were subjected to an LMC-representative liquid extraction, immunoassays functioned in a liquid extract and detected extracted pyrene. For the same model sample matrix without perchlorate salts, we observed anomalous assay signals that coincided with yellow coloration of the extracts. This unexpected observation is being studied further. This initial study indicates that the presence of perchlorate salts, at levels similar to those detected at the NASA Phoenix landing site, is unlikely to prevent the LMC from extracting and detecting organic molecules from

  19. The role of natural organic matter in the migration behaviour of americium in the Boom Clay - Part 1: migration experiments

    International Nuclear Information System (INIS)

    Full text of publication follows: In demonstrating the suitability of Boom Clay as reference site for studying the disposal of radioactive waste, the role of the relatively high amount of Natural Organic Matter (NOM) present in the Boom Clay on the mobility of critical radionuclides needs to be investigated thoroughly. It is generally accepted that trivalent actinides and lanthanides form strong complexes with humic substances. Complexation of these trivalent radionuclides with NOM present in the Boom Clay may therefore have two opposite effects. If complexed by the aqueous phase NOM (the mobile NOM), the radionuclide transport will be governed by the mobility of these dissolved radionuclide- NOM species. If complexed by the solid phase NOM (the immobile NOM) the migration will be retarded. One of the aims of the EC projects TRANCOM-Clay and TRANCOM-II was to investigate the role of mobile NOM as radionuclide carrier in order to develop a conceptual model for inclusion in a performance assessment (PA) model. The migration behaviour of Americium (used as an analogue for the critical radionuclide Pu) was investigated by complexing 241Am with radiolabelled (14C-labelled) NOM before passing through undisturbed Boom Clay cores contained in columns. The use of two different radionuclides, allows the migration behaviour of both the NOM and the Am to be followed. The results of the migration experiments showed that the Am-NOM complexes dissociated when they came into contact with Boom Clay and that the bulk of Am became immobilised (either as Am complexed to immobile NOM or sorbed to the mineral phase). Only a small percentage of the complex persisted as 'stabilised' Am-OM complex which exhibited slow dissociation kinetics upon moving through the Boom Clay. When the applied radionuclide source also contains Am in the form of an inorganic solid phase (when Am is applied above the solubility limit), a continuous source of Am exists to form 'temporarily stabilised' Am

  20. Experimental study of Americium-241 biokinetics in Homarus Gammarus lobster. Analysis of the accumulation and detoxication mechanisms at the sub-cellular level; Etude experimentale des biocinetiques de l`americium-241 chez le homard homarus gammarus. Analyse des mecanismes d`accumulation et de detoxication au niveau subcellulaire

    Energy Technology Data Exchange (ETDEWEB)

    Paquet, F.

    1991-12-01

    The Americium 241 radioelement accumulation and elimination rate and mechanisms in the lobster organism have been experimentally studied; incorporation and detoxification capacities of each organ are evaluated. The existence of various biological compartments is shown; the major role of the digestive gland in accumulation of the radioelement, its distribution towards the various organs, and its resorption is comprehensively described, with an analysis at the subcellular and molecular levels. 401 p., 65 fig., 43 tab., 428 ref.

  1. Microscopic observations of X-ray and gamma-ray induced decomposition of ammonium perchlorate crystals

    Science.gov (United States)

    Herley, P. J.; Levy, P. W.

    1972-01-01

    The X-ray and gamma-ray induced decomposition of ammonium perchlorate was studied by optical, transmission, and scanning electron microscopy. This material is a commonly used oxidizer in solid propellents which could be employed in deep-space probes, and where they will be subjected to a variety of radiations for as long as ten years. In some respects the radiation-induced damage closely resembles the effects produced by thermal decomposition, but in other respects the results differ markedly. Similar radiation and thermal effects include the following: (1) irregular or ill-defined circular etch pits are formed in both cases; (2) approximately the same size pits are produced; (3) the pit density is similar; (4) the c face is considerably more reactive than the m face; and (5) most importantly, many of the etch pits are aligned in crystallographic directions which are the same for thermal or radiolytic decomposition. Thus, dislocations play an important role in the radiolytic decomposition process.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. (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.

  8. Nano-cerium vanadate: A novel inorganic ion exchanger for removal of americium and uranium from simulated aqueous nuclear waste

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, Chayan; Dudwadkar, Nilesh [Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tripathi, Subhash Chandra, E-mail: sctri001@gmail.com [Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Gandhi, Pritam Maniklal [Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Grover, Vinita [Waste Management Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Kaushik, Chetan Prakash [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tyagi, Avesh Kumar, E-mail: aktyagi@barc.gov.in [Waste Management Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

    2014-09-15

    Highlights: • Template free, low temperature synthesis of CeVO{sub 4} nanopowders. • Thermodynamically and kinetically favourable uptake of Am(III) and U(VI) exhibited. • K{sub d} and ΔG° values for Am(III) and U(VI) uptake in pH 1–6 are reported. • Interdiffusion coefficients and zeta potential values in pH 1–6 are reported. • Possible application in low level aqueous nuclear waste remediation. - Abstract: Cerium vanadate nanopowders were synthesized by a facile low temperature co-precipitation method. The product was characterized by X-ray diffraction and transmission electron microscopy and found to consist of ∼25 nm spherical nanoparticles. The efficiency of these nanopowders for uptake of alpha-emitting radionuclides {sup 233}U (4.82 MeV α) and {sup 241}Am (5.49 MeV α, 60 keV γ) has been investigated. Thermodynamically and kinetically favorable uptake of these radionuclides resulted in their complete removal within 3 h from aqueous acidic feed solutions. The uptake capacity was observed to increase with increase in pH as the zeta potential value decreased with the increase in pH but effect of ionic strength was insignificant. Little influence of the ions like Sr{sup 2+}, Ru{sup 3+}, Fe{sup 3+}, etc., in the uptake process indicated CeVO{sub 4} nanopowders to be amenable for practical applications. The isotherms indicated predominant uptake of the radioactive metal ions in the solid phase of the exchanger at lower feed concentrations and linear Kielland plots with positive slopes indicated favorable exchange of the metal ions with the nanopowder. Performance comparison with the other sorbents reported indicated excellent potential of nano-cerium vanadate for removing americium and uranium from large volumes of aqueous acidic solutions.

  9. Plutonium, americium and radiocaesium in the marine environment close to the Vandellos I nuclear power plant before decommissioning

    International Nuclear Information System (INIS)

    The Vandellos nuclear power plant (NPP), releasing low-level radioactive liquid waste to the Mediterranean Sea, is the first to be decommissioned in Spain, after an incident which occurred in 1989. The presence, distribution and uptake of various artificial radionuclides (radiocaesium, plutonium and americium) in the environment close to the plant were studied in seawater, bottom sediments and biota, including Posidonia oceanica, fish, crustaceans and molluscs. Seawater, sediments and Posidonia oceanica showed enhanced levels in the close vicinity of the NPP, although the effect was restricted to its near environment. Maximum concentrations in seawater were 11.6±0.5 Bq m-3 and 16.9±1.2 mBq m-3 for 137Cs and 239,240Pu, respectively. When sediment concentrations were normalized to excess 210Pb, they showed both the short-distance transport of artificial radionuclides from the Vandellos plant and the long-distance transport of 137Cs from the Asco NPP. Posidonia oceanica showed the presence of various gamma-emitters attributed to the impact of the Chernobyl accident, on which the effect of the NPP was superimposed. Seawater, sediment and Posidonia oceanica collected near the plant also showed an enhancement of the plutonium isotopic ratio above the fallout value. The uptake of these radionuclides by marine organisms was detectable but limited. Pelagic fish showed relatively higher 137Cs concentrations and only in the case of demersal fish was the plutonium isotopic ratio increased. The reported levels constitute a set of baseline values against which the impact of the decommissioning operations of the Vandellos I NPP can be studied

  10. Molten salt extraction (MSE) of americium from plutonium metal in CaCl2-KCl-PuCl3 and CaCl2-PuCl3 salt systems

    International Nuclear Information System (INIS)

    Molten salt extraction (MSE) of americium-241 from reactor-grade plutonium has been developed using plutonium trichloride salt in stationary furnaces. Batch runs with oxidized and oxide-free metal have been conducted at temperature ranges between 750 and 945C, and plutonium trichloride concentrations from one to one hundred mole percent. Salt-to-metal ratios of 0.10, 0.15, and 0 30 were examined. The solvent salt was either eutectic 74 mole percent CaCl2 endash 26 mole percent KCl or pure CaCl2. Evidence of trivalent product americium, and effects of temperature, salt-to-metal ratio, and oxide contamination on the americium extraction efficiency are given. 24 refs, 20 figs, 13 tabs

  11. Transfer across the human gut of environmental plutonium, americium, cobalt, caesium and technetium: studies with cockles (Cerastoderma edule) from the Irish Sea.

    Science.gov (United States)

    Hunt, G J

    1998-06-01

    Our previous studies have indicated lower values of the gut transfer factor ('f1 values') for plutonium and americium in winkles (Littorina littorea) than adopted by ICRP. The present study was undertaken primarily to investigate whether this observation extends to other species. Samples of cockles (Carastoderma edule) from Ravenglass, Cumbria were eaten by volunteers who provided 24 h samples of urine and faeces. Urine samples indicated f1 values for cockles which were higher than for winkles; for plutonium these ranged overall up to 7 x 10(-4) with an arithmetic mean in the range (2-3) x 10(-4), and for americium up to 2.6 x 10(-4) with an arithmetic mean of 1.2 x 10(-4). Limited data based on volunteers eating cockles from the Solway suggest that f1 values for americium may be greater at distance from Sellafield. The measured values compare with 5 x 10(-4) used by the ICRP for environmental forms of both elements, which would appear to provide adequate protection when calculating doses from Cumbrian cockles. Data for other nuclides were obtained by analysing faecal samples from the volunteers who ate the Ravenglass cockles. Cobalt-60 showed an f1 value in the region of 0.2, twice the value currently used by ICRP. For 137Cs, variabilities were indicated in the range 0.08 to 0.43, within the ICRP value of f1 = 1.0. Technetium-99 gave f1 values up to about 0.6, in reasonable conformity with the ICRP value of 0.5.

  12. Transfer across the human gut of environmental plutonium, americium, cobalt, caesium and technetium: studies with cockles (Cerastoderma edule) from the Irish Sea

    Energy Technology Data Exchange (ETDEWEB)

    Hunt, G.J. [CEFAS Laboratory, Lowestoft, Suffolk NR33 0HT (United Kingdom)

    1998-06-01

    Our previous studies have indicated lower values of the gut transfer factor ('f{sub L} values') for plutonium and americium in winkles (Littorina littorea) than adopted by ICRP. The present study was undertaken primarily to investigate whether this observation extends to other species. Samples of cockles (Cerastoderma edule) from Ravenglass, Cumbria were eaten by volunteers who provided 24 samples of urine and faeces. Urine samples indicated f{sub L} values for cockles which were higher than for winkles; for plutonium these ranged overall up to 7x10{sup -4} with an arithmetic mean in the range (2-3)x10{sup -4}, and for americium up to 2.6x10{sup -4} with an arithmetic mean of 1.2x10{sup -4}. Limited data based on volunteers eating cockles from the Solway suggest that f{sub L} values for americium may be greater at distance from Sellafield. The measured values compare with 5x10{sup -4} used by the ICRP for environmental forms of both elements, which would appear to provide adequate protection when calculating doses from Cumbrian cockles. Data for other nuclides were obtained by analysing faecal samples from the volunteers who ate the Ravenglass cockles. Cobalt-60 showed an f{sub L} value in the region of 0.2, twice the value currently used by ICRP. For {sup 137}Cs, variabilities were indicated in the range 0.08 to 0.43, within the ICRP value of f{sub L}=1.0. Technetium-99 gave f{sub L} values up to about 0.6, in reasonable conformity with the ICRP value of 0.5. (author)

  13. Determination by gamma-ray spectrometry of the plutonium and americium content of the Pu/Am separation scraps. Application to molten salts; Determination par spectrometrie gamma de la teneur en plutonium et en americium de produits issus de separation Pu/Am. Application aux bains de sels

    Energy Technology Data Exchange (ETDEWEB)

    Godot, A. [CEA Valduc, Dept. de Traitement des Materiaux Nucleaires, 21 - Is-sur-Tille (France); Perot, B. [CEA Cadarache, Dept. de Technologie Nucleaire, Service de Modelisation des Transferts et Mesures Nucleaires, 13 - Saint-Paul-lez-Durance (France)

    2005-07-01

    Within the framework of plutonium recycling operations in CEA Valduc (France), americium is extracted from molten plutonium metal into a molten salt during an electrolysis process. The scraps (spent salt, cathode, and crucible) contain extracted americium and a part of plutonium. Nuclear material management requires a very accurate determination of the plutonium content. Gamma-ray spectroscopy is performed on Molten Salt Extraction (MSE) scraps located inside the glove box, in order to assess the plutonium and americium contents. The measurement accuracy is influenced by the device geometry, nuclear instrumentation, screens located between the sample and the detector, counting statistics and matrix attenuation, self-absorption within the spent salt being very important. The purpose of this study is to validate the 'infinite energy extrapolation' method employed to correct for self-attenuation, and to detect any potential bias. We present a numerical study performed with the MCNP computer code to identify the most influential parameters and some suggestions to improve the measurement accuracy. A final uncertainty of approximately 40% is achieved on the plutonium mass. (authors)

  14. An experimental study of americium-241 biokinetics in the Lobster Homarus Gammarus. Analysis of the accumulation/storage and detoxification processes at the subcellular level; Etude experimentale des biocinetiques de l`americium-241 chez le homard homarus gammarus. Analyse des mecanismes d`accumulation et de detoxication au niveau subcellulaire

    Energy Technology Data Exchange (ETDEWEB)

    Paquet, F.

    1993-01-01

    An experimental study of americium-241 kinetics has been conducted in the lobster Homarus gammmarus. The investigations were conducted at all the levels from the whole body to the subcellular and molecular levels. The animals were contaminated by a single or chronic ingestion of {sup 241} Am labelled mussels. Assessments of accumulation, elimination and distribution of the radionuclide were established on organisms kept in the laboratory; they made it possible to demonstrate the importance of the digestive gland in the radionuclide transfer pathways. The preliminary results led to structural then ultrastructural investigations of the digestive gland in association with radioautographic studies and cellular extractions methods. Four cellular types were demonstrated, only two of them being implied in the radionuclide retention, the former being responsible for americium intake and the latter for its long-term retention. By means of biochemical techniques, subcellular accumulation was studied and the organelles implied in the nuclide retention were specified. Finally, a method of cellular nuclei dissociation was developed; it made it possible to analyse the molecular nature of americium ligands and to demonstrate the function of the protein nuclear matrix in the nuclide retention.

  15. Dissertation on the computer-based exploitation of a coincidence multi parametric recording. Application to the study of the disintegration scheme of Americium 241

    International Nuclear Information System (INIS)

    After having presented the meaning of disintegration scheme (alpha and gamma emissions, internal conversion, mean lifetime), the author highlights the benefits of the use of multi-parametric chain for the recording of correlated parameters, and of the use of a computer for the analysis of bi-parametric information based on contour lines. Using the example of Americium 241, the author shows how these information are obtained (alpha and gamma spectrometry, time measurement), how they are chosen, coded, analysed and stored, and then processed by contour lines

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Preignition reactions of AP-HTPB propellants studied by IR spectrometry. [Ammonium Perchlorate-Hydroxyl Terminated PolyButadiene

    Science.gov (United States)

    Law, R. J.; Baer, A. D.; Ryan, N. W.

    1977-01-01

    IR absorption spectrometry was used to follow the disappearance of NH and CH bonds during the pyrolysis of a polymer film containing 30 weight percent ammonium perchlorate (AP). The remaining 70 weight percent consisted of a mixture of 92.5 weight percent hydroxyl-terminated polybutadiene (HTPB) and 7.5 weight percent isophrone diisocyanate (IPDI). The results indicate that polymer decomposition is induced by products of AP decomposition, and that about 2.5 CH bonds disappear for each NH bond that disappears. The diffusion process occurring in the later stages of the reaction is analyzed in an attempt to account for the unexpectedly low activation energy.

  3. On the adhesion between hydroxyl-terminated polybutadiene fuel-binder and ammonium perchlorate. Performance of bonding agents

    Energy Technology Data Exchange (ETDEWEB)

    Hori, K.; Iwama, A.; Fukuda, T.

    1985-12-01

    A simple method to evaluate the adhesive force between solid oxidizer and polymeric fuel-binder is presented. As an illustration, hydroxyl-terminated polybutadiene (HTPB) sticks including several different bonding agents are bonded on ammonium perchlorate (AP) single crystals, and stress-strain history unitl rupture occurs is obtained by applying uniaxial tensile stress perpendicularly to the adhesion surface. Further, whether each bonding agent reacts with AP or not was analysed with pursuing infrared absorption spectra. The hypothesis that the interfacial adhesive force arises from hydrogen bonding force is proposed.

  4. 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.

  5. A Hydrogen Ion-Selective Poly(Vinyl Chloride) Membrane Electrode Based on Calix[4]arene as a Perchlorate Ion-Selective Electrode

    OpenAIRE

    CANEL, Esin; ERDEN, Sevcan; ÖZEL, Ayça DEMİREL; MEMON, Sahahabuddin

    2008-01-01

    A hydrogen ion-selective electrode was prepared using 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetracyanometoxy-calix[4]arene and the possibility of its use as a perchlorate ion-selective electrode was investigated using its characteristic of becoming perchlorate sensitive in acidic regions. The electrode of the optimum characteristic had a composition of 1% ionophore, 66% o-NPOE, and 33% PVC. This electrode exhibited a linear response over the range 1.0 \\times 10-1-1.0 \\times 10-5 M o...

  6. 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.

  7. 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.

  8. 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.

