Concurrent microbial reduction of high concentrations of nitrate and perchlorate in an ion exchange membrane bioreactor.

PubMed

Fox, Shalom; Bruner, Tali; Oren, Yoram; Gilron, Jack; Ronen, Zeev

2016-09-01

We investigated effective simultaneous removal of high loads of nitrate and perchlorate from synthetic groundwater using an ion exchange membrane bioreactor (IEMB). The aim of this research was to characterize both transport aspects and biodegradation mechanisms involved in the treatment process of high loads of the two anions. Biodegradation process was proven to be efficient with over 99% efficiency of both perchlorate and nitrate, regardless of their load. The maximum biodegradation rates were 18.3 (mmol m(-2)  h(-1) ) and 5.5 (mmol m(-2)  h(-1) ) for nitrate and perchlorate, respectively. The presence of a biofilm on the bio-side of the membrane only slightly increased the nitrate and perchlorate transmembrane flux as compared to the measured flux during a Donnan dialysis experiment where there is no biodegradation of perchlorate and nitrate in the bio-compartment. The nitrate flux in presence of a biofilm was 18.3 (±1.9) (mmole m(-2)  h(-1) ), while without the biofilm, the flux was 16.9 (±1.5) (mmole m(-2)  h(-1) ) for the same feed inlet nitrate concentration of 4 mM. The perchlorate transmembrane flux increased similarly by an average of 5%. Samples of membrane biofilm and suspended bacteria from the bio-reactor were analyzed for diversity and abundance of the perchlorate and nitrate reducing bacteria. Klebsiella oxytoca, known as a glycerol fermenter, accounted for 70% of the suspended bacteria. In contrast, perchlorate and nitrate reducing bacteria predominated in the biofilm present on the membrane. These results are consistent with our proposed two stage biodegradation mechanism where glycerol is first fermented in the suspended phase of the bio-reactor and the fermentation products drive perchlorate and nitrate bio-reduction in the biofilm attached to the membrane. These results suggest that the niche exclusion of microbial populations in between the reactor and membrane is controlled by the fluxes of the electron donors and acceptors. Such a mechanism has important implications for controlling the bio-reduction reaction in the IEMB when using glycerol as a carbon source and allowing treating a complex contamination of high concentrations of perchlorate and nitrating in groundwater and successfully biodegrading them to non-hazardous components. Biotechnol. Bioeng. 2016;113: 1881-1891. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

Perchlorate (ClO4-) was first detected on Mars by the Phoenix Lander in 2008 [1] and has subsequently been detected by Curiosity in Gale Crater [2], in Mars meteorite EETA79001 [3], and has been proposed as a possible explanation for results obtained by Viking [4]. Perchlorate has also been shown to be formed under current Mars conditions via the oxidation of mineral chlorides, further supporting the theory that perchlorate is present globally on Mars [5]. The discovery of perchlorate on Mars has raised important questions about its effects on the survival and detection of organic molecules. Although it has been shown that pyrolysis in the presence of perchlorate results in the alteration or destruction of organic molecules [2, 4], few studies have been conducted on the potential effects of perchlorate and its precursors on organic molecules prior to analysis. Perchlorate is typically inert under Mars temperatures and pressures, but it has been shown to decompose to form reactive oxychlorine species such as chlorite (ClO2-), hypochlorite (ClO-) and chlorine dioxide (ClO2) when exposed to Mars conditions including ionizing radiation [6]. The oxidation of chloride to perchlorate also results in the formation of reactive oxychlorine species such as chlorate (ClO3-) [5]. Here we investigate the effects of perchlorate and its oxychlorine precursors on organic molecules. Experiments are performed in a Mars Simulation Chamber (MSC) capable of reproducing the temperature, pressure, atmospheric composition and UV flux found on Mars. Soil simulants are prepared consisting of Mojave Mars Simulant (MMS) [7] and each organic, as well as varying concentrations of perchlorate and/or chloride salts, and exposed in the MSC. Subsequent to exposure in the MSC samples are leached and the leachate analyzed by HPLC and LC-MS to determine the degree of degradation of the original organic and the identity of any potential decomposition products formed by oxidation or chlorination. References: [1] Hecht et al., Science, Vol. 325, 2009 [2] Glavin et al., J. Geophys. Res. Planets, Vol. 118, 2013 [3] Kounaves et al., Icarus, Vol. 229, 2014 [4] Navarro-Gonzalez et al., J. Geophys. Res., 115, 2010 [5] Carrier & Kounaves, Geophys. Res. Lett., Vol. 42, 2015 [6] Quinn et al, Astrobiology, Vol. 13, 2013 [7] Peters et al., Icarus, Vol. 197, 2008.

The Microbiology of Perchlorate in the Environment

NASA Astrophysics Data System (ADS)

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 at pH values as low as pH 5. Although studies have demonstrated microbial perchlorate reduction in salt brines as concentrated as 11% NaCl, to date no microorganism isolated has been demonstrated to grow by perchlorate respiration in salinities greater than 2%. The metabolism is negatively regulated by oxygen and nitrate. Preference for oxygen is observed even at low oxygen partial pressures while preference for nitrate is observed regardless of the nitrate to perchlorate ratio. Even when the DPRB are pre-grown anaerobically in perchlorate, nitrate is still preferentially reduced prior to perchlorate. Molecular studies reveal that electron acceptor utilization is regulated at the genetic level and is not simply a matter of chemical kinetics. Whole genome sequencing of Dechlormonas aromatica revealed a large number of signaling proteins, a high proportion of which were two component histidine kinase systems suggesting that this organism has exquisite sensitivity to its environment. This supported by the observed ability of this organism to sense, distinguish, and chemotax towards perchlorate or nitrate depending on the growth conditions. These studies demonstrate how the concerted efforts over the last decade have resulted in significant advances in our understanding of the geobiology of microorganisms capable of reductively transforming perchlorate into innocuous chloride. Several in-situ and ex-situ bioremediative processes have been engineered and many monitoring tools based on immunology, molecular biology, and stable isotope content are now available. As such, the rapid scientific response to this emerging contaminant offers great hope for its successful elimination from contaminated environments in the future.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Non-destructive chemical analyses of these compounds is important for process and environmental monitoring and X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride,more » and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. These compounds have unique spectral signatures that can be used to identify unknown samples.« less

Preliminary experiments on the reduction of the uranyl ion to uraninite by carbonaceous substances

USGS Publications Warehouse

Breger, Irving A.; Moore, Richard T.

1955-01-01

An aqueous solution of uranyl sulfate containing a suspension of subbituminous coal has been heated at 210 C for three days. Examination of the coal at the end of the experiment showed it to contain 31.8 percent uranium recognizable as uraninite by a sharp, strong X-ray diffraction pattern. A similar experiment with degraded spruce wood also led to the formation of uraninite but in lesser quantity and with broader lines in the X-ray diffraction pattern. The ability of coal or wood to reduce the uranyl ion is a critical factor in the correlation of studies of uraniferous coals containing the uranyl ion with studies of uraninite-bearing coalified wood from the Colorado Plateau. Although these results are based an preliminary experiments, they are extremely important geochemically and warrant the development of the series of controlled studies that are proposed.

A survey on the temporal and spatial distribution of perchlorate in the Potomac River.

PubMed

Impellitteri, Christopher A; Saxe, Jennie P; Schmitt, Ellen C; Young, K R

2011-08-01

Samples of river water and treated drinking water were obtained from eight sites along the Potomac River between western Maryland and Washington DC. Samples were collected each month from October 2007 to September 2008 and analyzed for perchlorate by ion chromatography/mass spectrometry. Data on anions were also collected for seven of the twelve months. Data were analyzed to identify spatial and temporal patterns for the occurrence of perchlorate in the Potomac. Over the year of sampling, the largest monthly increase occurred from June to July, with levels then decreasing from July to September. Samples from the period between December and May had lower perchlorate concentrations, relative to the remainder of the study year. Spatially, higher levels of perchlorate were found at sites located in west-central Maryland, the eastern panhandle of West Virginia, and central northern Virginia, with levels decreasing slightly as the Potomac approaches Washington DC. Within the sampling boundaries, river (untreated) water perchlorate concentrations ranged from 0.03 μg L(-1) to 7.63 μg L(-1), averaged 0.67 ± 0.97 μg L(-1) over the year-long period and had a median value of 0.37 μg L(-1). There was no evidence that any of the existing drinking water treatment technologies at the sampling sites were effective in removing perchlorate. There were no correlations found between the presence of perchlorate and any of the anions or water quality parameters examined in the source water with the exception of a weak positive correlation with water temperature. Results from the summer (June-August) and fall (September-November) months sampled in this study were generally higher than from the winter and spring months (December-May). All but one of the locations had annual average perchlorate levels below 1 μg L(-1); however, 7 of the 8 sites sampled had river water perchlorate detections over 1 μg L(-1) and 5 of the 8 sites had treated water detections over this level.

Chronic perchlorate exposure impairs stickleback reproductive behaviour and swimming performance

PubMed Central

Bernhardt, Richard R.; von Hippel, Frank A.

2011-01-01

Summary We describe behavioural changes in two generations of threespine stickleback (Gasterosteus aculeatus) exposed to environmentally relevant concentrations of perchlorate. The first generation (G0,2002) was exposed as two-year-old adults to perchlorate in experimental groups ranging in concentration from less than the method detection limit (<1.1 ppb) to 18.6 ppm for up to 22 days during their courtship, spawning, egg guarding, and first five days of fry guarding. No differences were noted in the behaviour or reproductive output of these fish that were exposed as adults. However, perchlorate exposure throughout development caused widespread effects in the second generation (G1,2003), which was spawned and raised through sexual maturity in one of four nominal experimental groups (0, 30 and 100 ppm, and a ‘variable’ treatment that progressively increased from <1.1 ppb to approximately 60 ppm perchlorate). Dose-dependent effects were found during the G1,2003’s swimming and behavioural evaluations, including higher mortality rates among treated fish following stressful events. Perchlorate-exposed fish had higher failure rates during swimming trials and failed at lower flow rates than control fish. A number of treated fish exhibited seizures. Progressively fewer males completed benchmark metrics, such as nest building, spawning, nursery formation, or fry production, in a dose-dependent manner. Fewer males from higher treatments courted females, and those that did initiated courtship later and had a reduced behavioural repertoire compared to fish from lower treatments. The lowest observed adverse effect level (LOAEL) for swimming performance, reproductive behaviour, survivorship and recruitment was 30 ppm perchlorate (our lowest G1,2003 treatment), and near complete inhibition of reproductive activity was noted among males raised in 100 ppm perchlorate. A small number of treated G1,2003 females were isolated in aquaria, and some performed reproductive behaviour typical of males, such as biting, leading and zig-zagging in the presence of gravid females. These findings have profound implications for recruitment in wild fish populations exposed to perchlorate, and suggest that perchlorate may disrupt behaviour in other vertebrates as well. PMID:22228909

[Effects of perchlorate on growth and chlorophyll fluorescence parameters of Alternanthera philoxeroides].

PubMed

Xie, Yin-feng; Cai, Xian-lei; Liu, Wei-long; Deng, Wei

2009-08-15

Perchlorate is a new emerging persistent pollutant, while no studies about its effects on plants have been reported both home and abroad. In order to explore the effects of perchlorate on growth and physiology of aquatic plant, Alternanthera philoxeroides were treated by 1/20 Hoagland nutrient solution with different concentrations (0, 1, 5, 20, 100, 500 mg/L) of ClO4- under the controlled conditions. The results showed as follow. (1) Under perchlorate treatment, relative growth yield,dry weight of root,shoot and leaves were inhibited at different degrees, in which root biomass under different treatments showed significant difference to the control. After treatment for 40 d, relative growth yield of different treatments at concentration from 1 mg/L to 500 mg/L were about 61.6%, 60.8%, 53.1%, 20.4% and 3.3% separately of the control. And the order of variation coefficients of biomass in different organ were as follows: leaf > root biomass > stem; the relationship of biomass allocation in different organs of Alternanthera philoxeroides under perchlorate treatment changed, and the proportion of stem biomass increased,while leaf decreased, in which 100 and 500 mg/L ClO4- treatment showed significant difference to the control. (2) Under perchlorate treatment, young leaves of Alternanthera philoxeroides presented injury symptoms (such as parietal roiling reversely, leaf edge getting black and withered etc), and the damaged degree of Alternanthera philoxeroides increased with the increase of treatment concentration and time. (3) Under perchlorate treatment, the relative chlorophyll content (SPAD value), primary maximal PSII efficiency(Fv/Fm), efficiency of excitation capture by open PSII centre (F'v,/F'm), actual photochemical efficiency of PSII (phi(PS II)), electron transport rate (ETR), maximal electron transport rate(ETR ,) and other indexes were inhibited at different degrees. SPAD and chlorophyll fluorescence parameters (phi(PS II)) etc. could be used as sensitive physiological indexes to reflect the effects of perchlorate stress. The results suggest that perchlorate treatment can damage the photosynthetic system and leaf, decrease photochemical efficiency, and inhibit growth of Alternanthera philoxeroides. Leaf and root show a higher sensitivity to perchlorate,while stem with a lower sensitivity.

Adaptive evolution of Desulfovibrio alaskensis G20 for developing resistance to perchlorate

NASA Astrophysics Data System (ADS)

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 resistance to perchlorate and suggest that adaptive evolution is a valuable tool to understand potential responses of microorganism to any environmental perturbations imposed during oil production.

The Perchlorate Reduction Genomic Island: Mechanisms and Pathways of Evolution by Horizontal Gene Transfer.

PubMed

Melnyk, Ryan A; Coates, John D

2015-10-26

Perchlorate is a widely distributed anion that is toxic to humans, but serves as a valuable electron acceptor for several lineages of bacteria. The ability to utilize perchlorate is conferred by a horizontally transferred piece of DNA called the perchlorate reduction genomic island (PRI). We compared genomes of perchlorate reducers using phylogenomics, SNP mapping, and differences in genomic architecture to interrogate the evolutionary history of perchlorate respiration. Here we report on the PRI of 13 genomes of perchlorate-reducing bacteria from four different classes of Phylum Proteobacteria (the Alpha-, Beta-, Gamma- and Epsilonproteobacteria). Among the different phylogenetic classes, the island varies considerably in genetic content as well as in its putative mechanism and location of integration. However, the islands of the densely sampled genera Azospira and Magnetospirillum have striking nucleotide identity despite divergent genomes, implying horizontal transfer and positive selection within narrow phylogenetic taxa. We also assess the phylogenetic origin of accessory genes in the various incarnations of the island, which can be traced to chromosomal paralogs from phylogenetically similar organisms. These observations suggest a complex phylogenetic history where the island is rarely transferred at the class level but undergoes frequent and continuous transfer within narrow phylogenetic groups. This restricted transfer is seen directly by the independent integration of near-identical islands within a genus and indirectly due to the acquisition of lineage-specific accessory genes. The genomic reversibility of perchlorate reduction may present a unique equilibrium for a metabolism that confers a competitive advantage only in the presence of an electron acceptor, which although widely distributed, is generally present at low concentrations in nature.

Developmental Exposure to Perchlorate Alters Synaptic Transmission in Hippocampus of the Adult Rat

PubMed Central

Gilbert, Mary E.; Sui, Li

2008-01-01

Background Perchlorate is an environmental contaminant that blocks iodine uptake into the thyroid gland and reduces thyroid hormones. This action of perchlorate raises significant concern over its effects on brain development. Objectives The purpose of this study was to evaluate neurologic function in rats after developmental exposure to perchlorate. Methods Pregnant rats were exposed to 0, 30, 300, or 1,000 ppm perchlorate in drinking water from gestational day 6 until weaning. Adult male offspring were evaluated on a series of behavioral tasks and neurophysiologic measures of synaptic function in the hippocampus. Results At the highest perchlorate dose, triiodothyronine (T3) and thyroxine (T4) were reduced in pups on postnatal day 21. T4 in dams was reduced relative to controls by 16%, 28%, and 60% in the 30-, 300-, and 1,000-ppm dose groups, respectively. Reductions in T4 were associated with increases in thyroid-stimulating hormone in the high-dose group. No changes were seen in serum T3. Perchlorate did not impair motor activity, spatial learning, or fear conditioning. However, significant reductions in baseline synaptic transmission were observed in hippocampal field potentials at all dose levels. Reductions in inhibitory function were evident at 300 and 1,000 ppm, and augmentations in long-term potentiation were observed in the population spike measure at the highest dose. Conclusions Dose-dependent deficits in hippocampal synaptic function were detectable with relatively minor perturbations of the thyroid axis, indicative of an irreversible impairment in synaptic transmission in response to developmental exposure to perchlorate. PMID:18560531

77 FR 31847 - Notification of a Public Meeting and Public Teleconference of the Science Advisory Board (SAB...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-05-30

... Teleconference of the Science Advisory Board (SAB); Perchlorate Advisory Panel AGENCY: Environmental Protection... public meeting and follow-up public teleconference of the SAB Perchlorate Advisory Panel to conduct an advisory activity related to the development of a maximum contaminant level goal (MCLG) for perchlorate...

ACCUMULATION AND FATE OF PERCHLORATE IN PLANTS

EPA Science Inventory

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...

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

USDA-ARS?s Scientific Manuscript database

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...

PERCHLORATE ENVIRONMENTAL CONTAMINATION: TOXICOLOGICAL REVIEW AND RISK CHARACTERIZATION BASED ON EMERGING INFORMATION (EXTERNAL REVIEW DRAFT) 1998

EPA Science Inventory

Perchlorate (ClO4-) is an anion that originates as a contaminant in ground water and surface waters from the dissolution of ammonium, potassium, magnesium, or sodium salts. Because perchlorate is nonlabile kinetically (i.e., the reduction of the central chlorine atom occurs extre...

Validation of a Novel Bioassay for Low-level Perchlorate Determination

DTIC Science & Technology

2014-04-01

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

Validation of a Novel Bioassay for Low-level Perchlorate Determination

DTIC Science & Technology

2013-05-01

since these reduce PMS2 , and it was thought they would interfere with the stoichiometry of NADH and perchlorate in the bioassay. With regard to the...reduce PMS2 directly, and would interfere with the stoichiometry of NADH and perchlorate in the bioassay. Thus the only approach that could be

Surface catalysis of uranium(VI) reduction by iron(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

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

USGS Publications Warehouse

Sturchio, N.C.; Böhlke, J.K.; Beloso, Abelardo 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.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

PubMed

Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

2012-02-07

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

M4FT-15OR03100415 - Update on COF-based Adsorbent Survey

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayes, Richard T.; Dai, Sheng

2015-02-01

This letter report provides an update on activities focused on generating nanoporous adsorbents involving covalent organic frameworks (COF) and zeolitic imidazolium frameworks (ZIF). The adsorbents have been generated and screened in a uranyl-spiked brine (6 ppm U) to understand uranyl-binding behavior. Porous organic polymers (POP) also qualify under this title and are similar to the COF PPN-6 that is discussed herein. Seven COF/POP and one 1 ZIF were synthesized and screened for uranyl adsorption. Seawater screening is on-going via batch testing while flow screening systems are being developed at PNNL.

Method for loading resin beds

DOEpatents

Notz, Karl J.; Rainey, Robert H.; Greene, Charles W.; Shockley, William E.

1978-01-01

An improved method of preparing nuclear reactor fuel by carbonizing a uranium loaded cation exchange resin provided by contacting a H.sup.+ loaded resin with a uranyl nitrate solution deficient in nitrate, comprises providing the nitrate deficient solution by a method comprising the steps of reacting in a reaction zone maintained between about 145.degree.-200.degree. C, a first aqueous component comprising a uranyl nitrate solution having a boiling point of at least 145.degree. C with a second aqueous component to provide a gaseous phase containing HNO.sub.3 and a reaction product comprising an aqueous uranyl nitrate solution deficient in nitrate.

Uranyl peroxide enhanced nuclear fuel corrosion in seawater

PubMed Central

Armstrong, Christopher R.; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E.; Burns, Peter C.; Navrotsky, Alexandra

2012-01-01

The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances. PMID:22308442

Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

DOE PAGES

Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

2014-02-05

Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO 2 2+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO 2Cl 2 ,more » 0.1 M NaCl). We find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si 4Al 2 rings near aluminum substitution sites.« less

Mechanistic Studies on the Radiolytic Decomposition of Perchlorates on the Martian Surface

NASA Astrophysics Data System (ADS)

Turner, Andrew M.; Abplanalp, Matthew J.; Kaiser, Ralf I.

2016-04-01

Perchlorates—inorganic compounds carrying the perchlorate ion ({{ClO}}4{}-)—were discovered at the north polar landing site of the Phoenix spacecraft and at the southern equatorial landing site of the Curiosity Rover within the Martian soil at levels of 0.4-0.6 wt%. This study explores in laboratory experiments the temperature-dependent decomposition mechanisms of hydrated perchlorates—namely magnesium perchlorate hexahydrate (Mg(ClO4)2·6H2O)—and provides yields of the oxygen-bearing species formed in these processes at Mars-relevant surface temperatures from 165 to 310 K in the presence of galactic cosmic-ray particles (GCRs). Our experiments reveal that the response of the perchlorates to the energetic electrons is dictated by the destruction of the perchlorate ion ({{ClO}}4{}-) and the inherent formation of chlorates ({{ClO}}3{}-) plus atomic oxygen (O). Isotopic substitution experiments reveal that the oxygen is released solely from the perchlorate ion and not from the water of hydration (H2O). As the mass spectrometer detects only molecular oxygen (O2) and no atomic oxygen (O), atomic oxygen recombines to molecular oxygen within the perchlorates, with the overall yield of molecular oxygen increasing as the temperature drops from 260 to 160 K. Absolute destruction rates and formation yields of oxygen are provided for the planetary modeling community.

Comparative effects of in ovo exposure to sodium perchlorate on development, growth, metabolism, and thyroid function in the common snapping turtle (Chelydra serpentina) and red-eared slider (Trachemys scripta elegans).

PubMed

Eisenreich, Karen M; Dean, Karen M; Ottinger, Mary Ann; Rowe, Christopher L

2012-11-01

Perchlorate is a surface and groundwater contaminant found in areas associated with munitions and rocket manufacturing and use. It is a thyroid-inhibiting compound, preventing uptake of iodide by the thyroid gland, ultimately reducing thyroid hormone production. As thyroid hormones influence metabolism, growth, and development, perchlorate exposure during the embryonic period may impact embryonic traits that ultimately influence hatchling performance. We topically exposed eggs of red-eared sliders (Trachemys scripta) and snapping turtles (Chelydra serpentina) to 200 and 177 μg/g of perchlorate (as NaClO(4)), respectively, to determine impacts on glandular thyroxine concentrations, embryonic growth and development, and metabolic rates of hatchlings for a period of 2 months post-hatching. In red-eared sliders, in ovo perchlorate exposure delayed hatching, increased external yolk size at hatching, increased hatchling mortality, and reduced total glandular thyroxine concentrations in hatchlings. In snapping turtles, hatching success and standard metabolic rates were reduced, liver and thyroid sizes were increased, and total glandular thyroxine concentrations in hatchlings were reduced after exposure to perchlorate. While both species were negatively affected by exposure, impacts on red-eared sliders were most severe, suggesting that the slider may be a more sensitive sentinel species for studying effects of perchlorate exposure to turtles. Copyright © 2012 Elsevier Inc. All rights reserved.

Perchlorate Formation on Mars Through Surface Radiolysis-Initiated Atmospheric Chemistry: A Potential Mechanism

NASA Technical Reports Server (NTRS)

Wilson, Eric H.; Atreya, Sushil K.; Kaiser, Ralf I.; Mahaffy, Paul R.

