Rate and extent of aqueous perchlorate removal by iron surfaces.

Science.gov (United States)

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

2003-07-15

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

Esterification from derivates of styrene by acetic acid using perchloric acid as a catalyzer; Esterificacion de derivados de estireno con acido acetico en presencia de acido perclorico como catalizador

Energy Technology Data Exchange (ETDEWEB)

Martinez de la Cuesta, P.J.; Rus Martinez, E.; Palomino sosa, R.; Palomino Perez, F. I. [Departamento deIngenieria Quimica, Facultad de Ciencias, Universidad de Malaga, Malaga (Spain)

1995-11-01

The present work is focused to develop the production of esters from derivatives of styrene by acetic acid using perchloric acid as a catalyst. The kinetics of the reaction was studied and analysis of the variables was carried out. 18 refs.

Perchlorate in seawater

Energy Technology Data Exchange (ETDEWEB)

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

2006-05-10

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

Perchlorate in seawater

International Nuclear Information System (INIS)

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

2006-01-01

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

Effects of Perchlorate on Organic Molecules under Simulated Mars Conditions

Science.gov (United States)

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

2014-12-01

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

Widespread Occurrence of Plant Perchlorate

Science.gov (United States)

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

2007-12-01

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

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

Directory of Open Access Journals (Sweden)

N. M. I. Alhaji

2011-01-01

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

Thermometric titrations of amines with nitrosyl perchlorate in acetonitrile solvent.

Science.gov (United States)

Gündüz, T; Kiliç, E; Cakirer, O

1996-05-01

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

SFG study of platinum electrodes in perchloric acid solutions

Science.gov (United States)

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

2002-04-01

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

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

Directory of Open Access Journals (Sweden)

Thiruvenkatachari Viraraghavan

2009-04-01

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

Bioelectrical Perchlorate Remediation

Science.gov (United States)

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

2007-12-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-01-01

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

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

International Nuclear Information System (INIS)

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

2011-01-01

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

Retention prediction and hydrophobicity estimation of weak acidic compounds by reversed-phase liquid chromatography using acetic and perchloric acids as ion suppressors.

Science.gov (United States)

Han, Shu-ying; Ming, Xin; Qi, Zheng-chun; Sheng, Dong; Lian, Hong-zhen

2010-11-01

Simple acids are usually applied to suppress the ionization of weakly ionizable acidic analytes in reversed-phase liquid chromatography. The purpose of this study is to investigate the retention behavior of various weak acidic compounds (monoprotic, diprotic, triprotic, and tetraprotic acids) using acetic or perchloric acid as ion suppressor in a binary hydroorganic mobile phase. The apparent n-octanol-water partition coefficient (K(ow)") was proposed to calibrate the n-octanol-water partition coefficient (K(ow)) of weak acidic compound. LogK(ow)" was found to have a better linear correlation with logk(w), the logarithm of the retention factor obtained by extrapolating to neat aqueous fraction of the mobile phase, for all weakly ionizable acidic compounds. This straightforward relationship offers a potential medium for direct measurement of K(ow) data of weak acidic analytes and can be used to predict retention behavior of these compounds in the ion suppression reversed-phase liquid chromatographic mode.

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

International Nuclear Information System (INIS)

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

1994-01-01

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

Jarosite dissolution rates in perchlorate brine

Science.gov (United States)

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

2018-02-01

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

Branched polymeric media: Perchlorate-selective resins from hyperbranched polyethyleneimine

KAUST Repository

Chen, Dennis P.

2012-10-02

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2003-07-25

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

4-Bromoanilinium perchlorate 18-crown-6 clathrate

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Min Guo

2010-11-01

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

Environmental perchlorate: Why it matters

International Nuclear Information System (INIS)

Kirk, Andrea B.

2006-01-01

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

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

Science.gov (United States)

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

2004-10-05

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

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

International Nuclear Information System (INIS)

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

2005-01-01

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

Sample processing method for the determination of perchlorate in milk

International Nuclear Information System (INIS)

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

2006-01-01

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

Stable Isotope Systematics of Martian Perchlorate

Science.gov (United States)

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

2015-12-01

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

Novel biomarkers of perchlorate exposure in zebrafish

Science.gov (United States)

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

2005-01-01

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

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

Science.gov (United States)

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

2018-08-01

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

Application of strong phosphoric acid to radiochemistry

International Nuclear Information System (INIS)

Terada, Kikuo

1977-01-01

Not only inorganic and organic compounds but also natural substrances, such as accumulations in soil, are completely decomposed and distilled by heating with strong phosphoric acid for 30 to 50 minutes. As applications of strong phosphoric acid to radiochemistry, determination of uranium and boron by use of solubilization effect of this substance, titration of uranyl ion by use of sulfuric iron (II) contained in this substance, application to tracer experiment, and determination of radioactive ruthenium in environmental samples are reviewed. Strong phosphoric acid is also applied to activation analysis, for example, determination of N in pyrographite with iodate potassium-strong phosphoric acid method, separation of Os and Ru with sulfuric cerium (IV) - strong phosphoric acid method or potassium dechromate-strong phosphoric acid method, analysis of Se, As and Sb rocks and accumulations with ammonium bromide, sodium chloride and sodium bromide-strong phosphoric acid method. (Kanao, N.)

Coulometric-potentiometric determination of autoprotolysis constant and relative acidity scale of water

Directory of Open Access Journals (Sweden)

Džudović Radmila M.

2010-01-01

Full Text Available The autoprotolysis constant and relative acidity scale of water were determined by applying the coulometric-potentiometric method and a hydrogen/palladium (H2/Pd generator anode. In the described procedure for the evaluation of autoprotolysis constant, a strong base generated coulometrically at the platinum cathode in situ in the electrolytic cell, in presence of sodium perchlorate as the supporting electrolyte, is titrated with hydrogen ions obtained by the anodic oxidation of hydrogen dissolved in palladium electrode. The titration was carried out with a glass-SCE electrode pair at 25.0±0.1°C. The value obtained pKw = 13.91 ± 0.06 is in agreement with literature data. The range of acidity scale of water is determined from the difference between the halfneutralization potentials of electrogenerated perchloric acid and that of sodium hydroxide in a sodium perchlorate medium. The halfneutralization potentials were measured using both a glass-SCE and a (H2/Pdind-SCE electrode pairs. A wider range of relative acidity scale of water was obtained with the glass-SCE electrode pair.

Thermal decomposition of beryllium perchlorate tetrahydrate

International Nuclear Information System (INIS)

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

1975-01-01

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

Analysis of tellurium-silicon alloys. Part 1. Determination of tellurium by the reduction from perchloric acid solution

International Nuclear Information System (INIS)

Teperek, J.

1977-01-01

When 100-150 mg of tellurium is dissolved in the solution containing 20 cm 3 72 wt.% of perchloric acid, the reduction of tellurium to elementary form is possible only after adding 60-100 milimoles of HCl. The reduction is performed by adding 1 cm 3 of saturated sodium pyrosulphite solution (Na 2 S 2 O 5 ) and 10 cm 3 of 10 wt.% hydrazine hydrochloride solution (N 2 H 4 .2HCl) to 80-90 cm 3 of cold solution of Te in HClO 4 -HCl mixture. The reduction is completed after 3-5 min. of boiling. When 150-200 mg sample of Te-Si alloy is dissolved in 20 cm 3 of hot 72% per chloric acid, the separation of components is reached. Tellurium can be determinated in filtrate by proposed procedure with high accuracy and precision. (author)

Biotechnological Applications of Microbial (Per)chlorate Reduction.

Science.gov (United States)

Wang, Ouwei; Coates, John D

2017-11-24

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

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

KAUST Repository

Balk, Melike

2010-08-03

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

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

KAUST Repository

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

2010-01-01

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

PERCHLORATE PHYTOREMEDIATION USING HARDWOOD TREES AND VASCULAR PLANTS

Science.gov (United States)

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

Interaction of perchlorate and trichloroethene bioreductions in mixed anaerobic culture

Energy Technology Data Exchange (ETDEWEB)

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

2016-11-15

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

(Per)chlorate in Biology on Earth and Beyond.

Science.gov (United States)

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

2016-09-08

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

PHYTOREMEDIATION OF PERCHLORATE BY TOBACCO PLANTS

Science.gov (United States)

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

The Microbiology of Perchlorate in the Environment

Science.gov (United States)

Coates, J. D.

2007-12-01

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

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

Science.gov (United States)

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

2009-05-15

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

Wet Deposition of Perchlorate Over the Continental United States

Science.gov (United States)

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

2007-12-01

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

Perchlorate Removal, Destruction, and Field Monitoring Demonstration

National Research Council Canada - National Science Library

Coppola, Edward N; Davis, Andrea

2006-01-01

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

High Tolerance of Hydrogenothermus marinus to Sodium Perchlorate

Directory of Open Access Journals (Sweden)

Kristina Beblo-Vranesevic

2017-07-01

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

Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate

Science.gov (United States)

Burton, A. S.; Locke, D. R.; Lewis, E. K.

2017-01-01

Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that

Biodegradation of Perchlorate in Laboratory Reactors Under Different Environmental Conditions

Science.gov (United States)

2010-07-01

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

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

International Nuclear Information System (INIS)

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

2005-01-01

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

Modeling In Situ Bioremediation of Perchlorate-Contaminated Groundwater

Science.gov (United States)

2007-03-01

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

Extraction of microplastic from biota: recommended acidic digestion destroys common plastic polymers

DEFF Research Database (Denmark)

Enders, Kristina; Lenz, Robin; Beer, Sabrina

2017-01-01

particles of various polymer types. In the present study we report that a digestion protocol recently recommended by ICES using nitric and perchloric acid has strong detrimental effects on several common plastic polymers, in particular polyamide and polyurethane and to a lesser degree acrylonitrile...

76 FR 7762 - Drinking Water: Regulatory Determination on Perchlorate

Science.gov (United States)

2011-02-11

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

Potentiometric perchlorate determination at nanomolar concentrations in vegetables.

Science.gov (United States)

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

2017-07-15

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

Determination of Perchlorate in Bottled Water from Italy

Directory of Open Access Journals (Sweden)

Patrizia Iannece

2013-06-01

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

Relative source contributions for perchlorate exposures in a lactating human cohort

Energy Technology Data Exchange (ETDEWEB)

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

2013-01-15

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

(2,2'-Bipyridine-4,4'-dicarboxylic acid-κ2N,N')chlorido(2,2':6',2''-terpyridyl-κ3N,N',N'')ruthenium(II) perchlorate ethanol monosolvate monohydrate

DEFF Research Database (Denmark)

Nielsen, Anne; McKenzie, Christine Joy; Bond, Andrew David

2012-01-01

,4 '-dicarboxylic acid ligands, with interplanar separations of 3.65 (1) and 3.72 (1) angstrom. Three O atoms of the perchlorate ion are each disordered equally over two positions. The hydroxy group of the ethanol molecule is also disordered over two sites with refined occupancies of 0.794 (9) and 0.206 (9)....

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

International Nuclear Information System (INIS)

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

2006-01-01

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

MARGINAL IODINE DEFICIENCY EXACERBATES PERCHLORATE THYROID TOXICITY.

Science.gov (United States)

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

Perchlorate in Fertilizers

National Research Council Canada - National Science Library

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

1999-01-01

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

Development of an extraction method for perchlorate in soils.

Science.gov (United States)

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

2006-03-01

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

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

Science.gov (United States)

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

2006-01-01

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

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

Science.gov (United States)

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

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-12-15

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

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

International Nuclear Information System (INIS)

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

2011-01-01

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

In-Situ Bioremediation of Perchlorate in Groundwater and Soil

OpenAIRE

Jin, Liyan

2012-01-01

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

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

Science.gov (United States)

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

2016-02-01

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

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

Science.gov (United States)

2013-05-31

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

Column adsorption of perchlorate by amine-crosslinked biopolymer based resin and its biological, chemical regeneration properties.

Science.gov (United States)

Song, Wen; Xu, Xing; Tan, Xin; Wang, Yan; Ling, Jianya; Gao, Baoyu; Yue, Qinyan

2015-01-22

Column adsorption of perchlorate by amine-crosslinked biopolymer based resin was investigated by considering the bed depth, stream flow rate and influent pH. The empty bed contact time (EBCT) increased with the growth of bed depths, meanwhile rising flow rate at constant bed depth (3.4 cm) decreased the breakthrough time. It was observed that perchlorate adsorption capacity was optimum at neutral condition (pH: 6.0, 170.4 mg/g), and decreased at acidic (pH: 3.0, 96.4 mg/g) or alkalic (pH: 12.0, 72.8 mg/g) influents. The predominant strains of the acclimated sludge for resin biological regeneration were the β-subclass of Proteobacteria. Biological regeneration of the saturated amine-crosslinked biopolymer based resin with mixed bacteria have shown its merit with regeneration and biological perchlorate destruction simultaneously, although its regeneration efficiency was only 61.2-84.1% by contrast to chemical regeneration with efficiency more than 95%. Copyright © 2014 Elsevier Ltd. All rights reserved.

Microbial (per)chlorate reduction in hot subsurface environments

NARCIS (Netherlands)

Liebensteiner, M.

2014-01-01

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

Crystal structure of iron(III perchlorate nonahydrate

Directory of Open Access Journals (Sweden)

Erik Hennings

2014-12-01

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

Morphological changes of porphine films on graphite by perchloric and phosphoric electrolytes. An electrochemical-AFM study

Science.gov (United States)

Yivlialin, Rossella; Penconi, Marta; Bussetti, Gianlorenzo; Biroli, Alessio Orbelli; Finazzi, Marco; Duò, Lamberto; Bossi, Alberto

2018-06-01

Organic molecules have been proposed as promising candidates for electrode protection in acidic electrolytes. The use of tetraphenyl-porphines (H2TPP) as graphite surface-protecting agents in sulphuric acid (H2SO4) is one of the newest. With the aim of unveiling the mechanism of such a protective effect, in this paper we test the stability of a H2TPP thin film immersed in perchloric and phosphoric acid solutions that differently interact with porphyrins. The protective role of H2TPP is tested in the electrochemical potential range where the pristine graphite undergoes an oxidation process that erodes the surface and eventually exfoliate the stratified crystal. The electrochemical analysis is performed in a three-electrode cell, while the surface morphology is monitored ex-situ and in-situ by atomic force microscopy. Electrospray mass analysis is also employed to investigate the presence of H2TPP fragments in the solution. We find that the organic film is not stable in perchloric solution, while it is stable and avoids graphite surface corrosion in phosphoric acid solution. These results provide a rationale for the role played by free-base porphines in graphite protection.

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-09-15

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

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

Directory of Open Access Journals (Sweden)

Ann M Petersen

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

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

Science.gov (United States)

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

2005-04-01

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

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

Science.gov (United States)

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

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

Science.gov (United States)

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

2011-11-09

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

The Effects of Ammonium Perchlorate on Reproduction and Development of Amphibians

Science.gov (United States)

2008-01-01

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

Perchlorate Questions and Answers

Science.gov (United States)

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

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

Science.gov (United States)

Lutter, Randall

2014-10-01

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

PERCHLORATE IDENTIFICATION IN FERTILIZERS AND ACCUMULATION IN LETTUCE SEEDLINGS

Science.gov (United States)

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

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

Science.gov (United States)

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

2017-12-01

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-06-30

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

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

Science.gov (United States)

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

2017-02-01

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

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

International Nuclear Information System (INIS)

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

2012-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-03-15

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

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

Science.gov (United States)

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.