  9. A novel hydrolysis method to synthesize chromium hydroxide nanoparticles and its catalytic effect in the thermal decomposition of ammonium perchlorate

    International Nuclear Information System (INIS)

    Highlights: ► Synthesis of Cr(OH)3 nanoparticles in Cr3+–F− aqueous solution. ► The F− ion tailors coagulated materials, Cr(OH)3 nanoparticles are obtained. ► Adding nanosized Cr(OH)3, AP thermal decomposition temperature decreases to 200 °C. ► The nanosized Cr(OH)3 catalyzes NH3 oxidation, accelerating AP thermal decomposition. - Abstract: A procedure for the preparation of spherical Cr(OH)3 nanoparticles was developed based on the aging of chromium nitrate aqueous solutions in the presence of sodium fluoride, urea, and polyvinylpyrrolidone. Using scanning electron microscopy, transmission electron microscopy, and energy dispersive spectroscopy, the morphological characteristics of Cr(OH)3 were controlled by altering the molar ratio of fluoride ion to chromium ion, as well as the initial pH and chromium ion concentration. The prepared nanosized Cr(OH)3 decreased the temperature required to decompose ammonium perchlorate from 450 °C to about 250 °C as the catalyst. The possible catalytic mechanism of the thermal decomposition of ammonium perchlorate was also discussed.

  10. 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.

  11. Use of starch and potato peel waste for perchlorate bioreduction in water.

    Science.gov (United States)

    Okeke, Benedict C; Frankenberger, William T

    2005-07-15

    The cost of carbon substrates for microbial reduction of perchlorate (ClO(4)(-)) is central to the success and competitiveness of a sustainable bioremediation strategy for ClO(4)(-). This study explored the potential application of starch in combination with an amylolytic bacterial consortia and potato peel waste for ClO(4)(-) bioreduction. We obtained a potent amylolytic bacterial consortium that consisted of a Citrobacter sp. S4, Streptomyces sp. S2, Flavobacterium sp. S6, Pseudoxanthomonas sp. S5, Streptomyces sp. S7, and an Aeromonas sp. S8 identified by 16S rDNA sequencing. ClO(4)(-) concentration substantially decreased in purified starch medium inoculated with the amylolytic bacterial consortium and Dechlorosoma sp. perclace. Potato peel waste supported ClO(4)(-) reduction by perclace with the rate of ClO(4)(-) reduction being dependent on the amount of potato peels. Over 90% ClO(4)(-) removal was achieved in 4 days in a single time point experiment with 2% (w/v) potato peels waste. ClO(4)(-) reduction in a non-sterile 0.5% potato peel media inoculated with perclace occurred with an initial concentration of 10.14+/-0.04 mg L(-1) to 2.87+/-0.4 mg L(-1) (71.7% reduction) within 5 days. ClO(4)(-) was not detected in the cultures in 6 days. In a non-sterile 0.5% potato media without perclace, ClO(4)(-) depletion occurred slowly from an initial value of 9.99+/-0.15 mg L(-1) to 6.33+/-0.43 mg L(-1) (36.63% reduction) in 5 days. Thereafter, ClO(4)(-) was rapidly degraded achieving 77.1% reduction in 7 days and not detected in 9 days. No susbstantial reduction of ClO(4)(-) was observed in the sterile potato peel media without perclace in 7 days. Redox potential of the potato peel cultures was favorable for ClO(4)(-) reduction, decreasing to as low as -294 mV in 24 h. Sugar levels remained very low in cultures effectively reducing ClO(4)(-) and was substantially higher in sterilized controls. Our results indicate that potato peel waste in combination with amylolytic

  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. Use of starch and potato peel waste for perchlorate bioreduction in water.

    Science.gov (United States)

    Okeke, Benedict C; Frankenberger, William T

    2005-07-15

    The cost of carbon substrates for microbial reduction of perchlorate (ClO(4)(-)) is central to the success and competitiveness of a sustainable bioremediation strategy for ClO(4)(-). This study explored the potential application of starch in combination with an amylolytic bacterial consortia and potato peel waste for ClO(4)(-) bioreduction. We obtained a potent amylolytic bacterial consortium that consisted of a Citrobacter sp. S4, Streptomyces sp. S2, Flavobacterium sp. S6, Pseudoxanthomonas sp. S5, Streptomyces sp. S7, and an Aeromonas sp. S8 identified by 16S rDNA sequencing. ClO(4)(-) concentration substantially decreased in purified starch medium inoculated with the amylolytic bacterial consortium and Dechlorosoma sp. perclace. Potato peel waste supported ClO(4)(-) reduction by perclace with the rate of ClO(4)(-) reduction being dependent on the amount of potato peels. Over 90% ClO(4)(-) removal was achieved in 4 days in a single time point experiment with 2% (w/v) potato peels waste. ClO(4)(-) reduction in a non-sterile 0.5% potato peel media inoculated with perclace occurred with an initial concentration of 10.14+/-0.04 mg L(-1) to 2.87+/-0.4 mg L(-1) (71.7% reduction) within 5 days. ClO(4)(-) was not detected in the cultures in 6 days. In a non-sterile 0.5% potato media without perclace, ClO(4)(-) depletion occurred slowly from an initial value of 9.99+/-0.15 mg L(-1) to 6.33+/-0.43 mg L(-1) (36.63% reduction) in 5 days. Thereafter, ClO(4)(-) was rapidly degraded achieving 77.1% reduction in 7 days and not detected in 9 days. No susbstantial reduction of ClO(4)(-) was observed in the sterile potato peel media without perclace in 7 days. Redox potential of the potato peel cultures was favorable for ClO(4)(-) reduction, decreasing to as low as -294 mV in 24 h. Sugar levels remained very low in cultures effectively reducing ClO(4)(-) and was substantially higher in sterilized controls. Our results indicate that potato peel waste in combination with amylolytic

  14. Inhaled americium dioxide

    International Nuclear Information System (INIS)

    This project includes experiments to determine the effects of Zn-DTPA therapy on the retention, translocation and biological effects of inhaled 241AmO2. Beagle dogs that received inhalation exposure to 241AmO2 developed leukopenia, clincial chemistry changes associated with hepatocellular damage, and were euthanized due to respiratory insufficiency caused by radiation pneumonitis 120 to 131 days after pulmonary deposition of 22 to 65 μCi 241Am. Another group of dogs that received inhalation exposure to 241AmO2 and were treated daily with Zn-DTPA had initial pulmonary deposition of 19 to 26 μCi 241Am. These dogs did not develop respiratory insufficiency, and hematologic and clinical chemistry changes were less severe than in the non-DTPA-treated dogs

  15. 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

  16. 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.

  17. 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...

  18. Recovery of Americium-241 from lightning rod by the method of chemical treatment; Recuperacion del Americio-241 provenientes de los pararrayos por el metodo de tratamiento quimico

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, W.H., E-mail: wcruz@ipen.gob.pe [Instituto Peruano de Energia Nuclear (GRRA/IPEN), Lima (Peru). Division de Gestion de Residuos Radiactivos

    2013-07-01

    About 95% of the lightning rods installed in the Peruvian territory have set in their structures, pose small amounts of radioactive sources such as Americium-241 ({sup 241}Am), fewer and Radium 226 ({sup 226}Ra) these are alpha emitters and have a half life of 432 years and 1600 years respectively. In this paper describes the recovery of radioactive sources of {sup 241}Am radioactive lightning rods using the conventional chemical treatment method using agents and acids to break down the slides. The {sup 241}Am recovered was as excitation source and alpha particle generator for analysing samples by X Ray Fluorescence, for fixing the stainless steel {sup 241}Am technique was used electrodeposition. (author)

  19. Partitioning studies in China and the separation of americium and fission product rare earths with dialkyl phosphinic acid and its thio-substituted derivatives

    International Nuclear Information System (INIS)

    Studies on the TRPO extractions process for recovering actinides from highly active waste (HAW) and its application to the pretreatment of Chinese HAW are described. The removal of Sr by di-cyclohexyl 18 crown 6 and the removal of Cs by spherical titanium ferrous hexa-cyanate from acidic waste are also described. Results of the extraction of trivalent americium and fission product rare earths (FPREs) by dialkyl-phosphinic, dialkyl-mono-thio-phosphinic and dialkyl-di-thio-phosphinic acids are reported. Dialkyl-thio-phosphinic acid (commercial product Cyanex 301, alkyl =2, 4, 4-methyl-pentyl) shows very high selectivity towards Am. Using 1M Cyanex 301 -kerosene as extractant, 99.9 % Am can be separated from 0.5M(Pr+Nd)(NO3)3 solution with 3-4 extraction stages and 3-4 scrubbing stages. (authors)

  20. Theoretical and experimental study of the bio-geochemical behaviour of americium 241 in simplified rhizosphere conditions. Application to a calcareous agricultural soil

    International Nuclear Information System (INIS)

    Americium 241, is one of the most radio-toxic contaminant produced during the nuclear fuel cycle. It can be found in all environmental compartments, in particular the soils. The main goals of this study are to identify, quantify and model the effect of the main factors controlling the mobility of 241Am in the rhizosphere and the agricultural soils. The physico-chemical parameters of the soil and of the soil solution, the potential role of microorganisms on the sorption-desorption processes, and the speciation of americium in solution have been more particularly studied. 241Am remobilization has been studied at the laboratory using leaching experiments performed in controlled conditions on reworked calcareous soils artificially contaminated with 241Am. The soil samples have been washed out in different hydrodynamic conditions by solutions with various compositions. The eluted solution has been analyzed (pH, conductivity, ionic composition, Fetot, organic acids, 241Am) and its bacterial biomass content too. The overall results indicate that 241Am remobilization is contrasted and strongly linked with the condition under study (pH, ionic strength, glucose and/or citrate concentration). Therefore, a solution in equilibrium with the soil or containing small exudate concentrations (10-4 M) re-mobilizes only a very small part of the americium fixed on the solid phase. The desorption of 241Am corresponds to a solid/liquid coefficient of partition (Kd) of about 105 L.kg-1. A significant addition of glucose induces an important dissolution of soil carbonates by the indirect action of microorganisms, but does not significantly favor the 241Am remobilization. On the other hand, the presence of strong citrate concentrations (≥ 10-2 M) allows 300 to 10000 time greater re-mobilizations by the complexing of 241Am released after the dissolution of the carrying phases. Finally, the colloidal transport of 241Am has been systematically observed in a limited but significant extend and

  1. 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.

  2. Safe handling of kilogram amounts of fuel-grade plutonium and of gram amounts of plutonium-238, americium-241 and curium-244

    International Nuclear Information System (INIS)

    During the past 10 years about 600 glove-boxes have been installed at the Institute for Transuranium Elements at Karlsruhe. About 80% of these glove-boxes have been designed and equipped for handling 100-g to 1-kg amounts of 239Pu containing 8-12% 240Pu (low-exposure plutonium). A small proportion of the glove-boxes is equipped with additional shielding in the form of lead sheet or lead glass for work with recycled plutonium. In these glove-boxes gram-amounts of 241Am have also been handled for preparation of Al-Am targets using tongs and additional shielding inside the glove-boxes themselves. Water- and lead-shielded glove-boxes equipped with telemanipulators have been installed for routine work with gram-amounts of 241Am, 243Am and 244Cm. A prediction of the expected radiation dose for the personnel is difficult and only valid for a preparation procedure with well-defined preparation steps, owing to the fact that gamma dose-rates depend strongly upon proximity and source seize. Gamma radiation dose measurements during non-routine work for 241Am target preparation showed that handling of gram amounts leads to a rather high irradiation dose for the personnel, despite lead or steel glove-box shielding and shielding within the glove-boxes. A direct glove-hand to americium contact must be avoided. For all glove-handling of materials with gamma radiation an irradiation control of the forearms of the personnel by, for example, thermoluminescence dosimeters is necessary. Routine handling of americium and curium should be executed with master-slave equipment behind neutron and gamma shielding. (author)

  3. 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.

  4. 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.

  5. 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.

  6. Thermal, optical, mechanical and electrical properties of a novel NLO active L-phenylalanine L-phenylalaninium perchlorate single crystals

    International Nuclear Information System (INIS)

    Single crystals of L-phenylalanine L-phenylalaninium perchlorate (LPAPCl), a semiorganic nonlinear (NLO) material have been successfully grown up to a size of 14 mmx5 mmx3 mm. The lattice parameters of the grown crystals are determined by single crystal XRD. The UV-Vis-NIR spectrum of LPAPCl show less optical absorption in the entire visible region. Nonlinear optical study reveals that the SHG efficiency of LPAPCl is nearly 1.4 times that of KDP. The laser damage density is found to be 7.4 GW/cm2. The crystals are subjected to microhardness studies and the variation of the microhardness with the applied load is studied. The response of dielectric constant in the frequency region of 50 Hz to 5 MHz has been investigated. AC and DC conductivity and photoconductivity experiments are also carried out and the results are discussed.

  7. Synthesis of N-(3-(Dimethylamino)-2-(4-Ethoxyphenyl) Alllidene)-N-Methylmethanaminium Perchlorate by Willgerodt-Kindler Reaction

    Institute of Scientific and Technical Information of China (English)

    REN Wei-min; WANG Xing-yong; YANG Hai-tao; SHI Gui-zhen; LI Feng

    2006-01-01

    Liquid crystals containing phenylpyrimidine units are the fascination condensed state of soft matter with unique electrical, optical and mechanical properties. In this paper, a novel and efficient route was reported for the synthesis of N-(3-(dimethylamino)-2-(4-ethoxyphenyl)allylidene)-N-methylmethanaminium perchlorate by the WillgerodtKindler reaction, which can be further applied to prepare liquid crystals containing phenylpyrimidine units. The product was confirmed by 1HNMR, MS, FT-IR and elemental analysis. The experimental conditions of the Willgerodt-Kindler reaction were also studied and the results show that the yield ofp-ethoxyphenyl-acetic acid increased remarkably with a reaction time up to 60 min, then decreased due to carbonization. On the other hand, the yield was also influenced by microwave power. It increased from 20.6 % to 78.8 % with a rise in the microwave power from 250 W to 450 W, but the product was carbonized at 640 W.

  8. Optimized pyroelectric properties of 0-3 composites of PZT particles in polyurethane doped with lithium perchlorate.

    Science.gov (United States)

    Ploss, Bernd; Krause, Markus

    2007-12-01

    A substantial improvement in the performance of pyroelectric 0-3 composites of ceramic particles in a polymer matrix has been achieved by doping the polymer matrix material. Readily prepared and polarized films with various volume fractions of lead zirconate-titanate (PZT) particles in polyurethane have been doped in a solution of lithium perchlorate in acetone to increase the conductivity. With an appropriate conductivity, the dielectric permittivities of the ceramic particles and the polymer matrix become matched, resulting in an improvement of the pyroelectric coefficient from about 6 microC/(m(2)K) to about 50 microC/(m(2)K). The experimental results are explained by theoretical predictions. PMID:18276541

  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. Effects of addition of surfactants on viscosity of uncured ammonium perchlorate(A/P)/hydroxyl-terminated polybutadiene (HTPB) propellant

    Energy Technology Data Exchange (ETDEWEB)

    Koga, M.; Hagihara, Y. [National Defense Academy, Kanagawa (Japan)

    1998-08-31

    In production of ammonium perchlorate (AP)/hydroxyl-terminated polybutadiene (HTPB) propellants, it is preferable that the uncured propellant has a low viscosity during the mixing and forming processes. In this study, effects of surfacant on viscosity of the uncured propellant are studied for a total of 11 types of surfacants. It is found that sodium lauryl sulfate decreases viscosity of the AP/HTPB mixture more efficiently than any other surfacants tested. Apparent viscosity decreases by 30%, and its optimum dosage will be 0.005wt% based on the mixture to sufficiently decrease viscosity of the mixture. Viscosity of the mixture can be also decreased by improving wettability between AP and HTPB prepolymer. Sodium lauryl sulfate also shows an effect of delaying the potlife, i.e., time extending from addition of a curing agent to a thermosetting resin until it is cured to be unserviceable. 6 refs., 4 figs., 2 tabs.

  11. 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.

  12. 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.)

  13. 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.

  14. Actinide Oxidation State and O/M Ratio in Hypostoichiometric Uranium-Plutonium-Americium U0.750Pu0.246Am0.004O2-x Mixed Oxides.