2016-01-01

Recent observations of the Martian surface by the Phoenix lander and the Sample Analysis at Mars indicate the presence of perchlorate (ClO4). The abundance and isotopic composition of these perchlorates suggest that the mechanisms responsible for their formation in the Martian environment may be unique in our solar system. With this in mind, we propose a potential mechanism for the production of Martian perchlorate: the radiolysis of the Martian surface by galactic cosmic rays, followed by the sublimation of chlorine oxides into the atmosphere and their subsequent synthesis to form perchloric acid (HClO4) in the atmosphere, and the surface deposition and subsequent mineralization of HClO4 in the regolith to form surface perchlorates. To evaluate the viability of this mechanism, we employ a one-dimensional chemical model, examining chlorine chemistry in the context of Martian atmospheric chemistry. Considering the chlorine oxide, OClO, we find that an OClO flux as low as 3.2 x 10(exp 7) molecules/sq cm/s 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.

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

EPA Science Inventory

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 ...

Biodegradation of rocket propellant waste, ammonium perchlorate

NASA Technical Reports Server (NTRS)

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

1975-01-01

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

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

NASA Technical Reports Server (NTRS)

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

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

PubMed

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

2003-10-01

Contamination of drinking water with perchlorate, a known thyrotropic agent, has been demonstrated in areas in the western United States. The health consequences of that exposure have been studied, particularly in the State of Nevada. Previous studies in Nevada, comparing the area with perchlorate in the drinking water and the areas without perchlorate in the drinking water, have found no difference in neonatal thyroxine (T(4)) or thyrotropin (TSH) levels, or in the prevalences of thyroid diseases and thyroid cancer. This same study design has now been applied to the major neurobehavioral diseases of childhood (i.e., attention deficit-hyperactivity disorder (ADHD) and autism) and to school performance in order to determine whether those conditions are more frequent in the area with perchlorate-contaminated water. Medical services data on ADHD and autism were obtained from the Nevada Medicaid system for the period of January 1, 1996, to December 31, 2000, with county of residence used as the basis for residential information. Analyses of fourth-grade school performance results for two recent time periods came from the state government. Perchlorate concentrations in drinking water had been determined by local water authorities. ADHD and autism rates for the area with perchlorate in the drinking water (Clark County) were calculated and compared with the rates for the other areas in the state, as were fourth-grade school performances. Analysis of the data from the Nevada Medicaid program shows that the rates for ADHD and for autism in the area where perchlorate was in the drinking water did not exceed the rates in those areas where there was no perchlorate contamination in the drinking water. Fourth-grade standardized test results for students in Clark County were not different from those of the remainder of the state. This ecological study of children in the exposure area did not find evidence of an increased risk of either ADHD or of autism caused by perchlorate contamination in the drinking water. Furthermore, no difference in overall fourth-grade school performance was observed. No evidence was found that children from the area with perchlorate in the drinking water (up to 24 microg/liter) had either an increase in pediatric neurobehavioral disease (ADHD and autism) or a decrease in fourth-grade academic performance. The limitations of this ecological study relate to diagnostic criteria and ascertainment of geographic and demographic differences and to data on individual residence and water consumption during pregnancy. Copyright 2003 Wiley-Liss, Inc.

Effects of water temperature on perchlorate toxicity to the thyroid and reproductive system of Oryzias latipes.

PubMed

Lee, Sangwoo; Ji, Kyunghee; Choi, Kyungho

2014-10-01

Water temperature is expected to increase in many parts of the world due to global climate change. The change in water temperature may affect ecosystems through alterations of the chemical properties or by affecting the susceptibility of organisms. Perchlorate can disrupt thyroid function of an organism by inhibiting iodide uptake. In the present study, the effect of water temperature on perchlorate toxicity was evaluated using Japanese medaka (Oryzias latipes). Pairs of adult medaka fish were exposed to a sublethal concentration of sodium perchlorate (100mg/L) and a control, at a 'low' (26°C), 'medium' (29°C) or 'high' water temperature (33°C) for seven days. The effects of the water temperature on reproduction, thyroid hormones and cortisol concentrations were determined. Transcription of several genes related to thyroid function and stress were also investigated. Significant down-regulation of thyroid hormone receptor alpha (THR-α) and beta (THR-β) transcripts and up-regulation of deiodinase 2 (DIO2) transcripts were observed in the fish exposed to perchlorate. Thyroxine (T4) concentrations were decreased, while triiodothyronine (T3) levels remained constant following exposure to perchlorate, and this effect became more pronounced under the high water temperature conditions (33°C). Up-regulation of the DIO2 gene may explain these observations. The total number of spawned eggs decreased slightly as the water temperature increased, and this reduction became significant when fish were exposed to perchlorate. Our observations indicate that exposure to perchlorate could affect thyroid function and overall reproductive fitness, and these effects could be aggravated under high water temperatures. Copyright © 2014 Elsevier Inc. All rights reserved.

Combined Effects of Perchlorate, Thiocyanate, and Iodine on Thyroid Function in the National Health and Nutrition Examination Survey 2007-8

PubMed Central

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

2013-01-01

Perchlorate, thiocyanate, and low iodine intake can all decrease iodide intake into the thyroid gland. This can reduce thyroid hormone production since iodide is a key component of thyroid hormone. Previous research has suggested that each of these factors alone may decrease thyroid hormone levels, but effect sizes are small. We hypothesized that people who have all three factors at the same time have substantially lower thyroid hormone levels than people who do not, and the effect of this combined exposure is substantially larger than the effects seen in analyses focused on only one factor at a time. Using data from the 2007-2008 National Health and Nutrition Examination Survey, subjects were categorized into exposure groups based on their urinary perchlorate, iodine, and thiocyanate concentrations, and mean serum thyroxine concentrations were compared between groups. Subjects with high perchlorate (n=1939) had thyroxine concentrations that were 5.0% lower (mean difference = 0.40 µg/dl, 95% confidence interval=0.14-0.65) than subjects with low perchlorate (n=2084). The individual effects of iodine and thiocyanate were even smaller. Subjects with high perchlorate, high thiocyanate, and low iodine combined (n=62) had thyroxine concentrations 12.9% lower (mean difference = 1.07 µg/dl, 95% confidence interval=0.55-1.59) than subjects with low perchlorate, low thiocyanate, and adequate iodine (n=376). Potential confounders had little impact on results. Overall, these results suggest that concomitant exposure to perchlorate, thiocyanate, and low iodine markedly reduces thyroxine production. This highlights the potential importance of examining the combined effects of multiple agents when evaluating the toxicity of thyroid-disrupting agents. PMID:23473920

Evaluation of ammonium perchlorate in the endocrine disruptor screening and testing program's male pubertal protocol: ability to detect effects on thyroid endpoints.

PubMed

Stoker, T E; Ferrell, J M; Laws, S C; Cooper, R L; Buckalew, A

2006-11-10

The U.S. EPA Endocrine Disruptor Screening Program (EDSP) Tier 1 male pubertal protocol was designed as a screen to detect endocrine-disrupting chemicals which may alter reproductive development or thyroid function. One purpose of this in vivo screening protocol is to detect thyrotoxicants via a number of different mechanisms of action, such as thyroid hormone synthesis or clearance. Here we evaluate the ability of this EDSP male pubertal protocol to detect the known thyrotoxicant ammonium perchlorate as an endocrine disruptor. Ammonium perchlorate is a primary ingredient in rocket fuel, fertilizers, paints, and lubricants. Over the past 50 years, potassium perchlorate has been used to treat hyperthyroidism in humans. Perchlorate alters thyroid hormone secretion by competitively inhibiting iodide uptake by the thyroid gland. In this study, ammonium perchlorate was administered at 62.5, 125, 250, and 500 mg/kg to male Wistar rats based on a pilot study of oral dosing. Doses of 125-500 mg/kg perchlorate decreased T4 in a dose-dependent manner. TSH was significantly increased in a dose-responsive manner at the same doses, while T3 was unchanged at any dose. Thyroid histology was significantly altered at all doses, even at the 62.5 mg/kg, with a clear dose-dependent decrease in colloid area and increase in follicular cell height. No effects on preputial separation, a marker of pubertal progression, or reproductive tract development were observed at any dose. These results demonstrate that the male pubertal protocol is useful for detecting thyrotoxicants which target the thyroid axis by this mechanism (altered uptake of iodide). This study also found that perchlorate exposure during this period did not alter any of the reproductive developmental endpoints.

Effect of fireworks display on perchlorate in air aerosols during the Spring Festival

NASA Astrophysics Data System (ADS)

Shi, Yali; Zhang, Ning; Gao, Jianmin; Li, Xin; Cai, Yaqi

2011-02-01

Perchlorate is regarded as a new emerging persistent inorganic environmental contaminant. It can result in important neurodevelopmental deficits and goiter in infants and children because of its inhibition of iodine uptake into the thyroid tissue. Furthermore, its presence in the human body can cause improper regulation of metabolism for adults. It is often used as ingredient in the production of fireworks. So fireworks display may influence the perchlorate levels in atmospheric particulate matter (PM). In this paper perchlorate was determined in air aerosol samples (Inhalable particulate matter (PM10) and larger particulate matter (PM10-100)) collected from two locations (Lanzhou City and Yuzhong County) in Gansu province over a month period (February 1rst to March 4th) during the Spring Festival (February 18th) in 2007 in order to study the effect of fireworks display on perchlorate in air aerosol. The results showed that different concentrations of perchlorate were detected in almost all samples, ranging from

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

PubMed

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

2007-09-01

To assess the effect of gestational perchlorate exposure through drinking water on neonatal thyroxine (T(4)). T(4) values were compared among newborns in Ramat Hasharon, Israel, whose mothers resided in suburbs where drinking water contained perchlorate < or = 340 microg/L (very high exposure, n = 97), 42-94 microg/L (high exposure, n = 216), and < 3 microg/L (low exposure, n = 843). In the very high and high exposure areas, T(4) values in newborns whose mothers drank tap water exclusively (as determined by a telephone interview) were analyzed as a subset. Serum perchlorate levels in blood from donors residing in the area were used as proxy indicators of exposure. Neonatal T(4) values (mean +/- SD) in the very high, high, and low exposure groups were 13.9 +/- 3.8, 13.9 +/- 3.4, and 14.0 +/- 3.5 microg/dL, respectively (p = NS). Serum perchlorate concentrations in blood from donors residing in areas corresponding to these groups were 5.99 +/- 3.89, 1.19 +/- 1.37, and 0.44 +/- 0.55 microg/L, respectively. T(4) levels of neonates with putative gestational exposure to perchlorate in drinking water were not statistically different from controls. This study finds no change in neonatal T(4) levels despite maternal consumption of drinking water that contains perchlorate at levels in excess of the Environmental Protection Agency (EPA) drinking water equivalent level (24.5 microg/L) based on the National Research Council reference dose (RfD) [0.7 microg/(kg.day)]. Therefore the perchlorate RfD is likely to be protective of thyroid function in neonates of mothers with adequate iodide intake.

Determination of trace level bromate and perchlorate in drinking water by ion chromatography with an evaporative preconcentration technique.

PubMed

Liu, Yongjian; Mou, Shifen; Heberling, Shawn

2002-05-17

A simple sample preconcentration technique employing microwave-based evaporation for the determination of trace level bromate and perchlorate in drinking water with ion chromatography is presented. With a hydrophilic anion-exchange column and a sodium hydroxide eluent in linear gradient, bromate and perchlorate can be determined in one injection within 35 min. Prior to ion chromatographic analysis, the drinking water sample was treated with an OnGuard-Ag cartridge to remove the superfluous chloride and concentrated 20-fold using a PTFE beaker in a domestic microwave oven for 15 min. The recoveries of the anions ranged from 94.6% for NO2- to 105.2% for F-. The detection limits for bromate, perchlorate, iodate and chlorate were 0.1, 0.2, 0.1 and 0.2 microg/l, respectively. The developed method is applicable for the quantitation of bromate and perchlorate in drinking water samples.

Highly Sensitive and Selective Uranium Detection in Natural Water Systems Using a Luminescent Mesoporous Metal-Organic Framework Equipped with Abundant Lewis Basic Sites: A Combined Batch, X-ray Absorption Spectroscopy, and First Principles Simulation Investigation.

PubMed

Liu, Wei; Dai, Xing; Bai, Zhuanling; Wang, Yanlong; Yang, Zaixing; Zhang, Linjuan; Xu, Lin; Chen, Lanhua; Li, Yuxiang; Gui, Daxiang; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2017-04-04

Uranium is not only a strategic resource for the nuclear industry but also a global contaminant with high toxicity. Although several strategies have been established for detecting uranyl ions in water, searching for new uranium sensor material with great sensitivity, selectivity, and stability remains a challenge. We introduce here a hydrolytically stable mesoporous terbium(III)-based MOF material compound 1, whose channels are as large as 27 Å × 23 Å and are equipped with abundant exposed Lewis basic sites, the luminescence intensity of which can be efficiently and selectively quenched by uranyl ions. The detection limit in deionized water reaches 0.9 μg/L, far below the maximum contamination standard of 30 μg/L in drinking water defined by the United States Environmental Protection Agency, making compound 1 currently the only MOF material that can achieve this goal. More importantly, this material exhibits great capability in detecting uranyl ions in natural water systems such as lake water and seawater with pH being adjusted to 4, where huge excesses of competing ions are present. The uranyl detection limits in Dushu Lake water and in seawater were calculated to be 14.0 and 3.5 μg/L, respectively. This great detection capability originates from the selective binding of uranyl ions onto the Lewis basic sites of the MOF material, as demonstrated by synchrotron radiation extended X-ray adsorption fine structure, X-ray adsorption near edge structure, and first principles calculations, further leading to an effective energy transfer between the uranyl ions and the MOF skeleton.

Crystal Chemistry of the Potassium and Rubidium Uranyl Borate Families Derived from Boric Acid Fluxes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Shuao; Alekseev, Evgeny V.; Stritzinger, Jared T.

2010-07-19

The reaction of uranyl nitrate with a large excess of molten boric acid in the presence of potassium or rubidium nitrate results in the formation of three new potassium uranyl borates, K{sub 2}[(UO{sub 2}){sub 2}B{sub 12}O{sub 19}(OH){sub 4}]·0.3H{sub 2}O (KUBO-1), K[(UO{sub 2}){sub 2}B{sub 10}O{sub 15}(OH){sub 5}] (KUBO-2), and K[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (KUBO-3) and two new rubidium uranyl borates Rb{sub 2}[(UO{sub 2}){sub 2}B{sub 13}O{sub 20}(OH){sub 5}] (RbUBO-1) and Rb[(UO{sub 2}){sub 2}B{sub 10}O{sub 16}(OH){sub 3}]·0.7H{sub 2}O (RbUBO-2). The latter is isotypic with KUBO-3. These compounds share a common structural motif consisting of a linear uranyl, UO{sub 2}{sup 2+},more » cation surrounded by BO{sub 3} triangles and BO{sub 4} tetrahedra to create an UO{sub 8} hexagonal bipyramidal environment around uranium. The borate anions bridge between uranyl units to create sheets. Additional BO{sub 3} triangles extend from the polyborate layers and are directed approximately perpendicular to the sheets. All of these compounds adopt layered structures. With the exception of KUBO-1, the structures are all centrosymmetric. All of these compounds fluoresce when irradiated with long-wavelength UV light. The fluorescence spectrum yields well-defined vibronically coupled charge-transfer features.« less

Bioelectrical Perchlorate Remediation

NASA Astrophysics Data System (ADS)

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 low-level perchlorate (100 μg.L-1) influent as well as mixed-waste influents more typically found in the environment containing both nitrate and perchlorate. Through extended periods of operation (>70 days), no loss in treatment efficiency was noted and no measurable growth in biomass was observed. Gas phase analysis indicated that low levels of H2 produced at the cathode surface through electrolysis can provide enough reducing equivalents to mediate this metabolism. The results of these studies demonstrate that perchlorate remediation can be facilitated through the use of a cathode as the primary electron donor, and that continuous treatment in such a system approaches current industry standards. This has important implications for the continuous treatment of this critical contaminant in industrial waste streams and drinking water. Such a process has the advantage of long-term, low-maintenance operation with ease of online monitoring and control while limiting the injection of additional chemicals into the water treatment process and outgrowth of the microbial populations. This would negate the need for the continual removal and disposal of biomass produced during treatment and also the downstream issues associated with corrosion and biofouling of distribution systems and the production of toxic disinfection byproducts.

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

NASA Astrophysics Data System (ADS)

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 from chloride. In this model isotopically normal perchlorate produced by an unspecified mechanism is reduced to chloride. Depending on the relative size of the reduced reservoir, the integrated product chloride can vary in isotopic composition from - 70 ‰ in the first increment all the way to the starting composition if the perchlorate is fully reduced. Thus, variable degrees of perchlorate reduction can produce chloride with the appropriate δ37Cl range. Combination of the two endmember models, in which the perchlorate subject to post-deposition reduction is isotopically negative from atmospheric reactions, is also possible. Determination of the phase hosting the Cl measured by SAM, an oxychlorine compound or chloride, is critical for selecting between these models, and for developing implications of the results for the Mars surficial Cl cycle. At present it is not possible to conclusively establish which phase is responsible (possibly both), but limited evidence favors the conclusion that the measured Cl derives mostly from an oxychlorine compound.

Identifying anthropogenic uranium compounds using soft X-ray near-edge absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ward, Jesse D.; Bowden, Mark; Tom Resch, C.; Eiden, Gregory C.; Pemmaraju, C. D.; Prendergast, David; Duffin, Andrew M.

2017-01-01

Uranium ores mined for industrial use are typically acid-leached to produce yellowcake and then converted into uranium halides for enrichment and purification. These anthropogenic chemical forms of uranium are distinct from their mineral counterparts. The purpose of this study is to use soft X-ray absorption spectroscopy to characterize several common anthropogenic uranium compounds important to the nuclear fuel cycle. Chemical analyses of these compounds are important for process and environmental monitoring. X-ray absorption techniques have several advantages in this regard, including element-specificity, chemical sensitivity, and high spectral resolution. Oxygen K-edge spectra were collected for uranyl nitrate, uranyl fluoride, and uranyl chloride, and fluorine K-edge spectra were collected for uranyl fluoride and uranium tetrafluoride. Interpretation of the data is aided by comparisons to calculated spectra. The effect of hydration state on the sample, a potential complication in interpreting oxygen K-edge spectra, is discussed. These compounds have unique spectral signatures that can be used to identify unknown samples.

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alam, Todd M.; Liao, Zuolei; Nyman, May

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

DOE PAGES

Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; ...

2015-11-12

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η 2 motifs proposed by small molecule andmore » computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ 2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

Sorption of uranium in uranyl nitrate solutions on strong cationic resins and its elution with ammonium sulfate. II. Effects of EDTA on thorium decontamination; Estudos de sorpcao de uranio contido em solucoes de nitrato de uranilo por resina cationica forte e sua eluicao com sulfato de amonio. Parte II: efeito de EDTA na descontaminacao do torio (in Portuguese)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ribas, Antonio G.S.; Abrao, Alcidio

1970-05-15

This paper describes the studies of decontamination of thorium present as impurity in uranyl nitrate solutions, which was carried out through strong cationic resin where the thorium was partially retained. Then, the final decontamination was performed percolating the uranyl solution on a second cationic resin, after complexation of thorium (and other impurities) with EDTA. The thorium decontamination and the uranium retention were studied as a function of EDTA/U ratio, uranium concentration and acidity of the influent uranyl nitrate. The elution conditions were also studied as a function of eluent flow rate, concentration and acidity. Several tables and graphs showing themore » final results are included. (tr-auth)« less

Synthesis and characterization of new ion-imprinted polymer for separation and preconcentration of uranyl (UO2(2+)) ions.

PubMed

Ahmadi, Seyed Javad; Noori-Kalkhoran, Omid; Shirvani-Arani, Simindokht

2010-03-15

UO(2)(2+) ion-imprinted polymer materials used for solid-phase extraction were prepared by copolymerization of a ternary complex of uranyl ions with styrene and divinyl benzene in the presence of 2,2'-azobisisobutyronitrile. The imprinted particles were leached by HCl 6M. Various parameters in polymerization steps such as DVB/STY ratio, time of polymerization and temperature of polymerization were varied to achieve the most efficient uranyl-imprinted polymer. X-ray diffraction (XRD), infra-red spectroscopy (IR), thermo gravimetric analysis (TGA), UV-vis and nitrogen sorption were used to characterize the polymer particles. The XRD results showed that uranyl ions were completely removed from the polymer after leaching process. IR Analysis indicated that the N,N'-ethylenebis(pyridoxylideneiminato) remained intact in the polymer even after leaching. Some parameters such as pH, weight of the polymer, elution time, eluent volume and aqueous phase volume which affects the efficiency of the polymer were studied. (c) 2009 Elsevier B.V. All rights reserved.

Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory

DOE PAGES

Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.

2015-04-02

The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K 1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO 2 2+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K 1 values are significantly overestimated. Accurate predictions of the absolute log K 1 values (root mean square deviation from experiment < 1.0 for logmore » K 1 values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.« less

Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

DOE PAGES

Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

2016-04-27

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO 2(OH) 2] (α-UOH) and hydrated uranyl hydroxide [(UO 2) 4O(OH) 6·5H 2O (metaschoepite). For the metaschoepite material, proton resonances of the μ 2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H– 1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization ofmore » local hydrogen-bond environments in uranyl U 24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

Uranium XAFS analysis of kidney from rats exposed to uranium

PubMed Central

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Homma-Takeda, Shino

2017-01-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III-edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate. PMID:28244440

Uranium XAFS analysis of kidney from rats exposed to uranium.

PubMed

Kitahara, Keisuke; Numako, Chiya; Terada, Yasuko; Nitta, Kiyohumi; Shimada, Yoshiya; Homma-Takeda, Shino

2017-03-01

The kidney is the critical target of uranium exposure because uranium accumulates in the proximal tubules and causes tubular damage, but the chemical nature of uranium in kidney, such as its chemical status in the toxic target site, is poorly understood. Micro-X-ray absorption fine-structure (µXAFS) analysis was used to examine renal thin sections of rats exposed to uranyl acetate. The U L III -edge X-ray absorption near-edge structure spectra of bulk renal specimens obtained at various toxicological phases were similar to that of uranyl acetate: their edge position did not shift compared with that of uranyl acetate (17.175 keV) although the peak widths for some kidney specimens were slightly narrowed. µXAFS measurements of spots of concentrated uranium in the micro-regions of the proximal tubules showed that the edge jump slightly shifted to lower energy. The results suggest that most uranium accumulated in kidney was uranium (VI) but a portion might have been biotransformed in rats exposed to uranyl acetate.