Evaluation of Acid Digestion Procedures to Estimate Mineral Contents in Materials from Animal Trials

Directory of Open Access Journals (Sweden)

M. N. N. Palma

2015-11-01

Full Text Available Rigorously standardized laboratory protocols are essential for meaningful comparison of data from multiple sites. Considering that interactions of minerals with organic matrices may vary depending on the material nature, there could be peculiar demands for each material with respect to digestion procedure. Acid digestion procedures were evaluated using different nitric to perchloric acid ratios and one- or two-step digestion to estimate the concentration of calcium, phosphorus, magnesium, and zinc in samples of carcass, bone, excreta, concentrate, forage, and feces. Six procedures were evaluated: ratio of nitric to perchloric acid at 2:1, 3:1, and 4:1 v/v in a one- or two-step digestion. There were no direct or interaction effects (p>0.01 of nitric to perchloric acid ratio or number of digestion steps on magnesium and zinc contents. Calcium and phosphorus contents presented a significant (p0.01 calcium or phosphorus contents in carcass, excreta, concentrate, forage, and feces. Number of digestion steps did not affect mineral content (p>0.01. Estimated concentration of calcium, phosphorus, magnesium, and zinc in carcass, excreta, concentrated, forage, and feces samples can be performed using digestion solution of nitric to perchloric acid 4:1 v/v in a one-step digestion. However, samples of bones demand a stronger digestion solution to analyze the mineral contents, which is represented by an increased proportion of perchloric acid, being recommended a digestion solution of nitric to perchloric acid 2:1 v/v in a one-step digestion.

Nitrate and Perchlorate removal from groundwater by ion exchange; TOPICAL

International Nuclear Information System (INIS)

Burge, S; Halden, R

1999-01-01

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

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

International Nuclear Information System (INIS)

Li Wenxian; Zheng Yushan; Sun Xiaojun; Chai Wenjuan; Ren Tie; Shi Xiaoyan

2010-01-01

Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C 6 H 5 COCH 2 SOCH 2 COC 6 H 5 ), salicylic acid as second ligand (L ' =C 6 H 4 OHCOO - ). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL 5 L'](ClO 4 ) 2 .nH 2 O (RE=Tb, Dy; n=6, 8 ). Based on IR, 1 HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L'), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.

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

International Nuclear Information System (INIS)

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

2014-01-01

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

RAMAN SPECTRAL ANALYSIS OF PERCHLORATE CONTAMINATION IN COMMONLY-USED FERTILIZERS

Science.gov (United States)

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

Perchlorate: environmental occurrence, interactions and treatment

National Research Council Canada - National Science Library

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

2006-01-01

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

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

Science.gov (United States)

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

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

Science.gov (United States)

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

2016-06-01

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

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

Science.gov (United States)

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

2004-01-01

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

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

Science.gov (United States)

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

2003-01-01

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

Validation of a Novel Bioassay for Low-level Perchlorate Determination

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-08-30

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

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

Science.gov (United States)

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

2007-09-01

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

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

Science.gov (United States)

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

2016-12-01

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

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

Science.gov (United States)

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

2015-01-01

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

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

Science.gov (United States)

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

2017-05-24

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

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

Science.gov (United States)

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

2012-12-01

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

Synthesis and stability of strongly acidic benzamide derivatives

DEFF Research Database (Denmark)

Diness, Frederik; Bjerrum, Niels J.; Begtrup, Mikael

2018-01-01

Reactivity studies of strong organic acids based on the replacement of one or both of the oxygens in benzoic acids with the trifluoromethanesulfonamide group are reported. Novel derivatives of these types of acids were synthesized in good yields. The generated N-triflylbenzamides were further...... functionalized through cross-coupling and nucleophilic aromatic substitution reactions. All compounds were stable in dilute aqueous solutions. Studies of stability under acidic and basic conditions are also reported....

Polarography of uranium(VI)-salicylic acid system

International Nuclear Information System (INIS)

Salah, El-Maraghy B.

1980-01-01

Uranium(VI)-salicylic acid system has been studied polarographically in perchloric acid medium. Varying concentrations of HClO 4 and salicylic acid have been used. The nature of the polarographic waves is irreversible. (author)

Polarography of uranium(VI)-salicylic acid system

Energy Technology Data Exchange (ETDEWEB)

Salah, E M.B. [Ain Shams Univ., Cairo (Egypt). Faculty of Education

1980-08-01

Uranium(VI)-salicylic acid system has been studied polarographically in perchloric acid medium. Varying concentrations of HClO/sub 4/ and salicylic acid have been used. The nature of the polarographic waves is irreversible.

Perchlorate and Volatiles in the Brine of Lake Vida (antarctica): Implication for the Analysis of Mars Sediments

Science.gov (United States)

Kenig, F. P. H.; Chou, L.; McKay, C.; Jackson, W. A.; Doran, P. T.; Murray, A. E.; Fritsen, C. H.

2015-12-01

A cold (-13.4 °C), saline (188 psu) evaporative brine is encapsulated in the thick (> 27 m) ice of Lake Vida (McMurdo Dry Valleys, Antarctica). The Lake Vida brine (LVBr), which contains abundant dissolved organic carbon (48.2 mmol/L), support an active but slow microbial community. LVBr contains oxychlorines with 50 μg/L of perchlorate and 11 μg/L of chlorate. The McMurdo Dry Valleys have often been considered as a good Mars analog. The oxychlorine-rich brine of Lake Vida constitutes a potential equivalent to perchlorate-rich preserved saline liquid water on Mars. We report here on the artifacts created by oxychlorines upon analysis of volatiles and volatile organic compounds (VOCs) of LVBr by direct immersion (DI) and head space (HS) solid phase micro extraction (SPME) gas chromatography-mass spectrometry (GCMS). We compare analytical blanks to a standard containing 40 μg/L of perchlorate and to actual LVBr sample runs. All blanks, perchlorate blanks and samples were analyzed using two types of SPME fibers, CarboxenTM/polydimethylsiloxane (PDMS) and divinylbenzene (DVB)/ PDMS. The similarities and differences between our results and those obtained by the Sample Analysis at Mars instruments of the rover Curiosity are discussed. The volatiles evolved from LVBr upon analysis with DI- and HS-SPME GCMS are dominated by CO2, dichloromethane, HCl, and volatile organic sulfur compounds (VOSCs, such as DMS, DMDS). The volatiles also include oxygenated compounds such as acids and ketones, aromatic compounds, hydrocarbons, chlorinated compounds (dominated by dichloromethane). Apart from the VOSCs, short chain hydrocarbons and some functionalized compounds derived from the brine itself, all compounds observed are artifacts formed upon oxychlorine breakdown in the injector of the GCMS. The distribution of aromatic compounds seems to be directly dependant on the type of SPME fiber used. The perchlorate blanks show a clear pattern of carbon limitation, likely affecting the

Photochemical decomposition of perfluorooctanoic acid mediated by iron in strongly acidic conditions

Energy Technology Data Exchange (ETDEWEB)

Ohno, Masaki, E-mail: mohno@hiroshima-u.ac.jp [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Ito, Masataka; Ohkura, Ryouichi [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Mino A, Esteban R. [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Kose, Tomohiro [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Okuda, Tetsuji [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Nakai, Satoshi [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527 (Japan); Kawata, Kuniaki [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Nishijima, Wataru [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan)

2014-03-01

Highlights: • Perfluorooctanoic acid (PFOA) was decomposed based on ferric ion performance. • Complete decomposition of PFOA was confirmed in strongly acidic conditions. • Fe{sup 2+} changed to Fe{sup 3+} to restore chemical equilibrium in this condition. • Fe{sup 3+} was only produced from Fe{sup 2+} by hydroxyl radical in weakly acidic conditions. • The Fe{sup 3+} regeneration mechanisms resulted in the performance of Fe{sup 3+} for PFOA. - Abstract: The performance of a ferric ion mediated photochemical process for perfluorooctanoic acid (PFOA) decomposition in strongly acidic conditions of pH 2.0 was evaluated in comparison with those in weakly acidic conditions, pH 3.7 or pH 5.0, based on iron species composition and ferric ion regeneration. Complete decomposition of PFOA under UV irradiation was confirmed at pH 2.0, whereas perfluoroheptanoic acid (PFHpA) and other intermediates were accumulated in weakly acidic conditions. Iron states at each pH were evaluated using a chemical equilibrium model, Visual MINTEQ. The main iron species at pH 2.0 is Fe{sup 3+} ion. Although Fe{sup 3+} ion is consumed and is transformed to Fe{sup 2+} ion by photochemical decomposition of PFOA and its intermediates, the produced Fe{sup 2+} ion will change to Fe{sup 3+} ion to restore chemical equilibrium. Continuous decomposition will occur at pH 2.0. However, half of the iron cannot be dissolved at pH 3.7. The main species of dissolved iron is Fe(OH){sup 2+}. At pH 3.7 or higher pH, Fe{sup 3+} ion will only be produced from the oxidation of Fe{sup 2+} ion by hydroxyl radical produced by Fe(OH){sup 2+} under UV irradiation. These different mechanisms of Fe{sup 3+} regeneration that prevail in strongly and weakly acidic conditions will engender different performances of the ferric ion.

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

Science.gov (United States)

2008-04-01

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

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

Science.gov (United States)

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

2015-06-01

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

The occurrence of perchlorate during drinking water electrolysis using BDD anodes

International Nuclear Information System (INIS)

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

2009-01-01

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

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

Science.gov (United States)

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

2011-08-01

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

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

Directory of Open Access Journals (Sweden)

Nirmala Bardiya

2016-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-03-21

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

Novel Electrochemical Process for Treatment of Perchlorate in Waste Water

Science.gov (United States)

2011-03-06

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

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

Science.gov (United States)

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

2011-01-01

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

Acid-base strengths in pyridine

NARCIS (Netherlands)

Bos, M.; Dahmen, E.A.M.F.

1971-01-01

Although pyridine is a solvent with a low dielectric constant, spectrophotometric determinations show simple dissociation without ion pairs as intermediates for some sulfonphthaleins and polynitrophenols in pyridine. The salts of a number of amines and hydrochloric acid, perchloric acid and picric

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

Directory of Open Access Journals (Sweden)

Irina A. Odarich

2016-02-01

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

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

Science.gov (United States)

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

2013-03-01

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

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

Science.gov (United States)

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

2007-01-01

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

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

2017-08-01

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

Assembled cross-species perchlorate dose-response data

Data.gov (United States)

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

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

Science.gov (United States)

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

2016-02-01

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

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

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

Lieberman, M.L.; Fleming, W.

1986-01-01

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

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

African Journals Online (AJOL)

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

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

Directory of Open Access Journals (Sweden)

O. Dahan

2017-08-01

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

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

Directory of Open Access Journals (Sweden)

Valentina A. Kalibabchuk

2010-12-01

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

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

Science.gov (United States)

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

2000-01-01

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

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

Science.gov (United States)

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

2010-05-01

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

Perchlorates on Mars enhance the bacteriocidal effects of UV light.

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-02-05

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

Dielectric loss property of strong acids doped polyaniline (PANi)

Science.gov (United States)

Amalia, Rianti; Hafizah, Mas Ayu Elita; Andreas, Manaf, Azwar

2018-04-01

In this study, strong acid doped polyaniline (PANi) has been successfully fabricated through the chemical oxidative polymerization process with various polymerization times. Nonconducting PANi resulting from the polymerization process at various polymerization times were then doped by a strong acid HClO4 to generate dielectric properties. Ammonium Persulfate (APS) as an initiator was used during Polymerization process to develop dark green precipitates which then called Emeraldine Base Polyaniline (PANi-EB). The PANi-EB was successively doped by strong acid HClO4 with dopant and PANi ratio 10:1 to enhance the electrical conductivity. The conductivity of doped PANi was evaluated by Four Point Probe. Results of evaluation showed that the conductivity values of HClO4 doped PANi were in the range 337-363 mS/cm. The dielectric properties of doped PANi were evaluated by Vector Network Analyzer (VNA) which suggested that an increase in the permittivity value in the conducting PANi. It is concluded that PANi could be a potential candidate for electromagnetic waves absorbing materials.

How strong are strong poly(sulfonic acids)? An example of the poly(2-acrylamido-2-methyl-1-propanesulfonic acid)

Czech Academy of Sciences Publication Activity Database

Gospodinova, Natalia; Tomšík, Elena; Omelchenko, Olga

2016-01-01

Roč. 74, January (2016), s. 130-135 ISSN 0014-3057 R&D Projects: GA ČR(CZ) GA15-14791S Institutional support: RVO:61389013 Keywords : polyelectrolytes * strong poly(acids) * proton conductors Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.531, year: 2016

Strong activation of bile acid-sensitive ion channel (BASIC) by ursodeoxycholic acid

Science.gov (United States)

Wiemuth, Dominik; Sahin, Hacer; Lefèvre, Cathérine M.T.; Wasmuth, Hermann E.; Gründer, Stefan

2013-01-01

Bile acid-sensitive ion channel (BASIC) is a member of the DEG/ENaC gene family of unknown function. Rat BASIC (rBASIC) is inactive at rest. We have recently shown that cholangiocytes, the epithelial cells lining the bile ducts, are the main site of BASIC expression in the liver and identified bile acids, in particular hyo- and chenodeoxycholic acid, as agonists of rBASIC. Moreover, it seems that extracellular divalent cations stabilize the resting state of rBASIC, because removal of extracellular divalent cations opens the channel. In this addendum, we demonstrate that removal of extracellular divalent cations potentiates the activation of rBASIC by bile acids, suggesting an allosteric mechanism. Furthermore, we show that rBASIC is strongly activated by the anticholestatic bile acid ursodeoxycholic acid (UDCA), suggesting that BASIC might mediate part of the therapeutic effects of UDCA. PMID:23064163

Modeling In Situ Bioremediation of Perchlorate-Contaminated Groundwater

National Research Council Canada - National Science Library

Secody, Roland E

2007-01-01

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

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

Science.gov (United States)

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

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

Science.gov (United States)

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

Potentiometric titrations in anhydrous acetic acid

International Nuclear Information System (INIS)

Le Port, L.

1966-03-01

The method used for studying anhydrous acetic acid is potentiometry with a glass electrode. We have in this way studied the titration of common inorganic acids (HClO 4 - HBr - H 2 SO 4 - HCl - HNO 3 - H 3 PO 4 ) and of some metallic salts. Furthermore we have shown that complex acids are formed between HCl and some metallic chlorides. An analysis of the titration curves for the inorganic acids against pyridinium chloride has made it possible to calculate a certain number of values for the dissociation pK of these acids and of the corresponding pyridinium salts. The titration of metallic perchlorates constitutes a method of studying the stability of acetates; we have thus been able to draw up a classification for some of these acetates. The metallic chlorides studied fall into two groups according to their behaviour in weak or strong acids. The differences have been explained on the basis of the role played by solvolysis. In the third part we have studied the acidic properties of mixtures of HCl with certain metallic chlorides. This work has demonstrated the existence, in certain cases, of acid complexes of the type (HCl) m MCl n . (author) [fr

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

Directory of Open Access Journals (Sweden)

Marisa R. Myers

2017-12-01

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

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

NARCIS (Netherlands)

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

2014-01-01

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

Cyclic voltammetry and reduction mechanistic studies of styrylpyrylium perchlorates

Directory of Open Access Journals (Sweden)

Y. L. Bonzi-Coulibaly

2013-04-01

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

Kinetics and mechanism of permanganate oxidation of iota- and lambda-carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions.

Science.gov (United States)

Hassan, Refat M; Fawzy, Ahmed; Ahmed, Gamal A; Zaafarany, Ishaq A; Asghar, Basim H; Takagi, Hideo D; Ikeda, Yasuhisa

2011-10-18

The kinetics of oxidation of iota- and lambda-carrageenan as sulfated carbohydrates by permanganate ion in aqueous perchlorate solutions at a constant ionic strength of 2.0 mol dm(-3) have been investigated spectrophotometrically. The pseudo-first-order plots were found to be of inverted S-shape throughout the entire courses of reactions. The initial rates were found to be relatively slow in the early stages, followed by an increase in the oxidation rates over longer time periods. The experimental observations showed first-order dependences in permanganate and fractional first-order kinetics with respect to both carrageenans concentration for both the induction and autoacceleration periods. The results obtained at various hydrogen ion concentrations showed that the oxidation processes in these redox systems are acid-catalyzed throughout the two stages of oxidation reactions. The added salts lead to the prediction that Mn(III) is the reactive species throughout the autoacceleration periods. Kinetic evidence for the formation of 1:1 intermediate complexes was revealed. The kinetic parameters have been evaluated and tentative reaction mechanisms in good agreement with the kinetic results are discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

International Nuclear Information System (INIS)

Jayasankar, H.; Indrasenan, P.