    Science.gov (United States)

    Vauchy, Romain; Belin, Renaud C; Robisson, Anne-Charlotte; Lebreton, Florent; Aufore, Laurence; Scheinost, Andreas C; Martin, Philippe M

    2016-03-01

    Innovative americium-bearing uranium-plutonium mixed oxides U1-yPuyO2-x are envisioned as nuclear fuel for sodium-cooled fast neutron reactors (SFRs). The oxygen-to-metal (O/M) ratio, directly related to the oxidation state of cations, affects many of the fuel properties. Thus, a thorough knowledge of its variation with the sintering conditions is essential. The aim of this work is to follow the oxidation state of uranium, plutonium, and americium, and so the O/M ratio, in U0.750Pu0.246Am0.004O2-x samples sintered for 4 h at 2023 K in various Ar + 5% H2 + z vpm H2O (z = ∼15, ∼90, and ∼200) gas mixtures. The O/M ratios were determined by gravimetry, XAS, and XRD and evidenced a partial oxidation of the samples at room temperature. Finally, by comparing XANES and EXAFS results to that of a previous study, we demonstrate that the presence of uranium does not influence the interactions between americium and plutonium and that the differences in the O/M ratio between the investigated conditions is controlled by the reduction of plutonium. We also discuss the role of the homogeneity of cation distribution, as determined by EPMA, on the mechanisms involved in the reduction process. PMID:26907589

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  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. Human bones obtained from routine joint replacement surgery as a tool for studies of plutonium, americium and {sup 90}Sr body-burden in general public

    Energy Technology Data Exchange (ETDEWEB)

    Mietelski, Jerzy W., E-mail: jerzy.mietelski@ifj.edu.pl [Henryk Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Cracow (Poland); Golec, Edward B. [Traumatology and Orthopaedic Clinic, 5th Military Clinical Hospital and Polyclinic, Independent Public Healthcare Facility, Wroclawska 1-3, 30-901 Cracow (Poland); Orthopaedic Rehabilitation Department, Chair of Clinical Rehabilitation, Faculty of Motor of the Bronislaw Czech' s Academy of Physical Education, Cracow (Poland); Department of Physical Therapy Basics, Faculty of Physical Therapy, Administration College, Bielsko-Biala (Poland); Tomankiewicz, Ewa [Henryk Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Cracow (Poland); Golec, Joanna [Orthopaedic Rehabilitation Department, Chair of Clinical Rehabilitation, Faculty of Motor of the Bronislaw Czech' s Academy of Physical Education, Cracow (Poland); Physical Therapy Department, Institute of Physical Therapy, Faculty of Heath Science, Jagiellonian University, Medical College, Cracow (Poland); Nowak, Sebastian [Traumatology and Orthopaedic Clinic, 5th Military Clinical Hospital and Polyclinic, Independent Public Healthcare Facility, Wroclawska 1-3, 30-901 Cracow (Poland); Orthopaedic Rehabilitation Department, Chair of Clinical Rehabilitation, Faculty of Motor of the Bronislaw Czech' s Academy of Physical Education, Cracow (Poland); Szczygiel, Elzbieta [Physical Therapy Department, Institute of Physical Therapy, Faculty of Heath Science, Jagiellonian University, Medical College, Cracow (Poland); Brudecki, Kamil [Henryk Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, 31-342 Cracow (Poland)

    2011-06-15

    The paper presents a new sampling method for studying in-body radioactive contamination by bone-seeking radionuclides such as {sup 90}Sr, {sup 239+240}Pu, {sup 238}Pu, {sup 241}Am and selected gamma-emitters, in human bones. The presented results were obtained for samples retrieved from routine surgeries, namely knee or hip joints replacements with implants, performed on individuals from Southern Poland. This allowed to collect representative sets of general public samples. The applied analytical radiochemical procedure for bone matrix is described in details. Due to low concentrations of {sup 238}Pu the ratio of Pu isotopes which might be used for Pu source identification is obtained only as upper limits other then global fallout (for example Chernobyl) origin of Pu. Calculated concentrations of radioisotopes are comparable to the existing data from post-mortem studies on human bones retrieved from autopsy or exhumations. Human bones removed during knee or hip joint surgery provide a simple and ethical way for obtaining samples for plutonium, americium and {sup 90}Sr in-body contamination studies in general public. - Highlights: > Surgery for joint replacement as novel sampling method for studying in-body radioactive contamination. > Proposed way of sampling is not causing ethic doubts. > It is a convenient way of collecting human bone samples from global population. > The applied analytical radiochemical procedure for bone matrix is described in details. > The opposite patient age correlations trends were found for 90Sr (negative) and Pu, Am (positive).

  1. The recycling of the actinides neptunium, americium and curium in a fast power reactor to reduce the long term activity in a final store

    International Nuclear Information System (INIS)

    The starting point for the considerations and calculations given in this dissertation is the inevitable production of radioactive materials in the use of nuclear energy, which creates a considerable potential danger in a final store for a very long period. As one possibility of alleviating this problem, a concept for recycling the waste actinides neptunium, americium and curium was proposed. The waste actinides are separated in the reprocessing of burnt-up fuel elements and reach a further irradiation circuit. There they pass through the stages 'manufacture of irradiation elements', 'use in a fast power reactor' and reprocessing of irradiation elements' several times. In each irradiation and subsequent storage, about 17% of the waste actinides are removed by fission or by conversion into nuclides which can be reused as fuel, so that during the life of 40 years of the fast recycling reacor, the waste actinides can be reduced in mass by one half. In order to determine this mass reduction effect, a model calculation was developed, which includes the representation of the neutron physics and thermal properties of the reactor core and the storage and reprocessing of the irradiation elements. (orig./RB)

  2. Human bones obtained from routine joint replacement surgery as a tool for studies of plutonium, americium and 90Sr body-burden in general public

    International Nuclear Information System (INIS)

    The paper presents a new sampling method for studying in-body radioactive contamination by bone-seeking radionuclides such as 90Sr, 239+240Pu, 238Pu, 241Am and selected gamma-emitters, in human bones. The presented results were obtained for samples retrieved from routine surgeries, namely knee or hip joints replacements with implants, performed on individuals from Southern Poland. This allowed to collect representative sets of general public samples. The applied analytical radiochemical procedure for bone matrix is described in details. Due to low concentrations of 238Pu the ratio of Pu isotopes which might be used for Pu source identification is obtained only as upper limits other then global fallout (for example Chernobyl) origin of Pu. Calculated concentrations of radioisotopes are comparable to the existing data from post-mortem studies on human bones retrieved from autopsy or exhumations. Human bones removed during knee or hip joint surgery provide a simple and ethical way for obtaining samples for plutonium, americium and 90Sr in-body contamination studies in general public. - Highlights: → Surgery for joint replacement as novel sampling method for studying in-body radioactive contamination. → Proposed way of sampling is not causing ethic doubts. → It is a convenient way of collecting human bone samples from global population. → The applied analytical radiochemical procedure for bone matrix is described in details. → The opposite patient age correlations trends were found for 90Sr (negative) and Pu, Am (positive).

  3. The estimation of reactions of hematopoietic systems of organisms to the effect, caused by americium and plutonium, of nuclear industry workers

    Energy Technology Data Exchange (ETDEWEB)

    Gasteva, G. N.; Ivanova, T. A.; Gordeeva, A. A.; Suvorova, L. A.; Molokanov, A. A.; Badine, I.

    2004-07-01

    Object of research are the workers having in an organism radioactive substance (Am-241 and Pu-239). The purpose of work was the estimation of reaction hemopoietic systems of an organism on influence of americium and plutonium at workers of the nuclear industry. At the surveyed contingent of persons the determined effects caused by total influence Am-241 and Pu-239 are ascertained; chronic radiation disease with development, besides diffusive a pneumoscleoris and a chronic toxic-chemical radiating bronchitis, reactions of system of blood, jet hepatopathy which frequency accrued with increase doses loadings and essentially did not depend on age. In peripheral blood on the foreground jet changes act: hyperglobulia, the tendency to neutrophilus leukocytosis, monocytosis, increase ESR, decrease (reduction ?/G of factor reflecting weight and processing of defeat bronchus and pulmonary of system. Stable downstroke in number thrombocytes and reticulocytes in peripheral blood, their direct dependence on a doze of an irradiation, reflect hypoplastic a background hemogenesis, caused by long influence incorporatedin a bone and a bone brain of radioactive substances. At cytologic research punctate a bone brain jet changes which are expressed in increase of functional activity erythro-and myelopoiesiscome to light and provide compensatory reaction of peripheral blood. At histologic research of a bone brain and a bone fabric attributes of development atrophic process which is expressed in reduction of volume parenchyma a bone brain (a fatty atrophy) and dysplasia to a bone fabric are observed.

  4. Biological Reduction of Perchlorate and Optimization%生物法降解高氯酸盐及其优化研究

    Institute of Scientific and Technical Information of China (English)

    钱慧静; 奚胜兰; 何平; 徐新华

    2009-01-01

    The potential of bioremediation to treat perchlorate-contaminated water by acclimating anaerobic activated sludge was investigated in this study. Factors such as carbon source,initial pH,temperature,domesticated sludge concentration and dissolved oxygen affecting the removal of perchlorate were studied in detail by shaking-bottle point tests using acetate as carbon source. Results showed that 50 mg/L perchlorate was completely reduced by 1.0 g of domesticated sludge added with 1.2 g/L of acetate under the conditions of 35℃ and initial pH 8.0. Dissolved oxygen in the system would restrain the reduction of perchlorate. In addition,column bioreactor was used to treat perchlorate continuously,with the minimum residence time of 6 h.%利用经过驯化处理的厌氧活性污泥来处理高氯酸盐废水,以醋酸根为碳源,通过摇床实验考察了碳源浓度、pH值、生长温度、泥量和溶解氧等因素对高氯酸盐降解率的影响,初步确定最佳反应条件.结果表明,在35℃、初始pH值为 8.0的条件下,添加1.2 g/L的醋酸根,1.0 g厌氧培养的活性污泥能将50 mg/L的高氯酸盐完全降解.体系中的溶解氧会抑制高氯酸盐的降解.此外,还考察了生物膜柱反应器连续处理高氯酸盐模拟废水的效果,结果表明完全降解高氯酸盐的最小停留时间为6 h.

  5. Syntheses and luminescence properties of two novel lanthanide (III) perchlorate complexes with phenacyl p-tolyl sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Shu-Yan [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Li, Wen-Xian, E-mail: nmglwx@163.com [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Yu-Shan [Inner Mongolia Autonomous Region Product Quality Inspection Institute, Hohhot 010070 (China); Xin, Xiao-Dong; Guo, Feng; Cao, Xiao-Fang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China)

    2015-06-15

    Two novel solid binary complexes of rare earth perchlorate with phenacyl p-tolyl sulfoxide were synthesized and characterized by elemental analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, {sup 1}HNMR and UV spectra. The results indicated that the composition of these complexes was REL{sub 7} (ClO{sub 4}){sub 3}·6H{sub 2}O (RE=Eu (III), Tb (III), L=C{sub 6}H{sub 5}COCH{sub 2}SOC{sub 6}H{sub 4}CH{sub 3}). The study on IR spectra and {sup 1}HNMR spectra revealed that phenacyl p-tolyl sulfoxide bonded with RE{sup 3+} ions by the oxygen atom in sulfinyl group. The emission spectra illustrated that both the Eu (III) and Tb (III) complexes displayed excellent luminescence in solid state, and The most intensive characteristic emission of the Eu(III) and Tb(III) complexes were 245,400 a.u. and 298,000 a.u. respectively. The slit with was 1 nm. By analysis luminescence and phosphorescence spectrum, it was found that the ligand had the advantage to absorb energy and transfer it to the Eu (III) and Tb (III) ions. The fluorescence lifetimes of the complexes were measured as well as the quantum yield of the Eu (III) complex.

  6. The angiogenic effect of dracorhodin perchlorate on human umbilical vein endothelial cells and its potential mechanism of action.

    Science.gov (United States)

    Li, Feng; Jiang, Tao; Liu, Wei; Hu, Quan; Yin, Huinan

    2016-08-01

    Hyperglycemia is the key clinical feature of diabetes, and may induce refractory wound lesions and impaired angiogenesis. Dracorhodin perchlorate (Dra) is the major ingredient of dragon's blood and it has been used as a medicine to treat chronic wounds, such as diabetic foot, since ancient times in many cultures. The current study aimed to investigate the effect of Dra on human umbilical vein endothelial cells (HUVECs) under high‑glucose (HG) stimulation and its potential mechanism. Dra was observed to increase the multiplication capacity of HUVECs both under low glucose (LG) and HG concentrations. Additionally, migration and tube formation in HUVECs was facilitated by Dra. The expression levels of Ras, mitogen‑activated protein kinase (MAPK) and vascular endothelial growth factor, which are key components of the Ras/MAPK pathway, were upregulated following Dra treatment. The present study is the first report, to the best of our knowledge, of the effects of Dra on wound healing, and the association with the Ras/MAPK signaling pathway. PMID:27357516

  7. Syntheses and luminescence properties of two novel lanthanide (III) perchlorate complexes with phenacyl p-tolyl sulfoxide

    International Nuclear Information System (INIS)

    Two novel solid binary complexes of rare earth perchlorate with phenacyl p-tolyl sulfoxide were synthesized and characterized by elemental analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, 1HNMR and UV spectra. The results indicated that the composition of these complexes was REL7 (ClO4)3·6H2O (RE=Eu (III), Tb (III), L=C6H5COCH2SOC6H4CH3). The study on IR spectra and 1HNMR spectra revealed that phenacyl p-tolyl sulfoxide bonded with RE3+ ions by the oxygen atom in sulfinyl group. The emission spectra illustrated that both the Eu (III) and Tb (III) complexes displayed excellent luminescence in solid state, and The most intensive characteristic emission of the Eu(III) and Tb(III) complexes were 245,400 a.u. and 298,000 a.u. respectively. The slit with was 1 nm. By analysis luminescence and phosphorescence spectrum, it was found that the ligand had the advantage to absorb energy and transfer it to the Eu (III) and Tb (III) ions. The fluorescence lifetimes of the complexes were measured as well as the quantum yield of the Eu (III) complex

  8. 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.

  9. Specific interactions of functionalised gold surfaces with ammonium perchlorate or starch; towards a chemical cartography of their mixture

    Science.gov (United States)

    Mercier, D.; Mercader, C.; Quere, S.; Hairault, L.; Méthivier, C.; Pradier, C. M.

    2012-10-01

    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.

  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. 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.

  12. The Investigation of Chlorate and Perchlorate/Saponite Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

    Science.gov (United States)

    Clark, J.; Sutter, B.; Min, D. W.; Mahaffy, P.

    2016-01-01

    The Sample Analysis at Mars (SAM) instrument on board the Curiosity Rover has detected O2 and HCl gas releases from all analyzed Gale Crater sediments, which are attributed to the presence of perchlorates and/or chlorates in martian sediment. Previous SAM analog laboratory analyses found that most pure perchlorates and chlorates release O2 and HCl at different temperatures than those observed in the SAM data. Subsequent studies examined the effects of perchlorate and chlorate mixtures with Gale Crater analog iron phases, which are known to catalyze oxychlorine decomposition. Several mixtures produced O2 releases at similar temperatures as Gale Crater materials, but most of these mixtures did not produce significant HCl releases comparable to those detected by the SAM instrument. In order to better explain the Gale Crater HCl releases, perchlorates and chlorates were mixed with Gale Crater analog saponite, which is found at abundances from 8 to 20 wt % in the John Klein and Cumberland drill samples. Mixtures of chlorates or perchlorates with calcium-saponite or ferrian-saponite were heated to 1000 deg C in a Labsys EVO differential scanning calorimeter/mass spectrometer configured to operate similarly to the SAM oven/quadrupole mass spectrometer system. Our results demonstrate that all chlorate and perchlorate mixtures produce significant HCl releases below 1000 deg C as well as depressed oxygen peak release temperatures when mixed with saponite. The type of saponite (calcium or ferrian saponite) did not affect the evolved gas results significantly. Saponite/Mg-perchlorate mixtures produced two HCl releases similar to the Cumberland drilled sample. Mg-chlorate mixed with saponite produced HCl releases similar to the Big Sky drilled sample in an eolian sandstone. A mixture of Ca-perchlorate and saponite produced HCl and oxygen releases similar to the Buckskin mudstone drilled sample and the Gobabeb 2 eolian dune material. Ca-chlorate mixed with saponite produced both

  13. 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.

  14. The construction of TRIGA-TRAP and direct high-precision Penning trap mass measurements on rare-earth elements and americium

    Energy Technology Data Exchange (ETDEWEB)

    Ketelaer, Jens

    2010-06-14

    The construction of TRIGA-TRAP and direct high-precision Penning trap mass measurements on rare-earth elements and americium: Nuclear masses are an important quantity to study nuclear structure since they reflect the sum of all nucleonic interactions. Many experimental possibilities exist to precisely measure masses, out of which the Penning trap is the tool to reach the highest precision. Moreover, absolute mass measurements can be performed using carbon, the atomic-mass standard, as a reference. The new double-Penning trap mass spectrometer TRIGA-TRAP has been installed and commissioned within this thesis work, which is the very first experimental setup of this kind located at a nuclear reactor. New technical developments have been carried out such as a reliable non-resonant laser ablation ion source for the production of carbon cluster ions and are still continued, like a non-destructive ion detection technique for single-ion measurements. Neutron-rich fission products will be available by the reactor that are important for nuclear astrophysics, especially the r-process. Prior to the on-line coupling to the reactor, TRIGA-TRAP already performed off-line mass measurements on stable and long-lived isotopes and will continue this program. The main focus within this thesis was on certain rare-earth nuclides in the well-established region of deformation around N {proportional_to} 90. Another field of interest are mass measurements on actinoids to test mass models and to provide direct links to the mass standard. Within this thesis, the mass of {sup 241}Am could be measured directly for the first time. (orig.)

  15. 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)(-).