Perchlorate Removal, Destruction and Field Monitoring Demonstration

DTIC Science & Technology

2007-03-01

perchlorate CSTR continuously stirred tank reactors DAB decyltrimethylammonium bromide DHS Department of Health Services DoD Department of Defense DWEL...reactors ( CSTR ) in series under anoxic conditions. A strong base anion resin was used to scavenge the concentrated spent regenerant solution as a super...evaluate perchlorate destruction in spent regenerant. The apparatus consisted of two 2.5-liter, continuously stirred tank reactors ( CSTR ) in

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

DTIC Science & Technology

2013-05-31

2000; p 529. 16. Schlosser, P.; Stute, M.; Dörr, H.; Sonntag, C.; Münnich, K. O., Tritium/3He dating of shallow groundwater. Earth and Planetary...57  5.3.2 Groundwater Dating ...Perchlorate ................ 91  7.1.4 Groundwater Dating and Other Supporting Data .......................................... 94  7.1.5 Summary of

Engineered Intrinsic Bioremediation of Ammonium Perchlorate in Groundwater

DTIC Science & Technology

2010-12-01

German Collection of Microorganisms and Cell Cultures) GA Genetic Algorithms GA-ANN Genetic Algorithm Artificial Neural Network GMO genetically...for in situ treatment of perchlorate in groundwater. This is accomplished without the addition of genetically engineered microorganisms ( GMOs ) to the...perchlorate, even in the presence of oxygen and without the addition of genetically engineered microorganisms ( GMOs ) to the environment. This approach

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

DTIC Science & Technology

2008-04-01

attenuation of perchlorate. Tier 3: Microbiological Indicators. For situations where additional lines of evidence are required, Tier 3 offers...USEPA, 1997). Like enhanced bioremediation, MNA requires an in-depth understanding of the microbiology , chemistry, and hydrogeology of the...nitrate, perchlorate (if present), and iron have been depleted in the microbiological treatment zone. Whereas sulfate concentration greater than 20

Regeneration of anion exchange resins by catalyzed electrochemical reduction

DOEpatents

Gu, Baohua; Brown, Gilbert M.

2002-01-01

Anion exchange resins sorbed with perchlorate may be regenerated by a combination of chemical reduction of perchlorate to chloride using a reducing agent and an electrochemical reduction of the oxidized reducing agent. Transitional metals including Ti, Re, and V are preferred chemical reagents for the reduction of perchlorate to chloride. Complexing agents such as oxalate are used to prevent the precipitation of the oxidized Ti(IV) species, and ethyl alcohol may be added to accelerate the reduction kinetics of perchlorate. The regeneration may be performed by continuously recycling the regenerating solution through the resin bed and an electrochemical cell so that the secondary waste generation is minimized.

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

NASA Astrophysics Data System (ADS)

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

2014-06-01

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

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

PubMed

Sutton, Paul M

2006-12-01

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

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

NASA Technical Reports Server (NTRS)

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 HCl and oxygen releases within the same range as the Rock-nest windblown deposit, the Greenhorn eolian sandstone, and the John Klein drilled mudstone. Overall, mixtures of perchlorates or chlorates with saponite provide the first explanation for the high temperature HCl releases in addition to the oxygen releases observed in Gale Crater materials.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure

PubMed Central

Chandwadkar, Pallavi; Nayak, Chandrani

2017-01-01

ABSTRACT Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa, to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. PMID:28258135

Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

NASA Astrophysics Data System (ADS)

Popescu (Hoştuc), Ioana-Carmen; Petru, Filip; Humelnicu, Ionel; Mateescu, Marina; Militaru, Ecaterina; Humelnicu, Doina

2014-10-01

Radioactive pollution is a significant threat for the people's health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives' utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

The Effect of Mars-relevant Minerals on the Water Uptake of Magnesium Perchlorate and Implications for the Near-surface of Mars

NASA Astrophysics Data System (ADS)

Primm, Katherine; Gough, Raina; Rivera-Valentin, Edgard G.; Tolbert, Margaret

2017-10-01

The water uptake and release by hygroscopic salts such as perchlorate has been well studied in the decade since they were first discovered on the surface of Mars. However, there have been few studies on the effect of the insoluble regolith minerals on this well documented interaction of perchlorate and water vapor. In this work, we investigate the effect that two insoluble Mars-relevant minerals, montmorillonite and Mojave Mars Simulant (MMS), have on the water uptake (deliquescence), ice formation, and recrystallization (efflorescence) of pure magnesium perchlorate. We studied mixtures of equal parts (by mass) magnesium perchlorate hexahydrate and either montmorillonite or MMS. Although montmorillonite and MMS are insoluble minerals that may serve as nuclei for either ice nucleation or salt efflorescence, we find that these minerals did not affect any of the phase transitions of magnesium perchlorate. The salt-mineral mixture behaved like pure magnesium perchlorate in all cases, with stable deliquescence as well as metastable brine supersaturation and supercooling observed. Experiments were performed in both N2 and CO2 atmospheres, with no detectable difference. We use data from the Rover Environmental Monitoring Station instrument on MSL and from the Thermal and Electrical Conductivity Probe instrument on Phoenix, as well as modeling of the shallow subsurface near the rover and lander, to determine the likelihood of liquid water and water ice at Gale Crater and the Phoenix landing site.

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

PubMed

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

2011-08-01

Concentrations of perchlorate were determined by both liquid-chromatography-mass spectrometry (LC-MS) and ion chromatography tandem mass spectrometry (IC-MS/MS) in 520 tap-water, 48 bottled-water, and 9 seawater samples obtained or purchased from >100 different locations in South Korea. The method detection limits were 0.013 μg/L for LC-MS and 0.005 μg/L for IC-MS/MS, and the limits of quantification (LOQs) were 0.10 μg/L for LC-MS and 0.032 μg/L for IC-MS/MS. Perchlorate was detected in most (80%) of the tap-water samples, with concentrations higher than the LOQ; the concentrations ranged from <1.0 to 6.1 μg/L (mean 0.56). Perchlorate was detected by IC-MS/MS in many (n = 23) of the bottled-water samples, with concentrations higher then the LOQ, ranging from 0.04 to 0.29 μg/L (mean 0.07 ± 0.01). The concentrations of perchlorate in all seawater samples collected from the various locations were higher than the LOQ, with a mean concentration of 1.15 ± 0.01 μg/L (maximum 6.11 and minimum 0.11). This study provides further evidence that drinking-water sources have been contaminated by perchlorate. To the best of our knowledge, this is the first comprehensive study on perchlorate assessment in drinking water and seawater in South Korea.

Process for the extraction of technetium from uranium

DOEpatents

Gong, Cynthia-May S.; Poineau, Frederic; Czerwinski, Kenneth R.

2010-12-21

A spent fuel reprocessing method contacts an aqueous solution containing Technetium(V) and uranyl with an acidic solution comprising hydroxylamine hydrochloride or acetohydroxamic acid to reduce Tc(V) to Tc(II, and then extracts the uranyl with an organic phase, leaving technetium(II) in aqueous solution.

Negative Stains Containing Trehalose: Application to Tubular and Filamentous Structures

NASA Astrophysics Data System (ADS)

Harris, J. Robin; Gerber, Max; Gebauer, Wolfgang; Wernicke, Wolfgang; Markl, Jürgen

1996-02-01

Several examples are presented that show the successful application of uranyl acetate and ammonium molybdate negative staining in the presence of trehalose for TEM studies of filamentous and tubular structures. The principal benefit to be gained from the inclusion of trehalose stems from the considerably reduced flattening of the large tubular structures and the greater orientational freedom of single molecules due to an increased depth of the negative stain in the presence of trehalose. Trehalose is likely to provide considerable protection to protein molecules and their assemblies during the drying of negatively stained specimens. Some reduction in the excessive density imparted by uranyl acetate around large assemblies is also achieved. Nevertheless, in the presence of 1% (w/v) trehalose, it is desirable to increase the concentration of negative stain to 5% (w/v) for ammonium molybdate and to 4% for uranyl acetate to produce satisfactory image contrast. In general, the ammonium molybdate-trehalose negative stain is more satisfactory than the uranyl acetate-trehalose combination, because of the greater electron beam sensitivity of the uranyl negative stain. Reassembled taxol-stabilized pig brain microtubules, together with collagen fibrils, sperm tails, helical filaments, and reassociated hemocyanin (KLH2), all from the giant keyhole limpet Megathura crenulata, have been studied by negative staining in the presence of trehalose. In all cases satisfactory TEM imaging conditions were readily obtained on the specimens, as long as regions of excessively deep stain were avoided.

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium

PubMed Central

Cooper, Karen L.; Dashner, Erica J.; Tsosie, Ranalda; Cho, Young Mi; Lewis, Johnnye

2015-01-01

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; <10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein. Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. PMID:26627003

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium.

PubMed

Cooper, Karen L; Dashner, Erica J; Tsosie, Ranalda; Cho, Young Mi; Lewis, Johnnye; Hudson, Laurie G

2016-01-15

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; <10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein. Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. Copyright © 2015 Elsevier Inc. All rights reserved.

Perchlorate Contamination of Drinking Water: Regulatory Issues and Legislative Actions

DTIC Science & Technology

2008-10-16

and water treatment costs, both of which are driven by federal and state standards. (California and Massachusetts have set standards.) EPA has spent... Hypothyroidism , Newborn Thyroid Function, and Environmental Perchlorate Exposure Among Residents of a Southern California Community,” Journal of Occupational... treatment technologies and for collecting occurrence data. In 1999, EPA required water systems to monitor for perchlorate under the Unregulated

The Effects of Ammonium Perchlorate on Reproduction and Development of Amphibians

DTIC Science & Technology

2008-01-01

Abstract: Ammonium perchlorate is a pervasive pollutant primarily from rocket fuel and fertilizers . It is know , among other things , to affect...females, their ovulated eggs collected, and in vitro fertilization conducted. Healthy ovulated eggs were selected and placed in Petri dishes...used and fertilization accomplished in vitro in the presence of perchlorate concentrations. *These tasks were not completed. Studies with Sodium

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

USGS Publications Warehouse

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 μg/L. Perchlorate concentrations in samples of the treated groundwater were similar to the concentrations from Well 1, which was the predominant source of the water supply at Mount Rushmore National Memorial during the study period (2011–15). Springflow upstream from the production wells in the West Fork Lafferty Gulch drainage had the greatest perchlorate concentrations, ranging from 21 to 54 μg/L. The groundwater site within Lafferty Gulch drainage basin but downstream from the park boundary also had a perchlorate concentration less than 0.20 μg/L in the one sample collected at the site. Water samples collected at reference sites generally had concentrations of metals within the same range of those sites within the Mount Rushmore National Memorial boundary, presenting little evidence of metal contamination due to anthropogenic factors within the park boundary. Soil samples were collected near most water sampling sites and within the Hall of Records Canyon where fireworks were launched. Perchlorate concentrations in soil were greatest in the West Fork Lafferty Gulch drainage and Hall of Records Canyon, which are topographically higher than the two groundwater wells.The perchlorate concentrations in groundwater and surface water within Lafferty Gulch drainage basin during 2011–15 were greater than the U.S. Environmental Protection Agency’s Interim Drinking Water Health Advisory benchmark of 15 μg/L. The perchlorate concentrations in the Mount Rushmore water supply relative to this benchmark are of concern; however, this health advisory is based on the assumption that consumers are using the supply as their primary water source and currently is not a regulated standard. The groundwater system at West Fork Lafferty Gulch is highly susceptible to contamination by way of recharge and is isolated from downstream movement by an intrusive body acting as a dam, which may explain why a contamination problem is not likely to disappear or disperse, as could happen in larger aquifer systems. The observed deposition of firework debris within Lafferty Gulch drainage basin coupled with the lack of alternative perchlorate sources indicates that past firework displays are the most probable source of perchlorate contamination.

SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

DOEpatents

Wilson, A.S.

1961-05-01

A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

Probing hydrogen and halogen-oxo interactions in uranyl coordination polymers: a combined crystallographic and computational study

DOE PAGES

Carter, Korey P.; Kalaj, Mark; Kerridge, Andrew; ...

2018-01-01

Four uranyl compounds containing either benzoic acid ( 1 ), m -chlorobenzoic acid ( 2 ), m -bromobenzoic acid ( 3 ), or m -iodobenzoic acid ( 4 ) are described, and the latter two compounds are used to probe non-covalent interaction strengths via structural, vibrational, and computational means.

The Radar Effects of Perchlorate-Doped Ice in the Martian Polar Layered Deposits

NASA Astrophysics Data System (ADS)

Stillman, D.; Winebrenner, D. P.; Grimm, R. E.; Pathare, A.

2010-12-01

The presence of perchlorate in soil at near-polar latitudes on Mars suggests that dust in the ice of the North Polar Layered Deposits (NPLD) may introduce perchlorate impurities to that ice. Because eutectic temperatures of perchlorate salts range as low as 206 K (for magnesium perchlorate), perchlorate doping of NPLD ice may result in grain-scale liquid veins and softening of ice rheology at temperatures comparable to those computed for the base of the NPLD in the present climate. Any such softening would be important for understanding how processes including ice flow have shaped the NPLD. Observable consequences of such softening, or of the combination of perchlorate doping and temperatures that could cause softening, are thus similarly important. In particular, the dielectric properties of perchlorate-laden ice in a temperature gradient will change relatively rapidly at the point in the gradient near the eutectic temperature. Here we investigate the radar reflectivity of such a eutectic transition in ice with a model in which perchlorate concentration is constant and temperature varies linearly with depth in the ice. We have conducted measurements of the complex permittivity of Mg and Na perchlorate-doped ice over a range of temperatures (183 - 273 K) and concentrations. Below the eutectic temperature, the perchlorate-doped ice has electrical properties similar to that of choride-doped ice. However, above the eutectic temperature, some of the ice melts forming liquid at triple junctions. At concentrations above 3 mM, the liquid at triple junctions become connected forming brine channels, which greatly increase the dc conductivity and radar attenuation. At concentrations below 3 mM, the liquid at triple junctions are not connected and do not affect the dc conductivity. However, the liquid H2O molecules are able to rotate their permanent dipole at radar frequencies, thus causing an increase in radar attenuation. The MARSIS and SHARAD attenuation rates increase with temperature as the strength of the loss increases with a greater amount of liquid water even though the relaxation frequency (maximum loss) shifts to higher frequencies. We combine our electrical property measurements with a model for radar reflection from a continuously-varying dielectric profile. Because the change in permittivity occurs over a range of depths depending on the value of the temperature gradient, radar detectability of the eutectic transition depends on the radar frequency as well as gradient and concentration values. We compute expected radar echo strengths for MARSIS and SHARAD and depths relative to the bed at which transitions may be expected, to address whether information of direct rheological relevance may be available from those instruments.

Detection of hexamethonium-perchlorate association complexes using NACE-MS.

PubMed

Groom, Carl A; Hawari, Jalal

2007-02-01

Perchlorate (ClO(4) (+)) and other chlorine oxide anions were observed to complex weakly with hexamethonium (1,6-bis-(trimethylammonium)-hexane) in both aqueous and polar nonaqueous solvents. The resultant positively charged complexes were resolved by NACE using 2-propanol/acetone electrolytes prior to mass spectrometric detection using an Agilent(3D)CE system coupled to a Bruker Esquire 3000+ quadrupole IT mass detector. Using electrokinetic injection, the method detection limit for perchlorate in nonaqueous media was 10 microg/L. The isotope patterns due to the presence of (35)Cl and (37)Cl in complex mass spectra allowed for unambiguous identification of perchlorate, chlorate (ClO(3) (+)), chlorite (ClO(2) (+)), and chloride (Cl(+)) in photoreaction samples.

The Detection of Evolved Oxygen from the Rocknest Eolian Bedform Material by the Sample Analysis at Mars(SAM) instrument at the Mars Curiosity Landing Site

NASA Technical Reports Server (NTRS)

Sutter, B.; Archer, D.; Ming, D.; Eigenbrode, J. L.; Franz, H.; Glavin, D. P.; McAdam, A.; Mahaffy, P.; Stern, J.; Navarro-Gonzalex, R.;

Production of Dioxygen in the Dark: Dismutases of Oxyanions

PubMed Central

Ojha, Sunil

2016-01-01

O2 generating reactions are exceedingly rare in biology and difficult to mimic synthetically. Perchlorate-respiring bacteria enzymatically detoxify chlorite (ClO2−), the end product of the perchlorate (ClO4−) respiratory pathway, by rapidly converting it to dioxygen (O2) and chloride (Cl−). This reaction is catalyzed by a heme-containing protein, called chlorite dismutase (Cld), which bears no structural or sequence relationships with known peroxidases or other heme proteins and is part of a large family of proteins with more than one biochemical function. The original assumptions from the 1990s that perchlorate is not a natural product and that perchlorate respiration might be confined to a taxonomically narrow group of species have been called into question, as have the roles of perchlorate respiration and Cld-mediated reactions in the global biogeochemical cycle of chlorine. In this chapter, the chemistry and biochemistry of Cld-mediated O2 generation, as well as the biological and geochemical context of this extraordinary reaction, are described. PMID:25707466

Direct Fixed-Bed Biological Perchlorate Destruction Demonstration

DTIC Science & Technology

2009-04-01

emerging drinking regulations, which primarily apply to distributed water quality, utilities will also have to consider how to handle the backwash (BW...installation and operation of a potable, FXB biological perchlorate treatment system must be applied for and received from the California Department of Public...perchlorate in the raw water (e.g., ~1 mg/L)? This issue targets the question of whether the FXB bioreactor system can be applied at a remediation

Determination of perchlorate from tea leaves using quaternary ammonium modified magnetic carboxyl-carbon nanotubes followed by liquid chromatography-tandem quadrupole mass spectrometry.

PubMed

Zhao, Yong-Gang; Zhang, Yun; Wang, Feng-Lian; Zhou, Jian; Zhao, Qi-Ming; Zeng, Xiu-Qiong; Hu, Mei-Qin; Jin, Mi-Cong; Zhu, Yan

2018-08-01

The novel quaternary ammonium modified magnetic carboxyl-carbon nanotubes (QA-Mag-CCNTs) have been synthesised and characterized. QA-Mag-CCNTs were applied in magnetic dispersive solid phase extraction (Mag-dSPE) for preconcentration of perchlorate from tea leaves prior to liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS) analysis. The Mag-dSPE procedure for preconcentration of perchlorate succeed in overcoming the flaw (containing target analyte randomly) of commercially available SPE cartridge. Under optimal conditions, the results showed higher extraction efficiency of QA-Mag-CCNTs, with recoveries between 85.2% and 107%. And the satisfactory precision with inter-day and intra-day RSD values were lower than 8.0%. Furthermore, QA-Mag-CCNTs were evaluated for reuse up to 20 times. The limit of quantification (LOQ) for perchlorate was 8.21 ng kg -1 . The developed method was successfully applied in tea leaves for food-safety risk monitoring in Zhejiang province, China. The results showed the concentrations of perchlorate in 229 out of 240 collected samples were in the range of 0.082-988 μg kg -1 . It was confirmed that QA-Mag-CCNTs were highly effective materials used for preconcentration of perchlorate. Copyright © 2018 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jang, M.; Cannon, F; Parette, R

2009-01-01

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

Stripping analysis of nanomolar perchlorate in drinking water with a voltammetric ion-selective electrode based on thin-layer liquid membrane.

PubMed

Kim, Yushin; Amemiya, Shigeru

2008-08-01

A highly sensitive analytical method is required for the assessment of nanomolar perchlorate contamination in drinking water as an emerging environmental problem. We developed the novel approach based on a voltammetric ion-selective electrode to enable the electrochemical detection of "redox-inactive" perchlorate at a nanomolar level without its electrolysis. The perchlorate-selective electrode is based on the submicrometer-thick plasticized poly(vinyl chloride) membrane spin-coated on the poly(3-octylthiophene)-modified gold electrode. The liquid membrane serves as the first thin-layer cell for ion-transfer stripping voltammetry to give low detection limits of 0.2-0.5 nM perchlorate in deionized water, commercial bottled water, and tap water under a rotating electrode configuration. The detection limits are not only much lower than the action limit (approximately 246 nM) set by the U.S. Environmental Protection Agency but also are comparable to the detection limits of the most sensitive analytical methods for detecting perchlorate, that is, ion chromatography coupled with a suppressed conductivity detector (0.55 nM) or electrospray ionization mass spectrometry (0.20-0.25 nM). The mass transfer of perchlorate in the thin-layer liquid membrane and aqueous sample as well as its transfer at the interface between the two phases were studied experimentally and theoretically to achieve the low detection limits. The advantages of ion-transfer stripping voltammetry with a thin-layer liquid membrane against traditional ion-selective potentiometry are demonstrated in terms of a detection limit, a response time, and selectivity.

Perchlorate Data for Streams and Groundwater in Selected Areas of the United States, 2004

USGS Publications Warehouse

Kalkhoff, Stephen J.; Stetson, Sarah J.; Lund, Kris D.; Wanty, Richard B.; Linder, Gregory L.

2010-01-01

This report presents data collected as part of a reconnaissance study to evaluate the occurrence of perchlorate in rivers and streams and in shallow aquifers in selected areas of the United States. Perchlorate, a component in rocket fuels, fireworks, and some explosives is soluble in water and persists in soils and water for long periods. It is biologically active at relatively low-levels in the environment, and has been identified as an endocrine-disrupting chemical. The purpose of this reconnaissance was to determine the occurrence of perchlorate in agricultural areas of the Midwestern and North-Central United States and in arid Central and Western parts of the United States. Samples were collected from 171 sites on rivers and streams and 146 sites from wells during the summer and early fall of 2004. Samples were collected from surface-water sites in 19 states and from wells in 5 states. Perchlorate was detected in samples collected in 15 states and was detected in 34 of 182 samples from rivers and streams and in 64 of 148 groundwater samples at concentrations equal to or greater than 0.4 micrograms per liter. Perchlorate concentrations were 1.0 micrograms per liter or greater in surface-water samples from seven states and in groundwater samples in four states. Only one surface-water and one groundwater sample had concentrations greater than 5.0 micrograms per liter. Perchlorate concentrations in followup samples collected from 1 to 3 months after the initial sample were unchanged at four of five stream sites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strietelmeier, E. A.; Nuttall, H. Eric; Hatzinger, Paul

Nitrate and perchlorate are growing worldwide problems as mobile anionic groundwater contaminants. Biological rduction of nitrate and perchlorate in groundwater is under development as a technology to address these problems.

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

PubMed

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

2014-07-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horton, Megan K., E-mail: megan.horton@mssm.edu; Blount, Benjamin C.; Valentin-Blasini, Liza

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

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

PubMed

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 martian samples.

CONTINUOUS PRECIPITATION METHOD FOR CONVERSION OF URANYL NITRATE TO URANIUM HEXAFLUORIDE

DOEpatents

Reinhart, G.M.; Collopy, T.J.

1962-11-13

A continuous precipitation process is given for converting a uranyl nitrate solution to uranium tetrafluoride. A stream of the uranyl nitrate solution and a stream of an aqueous ammonium hydroxide solution are continuously introduced into an agitated reaction zone maintained at a pH of 5.0 to 6.5. Flow rates are adjusted to provide a mean residence time of the resulting slurry in the reaction zone of at least 30 minutes. After a startup period of two hours the precipitate is recovered from the effluent stream by filtration and is converted to uranium tetrafluoride by reduction to uranium dioxide with hydrogen and reaction of the uranium dioxide with anhydrous hydrogen fluoride. (AEC)

On the origin of the cation templated self-assembly of uranyl-peroxide nanoclusters.

PubMed

Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël; Gil, Adrià; Bo, Carles

2010-12-22

Uranyl-peroxide nanoclusters display different topologies based on square, pentagonal and hexagonal building blocks. Computed complexation energies of different cations (Li(+), Na(+), K(+), Rb(+), and Cs(+)) with [UO(2)(O(2))(H(2)O)](n) (n = 4, 5, and 6) macrocycles suggest a strong cation templating effect. The inherent bent structure of a U-O(2)-U model dimer is demonstrated and justified through the analysis of its electronic structure, as well as of the inherent curvature of the four-, five-, and six-uranyl macrocyles. The curvature is enhaced by cation coordination, which is suggested to be the driving force for the self-assembly of the nanocapsules.

Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

PubMed Central

Conroy, David J.R.; Millner, Paul A.; Stewart, Douglas I.; Pollmann, Katrin

2010-01-01

The fabrication of novel uranyl (UO22+) binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+. PMID:22399904

The Investigation of Chlorate/Iron-Phase Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Clark, J.; Sutter, B.; Morris, R. V.; Archer, P. D.; Ming, D. W.; Niles, P.; Mahaffy, P.; Navarro-Gonzalez, R.