1988-01-01

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

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

Science.gov (United States)

Mukhi, S.; Patino, R.

2007-01-01

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

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

Directory of Open Access Journals (Sweden)

Martin G Liebensteiner

2014-09-01

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

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

Science.gov (United States)

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

2016-02-01

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

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

Science.gov (United States)

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

Fusibility diagram of strontium perchlorate-water system

International Nuclear Information System (INIS)

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

1986-01-01

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

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

Science.gov (United States)

2012-01-01

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

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

Science.gov (United States)

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

2018-06-26

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

Addition compounds of perchlorates from yttrium and lanthanides elements with the N,N,N',N'tetramethyl amide of phthalic acid

International Nuclear Information System (INIS)

Silva, C.P.G. da.

1974-01-01

The reaction between lanthanide perchlorates and yttrium with tetra methyl phthalamide (TMPA) was studied, and compounds of the general formula Ln (C 10 4 ) 3 . TMPA have been isolated. The compounds were characterized by analysis of their components, infra-red spectra, molar conductances in nitromethane and nitrobenzene, X ray powder patterns and thermal analysis. (author)

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

Science.gov (United States)

Fram, Miranda S.; Belitz, Kenneth

2011-01-01

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

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

Science.gov (United States)

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

2006-01-01

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

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

International Nuclear Information System (INIS)

Witherspoon, L.R.; Shuler, S.E.; Alyea, K.; Husserl, F.E.; Alton Ochsner Medical Foundation, New Orleans, LO)

1983-01-01

Heat inactivation has been proposed as an alternative to perchloric acid (PCA) precipitation for the extraction of carcinoembryonic antigen (CEA) from human plasma. A commercial RIA kit using heat inactivation was examined and results compared with those obtained with PCA precipitation. Adequate sensitivity (1.5 μg CEA/I plasma), satisfactory analytical recovery of CEA added to plasma, and dilutional linearity of samples found to have elevated CEA concentrations, were demonstrated for the heat-inactivation assay. Between-assay precision was better with the heat inactivation than with the PCA assay. Although the absolute concentration of CEA estimated after heat inactivation was consistently lower than that estimated after PCA extraction of plasma specimens, there was excellent correlation between results obtained with the two methods in colon cancer patients free of disease, colon cancer patients with residual or recurrent disease, patients with benign gastrointestinal disease, and in patients with chronic renal failure. The heat-inactivation assay is an excellent alternative to the PCA assay

Reactivity of nanoaggregations of platinum on supports of different nature in reactions of catalytic decomposition of hydrazine in acid media

International Nuclear Information System (INIS)

Anan'ev, A.V.; Boltoeva, M.Yu.; Grigor'ev, M.S.; Shilov, V.P.; Sharygin, L.M.

2006-01-01

Platinized catalysts on the basis of supports of different chemical nature are tested in reactions of catalytic hydrazine decomposition in perchloric and nitric acid solutions. In perchloric acid catalytic activity of catalysts on the basis of ceramic materials of Termoksid brand is higher of activity of catalysts on the basis of amorphous silica gel. In nitric acid solutions opposite dependence is observed. Tendency of ceramic supports to peptization in acid solutions is pointed out. Results obtained are interpreted using conceptions of energetic heterogeneity of surface atoms and hydrazine catalytic decomposition mechanisms in different media [ru

Treatment of amiodarone-induced hypothyroidism with potassium perchlorate

NARCIS (Netherlands)

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

1993-01-01

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

Study on mechanism for oxidation of N,N-dimethylhydroxylamine by nitrous acid

International Nuclear Information System (INIS)

Li Gaoliang; He Hui

2011-01-01

The oxidation of N,N-dimethylhydroxylamine (DMHAN) by nitrous acid is investigated in perchloric acid and nitric acid medium, respectively. The effects of H + , DMHAN, ionic strength and temperature on the reaction are studied. The rate equation in perchloric acid medium has been determined to be -d[HNO 2 ]/dt = k[DMHAN][HNO 2 ], where k = 12.8 ± 1.0 (mol/L) -1 min -1 when the temperature is 18.5 deg C and the ionic strength is 0.73 mol/L with an activation energy about 41.5 kJ mol -1 . The reaction becomes complicated when it is performed in nitric acid medium. When the molarity of HNO 3 is higher than 1.0 mol/L, nitrous acid will be produced via the reaction between nitric acid and DMHAN. The reaction products are analyzed and the reaction mechanism is discussed in this paper. (author)

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

International Nuclear Information System (INIS)

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

2015-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-11-15

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

Treatment of infectious skin defects or ulcers with electrolyzed strong acid aqueous solution.

Science.gov (United States)

Sekiya, S; Ohmori, K; Harii, K

1997-01-01

A chronic ulcer with an infection such as methicillin-resistant Staphylococcus aureus is hard to heal. Plastic and reconstructive surgeons often encounter such chronic ulcers that are resistant to surgical or various conservative treatments. We applied conservative treatment using an electrolyzed strong acid aqueous solution and obtained satisfactory results. The lesion was washed with the solution or soaked in a bowl of the solution for approximately 20 min twice a day. Fresh electrolyzed strong acid aqueous solution is unstable and should be stored in a cool, dark site in a sealed bottle. It should be used within a week after it has been produced. Here we report on 15 cases of infectious ulcers that were treated by electrolyzed strong acid aqueous solution. Of these cases, 7 patients were healed, 3 were granulated, and in 5, infection subsided. In most cases the lesion became less reddish and less edematous. Discharge or foul odor from the lesion was decreased. Electrolyzed strong acid aqueous solution was especially effective for treating a chronic refractory ulcer combined with diabetes melitus or peripheral circulatory insufficiency. This clinically applied therapy of electrolyzed strong acid aqueous solution was found to be effective so that this new therapeutic technique for ulcer treatment can now be conveniently utilized.

Nanotoxic Profiling of Novel Iron Oxide Nanoparticles Functionalized with Perchloric Acid and SiPEG as a Radiographic Contrast Medium

Directory of Open Access Journals (Sweden)

Muhamad Idham Mohamed

2015-01-01

Full Text Available Emerging syntheses and findings of new metallic nanoparticles (MNPs have become an important aspect in various fields including diagnostic imaging. To date, iodine has been utilized as a radiographic contrast medium. However, the raise concern of iodine threats on iodine-intolerance patient has led to search of new contrast media with lower toxic level. In this animal modeling study, 14 nm iron oxide nanoparticles (IONPs with silane-polyethylene glycol (SiPEG and perchloric acid have been assessed for toxicity level as compared to conventional iodine. The nanotoxicity of IONPs was evaluated in liver biochemistry, reactive oxygen species production (ROS, lipid peroxidation mechanism, and ultrastructural evaluation using transmission electron microscope (TEM. The hematological analysis and liver function test (LFT revealed that most of the liver enzymes were significantly higher in iodine-administered group as compared to those in normal and IONPs groups P<0.05. ROS production assay and lipid peroxidation indicator, malondialdehyde (MDA, also showed significant reductions in comparison with iodine group P<0.05. TEM evaluation yielded the aberration of nucleus structure of iodine-administered group as compared to those in control and IONPs groups. This study has demonstrated the less toxic properties of IONPs and it may postulate that IONPs are safe to be applied as radiographic contrast medium.

Background Perchlorate Source Identification Technical Guidance

Science.gov (United States)

2013-12-01

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

Stability and Concentration Verification of Ammonium Perchlorate Dosing Solutions

National Research Council Canada - National Science Library

Tsui, David

1998-01-01

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

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

Directory of Open Access Journals (Sweden)

Mohammad Mehdi Amin

2015-01-01

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

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

Science.gov (United States)

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

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

Energy Technology Data Exchange (ETDEWEB)

vonKiparski, G; Hillegonds, D

2011-04-04

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

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

Science.gov (United States)

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

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

International Nuclear Information System (INIS)

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

2013-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-05-15

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

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

Science.gov (United States)

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

2015-04-21

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

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

Science.gov (United States)

2015-03-01

matches, air bags , chlorine bleach, safety flares, perchloric acid, and chlorate herbicides (Trumpholt et al., 2005; Aziz et al., 2006, 2008). Based...L, assuming no losses to biodegradation or other removal processes. Additional information on Atacama NO3- fertilizers as a source of ClO4- can be...in each well), the IX columns were removed from the each well, sealed in Zip-Loc type bags , placed at 4oC (or on ice), and shipped to the UIC EIGL

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-04-24

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

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

Directory of Open Access Journals (Sweden)

Mohammad Reza Reisi

2011-09-01

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

Monitored Natural Attenuation of Perchlorate in Groundwater

Science.gov (United States)

2010-09-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Behrens, R.; Minier, L.

1998-03-24

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

Branched polymeric media: Perchlorate-selective resins from hyperbranched polyethyleneimine

KAUST Repository

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

2012-01-01

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

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

International Nuclear Information System (INIS)

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

2000-01-01

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

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

Science.gov (United States)

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.

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

Directory of Open Access Journals (Sweden)

Alexander N. Boyko

2010-09-01

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

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

Science.gov (United States)

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

2014-01-01

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

Titania nanotube powders obtained by rapid breakdown anodization in perchloric acid electrolytes

International Nuclear Information System (INIS)

Ali, Saima; Hannula, Simo-Pekka

2017-01-01

Titania nanotube (TNT) powders are prepared by rapid break down anodization (RBA) in a 0.1 M perchloric acid (HClO 4 ) solution (Process 1), and ethylene glycol (EG) mixture with HClO 4 and water (Process 2). A study of the as-prepared and calcined TNT powders obtained by both processes is implemented to evaluate and compare the morphology, crystal structure, specific surface area, and the composition of the nanotubes. Longer TNTs are formed in Process 1, while comparatively larger pore diameter and wall thickness are obtained for the nanotubes prepared by Process 2. The TNTs obtained by Process 1 are converted to nanorods at 350 °C, while nanotubes obtained by Process 2 preserve tubular morphology till 350 °C. In addition, the TNTs prepared by an aqueous electrolyte have a crystalline structure, whereas the TNTs obtained by Process 2 are amorphous. Samples calcined till 450 °C have XRD peaks from the anatase phase, while the rutile phase appears at 550 °C for the TNTs prepared by both processes. The Raman spectra also show clear anatase peaks for all samples except the as-prepared sample obtained by Process 2, thus supporting the XRD findings. FTIR spectra reveal the presence of O-H groups in the structure for the TNTs obtained by both processes. However, the presence is less prominent for annealed samples. Additionally, TNTs obtained by Process 2 have a carbonaceous impurity present in the structure attributed to the electrolyte used in that process. While a negligible weight loss is typical for TNTs prepared from aqueous electrolytes, a weight loss of 38.6% in the temperature range of 25–600 °C is found for TNTs prepared in EG electrolyte (Process 2). A large specific surface area of 179.2 m 2 g −1 is obtained for TNTs prepared by Process 1, whereas Process 2 produces nanotubes with a lower specific surface area. The difference appears to correspond to the dimensions of the nanotubes obtained by the two processes. - Graphical abstract: Titania nanotube

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

International Nuclear Information System (INIS)

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

2009-01-01

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

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

Science.gov (United States)

2016-12-31

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

CRYSTALLIZATION KINETICS OF AMMONIUM PERCHLORATE IN AN AGITATED VESSEL

Directory of Open Access Journals (Sweden)

Nahidh Kaseer

2013-05-01

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

Biomineralization of radioactive sulfide minerals in strong acidic Tamagawa hot springs

International Nuclear Information System (INIS)

Tazaki, Kazue; Watanabe, Hiroaki

2004-01-01

Bioaccumulation of radioactive sulfide minerals by bacteria in strong acidic hot spring water was found at Tamagawa Hot Springs, Akita prefecture in Japan. The hot spring water produces Hokutolite of radioactive minerals high radium and radon. The β-ray measurements of sediments and biofilms indicate 1850-2420 and 5700 cpm, respectively, which are 50-100 times higher than that of the water and the air (50-90 cpm). The characteristics of hot spring water show pH (1.2), Eh (140 mV), EC (29 mS/cm), DO (0.8 mg/l), and water temperature (99.5degC), indicating extremely strong acidic and reducing conditions. The hot spring water contains mainly HCl associated with high concentrations of Ca 2+ , Al 3+ , Fe 2+ , HSO 4 - and SO 4 2- . SEM-EDX and TEM demonstrate some insight into how microorganisms affect the chemistry and microbiological characteristics of the strong acidic surroundings with high S, As, Ba, and Ca contents in biofilms. Especially SEM-EDX, ED-XRF, and STEM-EDX elemental content maps illustrate the distribution of sulfur-bearing compounds of barite (BaSO 4 ), gypsum (CaSO 4 ·2H 2 O), elemental sulfur (S) and orpiment(As 2 S 3 ) in the reddish orange biofilms. The presence of a hydrogen sulfide-rich (H 2 S) thermal spring and gypsum deposits suggest the volatilization of H 2 S from the spring water, oxidation of the H 2 S gas to sulfuric acid, and reaction of the sulfuric acid. TEM micrographs of bacteria in the biofilms reveal in detail the intimate connections between biological and mineralogical processes that the cells are entirely accumulated with spherical grains, 100∼200 nm in diameter. The relationship among sulfide minerals, such as barite, gypsum, sulfur, orpiment, and Hakutolite, associated with bacteria implies that heavy metals have been transported from strong acidic hot spring water to sediments through bacteria metabolism. It is possible that the capability of radioactive sulfide biofilms for heavy metal immobilization can be used to

Degradation of Adenine on the Martian Surface in the Presence of Perchlorates and Ionizing Radiation: A Reflectron Time-of-flight Mass Spectrometric Study

Energy Technology Data Exchange (ETDEWEB)

Góbi, Sándor; Bergantini, Alexandre; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu [Department of Chemistry, University of Hawaii at Mānoa, Honolulu, HI 96822 (United States)

2017-04-01

The aim of the present work is to unravel the radiolytic decomposition of adenine (C{sub 5}H{sub 5}N{sub 5}) under conditions relevant to the Martian surface. Being the fundamental building block of (deoxy)ribonucleic acids, the possibility of survival of this biomolecule on the Martian surface is of primary importance to the astrobiology community. Here, neat adenine and adenine–magnesium perchlorate mixtures were prepared and irradiated with energetic electrons that simulate the secondary electrons originating from the interaction of the galactic cosmic rays with the Martian surface. Perchlorates were added to the samples since they are abundant—and therefore relevant oxidizers on the surface of Mars—and they have been previously shown to facilitate the radiolysis of organics such as glycine. The degradation of the samples were monitored in situ via Fourier transformation infrared spectroscopy and the electron ionization quadruple mass spectrometric method; temperature-programmed desorption profiles were then collected by means of the state-of-the-art single photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), allowing for the detection of the species subliming from the sample. The results showed that perchlorates do increase the destruction rate of adenine by opening alternative reaction channels, including the concurrent radiolysis/oxidation of the sample. This new pathway provides a plethora of different radiolysis products that were identified for the first time. These are carbon dioxide (CO{sub 2}), isocyanic acid (HNCO), isocyanate (OCN{sup −}), carbon monoxide (CO), and nitrogen monoxide (NO); an oxidation product containing carbonyl groups (R{sub 1}R{sub 2}–C=O) with a constrained five-membered cyclic structure could also be observed. Cyanamide (H{sub 2}N–C≡N) was detected in both irradiated samples as well.