  16. Preparation and characterization of novel solid polymer blend electrolytes based on poly (vinyl pyrrolidone) with various concentrations of lithium perchlorate

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • The maximum ionic conductivity value was found to be 0.2307 × 10−5 S cm−1 for PEO(90 wt%)/PVP(10 wt%)/LiClO4(8 wt%) based electrolyte at room temperature. • The structural and functional groups were studied by XRD and FTIR. • Both direct and indirect optical band gap values were evaluated from UV–vis analysis. • The change in viscosity of the polymer electrolytes was studied by photoluminescence spectra. - Abstract: A series of conducting novel solid polymer blend electrolytes (SPE) based on the fixed ratio of poly (ethylene oxide)/poly (vinyl pyrrolidone) (PEO/PVP) and various concentrations of salt lithium perchlorate (LiClO4) were prepared by solvent casting technique. Structural and complex formation of the prepared electrolytes was confirmed by X-ray diffraction and FTIR analyses. The maximum ionic conductivity value was found to be 0.2307 × 10−5 S cm−1 for 8 wt% of LiClO4 based system at ambient temperature. Thermal stability of the present system was studied by thermo gravimetric/differential thermal analysis (TG/DTA). Surface morphology of the sample having maximum ionic conductivity was studied by atomic force microscope (AFM). Optical properties like direct and indirect band gaps were investigated by UV–vis analysis. The change in viscosity of the polymer complexes were also identified using photoluminescence emission spectra. PEO(90)/PVP(10)/LiClO4(8) has the highest conductivity which is supported by the lowest optical band gap and lowest intensity in photoluminescence spectroscopy near 400–450 nm

  17. 6,6 '-bis (5,5,8,8-tetramethyl-5,6,7,8-tetra-hydro-benzo 1,2,4 triazine-3-yl) 2,2 ' bipyridine, an effective extracting agent for the separation of americium(III) and curium(III) from the lanthanides

    International Nuclear Information System (INIS)

    The extraction of americium(III), curium(III), and the lanthanides(III) from nitric acid by 6,6'- bis (5,5,8,8-tetramethyl-5,6,7,8-tetra-hydro-benzo[1,2,4]triazine-3-yl)-[2,2'] bipyridine (CyMe4-BTBP) has been studied. Since the extraction kinetics were slow, N,N'-dimethyl-N,N'-di-octyl-2-(2-hexyl-oxy-ethyl)malonamide (DMDOHEMA) was added as a phase transfer reagent. With a mixture of 0.01 M CyMe4-BTBP + 0.25 M DMDOHEMA in n -octanol, extraction equilibrium was reached within 5 min of mixing. At a nitric acid concentration of 1 M, an americium(III) distribution ratio of approx. 10 was achieved. Americium(III)/lanthanide(III) separation factors between 50 (dysprosium) and 1500 (lanthanum) were obtained. Whereas americium(III) and curium(III) were extracted as di-solvates, the stoichiometries of the lanthanide(III) complexes were not identified unambiguously, owing to the presence of DMDOHEMA. In the absence of DMDOHEMA, both americium(III) and europium(III) were extracted as di-solvates. Back-extraction with 0.1 M nitric acid was thermodynamically possible but rather slow. Using a buffered glycolate solution of pH=4, an americium(III) distribution ratio of 0.01 was obtained within 5 min of mixing. There was no evidence of degradation of the extractant, for example, the extraction performance of CyMe4-BTBP during hydrolysis with 1 M nitric acid did not change over a two month contact. (authors)

  18. Crystal structure of trans-bis(ethane-1,2-diamine-κ2N,N′)bis(thiocyanato-κN)chromium(III) perchlorate from synchrotron data

    OpenAIRE

    Dohyun Moon; Jong-Ha Choi

    2015-01-01

    The structure of the title compound, [Cr(NCS)2(C2H8N2)2]ClO4, has been determined from synchroton data. The asymmetric unit consists of one half of a centrosymmetric CrIII complex cation and half of a perchlorate anion with the Cl atom on a twofold rotation axis. The CrIII ion is coordinated by the four N atoms of two ethane-1,2-diamine (en) ligands in the equatorial plane and two N-bound thiocyanate (NCS−) anions in a trans-axial arrangement, displaying a slightly distorted octahedral geomet...

  19. 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.

  20. 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....

  1. The perchlorate anion is more effective than the trifluoroacetate anion as an ion-pairing reagent for reversed-phase chromatography of peptides

    OpenAIRE

    Shibue, M.; Mant, C.T.; Hodges, R.S.

    2005-01-01

    The addition of salts, specifically sodium perchlorate (NaClO4), to mobile phases at acidic pH as ion-pairing reagents for reversed-phase high-performance liquid chromatography (RP-HPLC) has been generally overlooked. To demonstrate the potential of NaClO4 as an effective anionic ion-pairing reagent, we applied RP-HPLC in the presence of 0–100 mM sodium chloride (NaCl), sodium trifluoroacetate (NaTFA) or NaClO4 to two mixtures of synthetic 18-residue peptides: a mixture of peptides with the s...

  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. 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)

  4. Impact of the cation distribution homogeneity on the americium oxidation state in the U0.54Pu0.45Am0.01O2-x mixed oxide

    Science.gov (United States)

    Vauchy, Romain; Robisson, Anne-Charlotte; Martin, Philippe M.; Belin, Renaud C.; Aufore, Laurence; Scheinost, Andreas C.; Hodaj, Fiqiri

    2015-01-01

    The impact of the cation distribution homogeneity of the U0.54Pu0.45Am0.01O2-x mixed oxide on the americium oxidation state was studied by coupling X-ray diffraction (XRD), electron probe micro analysis (EPMA) and X-ray absorption spectroscopy (XAS). Oxygen-hypostoichiometric Am-bearing uranium-plutonium mixed oxide pellets were fabricated by two different co-milling based processes in order to obtain different cation distribution homogeneities. The americium was generated from β- decay of 241Pu. The XRD analysis of the obtained compounds did not reveal any structural difference between the samples. EPMA, however, revealed a high homogeneity in the cation distribution for one sample, and substantial heterogeneity of the U-Pu (so Am) distribution for the other. The difference in cation distribution was linked to a difference in Am chemistry as investigated by XAS, with Am being present at mixed +III/+IV oxidation state in the heterogeneous compound, whereas only Am(IV) was observed in the homogeneous compound. Previously reported discrepancies on Am oxidation states can hence be explained by cation distribution homogeneity effects.

  5. Crystal structure of trans-bis(ethane-1,2-diamine-κ2N,N′bis(thiocyanato-κNchromium(III perchlorate from synchrotron data

    Directory of Open Access Journals (Sweden)

    Dohyun Moon

    2015-06-01

    Full Text Available The structure of the title compound, [Cr(NCS2(C2H8N22]ClO4, has been determined from synchroton data. The asymmetric unit consists of one half of a centrosymmetric CrIII complex cation and half of a perchlorate anion with the Cl atom on a twofold rotation axis. The CrIII ion is coordinated by the four N atoms of two ethane-1,2-diamine (en ligands in the equatorial plane and two N-bound thiocyanate (NCS− anions in a trans-axial arrangement, displaying a slightly distorted octahedral geometry with crystallographic inversion symmetry. The Cr—N(en bond lengths are in the range 2.053 (16–2.09 (2 Å, while the Cr—N(thiocyanate bond length is 1.983 (2 Å. The five-membered en rings are disordered over two sites, with occupancy ratios of 0.522 (16:0.478 (16. Each ClO4− anion is disordered over two sites with equal occupancy. The crystal structure is stabilized by intermolecular hydrogen bonds involving the en NH2 groups as donors and perchlorate O and thiocyanate S atoms as acceptors.

  6. Combustion aspects of the consolidated mixtures of 5-amino-1H-tetrazole and potassium perchlorate; 5-amino-1H-tetorazoru to kaensosankariumu kongobutsu no nensho tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Hasue, Kazuo.; Akanuma, Takanori.; Hodai, Harunori.; Date, Shingo. [National Defence Academy, Kanagawa (Japan). Dept. of Chemistry

    1999-02-28

    This paper describes the study concerning fundamental combustion features of the mixtures of 5-Amino-1H-tetrazole (HAT) and potassium perchlorate. Tetrazoles have been studied as a replacement for sodium azide and HAT, a typical tetrazole, is chosen in this study because it is readily available. The HAT/potassium perchlorate mixture was consolidated to form test strands. An optical strand burner was used to measure the burning rate of the strands. The maximum burning rate for HAT/KClO{sub 4} at 5MPa was about 32mm/s when the HAT concentration was 46wt% which is an excess amount of fuel. The extinction pressure increased as the concentration of HAT increased. The gaseous products of the combustions were analyzed by a gas chromatograph and the main products were CO{sub 2}, CO, and N{sub 2}. The heat of reaction of HAT/KClO{sub 4} reached a maximum when the HAT concentration was approximately 42wt%. (author)

  7. 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.

  8. Fabrication of targets for transmutation of americium : synthesis of inertial matrix by sol-gel method. Procedure study on the infiltration of a radioactive solutions

    International Nuclear Information System (INIS)

    addition a new and unexpected phase formed by the reaction of americium with spinel during the high temperature synthesis process has been identified. This new phase could provide a unique menas to stabilise Am in one particular oxidation state. (Author)

  9. Sorption and diffusion of cobalt, nickel, strontium, iodine, cesium and americium in natural fissure surfaces and drill core cups studied by autoradiography, 3

    International Nuclear Information System (INIS)

    This report summarizes the studies on sorption and diffusion of Cs, Sr, Co, Ni, Am and I in common rocks in Finnish bedrock carried out in laboratory experiments. Samples used in these studies were sections of drill cores containing filled and unfilled natural fracture surfaces and drill cores with a diamond drilled longitudinal cavity in the middle of the sample (drill core cups). Samples originated from the two nuclear power plant sites in Finland: tonalite and mica gneiss from Olkiluoto in Eurajoki and rapakivi granite from Haestholmen in Loviisa. The water used in the experiments was synthetic groundwater spiked at a time with one of the radionuclides: Cs-134, Sr-90, Co-60, Ni-63, Am-241 and I-125. Contact times from one week to one year were used to evaluate time dependence of diffusion. An autoradiographic method was used for determination of the penetration depths and diffusion pathways of elements. For determination of diffusion coefficients a quantitative computerized autoradiographic method was used to get the concentration profiles of the radionuclides in the drill cores. Sorption on natural fracture surfaces was more effective than on freshly drilled core samples. Filling materials on natural fracture surfaces, except calcite, increased sorption. The distribution coefficients for drill core cups were about the same as those for unfilled natural fracture surfaces after a contact time of one week and the sorption tendency of radionuclides was: Ka(Cs) > Ka(Co) > Ka(Am) > Ka(Ni) > Ka(Sr) > Ka(I). Radionuclides were observed to penetrate into fissures of the rock matrix and high-capacity minerals. Strontium was found as far as 35 mm in a filled natural fracture surface sample of rapakivi granite after a contact time of one year. The corresponding values were 3.0 mm for cesium, 2.1 mm for cobalt and 2.6 mm for nickel. For americium no diffusion could be observed (a-values for strontium was 6.6 x 10-16-1.1 x 10-13 m2/s, for cesium 4.7 x 10-16-7.2 x 10-15 m2/s

  10. Separation by sequential chromatography of americium, plutonium and neptunium elements: application to the study of trans-uranian elements migration in a European lacustrine system

    International Nuclear Information System (INIS)

    The nuclear tests carried out in the atmosphere in the Sixties, the accidents and in particular that to the power station of Chernobyl in 1986, were at the origin of the dispersion of a significant quantity of transuranic elements and fission products. The study of a lake system, such that of the Blelham Tarn in Great Britain, presented in this memory, can bring interesting answers to the problems of management of the environment. The determination of the radionuclides in sediment cores made it possible not only to establish the history of the depositions and consequently the origin of the radionuclides, but also to evaluate the various transfers which took place according to the parameters of the site and the properties of the elements. The studied transuranic elements are plutonium 238, 239-240, americium 241 and neptunium 237. Alpha emitting radionuclides, their determination requires complex radiochemical separations. A method was worked out to successively separate the three radioelements by using a same chromatographic column. Cesium 137 is the studied fission product, its determination is done by direct Gamma spectrometry. Lead 210, natural radionuclide, whose atmospheric flow can be supposed constant. makes it possible to obtain a chronology of the various events. The detailed vertical study of sediment cores showed that the accumulation mode of the studied elements is the same one and that the methods of dating converge. The cesium, more mobile than transuranic elements in the atmosphere, was detected in the 1963 and 1986 fallout whereas an activity out of transuranic elements appears only for the 1963 fallout. The activity of the 1963 cesium fallout is of the same order of magnitude as that of 1986. The calculation of the diffusion coefficients of the elements in the sediments shows an increased migration of cesium compared to transuranic elements. An inventory on the whole of the lake made it possible to note that the atmospheric fallout constitute the

  11. 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

  12. 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

  13. MANGANESE PERCHLORATE CATALYZED FACILE SYNTHESIS OF POLYHYDROQUINOLINES VIA HANTZSCH MULTI-COMPONENT CONDENSATION UNDER ULTRASONICATION Manganperchlorat KATALYSIERTEN einfache Synthese von POLYHYDROQUINOLINES VIA Hantzsch MULTI-COMPONENT CONDENSATION unter Ultraschallbehandlung

    Directory of Open Access Journals (Sweden)

    Bhupinder Kaur, Anupama Parmar and Harish Kumar

    2011-04-01

    Full Text Available Hydrated Manganese perchlorate has been found as an efficient catalyst for the one pot synthesis of polyhydroquinoline derivatives via four component hantzsch condensation under ultrasonic irradiation. High yields, shorter reaction time, simple work up procedure/ operational simplicity are the key features of this protocol

  14. A Review on Pollution Status and Microbial Remediation Technologies of Perchlorate in the Environmental Medium%环境介质中高氯酸盐污染及微生物修复技术研究进展

    Institute of Scientific and Technical Information of China (English)

    王蕊; 刘菲; 张苑; 陈鸿汉; 秦莉红

    2012-01-01

    高氯酸盐(ClO-4)是一种有毒的无机阴离子,其环境污染问题引起了广泛关注,控制与修复高氯酸盐污染环境成为新的研究热点,其中微生物修复技术最具应用前景.国外已开展环境中高氯酸盐污染现状的调查工作,利用微生物修复技术去除高氯酸盐取得了一定的成果,但我国的相关研究较少.文章综述了近年来国内外高氯酸盐的污染现状及微生物修复高氯酸盐的最新研究进展.由于高氯酸盐的高水溶性和低吸附性,当前研究最多的是高氯酸盐水体污染,这些水体通过饮用水(源水)或食物链直接或间接地对人类健康造成影响.在微生物修复方面,从有机电子供体,无机电子供体(H2、Fe0等),电子受体(O2、NO23、SO24-)及微生物的生长环境因素(pH值、温度、氧化还原电位、盐度)等方面总结了各因素对微生物修复技术去除高氯酸盐效果的影响,以期为我国开展微生物处理技术在高氯酸盐污染修复领域的实践应用提供参考.%Perchlorate (C104 ) is a toxic inorganic anion, and its environmental pollution problem has attracted wide attention. Control and restoration of perchlorate-contaminated environments has become a new research hotspot. Microbial remediation technologies are the most promising technologies to reduce perchlorate pollution. Studies of perchlorate pollution status have already been carried out and the bioremediation technologies of perchlorate in the environment have shown some success abroad. Environmental problems of perchlorate also exist in China, but few studies have been reported. This paper reviews the most recent research progress of perchlorate pollution status and the microbial remediation technologies worldwide. Due to its high water solubility and low adsorption, water pollution of perchlorate is the hotspot in current studies. Polluted waters have a direct or indirect influence on human health through drinking water (source

  15. Americium behaviour in plastic vessels

    Energy Technology Data Exchange (ETDEWEB)

    Legarda, F.; Herranz, M. [Departamento de Ingenieria Nuclear y Mecanica de Fluidos, Escuela Tecnica Superior de Ingenieria de Bilbao, Universidad del Pais Vasco (UPV/EHU), Alameda de Urquijo s/n, 48013 Bilbao (Spain); Idoeta, R., E-mail: raquel.idoeta@ehu.e [Departamento de Ingenieria Nuclear y Mecanica de Fluidos, Escuela Tecnica Superior de Ingenieria de Bilbao, Universidad del Pais Vasco (UPV/EHU), Alameda de Urquijo s/n, 48013 Bilbao (Spain); Abelairas, A. [Departamento de Ingenieria Nuclear y Mecanica de Fluidos, Escuela Tecnica Superior de Ingenieria de Bilbao, Universidad del Pais Vasco (UPV/EHU), Alameda de Urquijo s/n, 48013 Bilbao (Spain)

    2010-07-15

    The adsorption of {sup 241}Am dissolved in water in different plastic storage vessels was determined. Three different plastics were investigated with natural and distilled waters and the retention of {sup 241}Am by these plastics was studied. The same was done by varying vessel agitation time, vessel agitation speed, surface/volume ratio of water in the vessels and water pH. Adsorptions were measured to be between 0% and 70%. The adsorption of {sup 241}Am is minimized with no water agitation, with PET or PVC plastics, and by water acidification.

  16. Perchlorate Questions and Answers

    Science.gov (United States)

    ... issue of the scientific journal Analytical Chemistry (Analytical Chemistry. 2004, 76, 5518-5522). What is FDA's Total Diet Study? FDA's Total Diet Study (TDS) is the Agency's ongoing market basket survey in which 285 core foods (TDS foods) in the U.S. food supply are ...

  17. 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.

  18. 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%).

  19. A single-crystal proton ENDOR study of the ClO3 centre in γ-irradiated barium perchlorate at 120 K

    International Nuclear Information System (INIS)

    Hyperfine coupling tensors for 24 protons have been determined from electron nuclear double resonance (ENDOR) measurements of the C1O3 centre trapped in γ-irradiated single crystals of barium perchlorate trihydrate at 120 K. The tensors have small isotropic components and their dipolar components are close to axial so that their interpretation in the point-dipole approximation to reconstruct the proton geometry in the vicinity of the trapped radical is justifiable. The model thus obtained indicates that there is no severe distortion of the crystal structure in the immediate vicinity of the trapped radicals. There are two chemically identical but ENDOR-distinguishable sites related by a reflection in the a1a2 plane of the hexagonal crystal. The observation supports the assignment of the P63/m space group to the crystal. (author)

  20. Titanium subhydride potassium perchlorate (TiH1.65/KClO4) burn rates from hybrid closed bomb-strand burner experiments.

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, Marcia A.; Oliver, Michael S.

    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.

  1. Preparation of CoFe2O4 Nano crystallites by Solvo thermal Process and Its Catalytic Activity on the Thermal Decomposition of Ammonium Perchlorate

    International Nuclear Information System (INIS)

    Nanometer cobalt ferrite (CoFe2O4) was synthesized by polyol-medium solvo thermal 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 nano crystallites 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 nano crystallites 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 nano crystallites. A mechanism based on an proton transfer process has also been proposed for AP in the presence of CoFe2O4 nano crystallites.

  2. 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.

  3. 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.

  4. (2-Hydroxybenzoato-κO1[tris(1-methylbenzimidazol-2-ylmethyl-κN3amine-κN]cobalt(II perchlorate dimethylformamide sesquisolvate

    Directory of Open Access Journals (Sweden)

    Xuyang Fan

    2008-11-01

    Full Text Available In the title complex, [Co(C7H5O3(C27H27N7]ClO4·1.5C3H7NO, the CoII ion is five-coordinated by four N atoms from a tris(N-methylbenzimidazol-2-ylmethylamine (Mentb ligand and one O atom from a salicylate ligand in a distorted trigonal–bipyramidal geometry with approximate molecular C3 symmetry. The perchlorate ion is disordered over two sites with equal occupancy. One dimethylformamide solvent molecule lies on a general position and is disordered over two coplanar orientations with equal occupancy. A second dimethylformamide molecule is disordered about a twofold rotation axis. There is an intramolecular O—H...O hydrogen bond in the cation.