2016-01-01

The Sample Analysis at Mars (SAM) instrument on board the Curiosity Rover has detected oxygen and HCl gas releases from all analyzed Gale Crater sediments. The presence of perchlorate ClO4(sup-) and/or chlorates ClO3(sup-) are potential sources of the aforementioned O2 releases. The detections of O2 and HCl gas releases and chlorinated hydrocarbons by SAM coupled with the detection of perchlorates by Phoenix Lander's 2008 Wet Chemistry Laboratory all suggest that perchlorates, and possibly chorates, may be present in the Gale Crater sediments. Previous laboratory studies have attempted to replicate these O2 releases by heating perchlorates and chlorates in instruments operated similarly to those in the SAM instrument. Early studies found that pure perchlorates release O2 at temperatures higher than those observed in SAM data. Subsequently, studies were done to test the effects of mixing iron-phase minerals, analogous to those detected on Mars by ChemMin, with perchlorates. The iron in these minerals acts as a catalyst and causes O2 to be released from the perchlorate at a lower temperature. These studies found that perchlorate solutions mixed with either Hawaii palagonite or ferrihydrite produce O2 releases at temperatures similar to the Rocknest (RN) windblown deposit and the John Klein (JK) drill sample from the Sheepbed mudstone. The study also determined that perchlorate mixtures with magnetite, hematite, fayalite-magnetite, ilmentite, and pyrrhotite produce O2 releases at temperatures similar to the Confidence Hills (CH) drill sample from the Murray mudstone. Oxygen re-leases from pure chlorates were recently compared with the SAM data. Laboratory analyses determined that Ca-chlorate produces O2 and HCl peaks that are similar to those detected in RN and JK materials. Currently, no perchlorate/chlorate mixture with iron-phase minerals can explain the O2 releases from either the Cumberland (CB) drill sample from the Sheepbed mudstone or Windjana (WJ) drill sample from the Kimberly sandstone. Mixtures of chlorate solutions with iron-phase minerals may produce O2 peaks at temperatures that match those from CB and WJ materials. The goal of this work is to determine if heating chlorate solutions mixed with iron-phase minerals will produce O2 and HCl peak temperatures similar to O2 and HCl peak temperatures of sediments analyzed by SAM, particularly the WJ and CB materials.

ELECTROLYTIC PREPARATION OF UF$sub 4$

DOEpatents

Allen, A.L.; Anderson, R.W.; Powell, E.W.

1958-11-01

A method is presented for converting hexavalent aranium to uranium tetrafluoride. The method consists of electrolyzing a solution of uranyl fluoride in hydrofluoric acld at about 90 icient laborato C. The uranyl ions are reduced at the cathode and a hydrated uranium tetrafluoride precipitates. The precipitate is separated and subsequently dehydrated to UF/sub 4/.

Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

DOE PAGES

Miskowiec, Andrew J.; Kirkegaard, Marie C.; Huq, Ashfia; ...

2015-11-17

We report a novel production method for uranium oxy uoride [(UO 2) 7F 14(H 2O) 7] 4H 2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO 2F 2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO 2) 7F 14(H 2O) 7] 4H 2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorialmore » ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps -1) than their hydrogen-bonded partners (Dr = 28.7 ps -1).« less

Perchlorate Regulatory Determination Fact Sheets

EPA Pesticide Factsheets

Fact sheets have been developed for the perchlorate regulatory determination corresponding to the following stages published in the Federal Register: Final, Supplemental request for comments, and Preliminary.

Perchlorate Contamination of Drinking Water: Regulatory Issues and Legislative Actions

DTIC Science & Technology

2005-02-23

health risks of perchlorate exposures include effects on the developing nervous systems and thyroid tumors, based on rat studies that observed benign...supplies nationwide. The regulation required monitoring by all water systems serving more than 10,000 persons and by a representative sample of smaller... systems . In 2004, EPA reported that perchlorate has been detected in public water systems in 24 states and Puerto Rico.4 The agency also reported

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

PubMed

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. Key Words: Mars oxidants-Perchlorate-Dust electrification-Electrolysis. Astrobiology 16, 811-816.

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

PubMed

Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

2017-11-02

Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Ultrasensitive detection of uranyl by graphene oxide-based background reduction and RCDzyme-based enzyme strand recycling signal amplification.

PubMed

Li, Ming-Hui; Wang, Yong-Sheng; Cao, Jin-Xiu; Chen, Si-Han; Tang, Xian; Wang, Xiao-Feng; Zhu, Yu-Feng; Huang, Yan-Qin

2015-10-15

We proposed a novel strategy which combines graphene oxide-based background reduction with RCDzyme-based enzyme strand recycling amplification for ultrahigh sensitive detection of uranyl. The RCDzyme is designed to contain a guanine (G)-rich sequence that replaces the partial sequence in an uranyl-specific DNAzyme. This multifunctional probe can act as the target recognition element, DNAzyme and the primer of signal amplification. The presence of UO2(2+) can induce the cleavage of the substrate strands in RCDzyme. Then, each released enzyme strand can hybridize with another substrate strands to trigger many cycles of the cleavage by binding uranyl, leading to the formation of more G-quadruplexes by split guanine-rich oligonucleotide fragments. The resulting G-quadruplexes could bind to N-methyl-mesoporphyrin IX (NMM), causing an amplified detection signal for the target uranyl. Next, graphene oxide-based background reduction strategy was further employed for adsorbing free ssDNA and NMM, thereby providing a proximalis zero-background signal. The combination of RCDzyme signal amplification and proximalis zero-background signal remarkably improves the sensitivity of this method, achieving a dynamic range of two orders of magnitude and giving a detection limit down to 86 pM, which is much lower than those of related literature reports. These achievements might be helpful in the design of highly sensitive analytical platform for wide applications in environmental and biomedical fields. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of maleic acid and uranyl on mercurial diuresis in dogs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nigrovic, V.; Koechel, D.A.; Cafruny, E.J.

1973-01-01

The effects of two nephrotoxic agents were studied in anesthetized dogs undergoing mercurial diuresis. One of the agents, uranyl, accumulates in the kidneys when administered as the acetate salt but does not readily react with sulfhydryl groups. In acute experiments uranyl acetate in doses up to 5 ..mu..mol/kg produced no change in the urinary excretion of sodium or chloride. Uranyl acetate given before the injection of mercury(II) did not reduce the diuretic response to inorganic mercury. The other compound, maleic acid, accumulates in the kidneys and also reacts readily with sulfhydryl groups. The administration of small doses of maleic acidmore » did not change the excretion of sodium but it decreased the excretion of chloride. The administration of maleic acid either before or after the administration of mercury completely abolished the diuretic response. The inhibition occurred without significant changes in urinary pH. Diuretic responses to ethacrynic acid, furosemide, hydrochlorothiazide or acetazolamide were preserved in maleate-treated dogs. Both the lack of any effect of uranyl on mercurial diuresis and the specific inhibition of mercurial diuresis by maleic acid support the presently accepted view that the renal diuretic receptor for mercury(II) has at least one sulfhydryl binding site. Although the inhibition is ascribed to competition between mercury(II) and maleate for binding on the receptor, it is conceivable that the reduction in urinary chloride excretion produced by maleate may be responsible, in part, for refractoriness to mercury(II).« less

Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

PubMed

Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2012-09-17

Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

Hydrothermal synthesis of uranyl squarates and squarate-oxalates: hydrolysis trends and in situ oxalate formation.

PubMed

Rowland, Clare E; Cahill, Christopher L

2010-07-19

We report the synthesis of two uranyl squarates and two mixed-ligand uranyl squarate-oxalates from aqueous solutions under hydrothermal conditions. These products exhibit a range of uranyl building units from squarates with monomers in (UO(2))(2)(C(4)O(4))(5).6NH(4).4H(2)O (1; a = 16.731(17) A, b = 7.280(8) A, c = 15.872(16) A, beta = 113.294(16) degrees , monoclinic, P2(1)/c) and chains in (UO(2))(2)(OH)(2)(H(2)O)(2)(C(4)O(4)) (2; a = 12.909(5) A, b = 8.400(3) A, c = 10.322(4) A, beta = 100.056(7) degrees , monoclinic, C2/c) to two squarate-oxalate polymorphs with dimers in (UO(2))(2)(OH)(C(4)O(4))(C(2)O(4)).NH(4).H(2)O (3; a = 9.0601(7) A, b = 15.7299(12) A, c = 10.5108(8) A, beta = 106.394(1) degrees , monoclinic, P2(1)/n; and 4; a = 8.4469(6) A, b = 7.7589(5) A, c = 10.5257(7) A, beta = 105.696(1) degrees , monoclinic, P2(1)/m). The dominance at low pH of monomeric species and the increasing occurrence of oligomeric species with increasing pH suggests that uranyl hydrolysis, mUO(2)(2+) + nH(2)O right harpoon over left harpoon [(UO(2))(m)(OH)(n)](2m-n) + nH(+), has a significant role in the identity of the inorganic building unit. Additional factors that influence product assembly include in situ hydrolysis of squaric acid to oxalic acid, dynamic metal to ligand concentration, and additional binding modes resulting from the introduction of oxalate anions. These points and the effects of uranyl hydrolysis with changing pH are discussed in the context of the compounds presented herein.

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]²⁺ Asymmetric Stretch

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibson, John K.; Hu, Hanshi; Van Stipdonk, Michael J.

2015-04-09

The gas-phase complex UO₂(TMOGA)₂²⁺ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm⁻¹ was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm⁻¹ (<1%) and a maximum deviation of 21 cm⁻¹ (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν₃ mode, which appeared at 965 cm⁻¹ and was predicted by DFT as 953 cm⁻¹. This ν₃ frequency is red-shifted relative tomore » bare uranyl, UO₂²⁺, by ca. 150 cm⁻¹ due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO₂(acetone)₄²⁺. The uranyl ν₃ frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH₂. The computed ν₃ for UO₂(TMGA)₂²⁺, 950 cm⁻¹, is essentially the same as that for UO₂(TMOGA)₂²⁺, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν₃ asymmetric stretching frequencies for the three actinyl complexes, UO₂(TMOGA)₂²⁺, NpO₂(TMOGA)₂²⁺ and PuO₂(TMOGA)₂²⁺, are comparable. This similarity is discussed in the context of the relationship between ν₃ and intrinsic actinide-oxygen bond energies in actinyl complexes.« less

Mixed-Ligand Uranyl Polyrotaxanes Incorporating a Sulfate/Oxalate Coligand: Achieving Structural Diversity via pH-Dependent Competitive Effect.

PubMed

Xie, Zhen-Ni; Mei, Lei; Hu, Kong-Qiu; Xia, Liang-Shu; Chai, Zhi-Fang; Shi, Wei-Qun

2017-03-20

A mixed-ligand system provides an alternative route to tune the structures and properties of metal-organic compounds by introducing functional organic or inorganic coligands. In this work, five new uranyl-based polyrotaxane compounds incorporating a sulfate or oxalate coligand have been hydrothermally synthesized via a mixed-ligand method. Based on C6BPCA@CB6 (C6BPCA = 1,1'-(hexane-1,6-diyl)bis(4-(carbonyl)pyridin-1-ium), CB6 = cucurbit[6]uril) ligand, UPS1 (UO 2 (L) 0.5 (SO 4 )(H 2 O)·2H 2 O, L = C6BPCA@CB6) is formed by the alteration of initial aqueous solution pH to a higher acidity. The resulting 2D uranyl polyrotaxane sheet structure of UPS1 is based on uranyl-sulfate ribbons connected by the C6BPCA@CB6 pseudorotaxane linkers. By using oxalate ligand instead of sulfate, four oxalate-containing uranyl polyrotaxane compounds, UPO1-UPO4, have been acquired by tuning reaction pH and ligand concentration: UPO1 (UO 2 (L) 0.5 (C 2 O 4 ) 0.5 (NO 3 )·3H 2 O) in one-dimensional chain was obtained at a low pH value range (1.47-1.89) and UPO2 (UO 2 (L)(C 2 O 4 )(H 2 O)·7H 2 O)obtained at a higher pH value range (4.31-7.21). By lowering the amount of oxalate, another two uranyl polyrotaxane network UPO3 ((UO 2 ) 2 (L) 0.5 (C 2 O 4 ) 2 (H 2 O)) and UPO4 ((UO 2 ) 2 O(OH)(L) 0.5 (C 2 O 4 ) 0.5 (H 2 O)) could be acquired at a low pH value of 1.98 and a higher pH value over 6, respectively. The UPO1-UPO4 compounds, which display structural diversity via pH-dependent competitive effect of oxalate, represent the first series of mixed-ligand uranyl polyrotaxanes with organic ligand as the coligand. Moreover, the self-assembly process and its internal mechanism concerning pH-dependent competitive effect and other related factors such as concentration of the reagents and coordination behaviors of the coligands were discussed in detail.

Unusual Versatility of the Filamentous, Diazotrophic Cyanobacterium Anabaena torulosa Revealed for Its Survival during Prolonged Uranium Exposure.

PubMed

Acharya, Celin; Chandwadkar, Pallavi; Nayak, Chandrani

2017-05-01

Reports on interactions between cyanobacteria and uranyl carbonate are rare. Here, we present an interesting succession of the metabolic responses employed by a marine, filamentous, diazotrophic cyanobacterium, Anabaena torulosa for its survival following prolonged exposure to uranyl carbonate extending up to 384 h at pH 7.8 under phosphate-limited conditions. The cells sequestered uranium (U) within polyphosphates on initial exposure to 100 μM uranyl carbonate for 24 to 28 h. Further incubation until 120 h resulted in (i) significant degradation of cellular polyphosphates causing extensive chlorosis and cell lysis, (ii) akinete differentiation followed by (iii) extracellular uranyl precipitation. X-ray diffraction (XRD) analysis, fluorescence spectroscopy, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy established the identity of the bioprecipitated uranium as a U(VI) autunite-type mineral, which settled at the bottom of the vessel. Surprisingly, A. torulosa cells resurfaced as small green flakes typical of actively growing colonies on top of the test solutions within 192 to 240 h of U exposure. A consolidated investigation using kinetics, microscopy, and physiological and biochemical analyses suggested a role of inducible alkaline phosphatase activity of cell aggregates/akinetes in facilitating the germination of akinetes leading to substantial regeneration of A. torulosa by 384 h of uranyl incubation. The biomineralized uranium appeared to be stable following cell regeneration. Altogether, our results reveal novel insights into the survival mechanism adopted by A. torulosa to resist sustained uranium toxicity under phosphate-limited oxic conditions. IMPORTANCE Long-term effects of uranyl exposure in cyanobacteria under oxic phosphate-limited conditions have been inadequately explored. We conducted a comprehensive examination of the metabolic responses displayed by a marine cyanobacterium, Anabaena torulosa , to cope with prolonged exposure to uranyl carbonate at pH 7.8 under phosphate limitation. Our results highlight distinct adaptive mechanisms harbored by this cyanobacterium that enabled its natural regeneration following extensive cell lysis and uranium biomineralization under sustained uranium exposure. Such complex interactions between environmental microbes such as Anabaena torulosa and uranium over a broader time range advance our understanding on the impact of microbial processes on uranium biogeochemistry. Copyright © 2017 American Society for Microbiology.

Alteration, adsorption and nucleation processes on clay-water interfaces: Mechanisms for the retention of uranium by altered clay surfaces on the nanometer scale

NASA Astrophysics Data System (ADS)

Schindler, Michael; Legrand, Christine A.; Hochella, Michael F.

2015-03-01

Nano-scale processes on the solid-water interface of clay minerals control the mobility of metals in the environment. These processes can occur in confined pore spaces of clay buffers and barriers as well as in contaminated sediments and involve a combination of alteration, adsorption and nucleation processes of multiple species and phases. This study characterizes nano-scale processes on the interface between clay minerals and uranyl-bearing solution near neutral pH. Samples of clay minerals with a contact pH of ∼6.7 are collected from a U mill and mine tailings at Key Lake, Saskatchewan, Canada. The tailings material contains Cu-, As-, Co-, Mo-, Ni-, Se-bearing polymetallic phases and has been deposited with a surplus of Ca(OH)2 and Na2CO3 slaked lime. Small volumes of mill-process solutions containing sulfuric acid and U are occasionally discharged onto the surface of the tailings and are neutralized after discharge by reactions with the slaked lime. Transmission electron microscopy (TEM) in combination with the focused ion beam (FIB) technique and other analytical methods (SEM, XRD, XRF and ICP-OES) are used to characterize the chemical and mineralogical composition of phases within confined pore spaces of the clay minerals montmorillonite and kaolinite and in the surrounding tailings material. Alteration zones around the clay minerals are characterized by different generations of secondary silicates containing variable proportions of adsorbed uranyl- and arsenate-species and by the intergrowth of the silicates with the uranyl-minerals cuprosklodowskite, Cu[(UO2)2(SiO3OH)2](H2O)6 and metazeunerite, Cu[(UO2)(AsO4)2](H2O)8. The majority of alteration phases such as illite, illite-smectite, kaolinite and vermiculite have been most likely formed in the sedimentary basin of the U-ore deposit and contain low amounts of Fe (<5 at.%). Iron-enriched Al-silicates or illite-smectites (Fe >10 at.%) formed most likely in the limed tailings at high contact pH (∼10.5) and their structure is characterized by a low degree of long-range order. Adsorption of U and nucleation of metazeunerite and cuprosklodowskite are strongly controlled by the presence of the adsorbed oxy-anion species arsenate and silica on the Fe-enriched silicates. Heterogeneous nucleation of nano-crystals of the uranyl minerals occurs most likely on adsorption sites of binary uranyl-, arsenate- and silica-complexes as well as on ternary uranyl-arsenate or uranyl-silicate complexes. The uranyl minerals occur as aggregates of misoriented nano-size crystals and are the result of supersaturated solutions and a high number of nucleation sites that prevented the formation of larger crystals through Oswald ripening. The results of this study provide an understanding of interfacial nano-scale processes between uranyl species and altered clay buffers in a potential Nuclear Waste repository as similar alteration conditions of clays may occur in a multi-barrier system.

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

NASA Astrophysics Data System (ADS)

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.

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

USGS Publications Warehouse

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.

Uptake of N-nitrosodimethylamine (NDMA) from water by phreatophytes in the absence and presence of perchlorate as a co-contaminant.

PubMed

Yifru, Dawit D; Nzengung, Valentine A

2006-12-01

The uptake and fate of the emerging contaminants N-nitrosodimethylamine (NDMA) and perchlorate in phreatophytes was studied in a hydroponics system under greenhouse conditions. NDMA is a potent carcinogen, and perchlorate disrupts the functioning ofthe human thyroid gland. The rate of removal of NDMA from solution by rooted cuttings of black willow (Salix nigra) and hybrid poplar (Populus deltoides x nigra, DN34) trees varied seasonally, with faster removal in summer months when transpiration rates were highest. A linear correlation between the volume of water transpired and mass of NDMA removed from the root zone was observed, especially at higher NDMA concentrations. In bioreactors dosed with both NDMA (0.7-1.0 mg L(-1)) and perchlorate (27 mg L(-1)), no competitive uptake of NDMA and perchlorate was observed. While NDMA was primarily removed from solution by plant uptake, perchlorate was predominantly removed by rhizodegradation. In the presence of NDMA, a slower rate of rhizodegradation of perchlorate was observed, but still significantly faster than the rate of NDMA uptake. For experiments conducted with radiolabeled NDMA, 46.4 +/- 1.1% of the total 14C-activity was recovered in the plant tissues and 47.5% was phytovolatilized. The 46.4 +/- 1.1% recovered in the plants was distributed as follows: 18.8 +/- 1.4% in leaves, 15.9 +/- 5.9% in stems, 7.6 +/- 3.2% in branches, and 3.5 +/- 3.3% in roots. The poor extractability of NDMA with methanol-water (1:1 v/v) from stem and leaf tissues suggested that some fraction of NDMA was assimilated. The calculated transpiration stream concentration factor (TSCF) of 0.28 +/- 0.06 suggests that NDMA is passively taken up by phreatophytes, and mainly phytovolatilized.

Evaluation of perturbations in serum thyroid hormones during human pregnancy due to dietary iodide and perchlorate exposure using a biologically based dose-response model.

PubMed

Lumen, Annie; Mattie, David R; Fisher, Jeffrey W

2013-06-01

A biologically based dose-response model (BBDR) for the hypothalamic pituitary thyroid (HPT) axis was developed in the near-term pregnant mother and fetus. This model was calibrated to predict serum levels of iodide, total thyroxine (T4), free thyroxine (fT4), and total triiodothyronine (T3) in the mother and fetus for a range of dietary iodide intake. The model was extended to describe perchlorate, an environmental and food contaminant, that competes with the sodium iodide symporter protein for thyroidal uptake of iodide. Using this mode-of-action framework, simulations were performed to determine the daily ingestion rates of perchlorate that would be associated with hypothyroxinemia or onset of hypothyroidism for varying iodide intake. Model simulations suggested that a maternal iodide intake of 75 to 250 µg/day and an environmentally relevant exposure of perchlorate (~0.1 µg/kg/day) did not result in hypothyroxinemia or hypothyroidism. For a daily iodide-sufficient intake of 200 µg/day, the dose of perchlorate required to reduce maternal fT4 levels to a hypothyroxinemic state was estimated at 32.2 µg/kg/day. As iodide intake was lowered to 75 µg/day, the model simulated daily perchlorate dose required to cause hypothyroxinemia was reduced by eightfold. Similarly, the perchlorate intake rates associated with the onset of subclinical hypothyroidism ranged from 54.8 to 21.5 µg/kg/day for daily iodide intake of 250-75 µg/day. This BBDR-HPT axis model for pregnancy provides an example of a novel public health assessment tool that may be expanded to address other endocrine-active chemicals found in food and the environment.

Evaluation of Alternative Causes of Widespread, Low Concentration Perchlorate Impacts to Groundwater

DTIC Science & Technology

2008-07-01

burning ceased, the residue and remaining slag were collected. 5. The slag was weighed in order to approximate the extent to which the flare had...with triple distilled, deionized water. 7. The washings and slag from each flare were placed in separate round-bottom flasks and stirred for ten...remaining was 0.027% on average or 99.97% of the original perchlorate was consumed (Table 3.3). Nevertheless, a slag containing elevated perchlorate

PERCHLORATE INDUCES HERMAPHRODITISM IN THREESPINE STICKLEBACKS

PubMed Central

Bernhardt, Richard R.; von Hippel, Frank A.; Cresko, William A.

2011-01-01

Recently, concern regarding perchlorate contamination has arisen in many contexts. Perchlorate has many military, commercial, and domestic applications, and it has been found in milk, drinking and irrigation water, and produce. Perchlorate is harmful at low levels, yet it remains unregulated in the United States while the U.S. Environmental Protection Agency attempts to establish acceptable exposure levels. The present study investigated potential reproductive effects on vertebrates using a model fish species, the threespine stickleback (Gasterosteus aculeatus). Sticklebacks were raised from syngamy through sexual maturity in untreated water and in three target concentrations of sodium perchlorate–treated water. Perchlorate was found to interfere with the expression of nuptial coloration, courtship behavior, and normal sexual development. Genetic testing revealed that some females were masculinized to the extent that they produced both sperm and eggs, and histological analysis showed that these individuals had intersexual gonads (ovotestes) containing both oocytes and cells undergoing spermatogenesis. In vitro fertilizations revealed that those gametes were capable of self- and cross-fertilization. However, crosses using sperm derived from genetic females died either during the blastula phase or near the onset of organogenesis. Sperm derived from genetic males produced viable fry when crossed with eggs derived from genetic females from all treatments. To our knowledge, the present study provides the first evidence that perchlorate produces androgenic effects and is capable of inducing functional hermaphroditism in a nonhermaphroditic vertebrate. PMID:16916028

Using the natural biodegradation potential of shallow soils for in-situ remediation of deep vadose zone and groundwater.