Degradation of Adenine on the Martian Surface in the Presence of Perchlorates and Ionizing Radiation: A Reflectron Time-of-flight Mass Spectrometric Study

International Nuclear Information System (INIS)

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

2017-01-01

The aim of the present work is to unravel the radiolytic decomposition of adenine (C 5 H 5 N 5 ) under conditions relevant to the Martian surface. Being the fundamental building block of (deoxy)ribonucleic acids, the possibility of survival of this biomolecule on the Martian surface is of primary importance to the astrobiology community. Here, neat adenine and adenine–magnesium perchlorate mixtures were prepared and irradiated with energetic electrons that simulate the secondary electrons originating from the interaction of the galactic cosmic rays with the Martian surface. Perchlorates were added to the samples since they are abundant—and therefore relevant oxidizers on the surface of Mars—and they have been previously shown to facilitate the radiolysis of organics such as glycine. The degradation of the samples were monitored in situ via Fourier transformation infrared spectroscopy and the electron ionization quadruple mass spectrometric method; temperature-programmed desorption profiles were then collected by means of the state-of-the-art single photon photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS), allowing for the detection of the species subliming from the sample. The results showed that perchlorates do increase the destruction rate of adenine by opening alternative reaction channels, including the concurrent radiolysis/oxidation of the sample. This new pathway provides a plethora of different radiolysis products that were identified for the first time. These are carbon dioxide (CO 2 ), isocyanic acid (HNCO), isocyanate (OCN − ), carbon monoxide (CO), and nitrogen monoxide (NO); an oxidation product containing carbonyl groups (R 1 R 2 –C=O) with a constrained five-membered cyclic structure could also be observed. Cyanamide (H 2 N–C≡N) was detected in both irradiated samples as well.

Perchlorate Contamination of Drinking Water: Regulatory Issues and Legislative Actions

National Research Council Canada - National Science Library

Tiemann, Mary

2007-01-01

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

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

Science.gov (United States)

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

2012-01-01

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

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

International Nuclear Information System (INIS)

Sorensen, Mary A.; Jensen, Peter D.; Walton, William E.; Trumble, John T.

2006-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-12-15

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

Perchlorate Contamination of Drinking Water: Regulatory Issues and Legislative Actions

National Research Council Canada - National Science Library

Tiemann, Mary

2008-01-01

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

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

Science.gov (United States)

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

2014-11-01

Three planar miniaturized perchlorate membrane sensors (3×5 mm(2)) are prepared using a flexible Kaptan substrate coated with nitron-perchlorate (NT-ClO4) [sensor 1], methylene blue-perchlorate (MB-ClO4) [sensor II] and indium-porphyrin (In-Por) [sensor III] as electroactive materials in PVC membranes plasticized with 2-NPPE. Sensors I, II and III display near-Nernstian response for 1.0×10(-5)-1.0×10(-2), 3.1×10(-5)-1.0×10(-2) and 3.1×10(-6)-1.0×10(-2) mol L(-1) ClO4(-) with lower detection limits of 6.1×10(-6), 6.9×10(-6) and 1.2×10(-6) mol L(-1), and anionic calibration slopes of 50.9±0.4, 48.4±0.4 and 57.7±0.3 mV decade(-1), respectively. Methods for determining perchlorate using these sensors offer many attractive advantages including simplicity, flexibility, cost effectiveness, wide linear dynamic response range (0.1-1000 ppm), low detection limit (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.

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

Directory of Open Access Journals (Sweden)

Jing Xu

2012-06-01

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

Establishment of the conditions for the determination of the concentration of the uranyl ion in perchloric media by Fluorescence; Establecimiento de las condiciones para la determinacion de la concentracion del ion uranilo en medio perclorico por Fluorescencia

Energy Technology Data Exchange (ETDEWEB)

Contreras R, A.; Ordonez R, E.; Fernandez V, S.M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)]. e-mail: contraida@yahoo.com.mx

2004-07-01

The influence of the p H is reported in the spectra of luminescence of the ion uranyl in sodium perchlorate 2M. The best spectra were observed to ph <3 that to neutral and basic p Hs this is explained by the present species. They were carried out four calibration curves for the uranyl in perchloric acid media, taking into account the area under the curve, the maximum height of two characteristic peaks of this ion, in those that one observes a better correlation with the maximum height of the peak located to 486.7 nm. (Author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2007-08-15

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

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

Science.gov (United States)

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

2017-10-01

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

Evaluation of the risk of perchlorate exposure in a population of late-gestation pregnant women in the United States: Application of probabilistic biologically-based dose response modeling

International Nuclear Information System (INIS)

Lumen, A; George, N I

2017-01-01

The risk of ubiquitous perchlorate exposure and the dose-response on thyroid hormone levels in pregnant women in the United States (U.S.) have yet to be characterized. In the current work, we integrated a previously developed perchlorate submodel into a recently developed population-based pregnancy model to predict reductions in maternal serum free thyroxine (fT4) levels for late-gestation pregnant women in the U.S. Our findings indicated no significant difference in geometric mean estimates of fT4 when perchlorate exposure from food only was compared to no perchlorate exposure. The reduction in maternal fT4 levels reached statistical significance when an added contribution from drinking water (i.e., 15 μg/L, 20 μg/L, or 24.5 μg/L) was assumed in addition to the 90th percentile of food intake for pregnant women (0.198 μg/kg/day). We determined that a daily intake of 0.45 to 0.50 μg/kg/day of perchlorate was necessary to produce results that were significantly different than those obtained from no perchlorate exposure. Adjusting for this food intake dose, the relative source contribution of perchlorate from drinking water (or other non-dietary sources) was estimated to range from 0.25–0.3 μg/kg/day. Assuming a drinking water intake rate of 0.033 L/kg/day, the drinking water concentration allowance for perchlorate equates to 7.6–9.2 μg/L. In summary, we have demonstrated the utility of a probabilistic biologically-based dose-response model for perchlorate risk assessment in a sensitive life-stage at a population level; however, there is a need for continued monitoring in regions of the U.S. where perchlorate exposure may be higher. - Highlights: • Probabilistic risk assessment for perchlorate in U.S. pregnant women was conducted. • No significant change in maternal fT4 predicted due to perchlorate from food alone. • Drinking water concentration allowance for perchlorate estimated as 7.6–9.2 μg/L

Evaluation of the risk of perchlorate exposure in a population of late-gestation pregnant women in the United States: Application of probabilistic biologically-based dose response modeling

Energy Technology Data Exchange (ETDEWEB)

Lumen, A, E-mail: Annie.Lumen@fda.hhs.gov [Division of Biochemical Toxicology, National Center for Toxicological Research, U.S. Food and Drug Administration, 3900 NCTR Rd, HFT-110, Jefferson, AR 72079 (United States); George, N I, E-mail: Nysia.George@fda.hhs.gov [Division of Bioinformatics and Biostatistics, National Center for Toxicological Research, U.S. Food and Drug Administration, 3900 NCTR Rd, HFT-20, Jefferson, AR 72079 (United States)

2017-05-01

The risk of ubiquitous perchlorate exposure and the dose-response on thyroid hormone levels in pregnant women in the United States (U.S.) have yet to be characterized. In the current work, we integrated a previously developed perchlorate submodel into a recently developed population-based pregnancy model to predict reductions in maternal serum free thyroxine (fT4) levels for late-gestation pregnant women in the U.S. Our findings indicated no significant difference in geometric mean estimates of fT4 when perchlorate exposure from food only was compared to no perchlorate exposure. The reduction in maternal fT4 levels reached statistical significance when an added contribution from drinking water (i.e., 15 μg/L, 20 μg/L, or 24.5 μg/L) was assumed in addition to the 90th percentile of food intake for pregnant women (0.198 μg/kg/day). We determined that a daily intake of 0.45 to 0.50 μg/kg/day of perchlorate was necessary to produce results that were significantly different than those obtained from no perchlorate exposure. Adjusting for this food intake dose, the relative source contribution of perchlorate from drinking water (or other non-dietary sources) was estimated to range from 0.25–0.3 μg/kg/day. Assuming a drinking water intake rate of 0.033 L/kg/day, the drinking water concentration allowance for perchlorate equates to 7.6–9.2 μg/L. In summary, we have demonstrated the utility of a probabilistic biologically-based dose-response model for perchlorate risk assessment in a sensitive life-stage at a population level; however, there is a need for continued monitoring in regions of the U.S. where perchlorate exposure may be higher. - Highlights: • Probabilistic risk assessment for perchlorate in U.S. pregnant women was conducted. • No significant change in maternal fT4 predicted due to perchlorate from food alone. • Drinking water concentration allowance for perchlorate estimated as 7.6–9.2 μg/L.

Titania nanotube powders obtained by rapid breakdown anodization in perchloric acid electrolytes

Energy Technology Data Exchange (ETDEWEB)

Ali, Saima, E-mail: saima.ali@aalto.fi; Hannula, Simo-Pekka

2017-05-15

Titania nanotube (TNT) powders are prepared by rapid break down anodization (RBA) in a 0.1 M perchloric acid (HClO{sub 4}) solution (Process 1), and ethylene glycol (EG) mixture with HClO{sub 4} and water (Process 2). A study of the as-prepared and calcined TNT powders obtained by both processes is implemented to evaluate and compare the morphology, crystal structure, specific surface area, and the composition of the nanotubes. Longer TNTs are formed in Process 1, while comparatively larger pore diameter and wall thickness are obtained for the nanotubes prepared by Process 2. The TNTs obtained by Process 1 are converted to nanorods at 350 °C, while nanotubes obtained by Process 2 preserve tubular morphology till 350 °C. In addition, the TNTs prepared by an aqueous electrolyte have a crystalline structure, whereas the TNTs obtained by Process 2 are amorphous. Samples calcined till 450 °C have XRD peaks from the anatase phase, while the rutile phase appears at 550 °C for the TNTs prepared by both processes. The Raman spectra also show clear anatase peaks for all samples except the as-prepared sample obtained by Process 2, thus supporting the XRD findings. FTIR spectra reveal the presence of O-H groups in the structure for the TNTs obtained by both processes. However, the presence is less prominent for annealed samples. Additionally, TNTs obtained by Process 2 have a carbonaceous impurity present in the structure attributed to the electrolyte used in that process. While a negligible weight loss is typical for TNTs prepared from aqueous electrolytes, a weight loss of 38.6% in the temperature range of 25–600 °C is found for TNTs prepared in EG electrolyte (Process 2). A large specific surface area of 179.2 m{sup 2} g{sup −1} is obtained for TNTs prepared by Process 1, whereas Process 2 produces nanotubes with a lower specific surface area. The difference appears to correspond to the dimensions of the nanotubes obtained by the two processes. - Graphical abstract

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

Science.gov (United States)

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

PREDICTING FIELD PERFORMANCE OF HERBACEOUS SPECIES FOR PHYTOREMEDIATION OF PERCHLORATE

Science.gov (United States)

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...

Study of alkaline-earth element complexes in anhydrous acetic acid

International Nuclear Information System (INIS)

Petit, N.

1968-10-01

We have studied the complexes of alkaline-earth elements in anhydrous acetic acid. Using glass-electrode potentiometry we have studied the titration of alkaline earth acetates with perchloric acid which is the strongest acid in anhydrous acetic acid. These titrations have shown that the basic strength of these acetates increases as follows: Mg 4 ); the mixed acetate-acid sulfate complex of barium: Ba (OAc)(HSO 4 ); the mixed acetate-chloride of barium: Ba (OAc)(Cl). (author) [fr

RAMAN SPECTROSCOPIC ANALYSIS OF FERTILIZERS AND PLANT TISSUE FOR PERCHLORATE

Science.gov (United States)

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...

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

Science.gov (United States)

2009-09-11

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

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

International Nuclear Information System (INIS)

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

1992-01-01

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

Ligand isotopic exchange of tris(acetylacetonato)germanium(IV) perchlorate in organic solvents

International Nuclear Information System (INIS)

Nagasawa, Akira; Saito, Kazuo

1978-01-01

The ligand isotopic exchange between tris(acetylacetonato)germanium(IV) perchlorate and acetylacetone[ 14 C] has been studied in 1,1,2,2-tetrachloroethane (TCE), nitromethane (NM), and acetonitrile (AN), at 100 - 120 0 C. In these solvents, the rate formula was R = k[H 2 O][complex]; the concentrations of the complex, free ligand, and water in solution were in the ranges from 0.01 to 0.1 mol dm -3 . The activation enthalpies and entropies for the k's are 105, 98, and 90 kJ mol -1 ; and -25, -53, and -69 JK -1 mol -1 , in TCE, NM, and AN, respectively. Influence of acid and base concentrations, and deuterium isotope effect on the rate in AN suggest that the rate controlling step of the exchange is governed by the ease of the proton transfer between the leaving and the incoming acac - in an intermediate. (auth.)

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

Directory of Open Access Journals (Sweden)

Hai-Bin Zhu

2010-12-01

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

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

Directory of Open Access Journals (Sweden)

Ray J. Butcher

2008-01-01

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

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

Science.gov (United States)

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

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

Science.gov (United States)

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.

British strong-acid leach process targeted at refractory uranium ores

International Nuclear Information System (INIS)

Anon.

1975-01-01

The UKAEA-patented strong-acid leach process for refractory U ores is briefly outlined with emphasis on its variations from the conventional dilute-acid process and the projected economics for a processing plant using this process. The process uses 6N H 2 SO 4 with a sharply reduced leaching time over conventional processes. The solubilized U is removed by percolation and the use of only about 10 percent liquid produces less effluent. Conventional processing plant equipment can be used except at the feed preparation, acid mixing, curing, and washing stages. Ore can be processed at larger grain sizes and the milling is done in a dry rod mill. Alternatives to the percolation removal of U are listed. Other work being done by UKAEA on U recovery from ores is briefly indicated. (U.S.)

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

National Research Council Canada - National Science Library

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

1999-01-01

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

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

Science.gov (United States)

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

2009-12-01

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

Methylated Fatty Acids from Heartwood and Bark of Pinus sylvestris, Abies alba, Picea abies, and Larix decidua: Effect of Strong Acid Treatment

Directory of Open Access Journals (Sweden)

Mohamed Zidan Mohamed Salem

2015-09-01

Full Text Available Methylated fatty acid (FA compounds in the heartwood and bark of some softwood species, specifically Pinus sylvestris, Abies alba, Picea abies, and Larix decidua, grown in the Czech Republic were evaluated. Strong H2SO4 was used for methylation of the lipids. The highest content of lipid was found in P. abies bark (40.132 mg/g o.d. sample, and the lowest content was in A. alba wood (11.027 mg/g o.d. sample. The highest concentration of FAs was observed in L. decidua bark. The highest percentages of FAs in wood of P. sylvestris were arachidic acid and oleic acid. In bark, the highest percentages of FAs were stearic acid, palmitic acid, and oleic acid. The FAs with the highest concentrations in A. alba wood were arachidic acid, palmitic acid, pentadecanoic acid, and margarinic, and those in bark were behenic acid, lignoceric acid, and arachidic acid. P. abies wood FAs showed arachidic acid, palmitic acid, and margarinic acid, and the bark contained lignoceric acid and arachidic acid. The FAs of L. decidua wood were arachidic acid, palmitic acid, and stearic acid, and in bark they were pentacosylic acid, docosahexaenoic acid (DHA, lignoceric acid, arachidic acid, and behenic acid. The lack of typically dominant unsaturated fatty acids (e.g. 18:1, 18:2, compared to literature values were attributed to the application of strong acid for the hydrolysis.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-02-01

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Recovery of uranium from different acidic solutions by di-nonyl phenyl phosphoric acid (DNPPA) and TOPO

International Nuclear Information System (INIS)

Mishra, S.L.; Vijayalakshmi, R.; Singh, H.

2004-01-01

The extraction mechanism of uranium with DNPPA in combination with TOPO has been established from different acidic media. The extraction order of uranium from these media has been found as perchlorate>nitrate>chloride>sulphate>phosphate. Based on these results extraction of uranium from samples of leach liquors generated in the plant has been carried out and >99% recovery was obtained

Acid-Base Equilibria of Some N-Substituted Thiophene-2-Carboxamidoximes in Non-Aqueous Media

OpenAIRE

DÜRÜST, Nedime

2002-01-01

The protonation constants of the amino nitrogens of some N-substituted thiophene-2-carboxamidoximes have been determined in acetic acid by means of potentiometric titration with perchloric acid. pKa values of the title compounds were interpreted on the basis of structural effects due to the substituents and the main skeleton.