  5. Thyroid scintigraphy and perchlorate test after recombinant human TSH: a new tool for the differential diagnosis of congenital hypothyroidism during infancy

    International Nuclear Information System (INIS)

    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 μg/kg daily, i.m.) with 123I scintigraphy and perchlorate test on day 3. Three patients with an ultrasound diagnosis of thyroid dysgenesis received three rhTSH injections with 123I 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.)

  6. 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.)

  7. EURADOS action for determination of americium in skull measures in vivo and Monte Carlo simulation; Accion EURADOS para la determinacion de americio en craneo mediante medidas in-vivo y simulacion Monte Carlo

    Energy Technology Data Exchange (ETDEWEB)

    Lopez Ponte, M. A.; Navarro Amaro, J. F.; Perez Lopez, B.; Navarro Bravo, T.; Nogueira, P.; Vrba, T.

    2013-07-01

    From the Group of WG7 internal dosimetry of the EURADOS Organization (European Radiation Dosimetry group, e.V.) which It coordinates CIEMAT, international action for the vivo measurement of americium has been conducted in three mannequins type skull with detectors of Germanium by gamma spectrometry and simulation by Monte Carlo methods. Such action has been raised as two separate exercises, with the participation of institutions in Europe, America and Asia. Other actions similar precede this vivo intercomparison of measurement and modeling Monte Carlo1. The preliminary results and associated findings are presented in this work. The laboratory of the body radioactivity (CRC) of service counter of dosimetry staff internal (DPI) of the CIEMAT, it has been one of the participants in vivo measures exercise. On the other hand part, the Group of numerical dosimetry of CIEMAT is participant of the Monte Carlo2 simulation exercise. (Author)

  8. Critical and shielding parametric studies with the Monte Carlo code TRIPOLI to identify the key points to take into account during the transportation of blanket assemblies with high ratio of americium

    International Nuclear Information System (INIS)

    In the framework of French research program on Generation IV sodium cooled fast reactor, one possible option consists in burning minor actinides in this kind of Advanced Sodium Technological Reactor. Two types of transmutation mode are studied in the world : the homogeneous mode of transmutation where actinides are scattered with very low enrichment ratio in fissile assemblies and the heterogeneous mode where fissile core is surrounded by blanket assemblies filled with minor actinides with ratio of incorporated actinides up to 20%. Depending on which element is considered to be burnt and on its content, these minor actinides contents imply constraints on assemblies' transportation between Nuclear Power Plants and fuel cycle facilities. In this study, we present some academic studies in order to identify some key constraints linked to the residual power and neutron/gamma load of such kind of blanket assemblies. To simplify the approach, we considered a modeling of a 'model cask' dedicated to the transportation of a unique irradiated blanket assembly loaded with 20% of Americium and basically inspired from an existent cask designed initially for the damaged fissile Superphenix assembly transport. Thermal calculations performed with EDF-SYRTHES code have shown that due to thermal limitations on cladding temperature, the decay time to be considered before transportation is 20 years. This study is based on explicit 3D representations of the cask and the contained blanket assembly with the Monte Carlo code TRIPOLI/JEFF3.1.1 library and concludes that after such a decay time, the transportation of a unique Americium radial blanket is feasible only if the design of our model cask is modified in order to comply with the dose limitation criterion. (author)

  9. 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.

  10. How does the association of iron oxides and perchlorate salts influence organic matter evolution when using Sample Analysis at Mars pyrolysis onboard Curiosity?

    Science.gov (United States)

    François, Pascaline; Coll, Patrice; Szopa, Cyril; Buch, Arnaud; Cabane, Michel; McAdam, Amy; Freissinet, Caroline; Eigenbrode, Jennifer L.; Glavin, Daniel P.; Navarro-Gonzalez, Rafael; Mahaffy, Paul R.

    2014-05-01

    The Sample Analysis at Mars (SAM) instrument suite aboard the Curiosity rover is designed to characterize organic and inorganic volatiles thermally evolved from solid samples. It can analyze evolved volatiles directly with its quadrupole mass spectrometer (MS) to perform evolved gas analysis (EGA) or it can analyze volatiles after they have been sent through a gas chromatography column to perform pyrolysis-gas chromatograph-mass spectrometry (pyr-GC-MS) [1]. Three solid samples have been analyzed by SAM, a scoop of basaltic sand at Rocknest (RN) and two rocks drilled at Yellowknife Bay designated as John Klein (JK) and Cumberland (CB). All these samples contain an oxychlorine phase (e.g., a perchlorate salt) [2, 3] that evolves HCl, Cl2 and O2 on heating leading to the possible chlorination and/or combustion of organic molecules [4]. Chlorohydrocarbons detected at RN, JK and CB are derived from reactions between martian oxychlorine compounds and terrestrial carbon that is part of the SAM background (e.g., MTBSTFA [2]) as well as potentially reactions with martian carbon and/or thermal desorption directly from the samples for the production of chlorobenzene evolved during pyrolysis of CB. RN, JK and CB samples also contain iron oxides (e.g., hematite, magnetite) [5] which could oxidize organic compounds and catalyze their decomposition [6] leading to differences in the amount and/or nature of pyrolysis products. In order to help interpretation of in situ data obtained by SAM, we study the influence of an iron oxide, hematite, and an oxychlorine phase, Ca-perchlorate, individually, as well as mixed, on alanine, a common amino acid, under conditions simulating the SAM pyrolysis. This work aims to help to determine the influences of key sample minerals on the production of organic compounds detected with SAM in both GC-MS and EGA mode, and to identify potential parent molecules. References: [1] Mahaffy, P. et al. (2012), Space Sci Rev, 170, 401-478. [2] Glavin, D. et

  11. Green synthesis of Co3O4 nanoparticles and their applications in thermal decomposition of ammonium perchlorate and dye-sensitized solar cells

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • Co3O4 NPs were synthesized from the leaves extract of plant Calotropis gigantea. • Green synthesis of Co3O4 NPs is a cost effective and eco-friendly route. • Faster thermal decomposition of AP occurred in presence of the green synthesized Co3O4 NPs. • A high burning rate of CSP was observed. • Green synthesized Co3O4 NPs displays the good electrocatalytic activity to reduction of I3− to I− ions. - Abstract: In this paper, we report on the green synthesis of cobalt oxide nanoparticles (Co3O4 NPs) using leaves extract of plant Calotropis gigantea and characterize by X-ray diffraction (XRD), UV–vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). The green synthesized Co3O4 NPs showed excellent catalytic effect on the thermal decomposition of ammonium perchlorate (AP) and burning rate of composite solid propellants (CSPs). Kinetics of slow and rapid thermal decomposition has been investigated by isoconversional and ignition delay methods, respectively. Moreover, the electrocatalytic performance of green synthesized Co3O4 NPs in dye-sensitized solar cells (DSSC) has also been evaluated. The cyclic voltametry measurement shows good electrocatalytic activity of Co3O4 NPs toward the reduction of I3− to I− ions

  12. 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.

  13. Carcinoembryonic antigen: assay following heat compared with perchloric acid extraction in patients with colon cancer, non-neoplastic gastrointestinal diseases, or chronic renal failure.

    Science.gov (United States)

    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. We examined a commercial RIA kit using heat inactivation, and compared results with those obtained with PCA precipitation. Adequate sensitivity (1.5 micrograms CEA/l 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. We conclude that the heat-inactivation assay is an excellent alternative to the PCA assay.

  14. Constants and thermodynamics of the acid-base equilibria of triglycine in water-ethanol solutions containing sodium perchlorate at 298 K

    Science.gov (United States)

    Pham Tkhi, L.; Usacheva, T. R.; Tukumova, N. V.; Koryshev, N. E.; Khrenova, T. M.; Sharnin, V. A.

    2016-02-01

    The acid-base equilibrium constants for glycyl-glycyl-glycine (triglycine) in water-ethanol solvents containing 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol are determined by potentiometric titration at 298.15 K and an ionic strength of 0.1, maintained with sodium perchlorate. It is established that an increase in the ethanol content in the solvent reduces the dissociation constant of the carboxyl group of triglycine (increases p K 1) and increases the dissociation constant of the amino group of triglycine (decreases p K 2). It is noted that the weakening of the acidic properties of a triglycinium ion upon an increase of the ethanol content in the solvent is due to the attenuation of the solvation shell of the zwitterionic form of triglycine, and to the increased solvation of triglycinium ions. It is concluded that the acid strength of triglycine increases along with a rise in the EtOH content in the solvent, due to the desolvation of the tripeptide zwitterion and the enhanced solvation of protons.

  15. Nucleic Acid Biosensor for Detection of Human Immunodeficiency Virus Using Aquabis(1,10-phenanthroline)copper (Ⅱ) Perchlorate as Electrochemical Indicator

    Institute of Scientific and Technical Information of China (English)

    NIU,Shu-Yan; WANG,Shao-Juan; LI,Xue-Mei

    2008-01-01

    The electrochemical behavior of aquabis(1,10-phenanthroline)copper(Ⅱ) perchlorate[Cu(H2O)(phen)2]·2ClO4,where phen= 1,10-phenanthroline, on binding to DNA at a glassy carbon electrode (GCE) and in solution, was described. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) results showed that[Cu(H2O)(phen)2]2+.had excellent electrochemical activity on the GCE with a couple of quasi-reversible redox peaks. The interaction mode between[Cu(H2O)(phen)2]2+ and double-strand DNA (dsDNA) was identified to be intercalative binding. An electrochemical DNA biosensor was developed with covalent immobilization of human immunodeficiency virus (HIV) probe for single-strand DNA (ssDNA) on the modified GCE. Numerous factors affecting the probe immobilization, target hybridization, and indicator binding reactions were optimized to maximize the sensitivity and speed of the assay. With this approach, a sequence of the HIV could be quantified over the range from 7.8×10-9 to 3.1×10-7 mol·L-1 with a linear correlation of γ=0.9987 and a detection limit of 1.3×10-9 mol·L-1.

  16. 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, M.; Szopa, C.; Buch, A.; Belmahdi, I.; Coll, P.; Glavin, D. P.; Freissinet, C.; Archer, P. D., Jr.; Sutter, B.; Summons, R. E.; Mahaffy, P.

    2016-01-01

    The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gaschromatograph coupled to a quadrupole mass spectrometer (GC-QMS). The GC-QMS is devoted to the separation and identification of organic and inorganic material. 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. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1). For the second time after the Viking landers in 1976, SAM detected chlorinated organic compounds with the pyrolysis GC-QMS experiment. The detection of perchlorates salts (ClO4-) in soil at the Phoenix Landing site suggests that the chlorohydrocarbons detected could come from the reaction of organics with oxychlorines. Indeed, laboratory pyrolysis experiments have demonstrated that oxychlorines decomposed into molecular oxygen and volatile chlorine (HCl and/or Cl2) when heated which then react with the organic matter in the solid samples by oxidation and/or chlorination processes.

  17. Crystal structures of copper(II) nitrate, copper(II) chloride, and copper(II) perchlorate complexes with 2-formylpyridine semicarbazone

    International Nuclear Information System (INIS)

    Compounds dinitrato(2-formylpyridinesemicarbazone)copper (I), dichloro(2-formylpyridinesemicarbazone) copper hemihydrate (II), and bis(2-formylpyridinesemicarbazone)copper(2+) perchlorate hydrate (III) are synthesized and their crystal structures are determined. In compounds I-III, the neutral 2-formylpyridine semicarbazone molecule (L) is tridentately attached to the copper atom via the N,N,O set of donor atoms. In compounds I and II, the Cu: L ratio is equal to 1: 1, whereas, in III, it is 1: 2. In complex I, the coordination sphere of the copper atom includes two nitrate ions with different structural functions in addition to the L ligand. The structure is built as a one-dimensional polymer in which the NO3 bidentate group fulfills a bridging function. The coordination polyhedron of the copper(2+) atom can be considered a distorted tetragonal bipyramid (4 + 1 + 1). Compound II has an ionic structure in which the main element is the [CuLCl2 . Cu(H2O)LCl]+ dimer. In the dimer, the copper atoms are linked via one of the μ2-bridging chlorine atoms. The coordination polyhedra of the central atoms of the Cu(H2)LCl and CuLCl2 complex fragments are tetragonal bipyramid and tetragonal pyramid, respectively. In compound III, the copper atom is octahedrally surrounded by two L ligands in the mer configuration.

  18. Crystal structures of copper(II) nitrate, copper(II) chloride, and copper(II) perchlorate complexes with 2-formylpyridine semicarbazone

    Science.gov (United States)

    Chumakov, Yu. M.; Tsapkov, V. I.; Antosyak, B. Ya.; Bairac, N. N.; Simonov, Yu. A.; Bocelli, G.; Pahontu, E.; Gulea, A. P.

    2009-05-01

    Compounds dinitrato(2-formylpyridinesemicarbazone)copper ( I), dichloro(2-formylpyridinesemicarbazone) copper hemihydrate ( II), and bis(2-formylpyridinesemicarbazone)copper(2+) perchlorate hydrate ( III) are synthesized and their crystal structures are determined. In compounds I- III, the neutral 2-formylpyridine semicarbazone molecule ( L) is tridentately attached to the copper atom via the N,N,O set of donor atoms. In compounds I and II, the Cu: L ratio is equal to 1: 1, whereas, in III, it is 1: 2. In complex I, the coordination sphere of the copper atom includes two nitrate ions with different structural functions in addition to the L ligand. The structure is built as a one-dimensional polymer in which the NO3 bidentate group fulfills a bridging function. The coordination polyhedron of the copper(2+) atom can be considered a distorted tetragonal bipyramid (4 + 1 + 1). Compound II has an ionic structure in which the main element is the [Cu LCl2 · Cu(H2O) LCl]+ dimer. In the dimer, the copper atoms are linked via one of the μ2-bridging chlorine atoms. The coordination polyhedra of the central atoms of the Cu(H2) LCl and Cu LCl2 complex fragments are tetragonal bipyramid and tetragonal pyramid, respectively. In compound III, the copper atom is octahedrally surrounded by two L ligands in the mer configuration.

  19. Crystal structures of copper(II) nitrate, copper(II) chloride, and copper(II) perchlorate complexes with 2-formylpyridine semicarbazone

    Energy Technology Data Exchange (ETDEWEB)

    Chumakov, Yu. M. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I. [State University of Moldova (Moldova, Republic of); Antosyak, B. Ya. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Bairac, N. N. [State University of Moldova (Moldova, Republic of); Simonov, Yu. A., E-mail: simonov.xray@phys.asm.md [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Bocelli, G. [National Research Council (IMEM-CNR), Institute of Materials for Electronics and Magnetism (Italy); Pahontu, E. [University of Medicine and Pharmacy (Romania); Gulea, A. P. [State University of Moldova (Moldova, Republic of)

    2009-05-15

    Compounds dinitrato(2-formylpyridinesemicarbazone)copper (I), dichloro(2-formylpyridinesemicarbazone) copper hemihydrate (II), and bis(2-formylpyridinesemicarbazone)copper(2+) perchlorate hydrate (III) are synthesized and their crystal structures are determined. In compounds I-III, the neutral 2-formylpyridine semicarbazone molecule (L) is tridentately attached to the copper atom via the N,N,O set of donor atoms. In compounds I and II, the Cu: L ratio is equal to 1: 1, whereas, in III, it is 1: 2. In complex I, the coordination sphere of the copper atom includes two nitrate ions with different structural functions in addition to the L ligand. The structure is built as a one-dimensional polymer in which the NO{sub 3} bidentate group fulfills a bridging function. The coordination polyhedron of the copper(2+) atom can be considered a distorted tetragonal bipyramid (4 + 1 + 1). Compound II has an ionic structure in which the main element is the [CuLCl{sub 2} . Cu(H{sub 2}O)LCl]{sup +} dimer. In the dimer, the copper atoms are linked via one of the {mu}{sub 2}-bridging chlorine atoms. The coordination polyhedra of the central atoms of the Cu(H{sub 2})LCl and CuLCl{sub 2} complex fragments are tetragonal bipyramid and tetragonal pyramid, respectively. In compound III, the copper atom is octahedrally surrounded by two L ligands in the mer configuration.

  20. Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

    International Nuclear Information System (INIS)

    Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C6H5COCH2SOCH2COC6H5), salicylic acid as second ligand (L'=C6H4OHCOO-). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL5L'](ClO4)2.nH2O (RE=Tb, Dy; n=6, 8 ). Based on IR, 1HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L'), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.

  1. Experimental study on processability of ammonium perchlorate/hydroxyl-terminated polybutadiene composite propellant (I). Influences of operating temperature on viscosity of uncured propellant

    Energy Technology Data Exchange (ETDEWEB)

    Koga, M.; Hagihara, Y. [National Defense Academy, Kanagawa (Japan)

    1998-01-01

    Ammonium perchlorate (AP)/hydroxyl-terminated polybutadiene (HTPB) composite propellant was adopted in this study, because AP/HTPB composite propellant is the most widely used one at present. In order to design the formulation of AP/HTPB composite propellant, it is necessary to spread the range of a specific impulse of AP/HTPB composite propellant widely, especially towards a high specific impulse region. Specific impulse of AP/HTPB composite propellant increases with an increasing AP content and when the AP content is about 90wt% the maximum specific impulse can be realized theoretically. Because an upper limit of AP content in propellant exists technically for the size distribution of AP used, the upper limit of specific impulse must be so. In order to increase the upper limit of specific impulse, it is necessary to increase the upper limit of AP content. In this study, the relationships between the viscosity of HTPB with a curing agent or uncured propellant and the curing time were investigated at temperatures from 313K to 353K, and was made to find out the optimum operating temperature for mixing and casting of uncured propellant experimentally. 4 refs., 5 figs.