PubMed

Avishai, Lior; Siebner, Hagar; Dahan, Ofer; Ronen, Zeev

2017-02-15

In this study, we examined the ability of top soil to degrade perchlorate from infiltrating polluted groundwater under unsaturated conditions. Column experiments designed to simulate typical remediation operation of daily wetting and draining cycles of contaminated water amended with an electron donor. Covering the infiltration area with bentonite ensured anaerobic conditions. The soil remained unsaturated, and redox potential dropped to less than -200mV. Perchlorate was reduced continuously from ∼1150mg/L at the inlet to ∼300mg/L at the outlet in daily cycles. Removal efficiency was between 60 and 84%. No signs of bioclogging were observed during three operation months although occasional iron reduction observed due to excess electron donor. Changes in perchlorate reducing bacteria numbers were inferred from an increased in pcrA gene abundances from ∼10 5 to 10 7 copied per gram at the end of the experiment indicating the growth of perchlorate-reducing bacteria. We proposed that the topsoil may serve as a bioreactor to treat high concentrations of perchlorate from the contaminated groundwater. The treated water that infiltrates from the topsoil through the vadose zone could be used to flush perchlorate from the deep vadose zone into the groundwater where it is retrieved again for treatment in the topsoil. Copyright © 2016 Elsevier B.V. All rights reserved.

(Per)chlorate Reduction by the Thermophilic Bacterium Moorella perchloratireducens sp. nov., Isolated from Underground Gas Storage▿

PubMed Central

Balk, Melike; van Gelder, Ton; Weelink, Sander A.; Stams, Alfons J. M.

2008-01-01

A thermophilic bacterium, strain An10, was isolated from underground gas storage with methanol as a substrate and perchlorate as an electron acceptor. Cells were gram-positive straight rods, 0.4 to 0.6 μm in diameter and 2 to 8 μm in length, growing as single cells or in pairs. Spores were terminal with a bulged sporangium. The temperature range for growth was 40 to 70°C, with an optimum at 55 to 60°C. The pH optimum was around 7. The salinity range for growth was between 0 and 40 g NaCl liter−1 with an optimum at 10 g liter−1. Strain An10 was able to grow on CO, methanol, pyruvate, glucose, fructose, cellobiose, mannose, xylose, and pectin. The isolate was able to respire with (per)chlorate, nitrate, thiosulfate, neutralized Fe(III) complexes, and anthraquinone-2,6-disulfonate. The G+C content of the DNA was 57.6 mol%. On the basis of 16S rRNA analysis, strain An10 was most closely related to Moorella thermoacetica and Moorella thermoautotrophica. The bacterium reduced perchlorate and chlorate completely to chloride. Key enzymes, perchlorate reductase and chlorite dismutase, were detected in cell extracts. Strain An10 is the first thermophilic and gram-positive bacterium with the ability to use (per)chlorate as a terminal electron acceptor. PMID:17981952

Perchlorate Questions and Answers

MedlinePlus

... decision making on perchlorate under the Safe Drinking Water Act. Scientists from the EPA and the FDA’s National Center for Toxicological Research (NCTR) collaborated to develop this modeling work, which ...

Identification of an anaerobic bacterium which reduces perchlorate and chlorate as Wolinella succinogenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wallace, W.; Attaway, H.

1995-12-31

Perchlorate and chlorate salts are widely used by the chemical, aerospace and defense industries as oxidizers in propellant, explosives and pyrotechnics. The authors have isolated a anaerobic bacterium which is capable of the dissimilatory reduction of both perchlorate and chlorate for energy and growth. Strain HAP-1 is a gram negative, thin rod, non-sporeforming, highly motile strict anaerobe. Antibiotic resistance profiles, utilization of carbon substrates and electron acceptors demonstrated similar physiological characteristics to Wolinella succinogenes. Pairwise comparisons of 16S RNA sequences showed only a 0.75% divergence between strain HAP-1 and W. succinogenes. Physiological, morphological and 16S RRNA sequence data indicate strainmore » HAP-1 is a subspecies of W. succinogenes that can utilize perchlorate and chlorate as terminal electron acceptors.« less

Crystal structure of iron(III) perchlorate nona­hydrate

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

Since the discovery of perchlorate salts on Mars and the known occurrence of ferric salts in the regolith, there is a distinct possibility that the title compound could form on the surface of Mars. [Fe(H2O)6](ClO4)3·3H2O was crystallized from aqueous solutions at low temperatures according to the solid–liquid phase diagram. It consists of Fe(H2O)6 octa­hedra (point group symmetry -3.) and perchlorate anions (point group symmetry .2) as well as non-coordinating water mol­ecules, as part of a second hydrogen-bonded coordination sphere around the cation. The perchlorate appears to be slightly disordered, with major–minor component occupancies of 0.773 (9):0.227 (9). PMID:25552970

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

DTIC Science & Technology

2010-07-01

United States is through consumption of food (USFDA, 2007). This is a concern because high levels of perchlorate interfere with iodide uptake by the...from more that 50 mg/L to below detection using lactate as a food source; (and) the pH of the aquifer must be buffered to achieve optimal perchlorate...defined by a covering of Nelumbo lutea (American lotus ) which are visible beyond the Subtidal Channel in the photograph Figure 3-14. The main channel

Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arnold, John

The uranyl cation (UO 2 2+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due tomore » the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.« less

Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

PubMed

Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada; Venkateswaran, Gopala

2006-05-01

Major quantities of uranium find use as nuclear fuel in nuclear power reactors. In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to remove uranium from nuclear power reactor effluents before discharge into environment. Ion imprinted polymer (IIP) materials have traditionally been used for the recovery of uranium from dilute aqueous solutions prior to detection or from seawater. We now describe the use of IIP materials for selective removal of uranium from a typical synthetic nuclear power reactor effluent. The IIP materials were prepared for uranyl ion (imprint ion) by forming binary salicylaldoxime (SALO) or 4-vinylpyridine (VP) or ternary SALO-VP complexes in 2-methoxyethanol (porogen) and copolymerizing in the presence of styrene (monomer), divinylbenzene (cross-linking monomer), and 2,2'-azobisisobutyronitrile (initiator). The resulting materials were then ground and sieved to obtain unleached polymer particles. Leached IIP particles were obtained by leaching the imprint ions with 6.0 M HCl. Control polymer particles were also prepared analogously without the imprint ion. The IIP particles obtained with ternary complex alone gave quantitative removal of uranyl ion in the pH range 3.5-5.0 with as low as 0.08 g. The retention capacity of uranyl IIP particles was found to be 98.50 mg/g of polymer. The present study successfully demonstrates the feasibility of removing uranyl ions selectively in the range 5 microg - 300 mg present in 500 mL of synthetic nuclear power reactor effluent containing a host of other inorganic species.

Dehydration-driven evolution of topological complexity in ethylamonium uranyl selenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Krivovichev, Sergey V.; Tananaev, Ivan G.

Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules, (C{sub 2}H{sub 8}N){sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) (I), (C{sub 2}H{sub 8}N){sub 3}[(UO{sub 2})(SeO{sub 4}){sub 2}(HSeO{sub 4})] (II), (C{sub 2}H{sub 8}N)[(UO{sub 2})(SeO{sub 4})(HSeO{sub 3})] (III), and (C{sub 2}H{sub 8}N)(H{sub 3}O)[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (IV) have been prepared by isothermal evaporation from aqueous solutions. Uranyl-containing 1D and 2D units have been investigated using topological approach and information-based complexity measurements that demonstrate the evolution of structural units and the increase of topological complexity with the decrease of H{sub 2}O content. - Graphical abstract: Single crystals ofmore » four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules have been prepared by isothermal evaporation from aqueous solutions. Structural analysis and information-based topological complexity calculations points to the possible sequence of crystalline phases formation, showing both topological and structural branches of evolution. - Highlights: • Single crystals of four novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • Dehydration processes drives the evolution of topological complexity of 1D and 2D structural units.« less

FLAME DENITRATION AND REDUCTION OF URANIUM NITRATE TO URANIUM DIOXIDE

DOEpatents

Hedley, W.H.; Roehrs, R.J.; Henderson, C.M.

1962-06-26

A process is given for converting uranyl nitrate solution to uranium dioxide. The process comprises spraying fine droplets of aqueous uranyl nitrate solution into a hightemperature hydrocarbon flame, said flame being deficient in oxygen approximately 30%, retaining the feed in the flame for a sufficient length of time to reduce the nitrate to the dioxide, and recovering uranium dioxide. (AEC)

SHINE and Mini-SHINE Column Designs for Recovery of Mo from 140 g-U/L Uranyl Sulfate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stepinski, Dominique C.; Vandegrift, George F.

Argonne is assisting SHINE Medical Technologies (SHINE) in their efforts to develop an accelerator-driven process that utilizes a uranyl-sulfate solution for the production of fission Mo-99. In an effort to design a Mo-recovery system for the SHINE project using low-enriched uranium (LEU), we conducted batch, breakthrough, and pulse tests to determine the Mo isotherm, mass-transfer zone (MTZ), and system parameters for a 130 g-U/L uranyl sulfate solution at pH 1 and 80°C, as described previously. The VERSE program was utilized to calculate the MTZ under various loading times and velocities. The results were then used to design Mo separation andmore » recovery columns employing a pure titania sorbent (110-μm particles, S110, and 60 Å pore size). The plant-scale column designs assume Mo will be separated from 271 L of a 141 g-U/L uranyl sulfate solution, pH 1, containing 0.0023 mM Mo. The VERSE-designed recovery systems have been tested and verified in laboratory-scale experiments, and this approach was found to be very successful.« less

Structure, Kinetics, and Thermodynamics of the Aqueous Uranyl(VI) Cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien N.; Liu, Chongxuan

2013-08-20

Molecular simulation techniques are employed to gain insights into the structural, kinetic, and thermodynamic properties of the uranyl(VI) cation (UO22+) in aqueous solution. The simulations make use of an atomistic potential model (force field) derived in this work and based on the model of Guilbaud and Wipff (Guilbaud, P.; Wipff, G. J. Mol. Struct. (THEOCHEM) 1996, 366, 55-63). Reactive flux and thermodynamic integration calculations show that the derived potential model yields predictions for the water exchange rate and free energy of hydration, respectively, that are in agreement with experimental data. The water binding energies, hydration shell structure, and self-diffusion coefficientmore » are also calculated and discussed. Finally, a combination of metadynamics and transition path sampling simulations is employed to probe the mechanisms of water exchange reactions in the first hydration shell of the uranyl ion. These atomistic simulations indicate, based on two-dimensional free energy surfaces, that water exchanges follow an associative interchange mechanism. The nature and structure of the water exchange transition states are also determined. The improved potential model is expected to lead to more accurate predictions of uranyl adsorption energies at mineral surfaces using potential-based molecular dynamics simulations.« less

Selective colorimetric and fluorescent quenching determination of uranyl ion via its complexation with curcumin

NASA Astrophysics Data System (ADS)

Zhu, Jing-Hui; Zhao, Xin; Yang, Jidong; Tan, Yu-Ting; Zhang, Lei; Liu, Shao-Pu; Liu, Zhong-Fang; Hu, Xiao-Li

2016-04-01

Under pH 4.0 HAc-NaAc buffer medium, curcumin alone possesses extraordinary weak fluorescence emission. Nevertheless, the introduction of Triton X-100 micelles can largely enhance the fluorescence intensity of curcumin. Uranyl ions can complex with micelles-capped curcumin, along with the slight red shift of curcumin fluorescence (about 1-7 nm), a clear decrement of absorbance (424 nm) and fluorescence (507 nm) intensities, and a distinct color change from bright yellow to orange. The fluorescence decrements (ΔF, 507 nm) are positively correlated to the amount of uranyl ions in the concentration range of 3.7 × 10- 6-1.4 × 10- 5 mol L- 1. The detection limit of this fluorescence quenching methods is 3.7 × 10- 6 mol L- 1, which is nearly 9000 times lower than the maximum allowable level in drinking water proposed by World Health Organization. Good selectivity is achieved because of a majority of co-existing substances (such as Ce4 +, La3 +, and Th4 +) do not affect the detection. The content of uranyl ions in tap water samples was determined by the proposed method with satisfactory results.

Re: Request for Correction: Drinking Water: Determination on Perchlorate

EPA Pesticide Factsheets

Request for correction (RFC) of information developed and relied upon by the Environmental Protection Agency (EPA or Agency) to support its determination to regulate perchlorate under the Safe Drinking Water Act (SDWA).

Perchlorate Treatment Technology Update

EPA Pesticide Factsheets

This issue paper has been prepared by EPA's Federal Facilities Forum to provide information about technologies available for treatment of perchlorate contamination in environmental media, including technologies that have been used to date and others that..

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Periodic density functional theory investigation of the uranyl ion sorption on three mineral surfaces: a comparative study.

PubMed

Roques, Jérôme; Veilly, Edouard; Simoni, Eric

2009-06-04

Canister integrity and radionuclides retention is of prime importance for assessing the long term safety of nuclear waste stored in engineered geologic depositories. A comparative investigation of the interaction of uranyl ion with three different mineral surfaces has thus been undertaken in order to point out the influence of surface composition on the adsorption mechanism(s). Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed on the TiO(2)(110), Al(OH)(3)(001) and Ni(111) surfaces. This study has clearly shown that three parameters play an important role in the uranyl adsorption mechanism: the solvent (H(2)O) distribution at the interface, the nature of the adsorption site and finally, the surface atoms' protonation state.

Periodic Density Functional Theory Investigation of the Uranyl Ion Sorption on Three Mineral Surfaces: A Comparative Study

PubMed Central

Roques, Jérôme; Veilly, Edouard; Simoni, Eric

2009-01-01

Canister integrity and radionuclides retention is of prime importance for assessing the long term safety of nuclear waste stored in engineered geologic depositories. A comparative investigation of the interaction of uranyl ion with three different mineral surfaces has thus been undertaken in order to point out the influence of surface composition on the adsorption mechanism(s). Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed on the TiO2(110), Al(OH)3(001) and Ni(111) surfaces. This study has clearly shown that three parameters play an important role in the uranyl adsorption mechanism: the solvent (H2O) distribution at the interface, the nature of the adsorption site and finally, the surface atoms’ protonation state. PMID:19582222

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

2016-12-16

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dewji, Shaheen A.; Croft, Stephen; Hertel, Nolan E.

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systemsmore » in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Furthermore, quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.« less

Sensitivity analysis of high resolution gamma-ray detection for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Croft, S.; Hertel, N. E.

2017-03-01

Under the policies proposed by recent International Atomic Energy Agency (IAEA) circulars and policy papers, implementation of safeguards exists when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed in previous work to develop and validate gamma-ray nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP). Passive nondestructive assay techniques using high resolution gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely manner. Building upon the aforementioned previous validation work on detector sensitivity to varying concentrations of uranyl nitrate via a series of dilution measurements, this work investigates detector response parameter sensitivities to gamma-ray signatures of uranyl nitrate. The full energy peak efficiency of a detection system is dependent upon the sample, geometry, absorption, and intrinsic efficiency parameters. Perturbation of these parameters translates into corresponding variations of the 185.7 keV peak area of the 235U in uranyl nitrate. Such perturbations in the assayed signature impact the quality or versatility of the safeguards conclusions drawn. Given the potentially high throughput of uranyl nitrate in NUCPs, the ability to assay 1 SQ of material requires uncertainty «1%. Accounting for material self-shielding properties, pipe thickness, and source-detector orientation is instrumental in determining the robustness of gamma-ray detection in the process monitoring of uranyl nitrate in NUCPs. Monte Carlo models and ray-tracing models were employed to determine the sensitivity of the detected 185.7 keV photon to self-shielding properties, pipe thickness, and source-detector geometry. Considering the implementation of the detection of 1 SQ, diversion of 1 SQ becomes essentially undetectable given the systematic uncertainty, in addition to considerations such as propagating uncertainties due to pipe offset/position, as well as minor variations in pipe thickness. Consequently, pipe thickness was the most sensitive variable in affecting full energy efficiency of the 185.7 keV signature peak with up to 8% variation in efficiency for ±0.5 mm changes in Schedule 40 304L stainless steel piping. Furthermore, computation of the attenuation correction factor of the uranyl nitrate solution [CF(AT) (i.e. εsample)] using Parker's method using with the approximation for the geometrical factor κ≈π/4 was validated through experimental, Monte Carlo and ray-tracing calculations for a uranyl nitrate filled transfer pipe segment. Quantifying sensitivity in detector position, as well as voiding effects due to bubbly flow or laminar flow with an air gap in the uranyl nitrate becomes increasingly important as considerations from (static) design-scale measurements translate into (dynamic) field operations tests.

Effect of thiosulfate on rapid start-up of sulfur-based reduction of high concentrated perchlorate: A study of kinetics, extracellular polymeric substances (EPS) and bacterial community structure.

PubMed

Guo, Jianbo; Zhang, Chao; Lian, Jing; Lu, Caicai; Chen, Zhi; Song, Yuanyuan; Guo, Yankai; Xing, Yajuan

2017-11-01

Perchlorate (ClO 4 - ) contamination is more and more concerned due to the hazards to humans. Based on the common primary bacterium (Helicobacteraceae) of both thiosulfate-acclimated sludge (T-Acc) and sulfur-acclimated sludge (S-Acc) for perchlorate reduction, the rapid start-up of sulfur-based perchlorate reduction reactor (SBPRR) was hypothesized by inoculating T-Acc. Furthermore, the performance of SBPRR, the SO 4 2- yield, kinetics of ClO 4 - reduction and the extracellular polymeric substances (EPS) of biofilm confirmed the hypothesis. The start-up time of R3 (reactor inoculating T-Acc) was 0.18 and 0.21 times that of R1 (control) and R2 (reactor with the influent containing thiosulfate), respectively. The SO 4 2- yield of R3 was lower than that of R2 and R1 with perchlorate removal rate 166.7mg/(Lh). The kinetic study and EPS demonstrated that inoculating T-Acc was beneficial for the development of biofilm. Consequently, the present study indicated that SBPRR can be rapidly and successfully started-up via inoculation of T-Acc. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation.

PubMed

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand; Apte, Shree Kumar

2016-08-15

Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation

PubMed Central

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand

2016-01-01

ABSTRACT Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. IMPORTANCE The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. PMID:27287317

National Cost Implications of a Potentional Perchlorate Regulation

EPA Pesticide Factsheets

In this study, a screening level cost assessment was conducted to evaluate the national cost implications of five potential regulatory levels for perchlorate in drinking water 4, 6, 12, 18, and 24 ?g/L.

Biodegradation of rocket propellent waste, ammonium perchlorate

NASA Technical Reports Server (NTRS)

Naqui, S. M. Z.

1975-01-01

The impact of the biodegradation rate of ammonium perchlorate on the environment was studied in terms of growth, metabolic rate, and total biomass of selected animal and plant species. Brief methodology and detailed results are presented.

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

PROCESS FOR EXTRACTING NEPTUNIUM AND PLUTONIUM FROM NITRIC ACID SOLUTIONS OF SAME CONTAINING URANYL NITRATE WITH A TERTIARY AMINE

DOEpatents

Sheppard, J.C.

1962-07-31

A process of selectively extracting plutonium nitrate and neptunium nitrate with an organic solution of a tertiary amine, away from uranyl nitrate present in an aqueous solution in a maximum concentration of 1M is described. The nitric acid concentration is adjusted to about 4M and nitrous acid is added prior to extraction. (AEC)

[La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] the first lanthanum uranyl-vanadate with structure built from two types of sheets based upon the uranophane anion-topology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mer, A.; Obbade, S.; Rivenet, M.

2012-01-15

The new lanthanum uranyl vanadate divanadate, [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] was obtained by reaction at 800 Degree-Sign C between lanthanum chloride, uranium oxide (U{sub 3}O{sub 8}) and vanadium oxide (V{sub 2}O{sub 5}) and the structure was determined from single-crystal X-ray diffraction data. This compound crystallizes in the orthorhombic system with space group P2{sub 1}2{sub 1}2{sub 1} and unit-cell parameters a=6.9470(2) A, b=7.0934(2) A, c=25.7464(6) A, V=1268.73(5) A{sup 3}, Z=4. A full matrix least-squares refinement yielded R{sub 1}=0.0219 for 5493 independent reflections. The crystal structure is characterized by the stacking of uranophane-type sheets {sup 2}{sub {infinity}}[(UO{sub 2})(VO{sub 4})]{sup -}more » and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +} connected through La-O bonds involving the uranyl oxygen of the uranyl-vanadate sheets. The double layers result from the connection of two {sup 2}{sub {infinity}}[La(UO{sub 2})(VO{sub 4}){sub 2}]{sup -} sheets derived from the uranophane anion-topology by replacing half of the uranyl ions by lanthanum atoms and connected through the formation of divanadate entities. - Graphical abstract: A view of the three-dimensional structure of [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})]. Highlights: Black-Right-Pointing-Pointer New lanthanum uranyl vanadate divanadate has been synthesized. Black-Right-Pointing-Pointer Structure was determined from single-crystal X-ray diffraction data. Black-Right-Pointing-Pointer Structure is characterized by uranophane-type sheets and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +}.« less

A Reflectron Time-of-Flight Mass Spectrometric Study on the Degradation Pathways of Glycine on Mars in the Presence of Perchlorates and Ionizing Radiation

NASA Astrophysics Data System (ADS)

Góbi, Sándor; Förstel, Marko; Maksyutenko, Pavlo; Kaiser, Ralf I.

2017-02-01

The absence of abundant organics on the Martian surface is a much discussed observation. So far, no explanation is completely satisfactory. In this study we aim for a deeper understanding of the degradation processes of organics in the presence of perchlorates that can take place on the Martian surface. Our primary goal is to study the radiation-induced decomposition process of glycine (H2NCH2COOH) in the absence and presence of an oxidizer relevant to the Martian surface—perchlorate anions ({{{ClO}}4}-). Glycine and various samples of glycine-1-13C (+H3NC{{{{H}}}2}13COO-)-magnesium perchlorate hexahydrate (Mg(ClO4)2 · 6H2O) were exposed to energetic electrons mimicking secondary electrons originating from the interaction of galactic cosmic rays (GCRs) with the Martian regolith. Using isotope-labeled and deuterated pure glycine samples such as glycine-1-13C, glycine-d5 (+D3NCD2COO-), glycine-N,N,N-d3 (+D3NCH2COO-), and glycine-2,2-d2 (+H3NCD2COO-), we can conclude that decarboxylation (carbon dioxide loss) of the glycine molecule is exclusively the first decay step during irradiation regardless of whether perchlorate anions are present or not. In pure glycine samples, the decarboxylation co-product methylamine (CH3NH2) and its radiolytic decay product ammonia could both be detected explicitly for the first time. In the presence of perchlorates, (partial) oxidation of the glycine decarboxylation product CH3NH2 may occur. Because the decarboxylation is an equilibrium reaction and the CH3NH2 is effectively removed from the system by this oxidation, glycine cannot be recycled. Therefore the depletion of the CH3NH2 facilitates the process, resulting in an overall 10-fold increase in the formation rate of carbon dioxide and its elevated concentrations in the perchlorate-containing irradiated samples.

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

USGS Publications Warehouse

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

2009-01-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hatzinger, Paul B.; Bohlke, J. K.; Sturchio, N. C.