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

Science.gov (United States)

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

2011-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-09-15

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

Development of a Health-Protective Drinking Water Level for Perchlorate

Science.gov (United States)

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

2006-01-01

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

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

Science.gov (United States)

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

2012-10-01

By functionalising gold samples, planar wafers or AFM tips, with an acid- or an amino acid-terminated thiols, mercaptoundecanoic acid (MUA) and homocystein (H-Cyst) respectively, we were able to differentiate the interactions with ammonium perchlorate (AP) and starch (S), two components of a nanocomposition mixture. To do so, the interaction between gold functionalized surfaces and the two targeted compounds have been characterized and quantified by several complementary techniques. Polarisation modulation-infrared spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS), providing chemical analyses of gold surfaces after contacting S or AP, proved that both compounds were retained on MUA or H-Cyst-modified surfaces, but to various extents. Quartz crystal microbalance on-line measurements enabled to monitor the kinetics of interaction and showed distinct differences in the behaviour of MUA and H-Cyst-surfaces towards the two compounds. Having observed that only H-Cyst-modified surfaces enables to get a contrast on the chemical force microscopy (CFM) images, this new result could be well explained by examining the data obtained by combining the above-mentioned surface characterisation techniques.

A STUDY ON THE ACCUMULATION OF PERCHLORATE IN YOUNG HEAD LETTUCE

Science.gov (United States)

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

RAMAN ANALYSIS OF FERTILIZER AND PLANT TISSUE EXTRACTS FOR PERCHLORATE CONTAMINATION

Science.gov (United States)

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...

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

Science.gov (United States)

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.

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

Science.gov (United States)

Borden, Robert C.

2007-10-01

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

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

Science.gov (United States)

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 ...

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

KAUST Repository

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

2016-01-01

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

Subcritical water extraction of amino acids from Mars analog soils.

Science.gov (United States)

Noell, Aaron C; Fisher, Anita M; Fors-Francis, Kisa; Sherrit, Stewart

2018-01-18

For decades, the Martian regolith has stymied robotic mission efforts to catalog the organic molecules present. Perchlorate salts, found widely throughout Mars, are the main culprit as they breakdown and react with organics liberated from the regolith during pyrolysis, the primary extraction technique attempted to date on Mars. This work further develops subcritical water extraction (SCWE) as a technique for extraction of amino acids on future missions. The effect of SCWE temperature (185, 200, and 215°C) and duration of extraction (10-120 min) on the total amount and distribution of amino acids recovered was explored for three Mars analog soils (JSC Mars-1A simulant, an Atacama desert soil, and an Antarctic Dry Valleys soil) and bovine serum albumin (as a control solution of known amino acid content). Total amounts of amino acids extracted increased with both time and temperature; however, the distribution shifted notably due to the destruction of the amino acids with charged or polar side chains at the higher temperatures. The pure bovine serum albumin solution and JSC Mars 1A also showed lower yields than the Atacama and Antarctic extractions suggesting that SCWE may be less effective at hydrolyzing large or aggregated proteins. Changing solvent from water to a dilute (10 mM) HCl solution allowed total extraction efficiencies comparable to the higher temperature/time combinations while using the lowest temperature/time (185°C/20 min). The dilute HCl extractions also did not lead to the shift in amino acid distribution observed at the higher temperatures. Additionally, adding sodium perchlorate salt to the extraction did not interfere with recoveries. Native magnetite in the JSC Mars-1A may have been responsible for destruction of glycine, as evidenced by its uncharacteristic decrease as the temperature/time of extraction increased. This work shows that SCWE can extract high yields of native amino acids out of Mars analog soils with minimal disruption of the

The Effects of Perchlorate on Developing and Adult Birds

Science.gov (United States)

2003-06-01

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

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

Science.gov (United States)

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

2018-02-01

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

Isotopic tracing of perchlorate in the environment

Science.gov (United States)

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

2012-01-01

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

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

Science.gov (United States)

Li, Xiang; Danell, Ryan M; Brinckerhoff, William B; Pinnick, Veronica T; van Amerom, Friso; Arevalo, Ricardo D; Getty, Stephanie A; Mahaffy, Paul R; Steininger, Harald; Goesmann, Fred

2015-02-01

Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.

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

DEFF Research Database (Denmark)

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

1981-01-01

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

Strong ion difference in urine: new perspectives in acid-base assessment.

OpenAIRE

Gattinoni, L.; Carlesso, E.; Cadringher, P.; Caironi, P.

2006-01-01

The plasmatic strong ion difference (SID) is the difference between positively and negatively charged strong ions. At pH 7.4, temperature 37°C and partial carbon dioxide tension 40 mmHg, the ideal value of SID is 42 mEq/l. The buffer base is the sum of negatively charged weak acids ([HCO3 -], [A-], [H2PO4 -]) and its normal value is 42 mEq/l. According to the law of electroneutrality, the amount of positive and negative charges must be equal, and therefore the SID value is equal to the buffer...

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

International Nuclear Information System (INIS)

Tfouni, E.; Giesbrecht, E.

1983-01-01

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

Polyaniline: Aniline oxidation with strong and weak oxidants under various acidity

Energy Technology Data Exchange (ETDEWEB)

Bláha, Michal, E-mail: blaha@imc.cas.cz [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Trchová, Miroslava; Bober, Patrycja; Morávková, Zuzana [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Prokeš, Jan [Charles University, Faculty of Mathematics and Physics, 180 00 Prague 8 (Czech Republic); Stejskal, Jaroslav [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic)

2017-06-15

Aniline was oxidized with three strong inorganic oxidants (ammonium peroxydisulfate, cerium(IV) sulfate, potassium dichromate), two weak inorganic oxidants (iron(III) chloride, silver nitrate), and one organic oxidant (p-benzoquinone) in aqueous solutions of methanesulfonic acid (MSA) of various concentration. Whereas oxidation of aniline with ammonium peroxydisulfate yielded high-molecular-weight conducting polyaniline (PANI) in the whole acidity range, the oxidation with cerium(IV) sulfate led also to a single product close to PANI with considerably lower molecular weight and lower conductivity. Potassium dichromate gave PANI only at high concentration of MSA. The use of iron(III) chloride yielded composite mixtures of PANI and low-molecular-weight aniline oligomers. The oxidation of aniline with silver nitrate led to composites of silver and an organic part, which was constituted either by aniline oligomers or conducting polyaniline or both. p-Benzoquinone as oxidant produced mainly aniline oligomers with poor conductivity and 2,5-dianilino-p-benzoquinone-like structure detected in FTIR and Raman spectra when oxidation proceeded with weak oxidants. A general model of oxidation with strong and weak oxidants was formulated. - Highlights: • Comparison of aniline oxidation with oxidants of different redox potential. • UV–vis, FTIR and Raman spectroscopies combined with size-exclusion chromatography. • The contents of polymer and oligomers were analyzed and discussed. • General model of aniline oxidation with strong and weak oxidants was formulated.

Kinetics of Oxidation of Some Amino Acids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

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N. A. Mohamed Farook

2004-01-01

Full Text Available The kinetics of oxidation of some amino acids namely, glycine, alanine, aspartic acid, arginine, and histidine, (AA by N-chlorosaccharin (NCSA in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order in [AA], [NCSA] and of inverse fractional order in [H+]. The main product of the oxidation is the corresponding aldehyde. The ionic strength on the reaction rate has no significant effect. The effect of changing the dielectric constant of the medium on the rate indicates the reaction to be of dipole-dipole type. Hypochlorous acid has been postulated as the reactive oxidizing species. The reaction constants involved in the mechanism are derived. The activation parameters are computed with respect to slow step of the mechanism.

Radiative Ignition of fine-ammonium perchlorate composite propellants

Energy Technology Data Exchange (ETDEWEB)

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

2006-08-15

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

Crystal structure of 2-cyano-1-methylpyridinium perchlorate

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Vu D. Nguyen

2015-11-01

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

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

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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.

Extraction of some acids using aliphatic amines

International Nuclear Information System (INIS)

Matutano, L.

1964-06-01

Hydrochloric, nitric, sulphuric, perchloric, phosphoric, acetic and formic acids in aqueous solution (0.05 to 10 M) are extracted by amberlite LA2 and trilaurylamine in solution, 5 per cent by volume, in kerosene and xylene respectively. The extraction process consists of: neutralization of the amine salt; a 'molecular extraction', i.e. an extraction using an excess of acid with respect to the stoichiometry of the amine salt. According to the behaviour of the acid during the extraction, three groups may be distinguished: completely dissociated acids, carboxylic acids, phosphoric acid. This classification is also valid for the extraction of the water which occurs simultaneously with that of the acid. An extraction mechanism is put forward for formic acid and the formation constant of its amine salt is calculated. (author) [fr

Comparative Demonstration of Active and Semi-Passive In Situ Bioremediation Approaches for Perchlorate Impacted Groundwater: Active In Situ Bioremediation Demonstration

Science.gov (United States)

2013-04-01

http://www.itrcweb.org/Documents/PERC-1.pdf • ITRC Perchlorate Team. 2008. Remediation Technologies for Perchlorate Contamination in Water and Soil ...pdf • Solutions EIS. 2006. Protocol for Enhanced In Situ Bioremediation Using Emulsified Vegetable Oil . Prepared for ESTCP. May 2006. • http...Air Force. 2007. Protocol for In Situ Bioremediation of Chlorinated Solvents Using Edible Oil . Prepared for AFCEC - Environmental Science Division

Influence of variation in mobile phase pH and solute pK(a) with the change of organic modifier fraction on QSRRs of hydrophobicity and RP-HPLC retention of weakly acidic compounds.

Science.gov (United States)

Han, Shu-ying; Liang, Chao; Zou, Kuan; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin

2012-11-15

The variation in mobile phase pH and ionizable solute dissociation constant (pK(a)) with the change of organic modifier fraction in hydroorganic mobile phase has seemingly been a troublesome problem in studies and applications of reversed phase high performance liquid chromatography (RP-HPLC). Most of the early studies regarding the RP-HPLC of acid-base compounds have to measure the actual pH of the mixed mobile phase rigorously, sometimes bringing difficulties in the practices of liquid chromatographic separation. In this paper, the effect of this variation on the apparent n-octanol/water partition coefficient (K(ow)″) and the related quantitative structure-retention relationship (QSRR) of logK(ow)″ vs. logk(w), the logarithm of retention factor of analytes in neat aqueous mobile phases, was investigated for weakly acidic compounds. This QSRR is commonly used as a classical method for K(ow) measurement by RP-HPLC. The theoretical and experimental derivation revealed that the variation in mobile phase pH and solute pK(a) will not affect the QSRRs of acidic compounds. This conclusion is proved to be suitable for various types of ion-suppressors, i.e., strong acid (perchloric acid), weak acid (acetic acid) and buffer salt (potassium dihydrogen phosphate/phosphoric acid, PBS). The QSRRs of logK(ow)″ vs. logk(w) were modeled by 11 substituted benzoic acids using different types of ion-suppressors in a binary methanol-water mobile phase to confirm our deduction. Although different types of ion-suppressor all can be used as mobile phase pH modifiers, the QSRR model obtained by using perchloric acid as the ion-suppressor was found to have the best result, and the slightly inferior QSRRs were obtained by using acetic acid or PBS as the ion-suppressor. Copyright © 2012 Elsevier B.V. All rights reserved.

Perchlorate Detection at Nanomolar Concentrations by Surface-Enhanced Raman Scattering

Science.gov (United States)

2009-01-01

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

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

Science.gov (United States)

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

2008-05-19

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

Dissolution mechanism of aluminum hydroxides in acid media

Science.gov (United States)

Lainer, Yu. A.; Gorichev, I. G.; Tuzhilin, A. S.; Gololobova, E. G.

2008-08-01

The effects of the concentration, temperature, and potential at the hydroxide/electrolyte interface on the aluminum hydroxide dissolution in sulfuric, hydrochloric, and perchloric acids are studied. The limiting stage of the aluminum hydroxide dissolution in the acids is found to be the transition of the complexes that form on the aluminum hydroxide surface from the solid phase into the solution. The results of the calculation of the acid-base equilibrium constants at the oxide (hydroxide)/solution interface using the experimental data on the potentiometric titration of Al2O3 and AlOOH suspensions are analyzed. A mechanism is proposed for the dissolution of aluminum hydroxides in acid media.

A GC-ECD method for estimation of free and bound amino acids, gamma-aminobutyric acid, salicylic acid, and acetyl salicylic acid from Solanum lycopersicum (L.).

Science.gov (United States)

Meher, Hari Charan; Gajbhiye, Vijay T; Singh, Ghanendra

2011-01-01

A gas chromatograph with electron capture detection method for estimation of selected metabolites--amino acids (free and bound), gamma-aminobutyric acid (GABA), salicylic acid (SA), and acetyl salicylic acid (ASA) from tomato--is reported. The method is based on nitrophenylation of the metabolites by 1-fluoro-2, 4-dinitrobenzene under aqueous alkaline conditions to form dinitophenyl derivatives. The derivatives were stable under the operating conditions of GC. Analysis of bound amino acids comprised perchloric acid precipitation of protein, alkylation (carboxymethylation) with iodoacetic acid, vapor-phase hydrolysis, and derivatization with 1-fluoro-2,4-dinitrobenzene in that order. The metabolites were resolved in 35 min, using a temperature-programmed run. The method is rapid, sensitive, and precise. It easily measured the typical amino acids (aspartate, asparagine, glutamate, glutamine, alanine, leucine, lysine, and phenylalanine) used for identification and quantification of a protein, resolved amino acids of the same mass (leucine and isoleucine), satisfactorily measured sulfur amino acid (methionine, cystine, and cysteine), and quantified GABA, SA, and ASA, as well. The developed method was validated for specificity, linearity, and precision. It has been applied and recommended for estimation of 25 metabolites from Solanum lycopersicum (L.).

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

Science.gov (United States)

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.

Complex formation between glutamic acid and molybdenum (VI)

International Nuclear Information System (INIS)

Gharib, Farrokh; Khorrami, S.A.; Sharifi, Sasan

1997-01-01

Equilibria of the reaction of molybdenum (VI) with L-glutamic acid have been studied in aqueous solution in the pH range 2.5 to 9.5, using spectrophotometric and optical rotation methods at constant ionic strength (0.15 mol dm -3 sodium perchlorate) and temperature 25 ± 0.1 degC. Our studies have shown that glutamic acid forms a mononuclear complex with Mo(VI) of the type MoO 3 L 2- at pH 5.5. The stability constant of this complexation and the dissociation constants of L-glutamic acid have been determined. (author). 17 refs., 2 figs., 4 tabs

Evaluation of Potential for Monitored Natural Attenuation of Perchlorate in Groundwater

Science.gov (United States)

2010-09-01

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

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

Science.gov (United States)

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.

Uranium(VI) and ruthenium extraction by dialkyldithio-phosphoric acids

International Nuclear Information System (INIS)

Fitoussi, R.; Musikas, C.