  2. Use of radioactive methods for determination of uranium, neptunium, plutonium, americium and curium isotopes in waste radioactive; Utilizacao de metodos radioanaliticos para determinacao de isotopos de uranio, netunio, plutonio, americio e curio em rejeitos radioativos

    Energy Technology Data Exchange (ETDEWEB)

    Geraldo, Bianca

    2012-07-01

    Activated charcoal is a common type of radioactive waste that contains high concentrations of fission and activation products. The management of this waste includes its characterization aiming the determination and quantification of the specific radionuclides including those known as Difficult-to-Measure Radionuclides (RDM). The analysis of the RDM's generally involves complex radiochemical analysis for purification and separation of the radionuclides, which are expensive and time-consuming. The objective of this work was to define a methodology for sequential analysis of the isotopes of uranium, neptunium, plutonium, americium and curium present in a type of radioactive waste, evaluating chemical yield, analysis of time spent, amount of secondary waste generated and cost. Three methodologies were compared and validated that employ ion exchange (TI+EC), extraction chromatography (EC) and extraction with polymers (ECP). The waste chosen was the activated charcoal from the purification system of primary circuit water cooling the reactor IEA-R1. The charcoal samples were dissolved by acid digestion followed by purification and separation of isotopes with ion exchange resins, extraction and chromatographic extraction polymers. Isotopes were analyzed on an alpha spectrometer, equipped with surface barrier detectors. The chemical yields were satisfactory for the methods TI+EC and EC. ECP method was comparable with those methods only for uranium. Statistical analysis as well the analysis of time spent, amount of secondary waste generated and cost revealed that EC method is the most effective for identifying and quantifying U, Np, Pu, Am and Cm present in charcoal. (author)

  3. A New Bioinspired Perchlorate Reduction Catalyst with Significantly Enhanced Stability via Rational Tuning of Rhenium Coordination Chemistry and Heterogeneous Reaction Pathway.

    Science.gov (United States)

    Liu, Jinyong; Han, Mengwei; Wu, Dimao; Chen, Xi; Choe, Jong Kwon; Werth, Charles J; Strathmann, Timothy J

    2016-06-01

    Rapid reduction of aqueous ClO4(-) to Cl(-) by H2 has been realized by a heterogeneous Re(hoz)2-Pd/C catalyst integrating Re(O)(hoz)2Cl complex (hoz = oxazolinyl-phenolato bidentate ligand) and Pd nanoparticles on carbon support, but ClOx(-) intermediates formed during reactions with concentrated ClO4(-) promote irreversible Re complex decomposition and catalyst deactivation. The original catalyst design mimics the microbial ClO4(-) reductase, which integrates Mo(MGD)2 complex (MGD = molybdopterin guanine dinucleotide) for oxygen atom transfer (OAT). Perchlorate-reducing microorganisms employ a separate enzyme, chlorite dismutase, to prevent accumulation of the destructive ClO2(-) intermediate. The structural intricacy of MGD ligand and the two-enzyme mechanism for microbial ClO4(-) reduction inspired us to improve catalyst stability by rationally tuning Re ligand structure and adding a ClOx(-) scavenger. Two new Re complexes, Re(O)(htz)2Cl and Re(O)(hoz)(htz)Cl (htz = thiazolinyl-phenolato bidentate ligand), significantly mitigate Re complex decomposition by slightly lowering the OAT activity when immobilized in Pd/C. Further stability enhancement is then obtained by switching the nanoparticles from Pd to Rh, which exhibits high reactivity with ClOx(-) intermediates and thus prevents their deactivating reaction with the Re complex. Compared to Re(hoz)2-Pd/C, the new Re(hoz)(htz)-Rh/C catalyst exhibits similar ClO4(-) reduction activity but superior stability, evidenced by a decrease of Re leaching from 37% to 0.25% and stability of surface Re speciation following the treatment of a concentrated "challenge" solution containing 1000 ppm of ClO4(-). This work demonstrates the pivotal roles of coordination chemistry control and tuning of individual catalyst components for achieving both high activity and stability in environmental catalyst applications. PMID:27182602

  4. A New Bioinspired Perchlorate Reduction Catalyst with Significantly Enhanced Stability via Rational Tuning of Rhenium Coordination Chemistry and Heterogeneous Reaction Pathway.

    Science.gov (United States)

    Liu, Jinyong; Han, Mengwei; Wu, Dimao; Chen, Xi; Choe, Jong Kwon; Werth, Charles J; Strathmann, Timothy J

    2016-06-01

    Rapid reduction of aqueous ClO4(-) to Cl(-) by H2 has been realized by a heterogeneous Re(hoz)2-Pd/C catalyst integrating Re(O)(hoz)2Cl complex (hoz = oxazolinyl-phenolato bidentate ligand) and Pd nanoparticles on carbon support, but ClOx(-) intermediates formed during reactions with concentrated ClO4(-) promote irreversible Re complex decomposition and catalyst deactivation. The original catalyst design mimics the microbial ClO4(-) reductase, which integrates Mo(MGD)2 complex (MGD = molybdopterin guanine dinucleotide) for oxygen atom transfer (OAT). Perchlorate-reducing microorganisms employ a separate enzyme, chlorite dismutase, to prevent accumulation of the destructive ClO2(-) intermediate. The structural intricacy of MGD ligand and the two-enzyme mechanism for microbial ClO4(-) reduction inspired us to improve catalyst stability by rationally tuning Re ligand structure and adding a ClOx(-) scavenger. Two new Re complexes, Re(O)(htz)2Cl and Re(O)(hoz)(htz)Cl (htz = thiazolinyl-phenolato bidentate ligand), significantly mitigate Re complex decomposition by slightly lowering the OAT activity when immobilized in Pd/C. Further stability enhancement is then obtained by switching the nanoparticles from Pd to Rh, which exhibits high reactivity with ClOx(-) intermediates and thus prevents their deactivating reaction with the Re complex. Compared to Re(hoz)2-Pd/C, the new Re(hoz)(htz)-Rh/C catalyst exhibits similar ClO4(-) reduction activity but superior stability, evidenced by a decrease of Re leaching from 37% to 0.25% and stability of surface Re speciation following the treatment of a concentrated "challenge" solution containing 1000 ppm of ClO4(-). This work demonstrates the pivotal roles of coordination chemistry control and tuning of individual catalyst components for achieving both high activity and stability in environmental catalyst applications.

  5. Green synthesis of Co{sub 3}O{sub 4} nanoparticles and their applications in thermal decomposition of ammonium perchlorate and dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, J.K. [Department of Chemistry, Deen Dayal Upadhyay Gorakhpur University, Gorakhpur (India); Srivastava, Pratibha, E-mail: author.pratibhas1980@gmail.com [Department of Chemistry, Deen Dayal Upadhyay Gorakhpur University, Gorakhpur (India); Singh, Gurdip [Department of Chemistry, Deen Dayal Upadhyay Gorakhpur University, Gorakhpur (India); Akhtar, M. Shaheer [New & Renewable Energy Material Development Center (NewREC), Chonbuk National University, Jeonbuk (Korea, Republic of); Ameen, S. [Energy Materials & Surface Science Laboratory, Solar Energy Research Center, School of Chemical Engineering, Chonbuk National University, Jeonju 561-756 (Korea, Republic of)

    2015-03-15

    Graphical abstract: - Highlights: • Co{sub 3}O{sub 4} NPs were synthesized from the leaves extract of plant Calotropis gigantea. • Green synthesis of Co{sub 3}O{sub 4} NPs is a cost effective and eco-friendly route. • Faster thermal decomposition of AP occurred in presence of the green synthesized Co{sub 3}O{sub 4} NPs. • A high burning rate of CSP was observed. • Green synthesized Co{sub 3}O{sub 4} NPs displays the good electrocatalytic activity to reduction of I{sub 3}{sup −} to I{sup −} ions. - Abstract: In this paper, we report on the green synthesis of cobalt oxide nanoparticles (Co{sub 3}O{sub 4} NPs) using leaves extract of plant Calotropis gigantea and characterize by X-ray diffraction (XRD), UV–vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). The green synthesized Co{sub 3}O{sub 4} NPs showed excellent catalytic effect on the thermal decomposition of ammonium perchlorate (AP) and burning rate of composite solid propellants (CSPs). Kinetics of slow and rapid thermal decomposition has been investigated by isoconversional and ignition delay methods, respectively. Moreover, the electrocatalytic performance of green synthesized Co{sub 3}O{sub 4} NPs in dye-sensitized solar cells (DSSC) has also been evaluated. The cyclic voltametry measurement shows good electrocatalytic activity of Co{sub 3}O{sub 4} NPs toward the reduction of I{sub 3}{sup −} to I{sup −} ions.

  6. Bis[4,5-dimethyl-2-(2-pyridyl-1H-imidazole-κ2N2,N3](1H-imidazole-κN3copper(II bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Zhengping Chen

    2008-07-01

    Full Text Available In the title complex, [Cu(C3H4N2(C10H11N32](ClO42, the CuII cation has a distorted trigonal-bipyramidal geometry defined by a CuN2N′2N′′ donor set. The imidazole ligand is disordered over two orientations of equal occupancy. Two of the perchlorate ion sites are located on a twofold rotation axis, and one of is disordered over two sites of equal occupancy. In the crystal structure there is a two-dimensional infinite network of hydrogen-bonded molecules parallel to the ab plane.

  7. Synthesis and crystal structure of [2,7,12-trimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17,13,15-triene-κ4N]copper(II bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Edward Gabrielle V. Hilvano

    2016-07-01

    Full Text Available The title copper(II complex of a pyridine-containing macrocycle (PyMAC, [Cu(C16H28N4](ClO42, has been prepared. The crystal structure reveals the CuII atom to be octahedrally coordinated by a tetradentate aminopyridine macrocyclic ligand surrounding the metal cation in a square-planar geometry. Two weakly bound perchlorate counter-ions occupy the axial sites above and below the macrocyclic plane. The crystal studied was refined as a two-component pseudo-merohedral twin; the refined fractional contribution of the minor component is 38.77 (8%

  8. (2,2 '-Bipyridine-4,4 '-dicarboxylic acid-kappa N-2,N ')chlorido(2,2 ':6 ',2 ''-terpyridyl-kappa N-3,N ',N '')ruthenium(II) perchlorate ethanol monosolvate monohydrate

    DEFF Research Database (Denmark)

    Nielsen, A.; McKenzie, C. J.; Bond, A. D.

    2012-01-01

    center dot center dot O hydrogen bonds between the carboxyl groups and the crystal lattice water molecules into chains along [110]. Face-to-face stacking interactions are formed between terpyridine ligands, with interplanar separations of 3.66 (1) and 3.42 (1) angstrom, and between bipyridine-4......,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)....

  9. Solubility and speciation studies of waste radionuclides pertinent to geologic disposal at Yucca Mountain: Results on neptunium, plutonium and americium in J-13 groundwater; Letter report (R707): Reporting period, October 1, 1985--September 30, 1987

    Energy Technology Data Exchange (ETDEWEB)

    Nitsche, H.; Standifer, E.M.; Lee, S.C.; Gatti, R.C.; Tucker, D.B.

    1988-01-01

    We have studied the solubilities of neptunium, plutonium, and americium in J-13 groundwater from Yucca Mountain (Nevada) at three temperatures and hydrogen ion concentrations. They are 25{degree}, 60{degree}C, and 90{degree}C and pH 5.9, 7.0, and 8.5. The results for 25{degree}C are from a study which we did during FY 1984. We included these previous results in the tables to give more information on the solubility temperature dependence; they were, however, done at only one pH (7.0). The solubilities were studied from oversaturation. The nuclides were added at the beginning of each experiment as NpO{sub 2}{sup +}, Pu{sup 4+}, and Am{sup 3+}. The neptunium solubility decreased with increasing temperature and with increasing pH. The soluble neptunium did not change oxidation state at steady state. The pentavalent neptunium was increasingly complexed by carbonate with increasing pH. All solids were crystalline and contained carbonate, except the solid formed at 90{degree}C and pH 5.9. We identified this solid as crystalline Np{sub 2}P{sub 5}. The 25{degree}C, pH 7 solid was Na{sub 3}NpO{sub 2}(CO{sub 3}){sub 2} {center_dot} nH{sub 2}O. Plutonium concentrations decreased with increasing temperature and showed no trend with pH. Pu(V) and Pu(VI) were the dominant oxidation states in the supernatant solution; as the amount of Pu(V) increased with pH, Pu(VI) decreed. The steady-state solids were mostly amorphous, although some contained a crystalline component. They contained Pu(IV) polymer and unknown carbonates.

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

    Directory of Open Access Journals (Sweden)

    Biswanath Das

    2014-04-01

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

  11. catena-Poly[[[(pyridine-κN)copper(II)]-μ-3-{1-[(2-amino-eth-yl)imino]-eth-yl}-6-methyl-2-oxo-2H-pyran-4-olato-κN,N,O:O] perchlorate].

    Science.gov (United States)

    Ourari, Ali; Derafa, Wassila; Bouacida, Sofiane; Aggoun, Djouhra

    2011-12-01

    In the title compound, {[Cu(C(10)H(13)N(2)O(3))(C(5)H(5)N)]ClO(4)}(n), the Cu(II) atom has an N(3)O(2) coordination sphere. The complex contains two different ligands, viz. a pyridine mol-ecule and a Schiff base mol-ecule, resulting from the condensation of ethyl-enodiamine with dehydro-acetic acid. The Cu(II) atom exhibits a square-pyramidal geometry: three of the four donors of the pyramid base belong to the Schiff base ligand (an N atom from the amine group, a second N atom from the imine group and the O atom of the pyran-one residue) and the fourth donor is the pyridine N atom. The coordination around the metal ion is completed by a longer axial bond to the pyran-one O atom of an adjacent Schiff base, so forming a one-dimensional polymer. The complex has a +1 charge that is compensated by a perchlorate ion. The crystal packing, which can be described as alternating chains of cations and tetra-hedral perchlorate anions along the a axis, is stabilized by inter-molecular N-H⋯O, C-H⋯O and C-H⋯N hydrogen-bonding interactions. PMID:22199528

  12. catena-Poly[[[(pyridine-κNcopper(II]-μ-3-{1-[(2-aminoethylimino]ethyl}-6-methyl-2-oxo-2H-pyran-4-olato-κ4N,N,O4:O2] perchlorate

    Directory of Open Access Journals (Sweden)

    Ali Ourari

    2011-12-01

    Full Text Available In the title compound, {[Cu(C10H13N2O3(C5H5N]ClO4}n, the CuII atom has an N3O2 coordination sphere. The complex contains two different ligands, viz. a pyridine molecule and a Schiff base molecule, resulting from the condensation of ethylenodiamine with dehydroacetic acid. The CuII atom exhibits a square-pyramidal geometry: three of the four donors of the pyramid base belong to the Schiff base ligand (an N atom from the amine group, a second N atom from the imine group and the O atom of the pyranone residue and the fourth donor is the pyridine N atom. The coordination around the metal ion is completed by a longer axial bond to the pyranone O atom of an adjacent Schiff base, so forming a one-dimensional polymer. The complex has a +1 charge that is compensated by a perchlorate ion. The crystal packing, which can be described as alternating chains of cations and tetrahedral perchlorate anions along the a axis, is stabilized by intermolecular N—H...O, C—H...O and C—H...N hydrogen-bonding interactions.

  13. Complete doping in solid-state by silica-supported perchloric acid as dopant solid acid: Synthesis and characterization of the novel chiral composite of poly [(±)-2-(sec-butyl) aniline

    Science.gov (United States)

    Farrokhzadeh, Abdolkarim; Modarresi-Alam, Ali Reza

    2016-05-01

    Poly [(±)-2-(sec-butyl) aniline]/silica-supported perchloric acid composites were synthesized by combination of poly[(±)-2-sec-butylaniline] base (PSBA) and the silica-supported perchloric acid (SSPA) as dopant solid acid in solid-state. The X-ray photoelectron spectroscopy (XPS) and CHNS results confirm nigraniline oxidation state and complete doping for composites (about 75%) and non-complete for the PSBA·HCl salt (about 49%). The conductivity of samples was (≈0.07 S/cm) in agreement with the percent of doping obtained of the XPS analysis. Also, contact resistance was determined by circular-TLM measurement. The morphology of samples by the scanning electron microscopy (SEM) and their coating were investigated by XPS, SEM-map and energy-dispersive X-ray spectroscopy (EDX). The key benefits of this work are the preparation of conductive chiral composite with the delocalized polaron structure under green chemistry and solid-state condition, the improvement of the processability by inclusion of the 2-sec-butyl group and the use of dopant solid acid (SSPA) as dopant.