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 themore » injectate), perchlorate concentrations decreased by 78 % and nitrate concentrations decreased by 87 %, during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (ε18O/ε37Cl) 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 approximately 0.8 (ε18O/ε15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (ε18O/ε37Cl, ε18O/ε15N) derived from homogeneous laboratory systems (e.g., pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent  values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion.« less

Oxyanion flux characterization using passive flux meters: Development and field testing of surfactant-modified granular activated carbon

NASA Astrophysics Data System (ADS)

Lee, Jimi; Rao, P. S. C.; Poyer, Irene C.; Toole, Robyn M.; Annable, M. D.; Hatfield, K.

2007-07-01

We report here on the extension of Passive Flux Meter (PFM) applications for measuring fluxes of oxyanions in groundwater, and present results for laboratory and field studies. Granular activated carbon, with and without impregnated silver (GAC and SI-GAC, respectively), was modified with a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the anion exchange capacity (AEC). Langmuir isotherm sorption maxima for oxyanions measured in batch experiments were in the following order: perchlorate >> chromate > selenate, consistent with their selectivity. Linear sorption isotherms for several alcohols suggest that surfactant modification of GAC and SI-GAC reduced (˜ 30-45%) sorption of alcohols by GAC. Water and oxyanion fluxes (perchlorate and chromate) measured by deploying PFMs packed with surfactant-modified GAC (SM-GAC) or surfactant-modified, silver-impregnated GAC (SM-SI-GAC) in laboratory flow chambers were in close agreement with the imposed fluxes. The use of SM-SI-GAC as a PFM sorbent was evaluated at a field site with perchlorate contamination of a shallow unconfined aquifer. PFMs packed with SM-SI-GAC were deployed in three existing monitoring wells with a perchlorate concentration range of ˜ 2.5 to 190 mg/L. PFM-measured, depth-averaged, groundwater fluxes ranged from 1.8 to 7.6 cm/day, while depth-averaged perchlorate fluxes varied from 0.22 to 1.7 g/m 2/day. Groundwater and perchlorate flux distributions measured in two PFM deployments closely matched each other. Depth-averaged Darcy fluxes measured with PFMs were in line with an estimate from a borehole dilution test, but much smaller than those based on hydraulic conductivity and head gradients; this is likely due to flow divergence caused by well-screen clogging. Flux-averaged perchlorate concentrations measured with PFM deployments matched concentrations in groundwater samples taken from one well, but not in two other wells, pointing to the need for additional field testing. Use of the surfactant-modified GACs for measuring fluxes of other anions of environmental interest is discussed.

Oxyanion flux characterization using passive flux meters: development and field testing of surfactant-modified granular activated carbon.

PubMed

Lee, Jimi; Rao, P S C; Poyer, Irene C; Toole, Robyn M; Annable, M D; Hatfield, K

2007-07-17

We report here on the extension of Passive Flux Meter (PFM) applications for measuring fluxes of oxyanions in groundwater, and present results for laboratory and field studies. Granular activated carbon, with and without impregnated silver (GAC and SI-GAC, respectively), was modified with a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the anion exchange capacity (AEC). Langmuir isotherm sorption maxima for oxyanions measured in batch experiments were in the following order: perchlorate>chromate>selenate, consistent with their selectivity. Linear sorption isotherms for several alcohols suggest that surfactant modification of GAC and SI-GAC reduced (approximately 30-45%) sorption of alcohols by GAC. Water and oxyanion fluxes (perchlorate and chromate) measured by deploying PFMs packed with surfactant-modified GAC (SM-GAC) or surfactant-modified, silver-impregnated GAC (SM-SI-GAC) in laboratory flow chambers were in close agreement with the imposed fluxes. The use of SM-SI-GAC as a PFM sorbent was evaluated at a field site with perchlorate contamination of a shallow unconfined aquifer. PFMs packed with SM-SI-GAC were deployed in three existing monitoring wells with a perchlorate concentration range of approximately 2.5 to 190 mg/L. PFM-measured, depth-averaged, groundwater fluxes ranged from 1.8 to 7.6 cm/day, while depth-averaged perchlorate fluxes varied from 0.22 to 1.7 g/m2/day. Groundwater and perchlorate flux distributions measured in two PFM deployments closely matched each other. Depth-averaged Darcy fluxes measured with PFMs were in line with an estimate from a borehole dilution test, but much smaller than those based on hydraulic conductivity and head gradients; this is likely due to flow divergence caused by well-screen clogging. Flux-averaged perchlorate concentrations measured with PFM deployments matched concentrations in groundwater samples taken from one well, but not in two other wells, pointing to the need for additional field testing. Use of the surfactant-modified GACs for measuring fluxes of other anions of environmental interest is discussed.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Specht, Paul Elliott; Cooper, Marcia A.

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

Perchlorates on Mars enhance the bacteriocidal effects of UV light.

PubMed

Wadsworth, Jennifer; Cockell, Charles S

2017-07-06

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

Perchlorate radiolysis on Mars and the origin of martian soil reactivity.

PubMed

Quinn, Richard C; Martucci, Hana F H; Miller, Stephanie R; Bryson, Charles E; Grunthaner, Frank J; Grunthaner, Paula J

2013-06-01

Results from the Viking biology experiments indicate the presence of reactive oxidants in martian soils that have previously been attributed to peroxide and superoxide. Instruments on the Mars Phoenix Lander and the Mars Science Laboratory detected perchlorate in martian soil, which is nonreactive under the conditions of the Viking biology experiments. We show that calcium perchlorate exposed to gamma rays decomposes in a CO2 atmosphere to form hypochlorite (ClO(-)), trapped oxygen (O2), and chlorine dioxide (ClO2). Our results show that the release of trapped O2 (g) from radiation-damaged perchlorate salts and the reaction of ClO(-) with amino acids that were added to the martian soils can explain the results of the Viking biology experiments. We conclude that neither hydrogen peroxide nor superoxide is required to explain the results of the Viking biology experiments.

Inhibition of poly(ADP-ribose)polymerase-1 and DNA repair by uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooper, Karen L.; Dashner, Erica J.; Tsosie, Ranalda

Uranium has radiological and non-radiological effects within biological systems and there is increasing evidence for genotoxic and carcinogenic properties attributable to uranium through its heavy metal properties. In this study, we report that low concentrations of uranium (as uranyl acetate; < 10 μM) is not cytotoxic to human embryonic kidney cells or normal human keratinocytes; however, uranium exacerbates DNA damage and cytotoxicity induced by hydrogen peroxide, suggesting that uranium may inhibit DNA repair processes. Concentrations of uranyl acetate in the low micromolar range inhibited the zinc finger DNA repair protein poly(ADP-ribose) polymerase (PARP)-1 and caused zinc loss from PARP-1 protein.more » Uranyl acetate exposure also led to zinc loss from the zinc finger DNA repair proteins Xeroderma Pigmentosum, Complementation Group A (XPA) and aprataxin (APTX). In keeping with the observed inhibition of zinc finger function of DNA repair proteins, exposure to uranyl acetate enhanced retention of induced DNA damage. Co-incubation of uranyl acetate with zinc largely overcame the impact of uranium on PARP-1 activity and DNA damage. These findings present evidence that low concentrations of uranium can inhibit DNA repair through disruption of zinc finger domains of specific target DNA repair proteins. This may provide a mechanistic basis to account for the published observations that uranium exposure is associated with DNA repair deficiency in exposed human populations. - Highlights: • Low micromolar concentration of uranium inhibits polymerase-1 (PARP-1) activity. • Uranium causes zinc loss from multiple DNA repair proteins. • Uranium enhances retention of DNA damage caused by ultraviolet radiation. • Zinc reverses the effects of uranium on PARP activity and DNA damage repair.« less

Cyanex based uranyl sensitive polymeric membrane electrodes.

PubMed

Badr, Ibrahim H A; Zidan, W I; Akl, Z F

2014-01-01

Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO₂(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO₂(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. © 2013 Published by Elsevier B.V.

Construction of Uranyl Selective Electrode Based on Complex of Uranyl Ion with New Ligand Carboxybenzotriazole in PVC Matrix Membrane

NASA Astrophysics Data System (ADS)

Abu-Dalo, M. A.; Al-Rawashdeh, N. A. F.; Al-Mheidat, I. R.; Nassory, N. S.

2015-10-01

In the present study uranyl selective electrodes in polyvinyl chloride (PVC) matrix membrane were prepared based on a complex of uranyl ion (UO2) with carboxybenzotriazole (CBT) as ligand. The effect of the nature of plasticizer in PVC matrix were evaluated using three different plasticizers, these are dibutyl phthalate (DBP), dioctyl phthalate (DOP) and bis(2-ethylhexyl) sebacate (BHS). The results of this study indicated that the best plasticizer could be used is the DBP, which may be attributed to its lowest viscosity value compared to DOP and BHS. The electrodes with DBP as plasticizer exhibits a Nernstian response with a slope of 28.0 mV/ decade, over a wide range of concentration from 3.0×10-5-6.0×10-2 M and a detection limit of 4.0×10-6 M. It can be used in the pH range of 4.0-10.0 with a response time of less than 10 s for DBP and 25 s for both DOP and BHS. The effects of ions interferences on the electrode response were evaluated. The di- and tri-valent cations were found to interfere less than univalent cations, which was attributed to the high diffusion and the exchange rate between the univalent ions and the uranyl ion solution. The electrodes were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron microscopy (SEM). The results of the standard addition method were satisfactory with errors less than 7%. The developed electrode was found to be fast, sensitive and reliable indicated its potential use in measuring the uranly ion concentration in the field.

Incorporation of Np(V) and U(VI) in Carbonate and Sulfate Minerals Crystallized from Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming

2015-02-15

The neptunyl Np(V)O2 + and uranyl U(VI)O2 2+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is coprecipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factorsmore » that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals.« less

PROCESSES OF RECOVERING URANIUM FROM A CALUTRON

DOEpatents

Baird, D.O.; Zumwalt, L.R.

1958-07-15

An improved process is described for recovering the residue of a uranium compound which has been subjected to treatment in a calutron, from the parts of the calutron disposed in the source region upon which the residue is deposited. The process may be utilized when the uranium compound adheres to a surface containing metals of the group consisting of copper, iron, chromium, and nickel. The steps comprise washing the surface with an aqueous acidic oxidizing solvent for the uranium whereby there is obtained an acidic aqueous Solution containing uranium as uranyl ions and metals of said group as impurities, treating the acidic solution with sodium acetate in the presenee of added sodium nitrate to precipitate the uranium as sodium uranyl acetate away from the impurities in the solution, and separating the sodium uranyl acetate from the solution.

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

NASA Astrophysics Data System (ADS)

Nikolakakos, G.; Whiteway, J. A.

2015-12-01

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

Can perchlorates be transformed to hydrogen peroxide (H2O2) products by cosmic rays on the Martian surface?

NASA Astrophysics Data System (ADS)

Crandall, Parker B.; Góbi, Sándor; Gillis-Davis, Jeffrey; Kaiser, Ralf I.

2017-09-01

Due to their oxidizing properties, perchlorates (ClO4-) are suggested by the planetary science community to play a vital role in the scarcity of organics on the Martian surface. However, alternative oxidation agents such as hydrogen peroxide (H2O2) have received surprisingly little attention. In this study, samples of magnesium perchlorate hexahydrate (Mg(ClO4)2 · 6H2O) were exposed to monoenergetic electrons and D2+ ions separately, sequentially, and simultaneously to probe the effects of galactic cosmic ray exposure of perchlorates and the potential incorporation of hydrogen (deuterium) into these minerals. The experiments were carried out under ultrahigh-vacuum conditions at 50 K, after which the samples were slowly heated to 300 K while the subliming products were monitored by a quadrupole mass spectrometer. In all cases, molecular oxygen (O2) was detected upon the onset of irradiation and also during the warmup phase. In case of a simultaneous D2+-electron exposure, deuterated water (D2O) and deuterium peroxide (D2O2) were also detected in the warmup phase, whereas only small amounts of D2O2 were found after an exclusive D2+ irradiation. These experiments yield the first data identifying hydrogen peroxide as a potential product in the interaction of cosmic rays with perchlorates in the Martian regolith revealing that perchlorates are capable of producing multiple oxidizing agents (O2 and D2O2) that may account for the destruction of organics on the Martian surface.

Accumulation of perchlorate in aquatic and terrestrial plants at a field scale.

PubMed

Tan, Kui; Anderson, Todd A; Jones, Matthew W; Smith, Philip N; Jackson, W Andrew

2004-01-01

Previous laboratory-scale studies have documented perchlorate ClO(-)(4) uptake by different plant species, but less information is available at field scale, where ClO(-)(4) uptake may be affected by environmental conditions, such as distance to streams or shallow water tables, exposure duration, and species. This study examined uptake of ClO(-)(4) in smartweed (Polygonum spp.) and watercress (Nasturtium spp.) as well as more than forty trees, including ash (Fraxinus greggii A. Gray), chinaberry (Melia azedarach L.), elm (Ulmus parvifolia Jacq.), willow (Salix nigra Marshall), mulberry [Broussonetia papyrifera (L.) Vent.], and hackberry (Celtis laevigata Willd.) from multiple streams surrounding a perchlorate-contaminated site. Results indicate a large potential for ClO(-)(4) accumulation in aquatic and terrestrial plants, with ClO(-)(4) concentration in plant tissues approximately 100 times higher than that in bulk water. Perchlorate accumulation in leaves of terrestrial plants was also dependent on species, with hackberry, willow, and elm having a strong potential to accumulate ClO(-)(4). Generally, trees located closer to the stream had a higher ClO(-)(4) accumulation than trees located farther away from the stream. Seasonal leaf sampling of terrestrial plants indicated that ClO(-)(4) accumulation also was affected by exposure duration, with highest accumulation observed in the late growing cycle, although leaf concentrations for a given tree were highly variable. Perchlorate may be re-released into the environment via leaching and rainfall as indicated by lower perchlorate concentrations in collected leaf litter. Information obtained from this study will be helpful to understand the fate of ClO(-)(4) in macrophytes and natural systems.

Spatial distribution of perchlorate, iodide and thiocyanate in the aquatic environment of Tianjin, China: environmental source analysis.

PubMed

Qin, Xiaolei; Zhang, Tao; Gan, Zhiwei; Sun, Hongwen

2014-09-01

Although China is the largest producer of fireworks (perchlorate-containing products) in the world, the pathways through which perchlorate enters the environment have not been characterized completely in this country. In this study, perchlorate, iodide and thiocyanate were measured in 101 water samples, including waste water, surface water, sea water and paired samples of rain water and surface runoff collected in Tianjin, China. The concentrations of the target anions were generally on the order of rain>surface water≈waste water treatment plant (WWTP) influent>WWTP effluent. High concentrations of perchlorate, iodide and thiocyanate were detected in rain samples, ranging from 0.35 to 27.3 (median: 4.05), 0.51 to 8.33 (2.92), and 1.31 to 107 (5.62) ngmL(-)(1), respectively. Furthermore, the concentrations of the target anions in rain samples were significantly (r=0.596-0.750, p<0.01) positively correlated with the concentrations obtained in the paired surface runoff samples. The anions tested showed a clear spatial distribution, and higher concentrations were observed in the upper reaches of rivers, sea waters near the coast, and rain-surface runoff pairs sampled in urban areas. Our results revealed that precipitation may act as an important source of perchlorate, iodide and thiocyanate in surface water. Moreover, iodide concentrations in the Haihe River and Dagu Drainage Canal showed a good correlation with an ideal marker (acesulfame) of domestic waste water, indicating that input from domestic waste water was an important source of iodide in the surface waters of Tianjin. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

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

2015-11-01

Adequate maternal thyroid function during pregnancy is necessary for normal fetal brain development, making pregnancy a critical window of vulnerability to thyroid disrupting insults. Sodium/iodide symporter (NIS) inhibitors, namely perchlorate, nitrate, and thiocyanate, have been shown individually to competitively inhibit uptake of iodine by the thyroid. Several epidemiologic studies examined the association between these individual exposures and thyroid function. Few studies have examined the effect of this chemical mixture on thyroid function during pregnancy We examined the cross sectional association between urinary perchlorate, thiocyanate and nitrate concentrations and thyroid function among healthy pregnant women living in New York City using weighted quantile sum (WQS) regression. We measured thyroid stimulating hormone (TSH) and free thyroxine (FreeT4) in blood samples; perchlorate, thiocyanate, nitrate and iodide in urine samples collected from 284 pregnant women at 12 (±2.8) weeks gestation. We examined associations between urinary analyte concentrations and TSH or FreeT4 using linear regression or WQS adjusting for gestational age, urinary iodide and creatinine. Individual analyte concentrations in urine were significantly correlated (Spearman's r 0.4-0.5, p<0.001). Linear regression analyses did not suggest associations between individual concentrations and thyroid function. The WQS revealed a significant positive association between the weighted sum of urinary concentrations of the three analytes and increased TSH. Perchlorate had the largest weight in the index, indicating the largest contribution to the WQS. Co-exposure to perchlorate, nitrate and thiocyanate may alter maternal thyroid function, specifically TSH, during pregnancy. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

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

PubMed Central

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

2015-01-01

Background Adequate maternal thyroid function during pregnancy is necessary for normal fetal brain development, making pregnancy a critical window of vulnerability to thyroid disrupting insults. Sodium/iodide symporter (NIS) inhibitors, namely perchlorate, nitrate, and thiocyanate, have been shown individually to competitively inhibit uptake of iodine by the thyroid. Several epidemiologic studies examined the association between these individual exposures and thyroid function. Few studies have examined the effect of this chemical mixture on thyroid function during pregnancy. Objectives We examined the cross sectional association between urinary perchlorate, thiocyanate and nitrate concentrations and thyroid function among healthy pregnant women living in New York City using weighted quantile sum (WQS) regression. Methods We measured thyroid stimulating hormone (TSH) and free thyroxine (FreeT4) in blood samples; perchlorate, thiocyanate, nitrate and iodide in urine samples collected from 284 pregnant women at 12 (± 2.8) weeks gestation. We examined associations between urinary analyte concentrations and TSH or FreeT4 using linear regression or WQS adjusting for gestational age, urinary iodide and creatinine. Results Individual analyte concentrations in urine were significantly correlated (Spearman’s r 0.4–0.5, p < 0.001). Linear regression analyses did not suggest associations between individual concentrations and thyroid function. The WQS revealed a significant positive association between the weighted sum of urinary concentrations of the three analytes and increased TSH. Perchlorate had the largest weight in the index, indicating the largest contribution to the WQS. Conclusions Co-exposure to perchlorate, nitrate and thiocyanate may alter maternal thyroid function, specifically TSH, during pregnancy. PMID:26408806

Perchlorate in Drinking Water Frequent Questions

EPA Pesticide Factsheets

Perchlorate occurs naturally in arid states in the Southwest United States, in nitrate fertilizer deposits in Chile, and in potash ore in the United States and Canada. It has also been found in some public drinking water systems and in food.

Electrochemical synthesis of azanucleoside derivatives using a lithium perchlorate-nitromethane system.

PubMed

Kim, Shokaku; Shoji, Takao; Kitano, Yoshikazu; Chiba, Kazuhiro

2013-07-25

We have developed a highly efficient synthetic method for azanucleosides using a lithium perchlorate-nitromethane reaction medium, allowing direct and exclusive installation of various nucleophiles, including protected nucleobases into prolinol derivatives at the preferred 5-position.

Determination of active oxygen in the presence of barium and lead

USGS Publications Warehouse

Fleischer, M.

1943-01-01

The method of Mrgudich and Clark is modified by substituting 5 per cent (by volume) perchloric acid for 50 per cent perchloric acid. Titration by potassium permanganate may be substituted for electrometric titration with ceric sulfate.

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

EPA Science Inventory

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

Recuperation of uranyl ions from effluents by means of microbiological collectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cecal, A.; Palamaru, I.; Humelnicu, D.

1997-12-31

This paper deals with the study of bioaccumulation of uranyl ions (UO{sub 2}{sup 2+}) from industrial effluents, using microbiological collectors: Nostoc linkia sp., Tolipotrix sp., Spirulina sp., Porphyridium cruentum and also the glucide extract of P. cruentum. The values of retaining degree of UO{sub 2}{sup 2+} on the biomass, for several experimental conditions, were established between 14.22 and 91.99%.

Patch testing with uranyl acetate in veterans exposed to depleted uranium during the 1991 Gulf war and the Iraqi conflict.

PubMed

Shvartsbeyn, Marianna; Tuchinda, Papapit; Gaitens, Joanna; Squibb, Katherine S; McDiarmid, Melissa A; Gaspari, Anthony A

2011-01-01

The Depleted Uranium Follow-Up Program is a clinical surveillance program run by the Baltimore Veterans Affairs Medical Center since 1993 for veterans of the Gulf and Iraqi wars who were exposed to depleted uranium (DU) as a result of "friendly-fire" incidents. In 2009, 40 veterans from this cohort were screened for skin reactivity to metals by patch-testing with extended metal series and uranyl acetate (0.25%, 2.5%, and 25%). A control arm comprised 46 patients without any known occupational exposures to DU who were seen at the University of Maryland Dermatology Clinic for evaluation of allergic contact dermatitis. Excluding irritant reactions, no patch-test reactions to uranyl acetate were observed in the participants. Irritant reactions to DU were more common in the clinic cohort, likely reflective of the demographic differences between the two arms of the study. Biologic monitoring of urine uranium concentrations in the DU program participants with 24-hour urine samples showed evidence of percutaneous uranium absorption from the skin patches. We conclude that dermatitis observed in a subset of the veterans was unrelated to their military DU exposure. Our data suggest that future studies of skin testing with uranyl acetate should utilize 0.25%, the least irritating concentration.

KINETICS OF THE DISSOLUTION OF URANIUM DIOXIDE IN CARBONATE-BICARBONATE SOLUTIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schortmann, W.E.; DeSesa, M.A.

The kinetics of the dissolution of uranium dioxide in sodium carbonate- sodium bicarbonate solutions were determined. The study was undertaken in order to obtain fundamental information about the commercial carbonate process for leaching uranium from its ores. A rate equation incorporating the effects of surface area oxygen partial pressure, temperature, and reagent concentrations was empirically developed. A mechanism consisting essentially of two consecutive reactions at steady state is proposed. These reactions are the oxidation of U/ sup 4+/ to U/sup 6+/ and the subsequent formation of the uranyl dicarbonate complexion. Depending on the conditions, either or both of these reactionsmore » can determine the over-all rate. The conversion of uranyl dicarbonate to the uranyl tricarbonate complexion is postulated to be very rapid. In the suggested mechanism, the rate-determining phase of the oxidation is the dissociation of adsorbed molecular oxygen. and both the carbonate and bicarbonate ions play equivalent roles in the formation of the uranyl dicarbonate. As indicated by their high activation energies of about 13 and 14 kcal per mole uranium, both reactions are chemical rather than diffusional processes. A mathematical examination of the proposed mechanism produced a rate equation consistent with the experimental information. The credibility of the mechanism was thereby strengthened. (auth)« less

Cellular distribution of uranium after acute exposure of renal epithelial cells: SEM, TEM and nuclear microscopy analysis

NASA Astrophysics Data System (ADS)

Carrière, Marie; Gouget, Barbara; Gallien, Jean-Paul; Avoscan, Laure; Gobin, Renée; Verbavatz, Jean-Marc; Khodja, Hicham

2005-04-01

The major health effect of uranium exposure has been reported to be chemical kidney toxicity, functional and histological damages being mainly observed in proximal tubule cells. Uranium enters the proximal tubule as uranyl-bicarbonate or uranyl-citrate complexes. The aim of our research is to investigate the mechanisms of uranium toxicity, intracellular accumulation and repartition after acute intoxication of rat renal proximal tubule epithelial cells, as a function of its chemical form. Microscopic observations of renal epithelial cells after acute exposure to uranyl-bicarbonate showing the presence of intracellular precipitates as thin needles of uranyl-phosphate localized in cell lysosomes have been published. However the initial site of precipitates formation has not been identified yet: they could either be formed outside the cells before internalization, or directly inside the cells. Uranium solubility as a function and initial concentration was specified by ICP-MS analysis of culture media. In parallel, uranium uptake and distribution in cell monolayers exposed to U-bicarbonate was investigated by nuclear microprobe analyses. Finally, the presence of uranium precipitates was tested out by scanning electron microscopic observations (SEM), while extracellular and/or intracellular precipitates were observed on thin sections of cells by transmission electron microscopy (TEM).