1980-01-01

Oxygen donors like dialkylphosphoric acids are good extractants for actinide ions, but little is known about their sulfur homologs. Investigations of U(VI) and Ru extraction from various aqueous media are reported. This includes extraction of U(VI) from nitric, perchloric, and phosphoric acids by solutions of dialkyldithiophosphoric acids in dodecane or benzene. Extraction of U(VI) by synergistic mixtures, of which at least one of the components is a sulfur donor, has been investigated. The extracted species have been identified, and a comparison with the complexes obtained by extraction with the homologous oxygen donors is made. The sulfur-actinide bond is weaker than the oxygen-actinide one, but in some synergistic extractions the dialkyldithiophosphonates are more efficient than the oxygen donors. In addition to size effects, this behavior could be attributed to the weakness of the hydrogen bonds of the SH groups, which allows a greater variety of the ligands to enter the coordination sphere of the metal. Ruthenium, like the d-transition elements, gives strong bonds with the sulfur donors. However, its extraction from nitric acid is slow. We investigated the influence of several parameters on the distribution coefficients and found that the presence of a reagent which destroys nitrous ions is necessary to achieve quantitative extraction. The role of RuNO groups is also discussed

Simultaneous removal of perchlorate and arsenate by ion-exchange media modified with nanostructured iron (hydr)oxide

Energy Technology Data Exchange (ETDEWEB)

Hristovski, Kiril [Environmental Technology Laboratory, Arizona State University, 6075 S. WMS Campus Loop W, Mesa, AZ 85212 (United States)], E-mail: kiril.hristovski@asu.edu; Westerhoff, Paul [Department of Civil and Environmental Engineering, Arizona State University, Box 5306, Tempe, AZ 85287-5306 (United States)], E-mail: p.westerhoff@asu.edu; Moeller, Teresia [SolmeteX Inc., 50 Bearfoot Road, Northborough, MA 01532 (United States)], E-mail: tmoller@solmetex.com; Sylvester, Paul [SolmeteX Inc., 50 Bearfoot Road, Northborough, MA 01532 (United States)], E-mail: psylvester@solmetex.com; Condit, Wendy [Battelle, 505 King Avenue, Columbus, OH 43201 (United States)], E-mail: conditw@battelle.org; Mash, Heath [United States Environmental Protection Agency, 26W. Martin Luther King Dr., Cincinnati, OH 45268 (United States)], E-mail: mash.heath@epa.gov

2008-03-21

Hybrid ion-exchange (HIX) media for simultaneous removal of arsenate and perchlorate were prepared by impregnation of non-crystalline iron (hydr)oxide nanoparticles onto strong base ion-exchange (IX) resins using two different chemical treatment techniques. In situ precipitation of Fe(III) (M treatment) resulted in the formation of sphere-like clusters of nanomaterials with diameters of {approx}5 nm, while KMnO{sub 4}/Fe(II) treatments yielded rod-like nanomaterials with diameters of 10-50 nm inside the pores of the media. The iron content of most HIX media was >10% of dry weight. The HIX media prepared via the M treatment method consistently exhibited greater arsenate adsorption capacity. The fitted Freundlich adsorption intensity parameters (q=KxC{sub E}{sup 1/n}) for arsenate (1/n < 0.6) indicated favorable adsorption trends. The K values ranged between 2.5 and 34.7 mgAs/g dry resin and were generally higher for the M treated media in comparison to the permanganate treated media. The separation factors for perchlorate over chloride ({alpha}{sub Cl{sup -}}{sup ClO{sub 4}{sup -}}) for the HIX media were lower than its untreated counterparts. The HIX prepared via the M treatment, had higher {alpha}{sub Cl{sup -}}{sup ClO{sub 4}{sup -}} than the HIX obtained by the KMnO{sub 4}/Fe(II) treatments suggesting that permanganate may adversely impact the ion-exchange base media. Short bed adsorber (SBA) tests demonstrated that the mass transport kinetics for both ions are adequately rapid to permit simultaneous removal using HIX media in a fixed bed reactor.

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

Science.gov (United States)

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

2013-06-01

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

Fluorination of Boron-Doped Diamond Film Electrodes for Minimization of Perchlorate Formation.

Science.gov (United States)

Gayen, Pralay; Chaplin, Brian P

2017-08-23

This research investigated the effects of surface fluorination on both rates of organic compound oxidation (phenol and terephthalic acid (TA)) and ClO 4 - formation at boron-doped diamond (BDD) film anodes at 22 °C. Different fluorination methods (i.e., electrochemical oxidation with perfluorooctanoic acid (PFOA), radio frequency plasma, and silanization) were used to incorporate fluorinated moieties on the BDD surface, which was confirmed by X-ray photoelectron spectroscopy (XPS). The silanization method was found to be the most effective fluorination method using a 1H,1H,2H,2H-perfluorodecyltrichlorosilane precursor to form a self-assembled monolayer (SAM) on the oxygenated BDD surface. The ClO 4 - formation decreased from rates of 0.45 ± 0.03 mmol m -2 min -1 during 1 mM NaClO 3 oxidation and 0.28 ± 0.01 mmol m -2 min -1 during 10 mM NaCl oxidation on the BDD electrode to below detectable levels (layer on the BDD surface that inhibited charge transfer via steric hindrance and hydrophobic effects. The surface coverages and thicknesses of the fluorinated films controlled the charge transfer rates, which was confirmed by estimates of film thicknesses using XPS and density functional theory simulations. The aliphatic silanized electrode also showed very high stability during OH • production. Perchlorate formation rates were below the detection limit (<0.12 μmoles m -2 min -1 ) for up to 10 consecutive NaClO 3 oxidation experiments.

Anodic dissolution of UO2 in slightly alkaline sodium perchlorate solutions

International Nuclear Information System (INIS)

Sunder, S.; Strandlund, L.K.; Shoesmith, D.W.

1996-04-01

The anodic dissolution of UO 2 has been studied in aqueous sodium perchlorate solutions at pH ∼ 9.5. Under potentiostatic conditions two distinct regions of oxidation/dissolution behaviour were observed. In the potential (E) range 0.100 V A , Q C respectively) obtained by integration of the anodic current-time plots (Q A ) and cathodic potential scans to reduce accumulated oxidized surface films (Q C ), it was shown that > ∼ 90% of the anodic oxidation current went to produce these films. For E > ∼ 0.350 V, steady-state currents were obtained and measurements of Q A and Q C showed the majority of the current went to produce soluble species. The film blocking anodic dissolution appeared to be either UO 2.27 or, more probably, UO 3 .2H 2 O located primarily at grain boundaries. It is proposed that, at the higher potentials, rapid oxidation and dissolution followed by the hydrolysis of dissolved uranyl species leads to the development of acidic conditions in the grain boundaries. At these lower pH values the UO 3 .2H 2 O is soluble and therefore does not accumulate. Alternatively, if this oxide has been formed by prior oxidation at a lower potential, the formation of protons on oxidizing at E > ∼ 0.350V causes its redissolution, allowing the current to rise to a steady-state value. On the basis of Tafel slopes, an attempt was made to demonstrate that the observed behaviour was consistent with dissolution under acidic conditions. This analysis was only partially successful. (author) 34 refs. 11 figs

Purification of di-nonyl phenyl phosphoric acid (DNPPA) for synergistic extraction of uranium from strong phosphoric acid

International Nuclear Information System (INIS)

Singh, D.K.; Vijayalakshmi, R.; Singh, H.; Sharma, J.N.; Ruhela, R.

2009-01-01

Di-nonyl phenyl phosphoric acid (DNPPA) obtained from various synthesis methods is always associated with impurities such as mono-nonyl phenyl phosphoric acid and nonyl phenol which need to be separated for its effective use in the extraction of uranium from strong phosphoric acid. Two methods of purification namely liquid-solid separation method using neodymium salt and liquid-liquid separation method using methylene glycol have been described. In the liquid solid separation method the purity of DNPPA obtained was about 95% with less than 1.0% monoester, however it heavily suffers in the recovery aspect which is of the order of 50-60%. The methylene glycol treatment method, results in high purity and recovery of the product. Purity obtained was about 95.0% diester and less than 0.5% monoester and recovery was more than 90%. Analysis of DNPPA was done by potentiometric titration method using autotitrator. (author)

Kinetics of Strong Acid Hydrolysis of a Bleached Kraft Pulp for Producing Cellulose Nanocrystals (CNCs)

Science.gov (United States)

Qianqian Wang; Xuebing Zhao; J.Y. Zhu

2014-01-01

Cellulose nanocrytals (CNCs) are predominantly produced using the traditional strong acid hydrolysis process. In most reported studies, the typical CNC yield is low (approximately 30%) despite process optimization. This study investigated the hydrolysis of a bleached kraft eucalyptus pulp using sulfuric acid between 50 and 64 wt % at temperatures of 35−80 °C...

Reactions of enolisable ketones with dichloroisocyanuric acid in absence and presence of added chloride ions – a kinetic study

Directory of Open Access Journals (Sweden)

Y. L. Kumar

2015-01-01

Full Text Available Kinetics of reactions of enolisable ketones (S = acetone/2-butanone with dichloroisocyanuric acid (DCICA were studied in aqueous acetic acid and perchloric acid media in absence and presence of added chloride ions. The reactions were found to be pseudo zero order and pseudo first order on [DCICA] in absence and presence of chloride ions respectively. Both in presence and absence of chloride ions, first order and fractional order in substrate and perchloric acid were observed respectively. An increase in the rate of reaction was observed with an increase in chloride ion concentration as well as acetic acid composition. The results were interpreted in terms of probable mechanisms involving (i rate-determining enol formation from the conjugate acid of the ketone (SH+ in the absence of added chloride ions and (ii rate-determining interaction of SH+ with the most effective molecular chlorine species produced by the hydrolysis of DCICA (rather than a rate-determining interaction of enol with chlorine in the presence of added chloride ions, prior to the rapid steps of product formation. DOI: http://dx.doi.org/10.4314/bcse.v29i1.12

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

Science.gov (United States)

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

2016-01-01

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

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

International Nuclear Information System (INIS)

Blount, Benjamin C.; Valentin-Blasini, Liza

2006-01-01

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

Controlled-potential coulometric determination of plutonium with a hydrochloric acid-sulfamic acid electrolyte and phosphate complexing

International Nuclear Information System (INIS)

Jackson, D.D.; Hollen, R.M.; Roensch, F.R.; Rein, J.E.

1981-01-01

Total plutonium is selectively determined by a controlled-potential coulometric method in which plutonium is reduced to Pu(III) at 0.25 V (vs. SCE) in a 5.5 M hydrochloric acid-0.015 M sulfamic acid electrolyte, diverse ions are oxidized at 0.57 V, phosphate is added to reduce the Pu(III)-Pu(IV) potential, and Pu(III) is oxidized to Pu(IV) at 0.68 V. None of more than 50 metal ions present in nuclear fuel-cycle material interferes. Many anions are without effect and most interfering ones are removed by preliminary fuming with perchloric acid. The apparatus described consists mainly of commercial components. The relative standard deviation is < 0.1% at the 5-mg plutonium level

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

International Nuclear Information System (INIS)

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

1977-01-01

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

Diazotisation of Weakly Basic Aromatic and Heterocyclic Amines in Strongly Acid Media

Science.gov (United States)

Godovikova, Tamara I.; Rakitin, Oleg A.; Khmel'nitskii, Lenor I.

1983-05-01

The review is devoted to the diazotisation of weakly basic aromatic amines. The methods of synthesis of diazonium salts based on these amines by non-traditional methods are examined. Data on the mechanism of the diazotisation reaction in strongly acid media are surveyed. Reactions of diazonium salts leading to the synthesis of new compounds are presented. The bibliography includes 75 references.

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

Science.gov (United States)

2007-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Mercier, D. [CNRS, UMR CNRS 7609, Laboratoire de Reactivite de Surface, Paris (France); Universite Pierre et Marie Curie - UPMC Paris VI, Laboratoire de Reactivite de Surface, 4 place Jussieu, 75252 Paris Cedex 05 (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France); Mercader, C.; Quere, S.; Hairault, L. [CEA, DAM, Le Ripault, F-37260 Monts (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France); Methivier, C. [CNRS, UMR CNRS 7609, Laboratoire de Reactivite de Surface, Paris (France); Universite Pierre et Marie Curie - UPMC Paris VI, Laboratoire de Reactivite de Surface, 4 place Jussieu, 75252 Paris Cedex 05 (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France); Pradier, C.M., E-mail: claire-Marie.pradier@upmc.fr [CNRS, UMR CNRS 7609, Laboratoire de Reactivite de Surface, Paris (France); Universite Pierre et Marie Curie - UPMC Paris VI, Laboratoire de Reactivite de Surface, 4 place Jussieu, 75252 Paris Cedex 05 (France); Laboratoire de recherche conventionne CEA/UPMC n Degree-Sign 1, Paris (France)

2012-10-01

Highlights: Black-Right-Pointing-Pointer Measurements of interactions by Quartz Crystal Microbalance. Black-Right-Pointing-Pointer AFM and CFM measurements, tip functionalisation. Black-Right-Pointing-Pointer Surface nano-imaging. - Abstract: By functionalising gold samples, planar wafers or AFM tips, with an acid- or an amino acid-terminated thiols, mercaptoundecanoic acid (MUA) and homocystein (H-Cyst) respectively, we were able to differentiate the interactions with ammonium perchlorate (AP) and starch (S), two components of a nanocomposition mixture. To do so, the interaction between gold functionalized surfaces and the two targeted compounds have been characterized and quantified by several complementary techniques. Polarisation modulation-infrared spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS), providing chemical analyses of gold surfaces after contacting S or AP, proved that both compounds were retained on MUA or H-Cyst-modified surfaces, but to various extents. Quartz crystal microbalance on-line measurements enabled to monitor the kinetics of interaction and showed distinct differences in the behaviour of MUA and H-Cyst-surfaces towards the two compounds. Having observed that only H-Cyst-modified surfaces enables to get a contrast on the chemical force microscopy (CFM) images, this new result could be well explained by examining the data obtained by combining the above-mentioned surface characterisation techniques.

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

Science.gov (United States)

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 ...

Control of Sulfidogenesis Through Bio-oxidation of H₂S Coupled to (per)chlorate Reduction

Energy Technology Data Exchange (ETDEWEB)

Gregoire, Patrick [Univ. of California, Berkeley, CA (United States); Engelbrektson, Anna [Univ. of California, Berkeley, CA (United States); Hubbard, Christopher G. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Metlagel, Zoltan [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Csencsits, Roseann [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Auer, Manfred [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Conrad, Mark E. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Thieme, Jurgen [Brookhaven National Lab. (BNL), Upton, NY (United States); Northrup, Paul [Brookhaven National Lab. (BNL), Upton, NY (United States); Coates, John D. [Univ. of California, Berkeley, CA (United States)

2014-04-04

Here, we investigate H₂S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H₂S coupled to (per)chlorate reduction without sustaining growth. H₂S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. We also propose a novel hybrid enzymatic-abiotic mechanism for H₂S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

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).

Science.gov (United States)

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-04-14

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

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

Science.gov (United States)

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

2013-08-01

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

Effects of solvation on partition and dimerization of benzoic acid in mixed solvent systems.

Science.gov (United States)

Yamada, H; Yajima, K; Wada, H; Nakagawa, G

1995-06-01

The partition of benzoic acid between 0.1M perchloric acid solution and two kinds of mixed solvents has been carried out at 25 degrees C. The partition and dimerization constants of benzoic acid have been determined in the 1-octanol-benzene and 2-octanone-benzene systems. In both the mixed solvent systems, with increasing content of 1-octanol and 2-octanone in each mixed solvent, the partition constant of benzoic acid has been found to increase, and the dimerization constant of benzoic acid in each organic phase to decrease. These phenomena are attributable to solvation of monomeric benzoic acid by 1-octanol and 2-octanone molecules in each mixed solvent.

Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

KAUST Repository

Hatzell, Marta C.

2014-12-02

© 2014 American Chemical Society. The amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10^-5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g^-1) had a positive rise potential of 59 ± 4 mV in the LC solution, whereas the carbon with the highest concentration (0.36 mmol g^-1) had a negative rise potential (-31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to -6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. These results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.

Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

KAUST Repository

Hatzell, Marta C.; Raju, Muralikrishna; Watson, Valerie J.; Stack, Andrew G.; van Duin, Adri C. T.; Logan, Bruce E.

2014-01-01

© 2014 American Chemical Society. The amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10^-5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g^-1) had a positive rise potential of 59 ± 4 mV in the LC solution, whereas the carbon with the highest concentration (0.36 mmol g^-1) had a negative rise potential (-31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to -6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. These results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.

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

Science.gov (United States)

Shcherbakova, Viktoria; Oshurkova, Viktoria; Yoshimura, Yoshitaka

2015-09-09

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

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

Directory of Open Access Journals (Sweden)

Viktoria Shcherbakova

2015-09-01

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

Redox thermodynamic data of plutonium in acidic and carbonate media. Pu(V) stability

International Nuclear Information System (INIS)

Capdevila, H.