  14. Thermal Reactivity of Organic Molecules in the Presence of Chlorates and Perchlorates and the Quest for Organics on Mars with the SAM Experiment Onboard the Curiostiy Rover

    Science.gov (United States)

    Szopa, Cyril; Millan, Maeva; Buch, Arnaud; Belmahdi, Imene; Coll, Patrice; Glavin, Daniel P.; Freissinet, Caroline; Eigenbrode, Jennifer; archer, doug; sutter, brad; Summons, Roger; Navarro-Gonzalez, Rafael; Mahaffy, Paul; cabane, Michel

    2016-10-01

    One of the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples collected by Curiosity when they are heated up to ~850°C. With this aim SAM uses a gas-chromatograph coupled to a mass spectrometer (GC-MS) able to detect and identify both inorganic and organic molecules released by the samples.During the pyrolysis, chemical reactions occur between oxychlorines, probably homogeneously distributed at Mars's surface, and organic compounds SAM seeks for. This was confirmed by the first chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM that were entirely attributed to reaction products occurring between these oxychlorines and organics from instrument background. But SAM also detected in the Sheepbed mudstone of Gale crater, chloroalkanes produced by reaction between oxychlorines and Mars indigenous organics, proving for the first time the presence of organics in the soil of Mars. However, the identification of the molecules at the origin of these chloroalkanes is much more difficult due to the complexity of the reactivity occurring during the sample pyrolysis. If a first study has already been done recently with this aim, it was relatively limited in terms of parameters investigated.This is the reason why, we performed a systematic study in the laboratory to help understanding the influence of oxychlorines on organic matter during pyrolysis. With this aim, different organic compounds from various chemical families (e.g. amino and carboxylic acids) mixed with different perchlorates and chlorates, in concentrations compatible with the Mars soil from estimations done with SAM measurements, were pyrolyzed under SAM like conditions. The products of reaction were analyzed and identified by GC-MS in order to show a possible correlation between them and the parent molecule. Different parameters were tested for the pyrolysis to evaluate their potential influence on the

  15. Studies on reactions of cerium(4) reduction with alcohols. Part 3. Reactions of cerium(4) reduction with butane-2,3-diol, butane-1,3-diol and cis-butene-2-diol-1,4 in aqueous solutions of perchloric acid

    International Nuclear Information System (INIS)

    The basic study of the red-ox reaction kinetics of cerium ions -diols-water systems in presence of the perchloric acid is given. Dependence of the various agents and its concentrations on equilibrium constants the complex formation reactions and complex stability are discussed and compared. (B.Cz.)

  16. (5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene-κ4N1,N4,N8,N11(thiocyanato-κSnickel(II perchlorate monohydrate

    Directory of Open Access Journals (Sweden)

    Jian-Hong Bi

    2009-06-01

    Full Text Available In the title compound, [Ni(SCN(C16H32N4]ClO4·H2O, the NiII ion is coordinated by the four N atoms of the tetraazacyclotetradeca-4,11-diene macrocyclic ligand and by the S atom of a thiocyanate anion. The perchlorate anion is rotationally disordered around one Cl—O bond between two orientations; the occupancies refined to 0.61 (4 and 0.39 (4. Intermolecular O—H...N, N—H...O and N—H...N hydrogen bonds link two cations, two anions and two solvent water molecules into a centrosymmetric cluster. The crystal packing is further stabilized by weak intermolecular C—H...O hydrogen bonds.

  17. 钛基二氧化铅阳极电化合成高氯酸钠的研究%ELECTROLYTIC SYNTHESIS OF SODIUM PERCHLORATE BY LEAD DIOXIDE ANODE BASED TITANIUM METAL

    Institute of Scientific and Technical Information of China (English)

    孙洋洲; 姚沛

    2001-01-01

    介绍了以钛基体二氧化铅作为阳极,电解氯酸钠合成高氯酸钠的过程。考察了电解温度、电解液初始氯酸钠浓度及氯化钠浓度对电流效率的影响。得出了电解反应的最佳条件。%A process of electrolytic synthesis of sodium perchlorate from sodium chlorate solution by lead dioxide anode based titanium metal is introduced. The influence of temperature,the concentration of sodium chlorate and the concentration of sodium chloride on the current efficiency is investigated, and the optimum conditions of the electrolytic process are also obtained.

  18. The proliferation potential of neptunium and americium

    Energy Technology Data Exchange (ETDEWEB)

    An, J. S.; Shin, J. S.; Kim, J. S.; Kwack, E. H.; Kim, B. K

    2000-05-01

    It is recognized that some trans-uranic elements other than plutonium, in particular Np and Am, if will be available in sufficient quantities, could be used for nuclear explosive devices. The spent fuel has been accumulating in number of nuclear power plant and operation of large scale commercial reprocessing plants. However, these materials are not covered by the definition of special fissionable material in the Agency Statute. At the time when the Statute was adopted, the availability of meaningful quantities of separated Np and Am was remote and they were not included in the definition of special fissionable material. Then, IAEA Board decided a measure for control of Np and Am on September 1999. This report contains the control method and the characteristic of Np and Am for using domestic nuclear industries, and it can be useful for understanding how to report and account of Np and Am. (author)

  19. Delocalization and new phase in Americium: theory

    Energy Technology Data Exchange (ETDEWEB)

    Soderlind, P

    1999-04-23

    Density-functional electronic structure calculations have been used to investigate the high pressure behavior of Am. At about 80 kbar (8 GPa) calculations reveal a monoclinic phase similar to the ground state structure of plutonium ({alpha}-Pu). The experimentally suggested {alpha}-U structure is found to be substantially higher in energy. The phase transition from fcc to the low symmetry structure is shown to originate from a drastic change in the nature of the electronic structure induced by the elevated pressure. A calculated volume collapse of about 25% is associated with the transition. For the low density phase, an orbital polarization correction to the local spin density (LSD) theory was applied. Gradient terms of the electron density were included in the calculation of the exchange/correlation energy and potential, according to the generalized gradient approximation (GGA). The results are consistent with a Mott transition; the 5f electrons are delocalized and bonding on the high density side of the transition and chemically inert and non-bonding (localized) on the other. Theory compares rather well with recent experimental data which implies that electron correlation effects are reasonably modeled in our orbital polarization scheme.

  20. Evaluation of neutron data for americium-241

    Energy Technology Data Exchange (ETDEWEB)

    Maslov, V.M.; Sukhovitskij, E.Sh.; Porodzinskij, Yu.V.; Klepatskij, A.B.; Morogovskij, G.B. [Radiation Physics and Chemistry Problems Inst., Minsk-Sosny (Belarus)

    1997-03-01

    The evaluation of neutron data for {sup 241}Am is made in the energy region from 10{sup -5} eV up to 20 MeV. The results of the evaluation are compiled in the ENDF/B-VI format. This work is performed under the Project Agreement CIS-03-95 with the International Science and Technology Center (Moscow). The Financing Party for the Project is Japan. The evaluation was requested by Y. Kikuchi (JAERI). (author). 60 refs.

  1. Study on mechanism of thyroid cytotoxicity of ammonium perchlorate%过氯酸铵对甲状腺细胞毒作用机制的研究

    Institute of Scientific and Technical Information of China (English)

    刘琴; 丁淼鸿; 张娆; 陈红霞; 周星星; 徐慧芳; 陈卉; 彭开良

    2013-01-01

    目的 探讨过氯酸铵(AP)对甲状腺细胞的毒作用机制.方法 将甲状腺体外细胞培养到一定阶段,分别给予AP浓度为0、5、10、20、40、60 mmol/L的培养液进行细胞染毒,收集培养的细胞和上清液做以下指标测定.用噻唑蓝比色法(MTT法)测定细胞增殖,用流式细胞技术检测法测定细胞凋亡,用酶联免疫吸附试验(ELISA)测定甲状腺球蛋白(Tg)浓度,用比色法测定乳酸脱氢酶(LDH)、超氧化物歧化酶(SOD)、丙二醛(MDA)等指标.结果 60 mmol/L AP染毒组细胞12、24、48、72 h时,存活率分别为74.93%、42.26%、2.66%和0.99%,40 mmol/L AP染毒组细胞24、48、72 h时,细胞存活率分别为73.15%、30.91%和3.03%,与对照组(100%)比较,差异均有统计学意义(P<0.05或P<0.01).各染毒组细胞总凋亡率均较对照组明显增加,20、40、60 mmol/L剂量组细胞早期凋亡率分别为15.70%、15.84%和16.96%,较对照组(9.54%)明显增加(P<0.05或P<0.01);60 mmol/L剂量组细胞晚期凋亡率为16.54%,较对照组(6.11%)明显增加,差异均有统计学意义(P<0.05或P<0.01).40 mmol/L染毒组细胞LDH活力为0.70 U/ml,较对照组(0.55 U/ml)明显升高,差异有统计学意义(P<0.01);5mmol/L染毒组细胞MDA含量为1.08 mmol/L,较对照组(2.36 mmol/L)降低,差异亦有统计学意义(P<0.05).结论 AP作用于甲状腺细胞,可明显改变细胞形态,降低细胞存活率,这可能与AP抑制甲状腺细胞增殖,诱导甲状腺细胞凋亡,破坏甲状腺细胞膜完整性有关.AP对甲状腺细胞氧化损伤并不明显.%Objective To investigate the mechanism of thyroid cytotoxicity mechanism of ammonium perchlorate (AP).Methods Thyroid cells were cultured in vitro to a certain stage and then exposed to AP (0,5,10,20,40,and 60 mmol/L) in culture solution; the cultured cells and supernatant were collected.Cell viability was measured by MTT assay; cell apoptosis was determined by flow

  2. {sup 123}Iodine scintigraphy and perchlorate discharge test in the diagnosis of congenital hypothyroidism; {sup 123}I-Szintigraphie und Perchlorat-Depletionstest bei der Diagnostik der kongenitalen Hypothyreose

    Energy Technology Data Exchange (ETDEWEB)

    Meller, J.; Conrad, M.; Emrich, D.; Becker, W. [Goettingen Univ. (Germany). Abt. fuer Nuklearmedizin; Zappel, H.; Roth, C. [Goettingen Univ. (Germany). Abt. Paediatrie

    1998-01-01

    Aim: Thirty eight children suffering from congenital primary permanent hypothyroidism were studied to determine the diagnostic impact of {sup 123}I scintigraphy in comparison to laboratory findings and ultrasonography. Methods: In all patients {sup 123}I scintigraphy was performed after intravenous administration of 3,7 MBq {sup 123}I. If accumulation of the radiotracer in thyroid tissue occured a perchlorate discharge test was performed subsequently. Results: Scintigraphy revealed athyrosis in 7 children. In 9 children a lingual thyroid was observed. Deficiency in iodine organification was diagnosed by a significant discharge of {sup 123}I in 15 patients. In four of these children the diagnosis of Pendred`s syndrome could be established. Ectopic thyroid tissue could be demonstrated only by scintigraphy where clinical examination and sonography failed in the diagnosis in all cases. Hypoplasia of the thyroid gland as it was diagnosed in 2 cases by ultrasonography appeared to be unlikely because of normal {sup 123}I uptake was seen in these patients. In 2 patients with scintigraphic proven athyrosis an orthotopic gland had been falsely considered by ultrasound. In 44% of our patients the final diagnosis could only be established if {sup 123}I scintigraphy and perchlorate discharge test were performed. Conclusion: This findings suggest that scintigraphy is indispensible in the correct diagnostic work up of congenital hypothyroidism. (orig.) [Deutsch] Ziel: Die vorliegende retrospektive Studie an 38 Kindern soll Aufschluss ueber den aktuellen Stellenwert der {sup 123}I-Szintigraphie im Vergleich mit der Sonographie und laborchemischen Methoden bei der Diagnostik der kongenitalen primaeren Hypothyreose geben. Methoden: Alle Patienten erhielten 3,7 MBq {sup 123}I intravenoes zur Lokalisationsdiagnostik der Schilddruese. Liess sich {sup 123}I speicherndes Schilddruesengewebe nachweisen, wurde ein Depletionstest nach oraler Gabe von 300 mg Perchlorat (Irenat {sup trademark

  3. Radioactive Iodide (131I Excretion Profiles in Response to Potassium Iodide (KI and Ammonium Perchlorate (NH4ClO4 Prophylaxis

    Directory of Open Access Journals (Sweden)

    Jeffrey Fisher

    2012-08-01

    Full Text Available Radioactive iodide (131I 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 131I urinary excretion profiles for saline, and the thyroid protectants, potassium iodide (KI and ammonium perchlorate over a 75 hour time-course. Rats were administered 131I and 3 hours later dosed with either saline, 30 mg/kg of NH4ClO4 or 30 mg/kg of KI. Urinalysis of the first 36 hours of the time-course revealed that NH4ClO4 treated animals excreted significantly more 131I compared with KI and saline treatments. A second study followed the same protocol, but thyroxine (T4 was administered daily over a 3 day period. During the first 6–12 hour after 131I dosing, rats administered NH4ClO4 excreted significantly more 131I than the other treatment groups. T4 treatment resulted in increased retention of radioiodide in the thyroid gland 75 hour after 131I administration. We speculate that the T4 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 131I 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.

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

    Directory of Open Access Journals (Sweden)

    Olga V. Hordiyenko

    2015-02-01

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

  5. Effects of various lron oxides on burning rate of ammonium perchlorate/hydroxyl-terminated polybutadiene composite propellants. Part 1. AP/HTPB kei composite suishin'yaku no nensho sokudo ni oyobosu kakushu sankatetsu no koka. (1)

    Energy Technology Data Exchange (ETDEWEB)

    Hagihara, Y.; Ichikawa, T.; Suzuki, M.; Koga, M. (The National Defense Academy, Yokosuka (Japan))

    1991-12-31

    Effect of iron oxide catalysts on burning rate of ammonium perchlorate(AP)/hydroxyl-terminated polybutadine(HTPB) composite propellants with AP 80 % and HTPB 20 % by weight was studied combining 7 various particle sizes of iron oxide measured with scanning electron microscope within the pressure range of 0.4 MPa - 8 MPa. Burning rate has increased with the decrease of particle diameter and this decrement is in the order with the diameter 0.36{mu}m, 0.30{mu}m, 0.26{mu}m, 0.20{mu}m, 0.16{mu}m, 0.14{mu}m. Smaller the particle size the larger is the surface area and this results in the increase in the contact surface area. As a result it has been concluded that with the decrease of average diameter the burning rate is increased. Pressure exponent without catalyst is 0.46 and with catalyst it is 0.45-0.49. This has meant that catalyst does not effect pressure exponent. 3 refs., 4 figs., 3 tabs.

  6. 自养条件下高氯酸盐降解细菌群落研究%The Study of the Structure of Perchlorate(ClO4-)-degrading Bacterial Communities Under Autotrophic Conditions

    Institute of Scientific and Technical Information of China (English)

    谢宇轩; 关翔宇; 于丽莎; 刘菲

    2014-01-01

    For the purpose of further investigating the biological degradation under an autotrophic condition and well understanding the microbial community structures in a complex environment, hydrogen was used as an electron donor to completely reduce perchlorate(ClO4-)in this study. The composition of microbial communities after degradation was analyzed via the construction of a cloning library by using the High-Throughput Sequencing method(HiSeq 2000). 71 days were needed to completely degrade 10 mg/L ClO4-. Microbial phylogenic analysis of HD(hydrogen degradation)after degradation indicated that the relative abundance of total bacteria in the HD was 84.96%whereas the relative abundance of Proteobacteria was 68.11%, whose percentage accounting for the total bacteria reached to 80.16%. The relative abundance of Dechloromonas which is representative in PRB was 2.7%in the HD. Simultaneously, the relative abundance of Azospira was 3.1%. KEGG was used to analyze the function of bacteria in HD. The relative abundance of genes which engaged in carbohydrate metabolism was 4.75%, and the genes included in energy metabolism was 3.35%, whereas the genes participated in nitrogen cycle was 0.72%, and the genes involving chloride transformation was 0.83%. It was demonstrated that degradation of ClO4-in a complicated condition was achieved by various kinds of microbes rather than a single one. Adding hydrogen as an electron donor to change microbial community played a role in the purification or selection process in the system, which allowed the complex systems to have the specific capacity to remove given contaminates.%旨在研究自养条件下以氢气作为电子供体高氯酸根离子(ClO4-)的微生物降解机制,利用HiSeq 2000对微生物群落结构及多样性进行高通量测序及分析。结果表明,添加氢气的HD(hydrogen degradation)体系将10 mg/L ClO4-降至检出限以下共经历71 d。ClO4-完全降解后HD体系中总细菌的相对丰度为84

  7. Crystal structure of bis­(2-methyl-1H-imidazole-κN 3)(meso-tetra-p-tol­ylporphyrinato-κ4 N)iron(III) perchlorate tetra­hydro­furan sesquisolvate

    Science.gov (United States)

    Sun, Wenyan; Li, Jianfeng

    2016-01-01

    In the title compound, [Fe(C48H36N4)(C4H6N2)2]ClO4·1.5C4H8O, the iron(III) metal is coordinated in a distorted octa­hedral geometry by four pyrrole N atoms of the porphyrin ligand in the equatorial plane and two N atoms of 2-methyl­imidazole ligands in the axial sites. The complex has a highly ruffled porphyrin core with mean absolute core-atom displacements C a, C b, C m and C av of 0.25 (5), 0.17 (12), 0.432 (16) and 0.25 (13) Å, respectively. One of the four phenyl groups of the porphyrin is disordered over two sets of sites with refined occupancy ratio of 0.718 (7):0.282 (7). The mean Fe—Np (Np is a porphyrin N atom) bond length [1.975 (9) Å] indicates the low-spin state of the iron atom. The two 2-methyl­imidazole ligands are nearly perpendicular and form a dihedral angle of 86.93 (10)°. The dihedral angles between the 2-methyl­imidazole ligands and the closest Fe—Np vector are 38.04 (9) and 35.00 (7)°. In the crystal, the complex cations inter­act with the perchlorate anions through N—H⋯O hydrogen bonds, forming chains running parallel to [110]. PMID:27536394

  8. Configuration Control in the Synthesis of Homo- and Heteroleptic Bis(oxazolinylphenolato/thiazolinylphenolato) Chelate Ligand Complexes of Oxorhenium(V): Isomer Effect on Ancillary Ligand Exchange Dynamics and Implications for Perchlorate Reduction Catalysis.