Uranium: A Dentist's perspective

PubMed Central

Toor, R. S. S.; Brar, G. S.

2012-01-01

Uranium is a naturally occurring radionuclide found in granite and other mineral deposits. In its natural state, it consists of three isotopes (U-234, U-235 and U-238). On an average, 1% – 2% of ingested uranium is absorbed in the gastrointestinal tract in adults. The absorbed uranium rapidly enters the bloodstream and forms a diffusible ionic uranyl hydrogen carbonate complex (UO2HCO3+) which is in equilibrium with a nondiffusible uranyl albumin complex. In the skeleton, the uranyl ion replaces calcium in the hydroxyapatite complex of the bone crystal. Although in North India, there is a risk of radiological toxicity from orally ingested natural uranium, the principal health effects are chemical toxicity. The skeleton and kidney are the primary sites of uranium accumulation. Acute high dose of uranyl nitrate delays tooth eruption, and mandibular growth and development, probably due to its effect on target cells. Based on all previous research and recommendations, the role of a dentist is to educate the masses about the adverse effects of uranium on the overall as well as the dental health. The authors recommended that apart from the discontinuation of the addition of uranium to porcelain, the Public community water supplies must also comply with the Environmental Protection Agency (EPA) standards of uranium levels being not more than 30 ppb (parts per billion). PMID:24478959

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

PubMed

Stewart, Brandy D; Mayes, Melanie A; Fendorf, Scott

2010-02-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption.

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

NASA Technical Reports Server (NTRS)

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 incomplete data from the other two, US EPA/NCEA issued a document in December 1998 stating that the critical effects were hormone and histology data from the neurodevelopmental/behavioral toxicity study that had been performed in rats; an RfD was proposed based upon the observation of thyroid-follicular-cell hypertrophy in the 5-day-old pups (PND) of dams given perchlorate in drinking water at 0.1 mg/kg-day (the lowest dose tested) in this study. US EPA/NCEA also focused attention on a nonsignificant increase in motor activity observed in 14-day-old male pups in the same study at the same dose. In February 1999, a public workshop was convened at which an external peer-review panel determined that there was still insufficient data to support the development of a RfD. Additional studies were recommended. Since that time a clinical study revealed significant depression of thyroidal uptake of iodide in volunteers receiving potassium perchlorate at 10 mg/day for 14 days. Follow-up studies currently underway include a pathology working-group review of histology slides from the all of the previous studies, a motor activity study similar to the first behavioral study, an additional immunotoxicity study, male and female rat kinetic studies, a hormone interlaboratory study, and an effects study for thyroid and brain in developing rats. These studies are expected to be complete by mid-2000. A clinical study is planned to determine inhibition of iodide uptake and kinetic parameters in humans following 14-day perchlorate ingestion. The kinetics studies will provide data for developing physiologically based pharmacokinetic (PBPK) models for rats and humans needed to establish the RfD.

DETERMINATION OF PERCHLORATE IN INDUSTRIAL AND FOODGRADE CHEMICALS

EPA Science Inventory

Perchlorate anion has been found in numerous drinking water supplies at concentrations that recent studies indicate may adversely affect human health. In collaboration with the Office of Ground Water and Drinking Water (OGWDW) and Dionex Corporation, the National Exposure Resea...

ASSESSMENT OF PERCHLORATE IN FERTILIZERS

EPA Science Inventory

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

THE EFFECTS OF AMMONIUM PERCHLORATE ON THYROIDS (2000)

EPA Science Inventory

In response to recommendations made at the February 1999 external peer review of the December 1998 document entitled, Perchlorate Environmental Contamination: Toxicology Review and Risk Characterization , ...

POLISHING THE EFFLUENT FROM AN ANAEROBIC BIOLOGICAL PERCHLORATE TREATMENT PROCESS

EPA Science Inventory

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

The Impact of Temperature on Anaerobic Biological Perchlorate Treatment

EPA Science Inventory

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...

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

EPA Science Inventory

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...

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

EPA Science Inventory

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

Graphene-a promising material for removal of perchlorate (ClO4-) from water.

PubMed

Lakshmi, Jothinathan; Vasudevan, Subramanyan

2013-08-01

A batch adsorption process was applied to investigate the removal of perchlorate (ClO4 (-)) from water by graphene. In doing so, the thermodynamic adsorption isotherm and kinetic studies were also carried out. Graphene was prepared by a facile liquid-phase exfoliation. Graphene was characterized by Raman spectroscopy, Fourier-transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscope, and zeta potential measurements. A systematic study of the adsorption process was performed by varying pH, ionic strength, and temperature. The adsorption efficiency of graphene was 99.2 %, suggesting that graphene is an excellent adsorbent for ClO4 (-) removal from water. The rate constants for all these kinetic models were calculated, and the results indicate that second-order kinetics model was well suitable to model the kinetic adsorption of ClO4 (-). Equilibrium data were well described by the typical Langmuir adsorption isotherm. The experimental results showed that graphene is an excellent perchlorate adsorbent with an adsorbent capacity of up to 0.024 mg/g at initial perchlorate concentration of 2 mg/L and temperature of 298 K. Thermodynamic studies revealed that the adsorption reaction was a spontaneous and endothermic process. Graphene removed the perchlorate present in the water and reduced it to a permissible level making it drinkable.

Growth and Survival of Perchlorate-Reducing Bacteria in Media Containing Elevated Perchlorate Concentrations and UV-C Conditions

NASA Technical Reports Server (NTRS)

Bywaters, K. F.; Mckay, C. P.; Quinn, R. C.

2017-01-01

Introduction: The identification of perchlorate (ClO4(-)) on Mars has led to the possibility that complete redox couples are available for microbial metabolism in contemporary surface environments. Perchlorate-reducing bacteria (PRB) utilize ClO4(-) and chlorate (ClO3(-)) as terminal electron acceptors due to the high reduction potential. Additionally, ClO4(-) salts have been suggested as a possible source of brines on Mars and spectral evidence indicates that the hydration of ClO4(-) salts in the regolith of Martian is linked to the surface recurring slope lineae (RSL). For these reasons PRB may serve as analog organisms for possible life on Mars. However, there is very little information on the viability of PRB in aqueous environments that contain high levels of perchlorate Microorganisms on or near the surface of Mars, such as in the RSL, would potentially be exposed to high-salinity and high ultraviolet radiation environments. Under these extreme conditions, microorganisms must possess mechanisms for maintaining continued high genome fidelity. To assess possible microbial viability in contemporary Mars analog environments we are investigating the tolerance of two PRB strains in aqueous conditions under high UV-C conditions and high ClO4(-) concentrations.

Structure cristalline, caractérisation spectroscopique, calcul DFT et analyse de surface Hirshfeld du perchlorate de p-toluidinium.

PubMed

Ben Jomaa, Meriam; Chebbi, Hammouda; Fakhar Bourguiba, Noura; Zid, Mohamed Faouzi

2018-02-01

The synthesis of p -toluidinium perchlorate (systematic name: 4-methyl-anilinium perchlorate), C 7 H 10 N + ·ClO 4 - , was carried out from an aqueous reaction of perchloric acid with p -toluidine. This compound was characterized by powder XRD, IR and UV-Vis spectroscopy. The structure was further confirmed by a single-crystal X-ray diffraction study. The crystal structure is formed by a succession of two-dimensional mol-ecular layers consisting of perchlorate anions and organic cations parallel to the (100) plane and located at x = 2 n  + ½ ( n ∈ Z ). Each mixed layer is formed by infinite chains {C 7 H 10 N + ·ClO 4 - } n parallel to the [010] direction and developing along the c axis, generating R 2 4 (8), R 2 2 (4) and R 4 4 (12) graph-set motifs. The results of a theoretical study using the DFT method at the B3LYP/6-311++G(d,p) level are in good agreement with the experimental data. Hirshfeld surface and fingerprint plots reveal that the structure is dominated by O⋯H/H⋯O (54.2%), H⋯H (26.9%) and C-H ⋯π (14.3%) contacts. The studied crystal was refined as a two-component twin.

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

USGS Publications Warehouse

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

2015-01-01

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

Nonaqueous capillary electrophoresis with indirect electrochemical detection.

PubMed

Matysik, Frank-Michael; Marggraf, Daniela; Gläser, Petra; Broekaert, José A C

2002-11-01

Nonaqueous capillary electrophoresis (NACE) which makes use of organic solvents in place of conventional aqueous electrophoresis buffers is gaining increasing importance among modern separation techniques. Recently, it has been shown that amperometric detection in conjunction with acetonitrile-based NACE offers an extended accessible potential range and an enhanced long-term stability of the amperometric responses generated at solid electrodes. The present contribution takes advantage of the latter aspect to develop reliable systems for NACE with indirect electrochemical detection (IED). In this context, several compounds such as (ferrocenylmethyl)trimethylammonium perchlorate, tris(1,10-phenanthroline)cobalt(III) perchlorate and bis(1,4,7-triazacyclononane)nickel(II) perchlorate were studied regarding their suitability to act as electroactive buffer additives for IED in NACE. The performance characteristics for the respective buffer systems were evaluated. Tetraalkylammonium perchlorates served as model compounds for the optimization of the NACE-IED system. Target analytes choline and acetylcholine could easily be separated and determined by means of NACE-IED. In the case of a buffer system containing 10(-4) M tris(1,10-phenanthroline)cobalt(III) perchlorate the limits of detection were 2.5 x 10(-7) M and 4.6 x 10(-7) M for choline and acetylcholine, respectively. With the elaborated analytical procedure choline could be determined in pharmaceutical preparations.

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

NASA Astrophysics Data System (ADS)

Dewji, S. A.; Lee, D. L.; Croft, S.; Hertel, N. E.; Chapman, J. A.; McElroy, R. D.; Cleveland, S.

2016-07-01

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UO2(NO3)2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10-90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. Although calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.

ARC-2009-ACD09-0055-002

NASA Image and Video Library

2009-04-08

Directors Colloquium: Science Seminar by John Coates, Associate Professor of Microbiology at the University of California, Berkeley, on Microbial Perchlorate Reduction. The discovery of perchlorate in soils at the Phoenix Landing site, makes this type of organisms interesting analogues to potential life on Mars.

ARC-2009-ACD09-0055-005

NASA Image and Video Library

2009-04-08

Directors Colloquium: Science Seminar by John Coates, Associate Professor of Microbiology at the University of California, Berkeley, on Microbial Perchlorate Reduction. The discovery of perchlorate in soils at the Phoenix Landing site, makes this type of organisms interesting analogues to potential life on Mars.

ARC-2009-ACD09-0055-004

NASA Image and Video Library

2009-04-08

Directors Colloquium: Science Seminar by John Coates, Associate Professor of Microbiology at the University of California, Berkeley, on Microbial Perchlorate Reduction. The discovery of perchlorate in soils at the Phoenix Landing site, makes this type of organisms interesting analogues to potential life on Mars.

ARC-2009-ACD09-0055-003

NASA Image and Video Library

2009-04-08

Directors Colloquium: Science Seminar by John Coates, Associate Professor of Microbiology at the University of California, Berkeley, on Microbial Perchlorate Reduction. The discovery of perchlorate in soils at the Phoenix Landing site, makes this type of organisms interesting analogues to potential life on Mars.

ARC-2009-ACD09-0055-001

NASA Image and Video Library

2009-04-08

Directors Colloquium: Science Seminar by John Coates, Associate Professor of Microbiology at the University of California, Berkeley, on Microbial Perchlorate Reduction. The discovery of perchlorate in soils at the Phoenix Landing site, makes this type of organisms interesting analogues to potential life on Mars.

POLISHING EFFLUENT FROM A PERCHLORATE-REDUCING ANAEROBIC BIOLOGICAL CONTACTOR

EPA Science Inventory

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...

Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing

DOEpatents

De Poorter, Gerald L.; Rofer-De Poorter, Cheryl K.

1978-01-01

Uranyl ion in solution in tri-n-butyl phosphate is readily photochemically reduced to U(IV). The product U(IV) may effectively be used in the Purex process for treating spent nuclear fuels to reduce Pu(IV) to Pu(III). The Pu(III) is readily separated from uranium in solution in the tri-n-butyl phosphate by an aqueous strip.

Uranyl mediated photofootprinting reveals strong E. coli RNA polymerase--DNA backbone contacts in the +10 region of the DeoP1 promoter open complex.

PubMed Central

Jeppesen, C; Nielsen, P E

1989-01-01

Employing a newly developed uranyl photofootprinting technique (Nielsen et al. (1988) FEBS Lett. 235, 122), we have analyzed the structure of the E. coli RNA polymerase deoP1 promoter open complex. The results show strong polymerase DNA backbone contacts in the -40, -10, and most notably in the +10 region. These results suggest that unwinding of the -12 to +3 region of the promoter in the open complex is mediated through polymerase DNA backbone contacts on both sides of this region. The pattern of bases that are hyperreactive towards KMnO4 or uranyl within the -12 to +3 region furthermore argues against a model in which this region is simply unwound and/or single stranded. The results indicate specific protein contacts and/or a fixed DNA conformation within the -12 to +3 region. Images PMID:2503811

Synthesis of microspheres of triuranium octaoxide by simultaneous water and nitrate extraction from ascorbate-uranyl sols.

PubMed

Brykala, M; Deptula, A; Rogowski, M; Lada, W; Olczak, T; Wawszczak, D; Smolinski, T; Wojtowicz, P; Modolo, G

A new method for synthesis of uranium oxide microspheres (diameter <100 μm) has been developed. It is a variant of our patented Complex Sol-Gel Process, which has been used to synthesize high-quality powders of a wide variety of complex oxides. Starting uranyl-nitrate-ascorbate sols were prepared by addition of ascorbic acid to uranyl nitrate hexahydrate solution and alkalizing by aqueous ammonium hydroxide and then emulsified in 2-ethylhexanol-1 containing 1v/o SPAN-80. Drops of emulsion were firstly gelled by extraction of water by the solvent. Destruction of the microspheres during thermal treatment, owing to highly reactive components in the gels, requires modification of the gelation step by Double Extraction Process-simultaneously extraction of water and nitrates using Primene JMT, which completely eliminates these problem. Final step was calcination in air of obtained microspheres of gels to triuranium octaoxide.

Study of Pulsed Columns with the System. Uranyl Nitrate-Nitric Acid-Water- Tributylphosphate; ETUDE DES COLONNES A PULSATIONS A L'AIDE DU SYSTEME NITRATE D'URANYLE-ACIDE NITRIQUEEAU-TRIBUTYLPHOSPHATE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durandet, J.; Defives, D.; Choffe, B.

1959-10-31

The performsnce of a pulsed column with perforated plates was studied with the aid of a uranyl nitrate-nitric acid --water --tributyl phosphate system. The extraction of uranium from an aqueous acidic solution by an organic solvent and the extraction of uranium from organic solutions by water were the two cases investigated. The variation of the efficiency and the capacity of the pulsed column was determined as a function of the pulse amplitude and frequency, of the total flow rate, of the diameter of the holes, and of the choice of dispersed phase. The results showed that for a given amplitudemore » and total flow rate the efficiency has a maximum with an increase in frequency. (J.S.R.)« less

Thermal stability of uranyl complexes with neutral oxygen-containing organic bases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kobets, L.V.

1987-03-01

The thermal stability of uranyl chloride, nitrate, and oxalate with a series of neutral oxygen-containing organic ligands is discussed. It was found that the temperatures of removal of chlorine are higher than the stripping of the first molecule of the base in complexes UO/sub 2/Cl/sub 2/ x 2L. This is an indication of greater strength of the bonds of the Cl/sup -/ ions to the uranyl group in comparison with the investigated bases. It was shown that the temperatures of removal of a mole of neutral ligands depend little on the nature of the anions and exhibit a correlation withmore » the donor capacity of the bases: Ac < TBP < DMFA similarly ordered DMSO < TBPO similarly ordered PyO. The chemistry of the decomposition of the complexes and the strength of the binding of the acido- and neutral ligands in them are discussed.« less

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Kovrugin, Vadim M.; Tyumentseva, Olga S.

2015-09-15

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){submore » 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • The method of orientation matrices was applied to distinguish geometrical isomers. • The flexibility of structural complexes specifies the undulation of layered structural units.« less

Neptunium incorporation into select uranyl phases and thermal analysis of select uranyl phases

NASA Astrophysics Data System (ADS)

Klingensmith, Amanda Leigh

Alteration of spent nuclear fuel in a geological repository under oxidizing conditions is likely to result in abundant uranyl compounds. The proposed repository at Yucca Mountain, Nevada is intended to store about 70,000 metric tons of spent nuclear fuel in the unsaturated zone of a welded tuff sequence. Following failure of canisters that encapsulate the waste, contents may be exposed both to air and water and undergo repetitive wetting and drying events. Incorporation of radionuclides into the uranyl alteration phases may significantly reduce their mobility, thereby impacting repository performance. Of particular interest is 237Np owing to its long half-life (2.14 x 106 years) and potential mobility in groundwater. Powders of the synthetic uranyl phase soddyite, (UO2) 2(SiO4)(H2O)2, a framework type structure, and uranophane, Ca[(UO2)(SiO3OH)]2(H 2O)5, kasolite, Pb[(UO2)(SiO4)]H 2O, Na compreignacite, Na2[(UO2)3O 2(OH)3]2(H2O)7, and becquerelite, Ca[(UO2)3O2(OH)3]2(H 2O)8, all of which are sheet type structures, were synthesized in the presence of Np5+ under varying temperature and pH conditions. Uranophane, kasolite, boltwoodite K[(UO2)(SiO3OH)](H 2O)1.5, and Na boltwoodite K,Na[(UO2)(SiO 3OH)](H2O)1.5 were synthesized in the presence of Np as well as P, Ca and/or Mg. Single crystals of Na metaschoepite, Na[(UO 2)4O2(OH)5]˙5H2O were synthesized in the presence of Np5+ and laser ablation verified that Np can be incorporated within the structure of a uranyl phase. Incorporation of Np5+ into soddyite increased steadily with synthesis temperature. Np incorporation into uranophane, becquerelite, and kasolite was not dependent on synthesis temperature. Np uptake in uranophane and kasolite was found to be dependent on synthesis pH, with an increase in Np uptake with higher pH. Uranophane, boltwoodite and Na boltwoodite showed an increase in Np incorporation in the presence of P. Boltwoodite showed an even higher Np uptake when Mg and P were both present in the synthesis. Thermal analysis was completed for the uranyl phases soddyite, becquerelite, Na compreignacite, uranophane, and kasolite. TGA curves for becquerelite, Na compreignacite and uranophane showed loss of interlayer water groups by 100°C. Soddyite and kasolite showed more gradual TGA curves and retention of water groups up to 400°C for soddyite and 550°C for kasolite, with agreement shown by high temperature powder XRD data.

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

PubMed

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. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

(Per)Chlorate-Reducing Bacteria Can Utilize Aerobic and Anaerobic Pathways of Aromatic Degradation with (Per)Chlorate as an Electron Acceptor

PubMed Central

Carlström, Charlotte I.; Loutey, Dana; Bauer, Stefan; Clark, Iain C.; Rohde, Robert A.; Iavarone, Anthony T.; Lucas, Lauren

2015-01-01

ABSTRACT The pathways involved in aromatic compound oxidation under perchlorate and chlorate [collectively known as (per)chlorate]-reducing conditions are poorly understood. Previous studies suggest that these are oxygenase-dependent pathways involving O2 biogenically produced during (per)chlorate respiration. Recently, we described Sedimenticola selenatireducens CUZ and Dechloromarinus chlorophilus NSS, which oxidized phenylacetate and benzoate, two key intermediates in aromatic compound catabolism, coupled to the reduction of perchlorate or chlorate, respectively, and nitrate. While strain CUZ also oxidized benzoate and phenylacetate with oxygen as an electron acceptor, strain NSS oxidized only the latter, even at a very low oxygen concentration (1%, vol/vol). Strains CUZ and NSS contain similar genes for both the anaerobic and aerobic-hybrid pathways of benzoate and phenylacetate degradation; however, the key genes (paaABCD) encoding the epoxidase of the aerobic-hybrid phenylacetate pathway were not found in either genome. By using transcriptomics and proteomics, as well as by monitoring metabolic intermediates, we investigated the utilization of the anaerobic and aerobic-hybrid pathways on different electron acceptors. For strain CUZ, the results indicated utilization of the anaerobic pathways with perchlorate and nitrate as electron acceptors and of the aerobic-hybrid pathways in the presence of oxygen. In contrast, proteomic results suggest that strain NSS may use a combination of the anaerobic and aerobic-hybrid pathways when growing on phenylacetate with chlorate. Though microbial (per)chlorate reduction produces molecular oxygen through the dismutation of chlorite (ClO2−), this study demonstrates that anaerobic pathways for the degradation of aromatics can still be utilized by these novel organisms. PMID:25805732

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

EPA Science Inventory

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

PREDICTING FIELD PERFORMANCE OF HERBACEOUS SPECIES FOR PHYTOREMEDIATION OF PERCHLORATE

EPA Science Inventory

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

PERCHLORATE CHEMISTRY: IMPLICATIONS FOR ANALYSIS AND REMEDIATION

EPA Science Inventory

Since the discovery of perchlorate in the ground and surface waters of several western states, there has been increasing interest in the health effects resulting from chronic exposure to low (ppb) levels. With this concern has come a need to investigate technologies that might be...

Perchlorate Radiolysis on Mars and the Origin of Martian Soil Reactivity

PubMed Central

Martucci, Hana F.H.; Miller, Stephanie R.; Bryson, Charles E.; Grunthaner, Frank J.; Grunthaner, Paula J.

2013-01-01

Abstract Results from the Viking biology experiments indicate the presence of reactive oxidants in martian soils that have previously been attributed to peroxide and superoxide. Instruments on the Mars Phoenix Lander and the Mars Science Laboratory detected perchlorate in martian soil, which is nonreactive under the conditions of the Viking biology experiments. We show that calcium perchlorate exposed to gamma rays decomposes in a CO2 atmosphere to form hypochlorite (ClO−), trapped oxygen (O2), and chlorine dioxide (ClO2). Our results show that the release of trapped O2 (g) from radiation-damaged perchlorate salts and the reaction of ClO− with amino acids that were added to the martian soils can explain the results of the Viking biology experiments. We conclude that neither hydrogen peroxide nor superoxide is required to explain the results of the Viking biology experiments. Key Words: Mars—Radiolysis—Organic degradation—in situ measurement—Planetary habitability and biosignatures. Astrobiology 13, 515–520. PMID:23746165

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Perchlorate and Superfund Response to Uncertainty and the Geochemical Cycle

NASA Astrophysics Data System (ADS)

Mayer, K. P.