1992-01-01

Pu redox equilibria are studied in acidic and carbonate media in this thesis, to build a thermodynamic data bank consistent with the TDB (NEA-OECD) one and in connection with radioactive waste disposal programs. Literature is discussed and reinterpreted. The experimental method is tested with Uranium preliminary measurements. The reversible redox potentials (PuO 2 + and Pu 4+ /Pu 3+ ) are measured using the cyclic voltametric technique in perchloric media at several ionic strengths (from 0.5 to 3M) and temperatures (from 0 to 70 deg C). The Specific Interaction Theory (SIT) is used to measured activity coefficients and to extrapolate data to the standard conditions. The potentials variations versus temperature are linear in first approximation: the entropy changes are found constant from 0 to 70 deg C and the heat capacity changes are within uncertainties. The standard constant of PuO 2 + disproportionation into PuO 2 2+ and Pu 3+ is deduced from spectrophotometric measurements performed in perchloric media around pH=1 where Pu 4+ hydrolysis is discussed. The Pu non-reversible standard potentials (PuO 2 2+ /Pu 4+ for instance) are then calculated and validated with a spectrophotometric study of Pu 4+ formation from PuO 2 2+ and Pu 3+ in a 1M perchloric acidic solution. The Pu(VI/V) redox potential, activity coefficients and entropies are measured using the same technique in concentrated carbonate media. The limiting complex standard formation constants and the redox potential shifts (between acidic and carbonate media) are then discussed among the U, Np, Pu and Am actinides. A spectrophotometric study of the equilibrium between the complexes with 5 and 4 carbonate ligands allowed to measure Pu(IV) limiting complex stability at several ionic strengths. (author). 26 tabs., 46 figs., 95 refs

Investigation of the Structure, Optical and Electrical Properties of Lithium Perchlorate Doped Polyaniline Composite: Aloe Vera Used as a Bio-Plasticizer

Science.gov (United States)

Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vijeth, H.; Sharanappa, Chapi; Raghu, S.; Devendrappa, H.

2017-12-01

Bio-plasticizer based polyaniline (PANI)/lithium perchlorate (LiClO4) composites were synthesized by the facile in situ method. The composites were characterized using the Fourier transform infrared spectroscopy (FT-IR) to identify the chemical interactions. A band appeared at 1502 cm-1 due to the presence of the -H2CO- group and CH2 scissor mode vibration for the PAL15% composite. This considerable change in the morphology of LiClO4 homogeneous dispersion in a PANI matrix was investigated by scanning electron microscopy (SEM). The UV-Visible absorption (UV-Vis) showed 300-400 nm attributed to the π- π* transition and exhibited a red shift from 535 nm to 617 nm in the visible region, indicating a decrease in band gap. The variations in dielectric constant with the addition of lithium perchlorate (LiClO4) at different temperatures and in the frequency range of 20 Hz-1 MHz were assessed through impedance analysis. The temperature dependent electrical conductivity increased with increasing temperature as well as dopant concentration. High conductivity of 1.41 × 10-3 S/cm corresponding to activation energy of 0.02 eV and 2.95 eV optical band gap for 15 wt.% of LiClO4 concentration was observed. The cyclic voltammetry measurement revealed a typical rectangular shape of the integral area, suggesting that the composite has strong electrochemical strength and is a possible candidate for electrochemical super capacitor and solar cell applications.

Kinetics of [123I]iodide uptake and discharge by perchlorate in studies of inhibition of iodide binding by antithyroid drugs

International Nuclear Information System (INIS)

McCruden, D.C.; Connell, J.M.C.; Alexander, W.D.; Hilditch, T.E.

1985-01-01

Thyroidal binding of iodide was studied by kinetic analysis of [ 123 ]iodide uptake and its discharge by perchlorate in 80 hyperthyroid subjects receiving antithyroid drug therapy. Five dosage regimens ranging from 5 mg carbimazole twice daily to 15 mg methimazole twice daily were studied. Binding inhibition was estimated at 5-7 h after drug as an index of the mean effect of the 12 hourly regimen. In all cases, except one in the lowest dose group, binding was found to be markedly reduced with mean binding rates ranging from 0.002 to 0.020 min -1 (normal > 0.15 min -1 ). The net clearance of iodide in the lowest dose group was reduced to a mean value near the upper limit of the euthyroid range, whereas in the highest dose group it lay at the lower limit of the euthyroid range. These results were reflected in the serum thyroid hormone response. There was a reducing incidence of inadequate control of hyperthyroidism and an increasing incidence of hypothyroidism with increasing thiourylene dose. The exit rate constant of free iodide for the various doses showed values from 0.048 to 0.055 min -1 . Correpsonding mean values for the discharge rate constant after perchlorate were 0.087 to 0.105 min -1 . This suggests that perchlorate increases the rate of iodide release from the thyroid gland. Studies at a later interval after drug (12-14 h) showed no change in discharge rate constant. This leads to the conclusion that perchlorate may further inhibit iodide binding in subjects receiving antithyroid drug therapy. (author)

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

Science.gov (United States)

2012-10-19

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

Catalyzed oxidation reactions. IV. Picolinic acid catalysis of chromic acid oxidations

International Nuclear Information System (INIS)

Rocek, J.; Peng, T.Y.

1977-01-01

Picolinic acid and several closely related acids are effective catalysts in the chromic acid oxidation of primary and secondary alcohols; the oxidation of other substrates is accelerated only moderately. The reaction is first order in chromium-(VI), alcohol, and picolinic acid; it is second order in hydrogen ions at low acidity and approaches acidity independence at high perchloric acid concentrations. A primary deuterium kinetic isotope effect is observed at high but not at low acidities. At low acidity the reaction has a considerably lower activation energy and more negative activation entropy than at higher acidities. The reactive intermediate in the proposed mechanism is a negatively charged termolecular complex formed from chromic acid, picolinic acid, and alcohol. The rate-limiting step of the reaction changes with the acidity of the solution. At higher acidities the intermediate termolecular complex is formed reversibly and the overall reaction rate is determined by the rate of its decomposition into reaction products; at low acidities the formation of the complex is irreversible and hence rate limiting. Picolinic acids with a substituent in the 6 position show a greatly reduced catalytic activity. This observation is interpreted as suggesting a square pyramidal or octahedral structure for the reactive chromium (VI) intermediate. The temperature dependence of the deuterium isotope effect has been determined and the significance of the observed large values for E/sub a//sup D/ - E/sub a//sup H/ and A/sup D//A/sup H/ is discussed

Integrated Ion Exchange Regeneration Process for Perchlorate in Drinking Water

Science.gov (United States)

2010-08-01

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

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

Directory of Open Access Journals (Sweden)

James D. Buchner

2010-09-01

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

An online computer method for the potentiometric titration of mixtures of a strong and a weak acid

NARCIS (Netherlands)

Bos, M.

1977-01-01

A PDP-11 online computer method for the titration of mixtures or a strong and a weak acid is described.The method is based on multiparametric curve-fitting. One or the parameters found from the calculations is the dissociation constant of the weak acid, hence the method can be applied even when this

Effects of the anti-thyroidal compound potassium-perchlorate on the thyroid system of the zebrafish

Energy Technology Data Exchange (ETDEWEB)

Schmidt, Florian, E-mail: florian.schmidt@zoo.uni-heidelberg.de [Aquatic Ecology and Toxicology Group, Centre for Organismal Studies, University of Heidelberg, Im Neuenheimer Feld 230, D-69120 Heidelberg (Germany); Schnurr, Sarah; Wolf, Raoul; Braunbeck, Thomas [Aquatic Ecology and Toxicology Group, Centre for Organismal Studies, University of Heidelberg, Im Neuenheimer Feld 230, D-69120 Heidelberg (Germany)

2012-03-15

The increasing pollution of aquatic habitats with anthropogenic compounds has led to various test strategies to detect hazardous chemicals. However, information on effects of pollutants in the thyroid system in fish, which is essential for growth, development and parts of reproduction, is still scarce. Other vertebrate groups such as amphibians or mammals are well-studied; so the need for further knowledge especially in fish as a favored vertebrate model test organism is evident. Modified early life-stage tests were carried out with zebrafish exposed to the known thyroid inhibitor potassium perchlorate (0, 62.5, 125, 250, 500 and 5000 {mu}g/L) to identify adverse effects on the hypothalamic-pituitary-thyroid axis. Especially higher perchlorate concentrations led to conspicuous alterations in thyroidal tissue architecture and to effects in the pituitary. In the thyroid, severe hyperplasia at concentrations {>=}500 {mu}g/L together with an increase in follicle number could be detected. The most sensitive endpoint was the colloid, which showed alterations at {>=}250 {mu}g/L. The tinctorial properties and the texture of the colloid changed dramatically. Interestingly, effects on epithelial cell height were minor. The pituitary revealed significant proliferations of TSH-producing cells resulting in alterations in the ratio of adeno- to neurohypophysis. The liver as the main site of T4 deiodination showed severe glycogen depletion at concentrations {>=}250 {mu}g/L. In summary, the thyroid system in zebrafish showed effects by perchlorate from concentrations {>=}250 {mu}g/L, thus documenting a high sensitivity of the zebrafish thyroid gland for goitrogens. In the future, such distinct alterations could lead to a better understanding and identification of potential thyroid-disrupting chemicals.

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

Directory of Open Access Journals (Sweden)

Václav Eigner

2012-03-01

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

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

Science.gov (United States)

2013-11-18

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

Cellulose nanofiber isolation from palm oil Empty Fruit Bunches (EFB) through strong acid hydrolysis

Science.gov (United States)

Setyaningsih, Dwi; Uju; Muna, Neli; Isroi; Budi Suryawan, Nyoman; Azid Nurfauzi, Ami

2018-03-01

The palm oil industry produces about 25-26% of palm oil empty fruit bunches. The empty fruit bunch of palm oil contains cellulose up to 36.67%. This is a good opportunity for the synthesis of cellulose nanofiber (CNF). Cellulose nanofiber is a nano-sized cellulose material that has unique physical and mechanical properties. The synthesis was performed using a strong acid method with sulfuric acid. Sulfuric acid removes the amorphous region of cellulose so that the crystalline part can be isolated. CNF yield measurement showed that temperature, time, acid concentration, and interaction between each factor were affecting significantly to CNF yield. The result showed that yield of 14.98 grams, was obtained by hydrolysis at 35°C for 6 hours and 55% acid concentration. The crystallinity measurement showed that the temperature, time, acid concentration, and interaction between each factor during hydrolysis were not affected significantly to percent value of CNF crystallinity. The result showed that 31.1% of crystallinity, was obtained by hydrolysis at 45°C for 3 hours and 55% of acid concentration. The size measurement showed that the temperature, time, acid concentration and interaction between each factor were affected significantly. The result showed 894.25 nm as the best result, obtained by hydrolysis with 35°C and 60% acid concentration for 6 hours. CNF color was white with the best dispersion of hydrolysis at 35°C of 55% for 6 hours.

Synthesis,spectroscopic and biological study of 2-(3,3-dimethyl-1-triazeno) benzothiazole and morpholino acetyl-2- aminobenzothiazole derivatives

International Nuclear Information System (INIS)

Al-Azawi, A.M.

1985-01-01

Generally triazenes are prepared by coupling the diazonium salts of aromatic amines or heterocyclic amines with dimethyl amine or other amines.Primary aromatic amines react with nitrous acid to give diazonium compounds.Diazotization of 2-aminothiazoles and 2-aminobenzothiazoles occurs most readily in concentrated solutions of the oxygencontaining acids,such as sulfuric,perchloric,phosphoric and nitric acid.Diazotization in perchloric acid leads to the formation of diazonium perchlorate without by products.Diazotization takes place equally readily with sulphuric acid but with nitric acid the reaction proceeds less smoothyl owing to the low solubility of 2-aminothiazole nitrate.(11 tabs., 24 figs., 54 refs.)

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

National Research Council Canada - National Science Library

Craig, Daniel A

2008-01-01

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

Simultaneous estimation of a binary mixture of a weak acid and a strong acid by volumetric titration and pH measurement

International Nuclear Information System (INIS)

Karmakar, Sanat; Mallika, C.; Kamachi Mudali, U.

2012-01-01

High level liquid waste (HLLW) generated in the aqueous reprocessing of spent nuclear fuels for the separation of uranium and plutonium by PUREX process, comprises the fission and corrosion products in 4 M nitric acid. Reduction in waste volume is accomplished by destroying the acidity of the waste solution from 4 to less than 2 M by treating it with formaldehyde and subsequent concentration by evaporation. In the denitration by HCHO, nitric acid in the waste solution is reduced to NOx and water via nitrous acid as the intermediate product: whereas formaldehyde is oxidized to formic acid which is converted to CO 2 and H 2 O subsequently. The reaction is highly exothermic and the release of all gaseous products may lead to uncontrollable process conditions. Hence, for the safe operation, it is desirable to estimate the concentration of residual formic acid as well as nitric acid in the product stream as a function of time. The acidity in the feed solution is 4 M and the concentration of HNO 3 in the product solution is in the range 1- 4 M. Since the formic acid generated during the reaction will be consumed immediately, the concentration of residual acid will be in the range 0.05-0.5 M. A simultaneous titration method based on pH measurement and volumetric analysis has been developed in the present work for the quantitative determination of the weak acid (HCOOH)with known pKa value and the strong acid (HNO 3 ) in the binary mixture

Estimation of solubility of organo-phosphorus extractants by P determination using molybdovanadophosphoric acid method

International Nuclear Information System (INIS)

Gill, J.S.; Kotekar, M.K.; Singh, H.

2005-01-01

Solvent extraction processes have been found to be suitable for uranium recovery from phosphoric acid. Various extractants like di-2-ethyl hexylphosphoric acid (D2EHPA), di-nonylphenyl phosphoric acid (DNPPA) and synergistic agents like tri-butyl phosphate (TBP), tri-octyl phosphine oxide (TOPO) have been used in liquid-liquid extraction of uranium from phosphoric acid. Contents of these organo-phosphorus compounds in aqueous raffinates need estimation for process requirements. Solubility of Tri-butyl phosphate (TBP) and Di-2-ethylhexyl phosphoric acid (D2EHPA) extractants have been determined in different media of water, oxalic acid (0.6M) and sulphuric acid (3.75M) solutions. These compounds were estimated by determining their phosphorus (P) contents employing molybdovanadophosphoric acid method, after digesting and solubalizing them in nitric and perchloric acid. (author)

Kinetics and mechanism of the conversion of a coordinated thiol to a coordinated disulfide by the one-equivalent oxidants neptunium(VI) and cobalt(III) in aqueous perchloric acid

International Nuclear Information System (INIS)

Woods, M.; Karbwang, J.; Sullivan, J.C.; Deutsch, E.