    Science.gov (United States)

    Liu, Jinyong; Wu, Dimao; Su, Xiaoge; Han, Mengwei; Kimura, Susana Y; Gray, Danielle L; Shapley, John R; Abu-Omar, Mahdi M; Werth, Charles J; Strathmann, Timothy J

    2016-03-01

    This study develops synthetic strategies for N,N-trans and N,N-cis Re(O)(LO-N)2Cl complexes and investigates the effects of the coordination spheres and ligand structures on ancillary ligand exchange dynamics and catalytic perchlorate reduction activities of the corresponding [Re(O)(LO-N)2](+) cations. The 2-(2'-hydroxyphenyl)-2-oxazoline (Hhoz) and 2-(2'-hydroxyphenyl)-2-thiazoline (Hhtz) ligands are used to prepare homoleptic N,N-trans and N,N-cis isomers of both Re(O)(hoz)2Cl and Re(O)(htz)2Cl and one heteroleptic N,N-trans Re(O)(hoz)(htz)Cl. Selection of hoz/htz ligands determines the preferred isomeric coordination sphere, and the use of substituted pyridine bases with varying degrees of steric hindrance during complex synthesis controls the rate of isomer interconversion. The five corresponding [Re(O)(LO-N)2](+) cations exhibit a wide range of solvent exchange rates (1.4 to 24,000 s(-1) at 25 °C) and different LO-N movement patterns, as influenced by the coordination sphere of Re (trans/cis), the noncoordinating heteroatom on LO-N ligands (O/S), and the combination of the two LO-N ligands (homoleptic/heteroleptic). Ligand exchange dynamics also correlate with the activity of catalytic reduction of aqueous ClO4(-) by H2 when the Re(O)(LO-N)2Cl complexes are immobilized onto Pd/C. Findings from this study provide novel synthetic strategies and mechanistic insights for innovations in catalytic, environmental, and biomedical research.

  9. Crystal structure of bis-(2-methyl-1H-imidazole-κN (3))(meso-tetra-p-tol-ylporphyrinato-κ(4) N)iron(III) perchlorate tetra-hydro-furan sesquisolvate.

    Science.gov (United States)

    Sun, Wenyan; Li, Jianfeng

    2016-08-01

    In the title compound, [Fe(C48H36N4)(C4H6N2)2]ClO4·1.5C4H8O, the iron(III) metal is coordinated in a distorted octa-hedral geometry by four pyrrole N atoms of the porphyrin ligand in the equatorial plane and two N atoms of 2-methyl-imidazole ligands in the axial sites. The complex has a highly ruffled porphyrin core with mean absolute core-atom displacements C a, C b, C m and C av of 0.25 (5), 0.17 (12), 0.432 (16) and 0.25 (13) Å, respectively. One of the four phenyl groups of the porphyrin is disordered over two sets of sites with refined occupancy ratio of 0.718 (7):0.282 (7). The mean Fe-Np (Np is a porphyrin N atom) bond length [1.975 (9) Å] indicates the low-spin state of the iron atom. The two 2-methyl-imidazole ligands are nearly perpendicular and form a dihedral angle of 86.93 (10)°. The dihedral angles between the 2-methyl-imidazole ligands and the closest Fe-Np vector are 38.04 (9) and 35.00 (7)°. In the crystal, the complex cations inter-act with the perchlorate anions through N-H⋯O hydrogen bonds, forming chains running parallel to [110]. PMID:27536394

  10. Synthesis and crystal structure of [2,7,12-trimethyl-3,7,11,17-tetra­aza­bicyclo­[11.3.1]hepta­deca-1(17),13,15-triene-κ4 N]copper(II) bis­(perchlorate)

    Science.gov (United States)

    Hilvano, Edward Gabrielle V.; Yang, Guang; Emnacen, Inno A.; Rybak-Akimova, Elena V.; Billones, Junie B.; Carrillo, Maria Constancia O.; Noll, Bruce C.; Organo, Voltaire G.

    2016-01-01

    The title copper(II) complex of a pyridine-containing macrocycle (PyMAC), [Cu(C16H28N4)](ClO4)2, has been prepared. The crystal structure reveals the CuII atom to be octahedrally coordinated by a tetradentate aminopyridine macrocyclic ligand surrounding the metal cation in a square-planar geometry. Two weakly bound perchlorate counter-ions occupy the axial sites above and below the macrocyclic plane. The crystal studied was refined as a two-component pseudo-merohedral twin; the refined fractional contribution of the minor component is 38.77 (8)% PMID:27555952

  11. 新型富氮含能配合物——高氯酸·四氨·双(5-硝基四唑)(合钴)(Ⅲ)二水合物的结构研究%Structure Investigation of a Novel Nitrogen-rich Energetic Complex:Tetrammine-cis-bis(5-nitro-2H-tetrazole-N2) Cobalt(Ⅲ) Perchlorate Dihydrate

    Institute of Scientific and Technical Information of China (English)

    李志敏; 殷明; 张建国; 张同来; 舒远杰; 杨利; 武碧栋

    2011-01-01

    @@ Energetic coordination compound with 5-nitro-tetrazole (NT) as ligand has gained more and more attentions due to its extreme explosive properties and ecological friendly pyrolysis products[1-6].The research results in 1994 proposed from Sandia National Laboratories proves tetrammine-cis-bis (5-nitro-2H-tetrazole-N) cobalt (Ⅲ) perchlorate (BNCP) to be a more powerful explosive and undergoes deflagration-to-detonation (DDT) transition more rapidly than pentaammine (5-cyanotetrazolato-N) cobalt (Ⅲ) perchlorate (CP), has been used as a promising lead-free primary explosive in semi-conductor bridge detonator, DDT detonator and laser ignition in the area of national defense in USA[2-3].

  12. (Acetonitrile{2-[bis(pyridin-2-ylmethyl-κ2Namino-κN]-N-(2,6-dimethylphenylacetamide-κO}(perchlorato-κOzinc (acetonitrile{2-[bis(pyridin-2-ylmethyl-κ2Namino-κN]-N-(2,6-dimethylphenylacetamide-κO}zinc tris(perchlorate

    Directory of Open Access Journals (Sweden)

    Ove Alexander Høgmoen Åstrand

    2013-02-01

    Full Text Available In the title salt, [Zn(C22H24N4O(CH3CN][Zn(ClO4(C22H24N4O(CH3CN](ClO43, two differently coordinated zinc cations occur. In the first complex, the metal ion is coordinated by the N,N′,N′′,O-tetradentate acetamide ligand and an acetonitrile N atom, generating an approximate trigonal–bipyramidal coordination geometry, with the O atom in an equatorial site and the acetonitrile N atom in an axial site. In the second complex ion, a perchlorate ion is also bonded to the zinc ion, generating a distorted trans-ZnO2N4 octahedron. Of the uncoordinating perchlorate ions, one lies on a crystallographic twofold axis and one lies close to a twofold axis and has a site occupancy of 0.5. N—H...O and N—H...(O,O hydrogen bonds are observed in the crystal. Disordered solvent molecules occupy about 11% of the unit-cell volume; their contribution to the scattering was removed with the SQUEEZE routine of the PLATON program [Spek (2009. Acta Cryst. D65, 148–155.].

  13. (Acetonitrile){2-[bis-(pyridin-2-ylmethyl-κ(2)N)amino-κN]-N-(2,6-dimethyl-phen-yl)acetamide-κO}(perchlorato-κO)zinc (acetonitrile){2-[bis-(pyridin-2-ylmethyl-κ(2)N)amino-κN]-N-(2,6-dimethyl-phen-yl)acetamide-κO}zinc tris-(perchlorate).

    Science.gov (United States)

    Astrand, Ove Alexander Høgmoen; Görbitz, Carl Henrik; Kristoffersen, Kenneth Aase; Rongved, Pål

    2013-02-01

    In the title salt, [Zn(C(22)H(24)N(4)O)(CH(3)CN)][Zn(ClO(4))(C(22)H(24)N(4)O)(CH(3)CN)](ClO(4))(3), two differently coordinated zinc cations occur. In the first complex, the metal ion is coordinated by the N,N',N'',O-tetra-dentate acetamide ligand and an acetonitrile N atom, generating an approximate trigonal-bipyramidal coordination geometry, with the O atom in an equatorial site and the acetonitrile N atom in an axial site. In the second complex ion, a perchlorate ion is also bonded to the zinc ion, generating a distorted trans-ZnO(2)N(4) octa-hedron. Of the uncoordinating perchlorate ions, one lies on a crystallographic twofold axis and one lies close to a twofold axis and has a site occupancy of 0.5. N-H⋯O and N-H⋯(O,O) hydrogen bonds are observed in the crystal. Disordered solvent mol-ecules occupy about 11% of the unit-cell volume; their contribution to the scattering was removed with the SQUEEZE routine of the PLATON program [Spek (2009 ▶). Acta Cryst. D65, 148-155.]. PMID:23424407

  14. 二氧化硅负载高氯酸催化合成香兰素缩1,2-丙二醇%Synthesis of Vanillin 1,2-propylene glycol acetal catalyzed by silica supported perchloric acid

    Institute of Scientific and Technical Information of China (English)

    王宏社

    2013-01-01

    以二氧化硅负载高氯酸(HClO4/SiO2)为催化剂,香兰素和1,2-丙二醇经缩合反应合成香兰素缩1,2-丙二醇.考察了醛醇物质的量比、催化剂用量、反应温度和反应时间对产品收率的影响.实验表明,较佳反应条件为:当香兰素的用量为0.1 mol,1,2-丙二醇的用量为0.16 mol,即n(香兰素)∶n(1,2-丙二醇)=1∶1.6,催化剂用量1.5g,反应温度80℃,反应时间45 min,香兰素缩1,2-丙二醇的收率达87.1%以上.HClO4/SiO2是一种热稳定性好、简单易制、可循环使用的高效非均相催化剂.%Vanillin 1, 2-propylene glycol acetal was synthesized through the condensation of Vanillin with 1, 2-propylene glycol using silica supported perchloric acid (HClO4/SiO2) as a catalyst. The effects of the molar ratio of reactant, the amount of catalyst, reaction temperature and reaction time on the yield of product were discussed. The results showed that the optimized reaction conditions are as follows; the molar ratio of Vanillin (0.1 mol) to 1, 2-propylene glycol (0.16 mol) is 1:1.6; the amount of catalyst is 1.5 g, reaction temperature is 80 ℃ and the reaction time is 45 min. Under the optimum conditions mentioned above, the yield of Vanillin 1, 2-propylene glycol acetal reached more than 87.1%. HClO4/SiO2 as a heterogeneous catalyst has many advantages of high thermal stability, ease of preparation and reusability.

  15. 3-Cyano-N-methylpyridinium perchlorate

    Directory of Open Access Journals (Sweden)

    Cameron A. McCormick

    2014-07-01

    Full Text Available In the crystal of the title molecular salt, C7H7N2+·ClO4−, the components are linked by C—H...O and C—H...N interactions, generating zigzag chains running parallel to [100].

  16. Treatment of Trace Perchlorate from Water by Calcined MgAl-CO_3 Layered Double Hydroxides%焙烧态MgAl-CO_3双羟基层状金属化合物去除水中痕量高氯酸盐

    Institute of Scientific and Technical Information of China (English)

    杨一琼; 高乃云; 郭洪光; 马艳

    2012-01-01

    MgAl-CO3 hydrotalcites with different Mg/Al mole ratios were prepared by co-precipitation method,and calcined to get the calcined samples.The adsorption capacity of trace perchlorate ion from water on calcined samples was measured,the influence of initial perchlorate concentration,varying pH of solution,temperature,particle size,and co-existed anions concentration on the adsorption capacity of calcined samples were studied,kinetic parameters were obtained.Results showed that the best synthesis conditions to maximize the perchlorate adsorption capacity of the calcined MgAl-CO3 layered double hydroxides are the calcination temperature of 550 ℃ and n(Mg2+)/n(Al3+),which fit well with second-order kinetic equation and Freundlich isotherm model.It could be used as a buffer.in a wide range of pH But in strong acid conditions,the calcined hydrotalcite may be dissolved,while in strong alkali condition,the perchlorate removal was lower as a consequence of the competition between OH-and ClO4-.%用共沉淀法制备了不同配比的MgAl-CO3双羟基层状金属化合物,焙烧后制得焙烧态水滑石。考察了MgAl-CO3双羟基层状金属化合物及其焙烧产物对水中痕量高氯酸根离子的吸附性能,研究了初始浓度、pH值、温度、粒径、共存阴离子等对去除效能的影响,计算得到了有关动力学参数。结果表明:550℃焙烧态水滑石(n(Mg2+)/n(Al3+)=3)对ClO4-的吸附效果最好,且符合准二级反应动力学方程和Freundlich等温吸附模型。焙烧态水滑石对溶液的pH值具有一定的缓冲作用,在较宽的pH范围均可广泛应用。但是在强酸条件下水滑石会发生溶解;强碱条件下OH-会与ClO4-形成吸附竞争。

  17. Study of the electrochemical oxidation of Am with lacunary heteropolyanions and silver nitrate; Etude de l'oxydation electrochimique de l'americium en presence d'heteropolyanions lacunaires et de nitrate d'argent en milieu aqueux acide

    Energy Technology Data Exchange (ETDEWEB)

    Chartier, D

    1999-07-01

    Electrochemical oxidation of Am(III) with certain lacunary heteropolyanions (LHPA {alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}{sup 10-} or {alpha}SiW{sub 11}O{sub 39}{sup 8-}) and silver nitrate is an efficient way to prepare Am(VI). This document presents bibliographic data and an experimental study of the process. Thus, it has been established that Am(IV) is an intermediate species in the reaction and occurs in 1:1 (Amt{sup IV}LHPA) or 1:2 (Am {sup IV}(LHAP){sub 2}) complexes with the relevant LHPA. These 1:1 complexes of Am(IV) have been identified and isolated in this work whereas 1:2 complexes were known from previous studies. The reactivity of these complexes in oxidation shows that 1:1 complexes of Am(IV) are oxidised much more quickly than 1:2 complexes. Apparent stability constants of Am(III) and Am(IV) complexes with the relevant LHPA have been measured for a 1 M nitric acid medium. Thermodynamic data of the reaction are then assessed: redox potentials of Am pairs are computed for a 1 M nitric acid medium containing various amount of LHPA ligands. Those results show that the role of LHPA is to stabilize the intermediate species Am(IV) by lowering the Am(IV)/Am(III) pair potential of about 1 Volt. Nevertheless, if this stabilisation is too strong (i.e. of tungsto-silicate), the oxidation of Am(IV) requires high anodic potential (more than 2 V/ENH). Then, the faradic yield of the oxidation of americium is poor because of water oxidation. This study has also shown that the main role of silver is to catalyze the electrochemical oxidation of Am{sup IV}(LHPA){sub X} complexes. Indeed, these oxidations without silver are extremely slow. An oxygen tracer experiment has been performed during the oxidation of Am(III) in Am(VI). It has been shown that the oxygen atoms of Am(VI) (AMO{sub 2}{sup 2+}) come from water molecules of the solvent and not from the complexing oxygen atoms of the ligands. (author)

  18. Fabrication of targets for transmutation of americium : synthesis of inertial matrix by sol-gel method. Procedure study on the infiltration of a radioactive solutions; Fabricacion de blancos para la transmutacion de americio: sintesis de matrices inertes por el metodo sol-gel. Estudio del procedimiento de infiltracion de disoluciones radiactivas

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez Carretero, A. [Universidad Complutense de Madrid (Spain)

    2002-07-01

    made. In addition a new and unexpected phase formed by the reaction of americium with spinel during the high temperature synthesis process has been identified. This new phase could provide a unique menas to stabilise Am in one particular oxidation state. (Author)

  19. Natural Origins, Formation Environmental Mechanisms, and Fate of Perchlorate%环境中高氯酸盐的自然来源、形成机制及其归趋行为

    Institute of Scientific and Technical Information of China (English)

    方齐乐; 陈宝梁

    2012-01-01

    高氯酸盐(Cl04^-)作为新型的环境有毒污染物,其环境污染问题已引起国内外学者的极大关注,但有关ClO4^-的自然来源及形成机制的研究则刚刚起步。ClO4^-的自然来源、在不同环境介质中的背景浓度及迁移转化行为,对制定ClO4^-的环境质量标准和系列安全浓度限值至关重要,但国内相关研究几乎为空白。本文总结了ClO4^-在对流层和平流层气溶胶、大气湿沉降(雨和雪)、地下水、海水、土壤及矿物等环境介质中的背景浓度水平,不同环境介质中涉及样品数为气溶胶3个、雨水1600多个、降雪样品3个、地下水2100多个、海水2个、土壤(矿物)10多个、火星土壤样品1个;重点评述了自然源ClO4^-的前体物质及大气反应形成机制(臭氧氧化、光化学反应和闪电作用),提出ClO2^-/ClO2是大气中ClO4^-自然形成的关键前体物质;归纳了自然源ClO4^-在各环境介质间的迁移转化及归趋行为,最后简单介绍了识别ClO4^-自然来源的同位素示踪技术,并展望相关研究。%Perchlorate (ClO4^-) as an emerging trace pollutant, has caused a great concern about its environmental pollution problems. The natural origin of ClO4^- as well as its formation mechanisms is a new research focus. In order to establish new environmental quality standards and safety concentration limits of ClO4^-, it is quite important to recognize its natural origins, background concentrations, transport and fate in various environmental media, but few researches were reported in China. In this paper, the background concentration levels of ClO4^- in tropospheric and stratospheric aerosol, atmospheric wet deposition (rain and snow), groundwater, seawater, soil and minerals are summarized. The data for ClO4^- concentrations in the aerosol were very limited, such as 0. 5-5 ppt in the stratospheric aerosol, 〈 1.8 ng/m^3 (Japan) and-5.0 ng/m^3 (China) in the

  20. Preparation of americium targets for nuclear chemistry experiments at DANCE

    International Nuclear Information System (INIS)

    Using 1 gram of 241Am from LANL stocks, the purification steps required to obtain a solution of 241Am from the original material are described. Part of the purified solution was submitted for purity analysis by mass spectrometry, radiochemistry and trace metals analysis. The impurities were expected to be 239Pu and 237Np. A second fraction of this material was used for electroplating three samples onto titanium disks that were suitable for insertion into an instrument package to be placed into the DANCE detector. The purification methods used, the electroplating setup and the solutions to various problems that were encountered in making these targets are discussed. The analytical results are discussed as well as the yields from the electrodeposition process. Comparison of these yields with those from similar experiments utilizing 235U and 243Am are also discussed. (author)