2007-12-01

Perchlorate, a chemical that had been known both in nature and through synthesis since the nineteenth century, only emerged into the limelight as an environmental contaminant in 1997. US EPA's Superfund Program became involved in perchlorate issues in the late 1980s and early 1990s due to the chemical's presence mixed with other contaminants at cleanup sites. Relying largely on pharmaceutical studies primarily from the 1950s and 1960s, EPA scientists in 1992 made a provisional estimate of toxicity and estimated that about 4 micrograms per liter (parts per billion or ppb) in drinking water would be protective. "Uncertainty factors" were incorporated to address for several identified information gaps. Results of new animal and human studies funded by the Defense Department and industry in the late 1990s shifted the concern from affects on adults with unhealthy thyroids to the potential developmental health risks to infants and children. EPA's January, 2002, draft toxicity assessment was referred to a committee of the National Research Council. In January, 2005, this committee recommended a "reference dose" based primarily on human clinical data. Many decisions remain on interpretation of the scientific recommendations for regulatory applications. After California's 1997 development of an analytical method to detect perchlorate in water to 4 ppb, EPA and state officials quickly discovered this chemical at 10 Superfund sites in the Pacific Southwest Region and at more than 30 other locations in California, Arizona and Nevada. Even before current research on the potential for natural sources of this anion, reported detections of perchlorate were investigated with reasonable care and appropriate skepticism. A brief overview of the search for likely sources of perchlorate detected in California water supplies is presented from a regional Superfund perspective. Some are clearly anthropogenic and others may be unrelated to industrial or disposal practices. Currently, there is no Federal standard for perchlorate. In March, 2004, California established Public Health Goal of 6 ppb in drinking water and a drinking water standard may be promulgated by November 2007. Seven other states have advisory levels ranging from 1 to 51 ppb.

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

PubMed

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 (<1.2×10(-6) mol L(-1)≡0.1 ppm), small sample test volume (100 μL), safety, short response time (<20 s), long life span (~8 weeks), and extended wide working pH range (4.5-8.0). The 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. Copyright © 2014 Elsevier B.V. All rights reserved.

Efflorescence of Magnesium Perchlorate by Contact with Mineral Dust Particles

NASA Astrophysics Data System (ADS)

Ushijima, S.; Tolbert, M. A.; Gough, R. V.

2017-12-01

Liquid water was not uncommon on early Mars and it shaped geologic features on the surface that are still seen today. Due to the extremely cold and dry conditions of Mars currently, only water ice and water vapor have been observed and or detected. However, it has been suggested that liquid may form seasonally based on the observations of recurring slope lineae (RSL). The liquid may be a brine composed of hygroscopic salts such as perchlorates whose hydrated form has recently been detected in an RSL by the Mars Reconnaissance Orbiter. Through a process called deliquescence, the salts can absorb water from the surrounding environment and become a brine above a specific relative humidity (RH) known as the deliquescence relative humidity (DRH). The reverse process, recrystallization or efflorescence, often occurs at a much lower RH called the efflorescence relative humidity (ERH). The hysteresis effect caused by the distinctly different RH values allows for liquid brines to be metastable even under dry conditions. However, there is evidence that ERH can be raised when a mineral particle encounters the surface of the brine or it is immersed inside, effectively diminishing the metastability potential of liquid brines. If the brines are responsible for RSL formation, the brine will inevitably mix with the Martian soil. Thus, it is important to understand the effects that mineral particles can have on efflorescence. Here we use optical trapping to examine efflorescence of magnesium perchlorate in the presence of montmorillonite and halite. Studies on the efflorescence and deliquescence of magnesium perchlorate has shown that its brine could be stable in the subsurface of Mars during certain periods of time. Both montmorillonite and halite have been suggested to be a part of or similar to components of the Martian soil. Results at ambient conditions have shown that efflorescence of magnesium perchlorate is unaffected by the presence of either minerals. Whether the droplet of magnesium perchlorate was pure or exposed to halite or montmorillonite the ERH was near 13% RH at room temperature. Although not under Mars conditions, the results suggest that the stability of magnesium perchlorate brine could be unaffected by the surrounding mineral and could still possibly contribute to RSL formation.

Organic Combustion in the Presence of Ca-Carbonate and Mg-Perchlorate: A Possible Source for the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

NASA Technical Reports Server (NTRS)

Archer, Douglas; Ming, D.; Niles, P.; Sutter, B.; Lauer, H.

2012-01-01

Two of the most important discoveries of the Phoenix Lander were the detection of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in landing site soils. The Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander could heat samples up to approx.1000 C and monitor evolved gases with a mass spectrometer. TEGA detected a low (approx.350 C) and high (approx.750 C) temperature CO2 release. The high temp release was attributed to the thermal decomposition of Ca-carbonate (calcite). The low temperature CO2 release could be due to desorption of CO2, decomposition of a different carbonate mineral, or the combustion of organic material. A new hypothesis has also been proposed that the low temperature CO2 release could be due to the early breakdown of calcite in the presence of the decomposition products of certain perchlorate salts [3]. We have investigated whether or not this new hypothesis is also compatible with organic combustion. Magnesium perchlorate is stable as Mg(ClO4)2-6H2O on the martian surface [4]. During thermal decomposition, this perchlorate salt releases H2O, Cl2, and O2 gases. The Cl2 can react with water to form HCl which then reacts with calcite, releasing CO2 below the standard thermal decomposition temperature of calcite. However, when using concentrations of perchlorate and calcite similar to what was detected by Phoenix, the ratio of high:low temperature CO2 evolved is much larger in the lab, indicating that although this process might contribute to the low temp CO2 release, it cannot account for all of it. While H2O and Cl2 cause calcite decomposition, the O2 evolved during perchlorate decomposition can lead to the combustion of any reduced carbon present in the sample [5]. We investigate the possible contribution of organic molecules to the low temperature CO2 release seen on Mars.

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

NASA Technical Reports Server (NTRS)

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.

RAMAN SPECTROSCOPIC ANALYSIS OF FERTILIZERS AND PLANT TISSUE FOR PERCHLORATE

EPA Science Inventory

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

RAMAN SPECTROSCOPIC ANALYSIS OF FERTILIZERS AND C FOR PERCHLORATE-JOURNAL ARTICLE

EPA Science Inventory

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

A SIMPLE MODEL FOR THE UPTAKE, TRANSLOCATION, AND ACCUMULATION OF PERCHLORATE IN TOBACCO PLANTS

EPA Science Inventory

A simple mathematical model is being developed to describe the uptake, translocation, and accumulation of perchlorate in tobacco plants. The model defines a plant as a set of compartments, consisting of mass balance differential equations and plant-specific physiological paramet...

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

EPA Science Inventory

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)

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

EPA Science Inventory

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 ...

Response to the comment “Uranyl-chloride speciation and uranium transport in hydrothermal brines: Comment on Migdisov et al. (2018)” by Dargent et al.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Migdisov, A. A.; Runde, W.; Williams-Jones, A. E.

We welcome the comments provided by Dargent et al. (2018) and appreciate the effort they have made to evaluate our recently reported data on the stability of uranyl(VI) chloride complexes as function of temperature (Migdisov et al., 2018). We also appreciate the opportunity provided by the editor to clarify issues in our paper that were not clearly articulated or in error.

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

USGS Publications Warehouse

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 reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (18O/37Cl, 18O/15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion. ?? CSIRO 2009.

A roadmap to uranium ionic liquids: anti-crystal engineering.

PubMed

Yaprak, Damla; Spielberg, Eike T; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja-Verena

2014-05-19

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO2(2+) unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim to establish structure-property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. These materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of vibration frequencies of uranyl ion in complexes with neutral bases (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kobets, L.V.; Umreiko, D.S.

1986-12-01

It has been shown that any estimate of the changes in vibration frequencies of UO/sub 2//sup 2 +/ applies only to the series of isostructural compounds with similar stoichiometry. Either the same values of stretching vibration frequencies of uranyl correspond to complexes with ligands that have different donor abilities, or changes in these frequencies are not great and do not reflect the real increase in the donor ability of the bases with respect to proton-containing acceptors. When the acido ligands are replaced or the stoichiometry of the complexes is changed, no correlations can be carried out, since, besides the basicitiesmore » of donors, other parameters such as the dentateness of the ligand, and hence the symmetry and the structure of the compound, are also varied. In this paper, the authors evaluate the contributions of the ligands to the shift of the vibration frequencies of uranyl that have been made and do not take into account the characteristic features of the compounds which therefore led to very different values of the contributions for one and the same ligand in different compounds. To evaluate the shifts produced by the ligands, the value of 1065 cm/sup -1/ was taken as the vibration frequency of a hypothetical fee uranyl ion, not perturbed by bonds with equatorial ligands. The authors also evaluate the contributions of ions able to form polymer structures.« less

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stewart, B.D.; Mayes, Melanie; Fendorf, Scott

2010-01-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a rangemore » of aqueous uranyl species. U(VI) adsorption is directly linked to UO{sub 2}{sup 2+} speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K{sub d} values decrease from 48 to 17 L kg{sup -1} for goethite, from 64 to 29 L kg{sup -1} for Hanford sediments, and from 95 to 51 L kg{sup -1} for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ({approx}5) and limited dissolved calcium are optimal for uranium adsorption.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium immobilization and nanofilm formation on magnesium-rich minerals

DOE PAGES

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.; ...

2016-03-18

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium Immobilization and Nanofilm Formation on Magnesium-Rich Minerals.

PubMed

van Veelen, Arjen; Bargar, John R; Law, Gareth T W; Brown, Gordon E; Wogelius, Roy A

2016-04-05

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO3] and brucite [Mg(OH)2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (PCO2 = 10(-3.5)) or reduced partial pressures of carbon dioxide (PCO2 = 10(-4.5)). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented with its Oaxial═U(VI)═Oaxial linkage at high angles (60-80°) to both magnesite (101̅4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the "effective" number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ∼ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. These results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.

A roadmap to uranium ionic liquids: Anti-crystal engineering

DOE PAGES

Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; ...

2014-04-15

In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C 4mim) cation. As dithiocarbamate ligands binding to the UO 2 2+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand withmore » the aim to establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.« less

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

PubMed

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

2018-06-01

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

The Investigation of Chlorates as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Sutter, B.; Archer, D. P.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Glavin, D. P.; McAdam, A. C.; Mahaffy, P; Stern, J. C.;

DETERMINATION OF PERCHLORATE AT PARTS-PER-BILLION LEVELS IN PLANTS BY ION CHROMATOGRAPHY

EPA Science Inventory

A method for the analysis of perchlorate in plants was developed, based on dry weight, and applied to the analysis of plant organs, foodstuffs, and plant products. The method reduced greatly the ionic interferences in water extracts of plant materials. The high background conduct...

Research Advances

ERIC Educational Resources Information Center

King, Angela G.

2005-01-01

Scientists at Texas Tech University measured perchlorate levels in breast milk and store-bought milk from across the US. Findings revealed that high levels of perchlorate might be correlated with low levels of iodide in breast milk, which can inhibit thyroid function in nursing women, an essential component for proper neural development of the…

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

EPA Science Inventory

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

RAMAN ANALYSIS OF FERTILIZER AND PLANT TISSUE EXTRACTS FOR PERCHLORATE CONTAMINATION

EPA Science Inventory

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

METHOD FOR THE DETERMINATION OF PERCHLORATE ANION IN PLANT AND SOLID MATRICES BY ION CHROMATOGRAPHY

EPA Science Inventory

A standardized method for the analysis of perchlorate in plants was developed, based on dry weight, and applied to the analysis of plant organs, foodstuffs, and plant products. The procedure greatly reduced the ionic interferences in water extracts of plant materials. Ion chro...

A Survey on the Temporal and Spatial Distribution of Perchlorate in the Potomac River

EPA Science Inventory

Samples of river water and treated drinking water were obtained from eight sites along the Potomac River between western Maryland and Washington DC. Samples were collected each month from October 2007 to September 2008 and analyzed for perchlorate by ion chromatography/mass spec...

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

EPA Science Inventory

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

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

EPA Science Inventory

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...

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

EPA Science Inventory

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...

Peer Review for EPA’s Biologically Based Dose-Response (BBDR) Model for Perchlorate

EPA Science Inventory

EPA is developing a regulation for perchlorate in drinking water. As part the regulatory process EPA must develop a Maximum Contaminant Level Goal (MCLG). FDA and EPA scientists developed a biologically based dose-response (BBDR) model to assist in deriving the MCLG. This mode...

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

EPA Science Inventory

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

PERCHLORATE LEVELS IN SAMPLES OF SODIUM NITRATE FERTILIZER DERIVED FROM CHILEAN CALICHE

EPA Science Inventory

Paleogeochemical deposits in northern Chile are a rich source of naturally occurring sodium nitrate. These caliche ores are mined and processed to isolate NaNO3 (16-0-0) for use in fertilizers. Coincidentally, these very same deposits are a natural soure of perchlorate anion (C...

A STUDY ON THE ACCUMULATION OF PERCHLORATE IN YOUNG HEAD LETTUCE

EPA Science Inventory

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 ...

Electrochemically Initiated Chain Polymerization of Pyrrole in Aqueous Media

DTIC Science & Technology

1991-10-21

NaCI), sodium dodecylsulfate (NaDS), sodium nitrate (NaNO3), sodium perchlorate (NaCIO 4 ), lithium perchlorate (LiCIO 4 ), sodium tetrafluoroborate...NaBF 4), tetraethylammonium tetrafluoroborate (Et4NTBF 4), potassium hexafluorophosphate (KPF6 ), sodium copper phthalocyanine-3,4’,4",4"’- te

PERCHLORATE UPTAKE AND TRANSFORMATION IN AQUATIC PLANTS

EPA Science Inventory

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...

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

EPA Science Inventory

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...

Zero-valent iron/biotic treatment system for perchlorate-contaminated water: lab-scale performance, modeling, and full-scale implications

EPA Science Inventory

The computer program AQUASIM was used to model biological treatment of perchlorate-contaminated water using zero-valent iron corrosion as the hydrogen gas source. The laboratory-scale column was seeded with an autohydrogenotrophic microbial consortium previously shown to degrade ...

TREATMENT OF PERCHLORATE CONTAMINATED WATER USING A COMBINED BIOTIC/ABIOTIC PROCESS

EPA Science Inventory

The results from the project will allow us to evaluate both in-situ remediation and ex-situ treatment of perchlorate contaminated waters. A project duration of three years is proposed with a first-year budget of $69,442; a budget of approximately $70,000 per year i...

76 FR 7762 - Drinking Water: Regulatory Determination on Perchlorate

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-11

... NOEL--no observed effect level NPDWR--National Primary Drinking Water Regulation NRC--National Research... Research Council (NRC) published ``Health Implications of Perchlorate Ingestion,'' a review of the state of... the threshold. For example, if a PWS with 10 entry points serving 200,000 people had a sample from a...

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

DTIC Science & Technology

2011-12-01

UCMR) data Hockley County, TX (s)Improper Cathodic Protection Elevated Storage Tank 32 TX Lone Star Army Ammunition Plant Texarkana ...River Army Depot Texarkana , TX Propellant Handling Monitoring Well 80 UT Alliant Tech Systems Magna, UT Rocket Manufacturing Public Water Supply Well

LOW-LEVEL DETERMINATION OF PERCHLORATE IN DRINKING WATER USING ION CHROMATOGRAPHY MASS SPECTROMETRY

EPA Science Inventory

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

ISSUES IN MANAGING THE RISKS ASSOCIATED WITH PERCHLORATE IN DRINKING WATER

EPA Science Inventory

Perchlorate (ClO₄^-) contamination of ground and surface waters has placed drinking water supplies at risk in communities throughout the US, especially in the West. Several major assessment studies of that risk in terms of health and environmental impact are ...

Developmental exposure to perchlorate alters synaptic transmission in hippocampus of the adult rat.

EPA Science Inventory

The Food Quality Protection Act and Safe Drinking Water Act mandate the EPA to identify potential health risks associated with chemicals that act on the endocrine system. Perchlorate, a contaminant found in food and water supplies throughout the USA, blocks iodine uptake into the...

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

EPA Science Inventory

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

DETERMINATION OF PERCHLORATE AT PARTS-PER-BILLION LEVELS IN PLANTS BY ION CHROMATOGRAPHY

EPA Science Inventory

A standardized method for the analysis of perchlorate in plants was developed, based on dry weight, and applied to the analysis of plant organs, foodstuffs, and plant products. The procedure greatly reduced the ionic interferences in water extracts of plant materials. The high ba...

Validation of gamma-ray detection techniques for safeguards monitoring at natural uranium conversion facilities

DOE PAGES

Dewji, Shaheen A.; Lee, Denise L.; Croft, Stephen; ...

2016-03-28

Recent IAEA circulars and policy papers have sought to implement safeguards when any purified aqueous uranium solution or uranium oxides suitable for isotopic enrichment or fuel fabrication exists. Under the revised policy, IAEA Policy Paper 18, the starting point for nuclear material under safeguards was reinterpreted, suggesting that purified uranium compounds should be subject to safeguards procedures no later than the first point in the conversion process. In response to this technical need, a combination of simulation models and experimental measurements were employed to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP).more » In particular, uranyl nitrate (UO 2(NO 3) 2) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. Nondestructive assay techniques using gamma-ray spectroscopy were evaluated to determine their viability as a technical means for drawing safeguards conclusions at NUCPs, and if the IAEA detection requirements of 1 significant quantity (SQ) can be met in a timely way. This work investigated gamma-ray signatures of uranyl nitrate circulating in the UNCLE facility and evaluated various gamma-ray detector sensitivities to uranyl nitrate. These detector validation activities include assessing detector responses to the uranyl nitrate gamma-ray signatures for spectrometers based on sodium iodide, lanthanum bromide, and high-purity germanium detectors. The results of measurements under static and dynamic operating conditions at concentrations ranging from 10–90 g U/L of natural uranyl nitrate are presented. A range of gamma-ray lines is examined, including attenuation for transmission measurement of density and concentration. It was determined that transmission-corrected gamma-ray spectra provide a reliable way to monitor the 235U concentration of uranyl nitrate solution in transfer pipes in NUCPs. Furthermore, existing predictive and analysis methods are adequate to design and realize practical designs. The 137Cs transmission source employed in this work is viable but not optimal for 235U densitometry determination. Validated simulations assessed the viability of 133Ba and 57Co as alternative densitometry sources. All three gamma-ray detectors are viable for monitoring natural uranium feed; although high-purity germanium is easiest to interpret, it is, however, the least attractive as an installation instrument. Overall, for monitoring throughput in a facility such as UNCLE, emulating the uranium concentration and pump speeds of the Springfields conversion facility in the United Kingdom, an uncertainty of less than 0.17% is required in order to detect the diversion of 1 SQ of uranyl nitrate through changes in uranium concentration over an accountancy period of one year with a detection probability of 50%. As a result, calibrated gamma-ray detection systems are capable of determining the concentration of uranium content in NUCPs, it is only in combination with verifiable operator declarations and supporting data, such as flow rate and enrichment, that safeguards conclusions can be drawn.« less

Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

NASA Astrophysics Data System (ADS)

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 accumulation of chloride ions either in spent media or in slurries prepared from Searsville Lake soil, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soils enriched in methanotrophs. This result leads us to surmise that the release of O2 during enzymatic perchlorate reduction was low, and that the oxygen produced was unavailable to the aerobic methanotrophs. This was borne out by patterns of O2 and CO2 production during experiments with lake soil, growth media, and pure cultures of dissimilatory perchlorate reducing bacteria. We observed that O2 release during incubation of D. agitata CKB with 10 mM ClO4- or ClO3- was decoupled from metabolism. More O2 was released during incubations without added acetate than with 10 mM acetate and an even greater amount of O2 was released during incubation with heat-killed cells. This suggests a chemical mechanism of O2 production during reaction with ClO4- and ClO3-. Hence, perchlorate reducing bacteria need not be present to facilitate O2 release from the surface of Mars, in support of recent interpretations of Viking LR and GEx experiments.

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

GRAPHITE PRODUCTION UTILIZING URANYL NITRATE HEXAHYDRATE CATALYST

DOEpatents

Sheinberg, H.; Armstrong, J.R.; Schell, D.H.

1964-03-10

ABS>The graphitizing of a mixture composed of furfuryl alcohol binder and uranyl nitrate hexahydrate hardener and the subsequent curing, baking, and graphitizing with pressure being initially applied prior to curing are described. The pressure step may be carried out by extrusion, methyl cellulose being added to the mixture before the completion of extrusion. Uranium oxide may be added to the graphitizable mixture prior to the heating and pressure steps. The graphitizable mixture may consist of discrete layers of different compositions. (AEC)

Method of precipitating uranium from an aqueous solution and/or sediment

DOEpatents

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

Criticality experiments and analysis of molybdenum reflected cylindrical uranyl fluoride water solution reactors

NASA Technical Reports Server (NTRS)

Fieno, D.; Fox, T.; Mueller, R.

1972-01-01

Clean criticality data were obtained from molybdenum-reflected cylindrical uranyl-fluoride-water solution reactors. Using ENDF/B molybdenum cross sections, a nine energy group two-dimensional transport calculation of a reflected reactor configuration predicted criticality to within 7 cents of the experimental value. For these reactors, it was necessary to compute the reflector resonance integral by a detailed transport calculation at the core-reflector interface volume in the energy region of the two dominant resonances of natural molybdenum.

Carbonate-H2O2 Leaching for Sequestering Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Horng-Bin; Weisheng, Liao; Wai, Chien

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with little loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

Carbonate-H₂O₂ leaching for sequestering uranium from seawater.

PubMed

Pan, Horng-Bin; Liao, Weisheng; Wai, Chien M; Oyola, Yatsandra; Janke, Christopher J; Tian, Guoxin; Rao, Linfeng

2014-07-28

Uranium adsorbed on amidoxime-based polyethylene fiber in simulated seawater can be quantitatively eluted at room temperature using 1 M Na2CO3 containing 0.1 M H2O2. This efficient elution process is probably due to the formation of an extremely stable uranyl-peroxo-carbonato complex in the carbonate solution. After washing with water, the sorbent can be reused with minimal loss of uranium loading capacity. Possible existence of this stable uranyl species in ocean water is also discussed.

Control of Sulfidogenesis Through Bio-oxidation of H 2S Coupled to (per)chlorate Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G.

2014-04-04

Here, we investigate H 2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H 2S coupled to (per)chlorate reduction without sustaining growth. H 2S 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 H 2S 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.

Release Of Gaseous NH(3) From NH(4)CIO(4) By HTPB-Bonding Agents

NASA Technical Reports Server (NTRS)

Mccomb, James C.

1993-01-01

Report describes experimental study of rate of generation of ammonia and total amount of ammonia generated by chemical reactions between bonding agents and grains of ammonium perchlorate in solid rocket propellants. Also provides insight into mechanisms of chemical reactions between several types of organic amines with solid ammonium perchlorate.

Project Overview: Inhibition of the Sodium-Iodide Symporter by Perchlorate: Evaluation of Lifestage Sensitivity Using PBPK Modeling

EPA Science Inventory

Perchlorate (ClO4-) competitively inhibits uptake of iodide by the sodium-iodide symporter (NIS) in laboratory animals and humans. NIS is found in many tissues, but is primarily responsible for sequestering iodide into the thyroid, enabling biosynthesis of thyroid hormones. The N...

QUANTITATION OF PERCHLORATE ION: PRACTICES AND ADVANCES APPLIED TO THE ANALYSIS OF COMMON MATRICES

EPA Science Inventory

In 1997, low level perchlorate contamination (<50 ng mL-1 or parts per billion) was discovered in the western United States. Since that time, it has been found in sites scattered around the nation. Although the Environmental Protection Agency has not established a regulation fo...