1976-01-01

Reaction of excess (2-mercaptoethylamine-N,S)bis(ethylenediamine)cobalt(III), I, with the 1-equiv oxidant Np(VI) (or Co 3+ (aq)) in aqueous perchloric acid media is shown to lead to (2-aminoethyl-N 2-ammonioethyl disulfide-S 1 ) bis(ethylenediamine)cobalt(III), II, according to the stoichiometry 5H + + 2I + Np(VI) → II + Co 2+ (aq) + Np(V) + 2enH 2 2+ . This reaction follows the rate law -d[I]/dt = k'' [I] [oxidant]. For Np(VI) as oxidant k'' is independent of [H + ]; at 25 0 C, μ = 1.00 M (LiClO 4 ), k'' = k 0 = 2842 +- 15 M -1 s -1 , ΔH 0 * = 7.57 +- 0.08 kcal/mol, and ΔS 0 * = -17.4 +- 0.3 eu. For Co 3+ (aq) as oxidant, k'' = k 0 + k/sub -1/[H + ] -1 where the inverse acid path is taken to reflect oxidation by CoOH 2+ (aq); at 25 0 C, μ = 1.00 M (LiClO 4 ), k 0 = 933 +- 32 M -1 s -1 , k/sub -1/ = 1152 +- 22 s -1 , ΔH 0 * = 12.5 +- 0.7 kcal/mol, ΔH*/sub -1/ = 18.0 +- 0.4 kcal/mol, ΔS 0 *= -3.1 +- 2.4 eu, and ΔS*/sub -1/ = 15.8 +- 1.2 eu. It is proposed that the conversion of I to II proceeds by initial 1-equiv oxidation of the coordinated thiol, reaction of the resultant coordinated thiol radical (RS.) with additional I to form a relatively stable radical ion dimer (RSSR. - ), and then internal electron transfer within the dimer to yield Co 2+ (aq) and II which contains a coordinated disulfide. The possible generality of this mechanism and its relevance to biological metal-thiol-disulfide interactions are noted

Carbon-based strong solid acid for cornstarch hydrolysis

Energy Technology Data Exchange (ETDEWEB)

Nata, Iryanti Fatyasari, E-mail: yanti_tkunlam@yahoo.com [Chemical Engineering Study Program, Faculty of Engineering, Lambung Mangkurat University, Jl. A. Yani Km. 36 Banjarbaru, South Kalimantan 70714 (Indonesia); Irawan, Chairul; Mardina, Primata [Chemical Engineering Study Program, Faculty of Engineering, Lambung Mangkurat University, Jl. A. Yani Km. 36 Banjarbaru, South Kalimantan 70714 (Indonesia); Lee, Cheng-Kang, E-mail: cklee@mail.ntust.edu.tw [Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Rd. Sec.4, Taipei 106, Taiwan (China)

2015-10-15

Highly sulfonated carbonaceous spheres with diameter of 100–500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO{sub 3}H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO{sub 3}H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRS concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst. - Highlights: • Carbon solid acid was successfully prepared by one-step hydrothermal carbonization. • The acrylic acid as monomer was effectively reduce the diameter size of particle. • The solid acid catalyst show good catalytic performance of starch hydrolysis. • The solid acid catalyst is not significantly deteriorated after repeated use.

Carbon-based strong solid acid for cornstarch hydrolysis

International Nuclear Information System (INIS)

Nata, Iryanti Fatyasari; Irawan, Chairul; Mardina, Primata; Lee, Cheng-Kang

2015-01-01

Highly sulfonated carbonaceous spheres with diameter of 100–500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO 3 H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO 3 H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRS concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst. - Highlights: • Carbon solid acid was successfully prepared by one-step hydrothermal carbonization. • The acrylic acid as monomer was effectively reduce the diameter size of particle. • The solid acid catalyst show good catalytic performance of starch hydrolysis. • The solid acid catalyst is not significantly deteriorated after repeated use

The effect of temperature on the stability of compounds used as UV-MALDI-MS matrix: 2,5-dihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, alpha-cyano-4-hydroxycinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, nor-harmane and harmane.

Science.gov (United States)

Tarzi, Olga I; Nonami, Hiroshi; Erra-Balsells, Rosa

2009-02-01

The thermal stability of several commonly used crystalline matrix-assisted ultraviolet laser desorption/ionization mass spectrometry (UV-MALDI-MS) matrices, 2,5-dihydroxybenzoic acid (gentisic acid; GA), 2,4,6-trihydroxyacetophenone (THA), alpha-cyano-4-hydroxycinnamic acid (CHC), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid; SA), 9H-pirido[3,4-b]indole (nor-harmane; nor-Ho), 1-methyl-9H-pirido[3,4-b]indole (harmane; Ho), perchlorate of nor-harmanonium ([nor-Ho+H]+) and perchlorate of harmanonium ([Ho+H]+) was studied by heating them at their melting point and characterizing the remaining material by using different MS techniques [electron ionization mass spectrometry (EI-MS), ultraviolet laserdesorption/ionization-time-of-flight-mass spectrometry (UV-LDI-TOF-MS) and electrospray ionization-time-of-flight-mass spectrometry (ESI-TOF-MS)] as well as by thin layer chromatography analysis (TLC), electronic spectroscopy (UV-absorption, fluorescence emission and excitation spectroscopy) and 1H nuclear magnetic resonance spectroscopy (1H-NMR). In general, all compounds, except for CHC and SA, remained unchanged after fusion. CHC showed loss of CO2, yielding the trans-/cis-4-hydroxyphenylacrilonitrile mixture. This mixture was unambiguously characterized by MS and 1H-NMR spectroscopy, and its sublimation capability was demonstrated. These results explain the well-known cluster formation, fading (vanishing) and further recovering of CHC when used as a matrix in UV-MALDI-MS. Commercial SA (SA 98%; trans-SA/cis-SA 5:1) showed mainly cis- to-trans thermal isomerization and, with very poor yield, loss of CO2, yielding (3',5'-dimethoxy-4'-hydroxyphenyl)-1-ethene as the decarboxilated product. These thermal conversions would not drastically affect its behavior as a UV-MALDI matrix as happens in the case of CHC. Complementary studies of the photochemical stability of these matrices in solid state were also conducted. Copyright (c) 2008 John Wiley & Sons, Ltd.

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

Science.gov (United States)

2009-03-26

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

Development of a Textile Nanocomposite as Naked Eye Indicator of the Exposition to Strong Acids

Directory of Open Access Journals (Sweden)

Isabel Pallás

2017-09-01

Full Text Available Chemical burns, mainly produced by acids, are a topic of concern. A new sensing material for the detection of strong acids able to be incorporated into textiles has been developed. The material is prepared by the covalent attachment of 2,2′,4,4′,4″-pentamethoxy triphenyl methanol to a mesoporous material which further is included in a nitro resin to obtain a colourless composite. The response of this composite to diverse acid solutions was tested showing the appearance of an intense purple colour (with a colour difference higher than 160 that can be monitored by the naked eye or could be easily digitised to feed an instrumental sensor. Reversibility and resistance to washing cycles were studied with positive results. Finally, the response of the sensing composite to acid vapours was assayed, observing a colour change similar to that found in solution.

Optimized geometry, vibration (IR and Raman spectra and nonlinear optical activity of p-nitroanilinium perchlorate molecule: A theoretical study

Directory of Open Access Journals (Sweden)

Tamer Ömer

2016-03-01

Full Text Available The molecular modeling of p-nitroanilinium perchlorate molecule was carried out by using B3LYP and HSEH1PBE levels of density functional theory (DFT. The IR and Raman spectra were simulated and the assignments of vibrational modes were performed on the basis of relative contribution of various internal co-ordinates. NBO analysis was performed to demonstrate charge transfer, conjugative interactions and the formation of intramolecular hydrogen bonding interactions within PNAPC. Obtained large dipole moment values showed that PNAPC is a highly polarizable complex, and the charge transfer occurs within PNAPC. Hydrogen bonding and charge transfer interactions were also displayed by small HOMO-LUMO gap and molecular electrostatic potential (MEP surface. The strong evidences that the material can be used as an efficient nonlinear optical (NLO material of PNAPC were demonstrated by considerable polarizability and hyperpolarizability values obtained at DFT levels.

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

Science.gov (United States)

Zapata, Félix; García-Ruiz, Carmen

2018-01-01

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

Determination of low levels of perchlorate in lettuce and spinach using ion chromatography-electrospray ionization mass spectrometry (IC-ESI-MS).

Science.gov (United States)

Seyfferth, Angelia L; Parker, David R

2006-03-22

A sample preparation method was developed to quantify environmentally relevant (low micrograms per liter) concentrations of perchlorate (ClO4(-)) in leafy vegetables using IC-ESI-MS. Lettuce and spinach were macerated, centrifuged, and filtered, and the aqueous extracts were rendered water-clear using a one-step solid-phase extraction method. Total time for extraction and sample preparation was 6 h. Ion suppression was demonstrated and was likely due to unknown organics still present in the extract solution after cleanup. However, this interference was readily eliminated using a Cl(18)O4(-) internal standard at 1 microg/L in all standards and samples. Hydroponically grown perchlorate-free butterhead lettuce was spiked to either 10.3 or 37.7 microg/kg of fresh weight (FW), and recoveries were between 91 and 98% and between 93 and 101%, respectively. Five types of lettuce and spinach from a local grocery store were then analyzed; they contained from 0.6 to 6.4 microg/kg of FW. Spike recoveries using the store-bought samples ranged from 89 to 100%. The method detection limit for perchlorate in plant extracts is 40 ng/L, and the corresponding minimum reporting limit is 200 ng/L or 0.8 microg/kg of FW.

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

International Nuclear Information System (INIS)

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

1996-01-01

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

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

Science.gov (United States)

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

2015-11-03

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

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

Science.gov (United States)

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

Some studies on the reaction between nitrous acid and plutonium(IV)

International Nuclear Information System (INIS)

Vasudeva Rao, P.R.; Bagawde, S.V.; Ramakrishna, V.V.; Patil, S.K.

1976-01-01

In the ion exchange and solvent extraction studies nitrous acid is used as an oxidant for Pu(IV) in perchloric acid. Earlier studies had indicated that Pu(IV) forms complex with nitrous acid. The present investigation aimed to study this complex formation by solvent extraction and spectrophotometric methods, revealed that is no significant complex formation between Pu(IV) and nitrous acid. The high apparent equilibrium constant for the complex formation is caused by the partial reduction of Pu(IV) to Pu(III) by nitrous acid. The nitrate complexing is negligible in the case of Th(IV) and Np(IV) as well. Systematic investigation on the redox reactions of plutonium in different oxidation states with nitrous acid is now in progress. The preliminary results obtained indicate that Pu(IV) is reduced to Pu(III) by nitrous acid with a rate that can be conveniently followed spectrophotometrically. (T.I.)

Carbon-based strong solid acid for cornstarch hydrolysis

Science.gov (United States)

Nata, Iryanti Fatyasari; Irawan, Chairul; Mardina, Primata; Lee, Cheng-Kang

2015-10-01

Highly sulfonated carbonaceous spheres with diameter of 100-500 nm can be generated by hydrothermal carbonization of glucose in the presence of hydroxyethylsulfonic acid and acrylic acid at 180 °C for 4 h. The acidity of the prepared carbonaceous sphere C4-SO3H can reach 2.10 mmol/g. It was used as a solid acid catalyst for the hydrolysis of cornstarch. Total reducing sugar (TRS) concentration of 19.91 mg/mL could be obtained by hydrolyzing 20 mg/mL cornstarch at 150 °C for 6 h using C4-SO3H as solid acid catalyst. The solid acid catalyst demonstrated good stability that only 9% decrease in TRS concentration was observed after five repeat uses. The as-prepared carbon-based solid acid catalyst can be an environmentally benign replacement for homogeneous catalyst.

Strong Quantum Confinement Effects and Chiral Excitons in Bio-Inspired ZnO–Amino Acid Cocrystals

KAUST Repository

Muhammed, Madathumpady Abubaker Habeeb

2018-02-20

Elucidating the underlying principles behind band gap engineering is paramount for the successful implementation of semiconductors in photonic and optoelectronic devices. Recently it has been shown that the band gap of a wide and direct band gap semiconductor, such as ZnO, can be modified upon cocrystallization with amino acids, with the role of the biomolecules remaining unclear. Here, by probing and modeling the light-emitting properties of ZnO-amino acid cocrystals, we identify the amino acids\\' role on this band gap modulation and demonstrate their effective chirality transfer to the interband excitations in ZnO. Our 3D quantum model suggests that the strong band edge emission blue-shift in the cocrystals can be explained by a quasi-periodic distribution of amino acid potential barriers within the ZnO crystal lattice. Overall, our findings indicate that biomolecule cocrystallization can be used as a truly bio-inspired means to induce chiral quantum confinement effects in quasi-bulk semiconductors.

Developing a rapid method for the determination of uranium in pure phosphoric acid and D2 EHPA

International Nuclear Information System (INIS)

Koudsi, Y.; Stas, J.; Al-Merey, R.; shaddoud, G.

1996-02-01

Arsenazo (III) used in titrate uranium spectrophotometrically in phosphoric acid after its extraction into organic phase. In this work we used arsenazo(III) to complex uranyl ion in pure phosphoric acid and in the aqueous phase. The spectrum of the complex shows that λ max is at 650 nm. The linearity of the method is corelated with acid molarity, it is (1 -4, 10 - 30, 10 - 40) ppm uranium for (0.2, 1, 2) M of phosphoric acid respectively. Uranium in D 2 EHPA stripped by phosphoric acid and then determined by this method. Also it has been applied to determine uranium in pure perchloric acid. The method is direct, rapid, very cheap and relatively accurate. (author)

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

Science.gov (United States)

2003-04-01

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

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

Science.gov (United States)

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

Photochemical reactions of aqueous plutonium systems

International Nuclear Information System (INIS)

Friedman, H.A.; Toth, L.M.; Bell, J.T.

1977-01-01

The photochemical shift of the Pu 4+ disproportionation equilibrium in aqueous perchloric acid solutions has been measured and shown to be reversible. Ratios of equilibrium quotients between light and dark conditions have been measured for 0.01 M Pu ion concentrations in 0.53 to 1.24 N acid solutions exposed to 0.5 Watt of UV light. The photodecomposition of time- and temperature-aged Pu(IV) polymers in perchloric and nitric acid solutions have been examined as a function of aging conditions. Effects similar to those seen previously for fresh polymers have been observed in the aged perchloric acid solutions. (author)

Electrical characterization of proton conducting polymer electrolyte based on bio polymer with acid dopant

Energy Technology Data Exchange (ETDEWEB)

Kalaiselvimary, J.; Pradeepa, P.; Sowmya, G.; Edwinraj, S.; Prabhu, M. Ramesh, E-mail: email-mkram83@gmail.com [Department of Physics, Alagappa University, Karaikudi – 630 004, India. (India)

2016-05-06

This study describes the biodegradable acid doped films composed of chitosan and Perchloric acid with different ratios (2.5 wt %, 5 wt %, 7.5 wt %, 10 wt %) was prepared by the solution casting technique. The temperature dependence of the proton conductivity of complex electrolytes obeys the Arrhenius relationship. Proton conductivity of the prepared polymer electrolyte of the bio polymer with acid doped was measured to be approximately 5.90 × 10{sup −4} Scm{sup −1}. The dielectric data were analyzed using Complex impedance Z*, Dielectric loss ε’, Tangent loss for prepared polymer electrolyte membrane with the highest conductivity samples at various temperature.

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

Directory of Open Access Journals (Sweden)

Chuan Chen

2012-06-01

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

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

Science.gov (United States)

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

2018-01-01

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

Spectral Properties of Dyes with Interfragmental Charge Transfer: Solvatochromism and Solvatofluorochromism of 2-(3-Coumaroyl-benzopyrylium Perchlorates

Directory of Open Access Journals (Sweden)

Edward V. Sanin

2014-01-01

Full Text Available The paper deals with the spectral properties of dyes with interfragmental charge transfer, in particular, derivatives of 2-(3-coumaroylbenzopyrylium (CBP perchlorates. The positions of long-wavelength absorption and emission bands, quantum yields, and lifetimes of fluorescence were measured, mostly in aprotic solvents. Regression analysis of the relationship between the spectral characteristics of CBP and the main solvent parameters (polarity, polarisability, nucleophilicity, and electrophilicity was carried out. It was found that the characteristics of CBP depend mainly on two solvent parameters—polarity and/or nucleophilicity. An increase in these parameters results in a hypsochromic shift of absorption bands and a decrease of lifetimes and fluorescence intensity. The positions of the emission bands can demonstrate either hypsochromism or bathochromism, depending on the nature of the substituents. The solvatofluorochromic effects are not as strong as the solvatochromic ones. We believe that the spectral behaviour of CBP can be explained by cation depolarisation and by a decrease in the stability of nucleophilic complexes with solvent molecules that is associated with interfragmental charge transfer following excitation, relaxation, and radiative deactivation of the excited state.

Preliminary results for complexation of Pu with humic acid

Energy Technology Data Exchange (ETDEWEB)

Guczi, J.; Szabo, G. [National Research Inst. for Radiobiology and Radiohygi ene, Budapest, H-1775 (Hungary)]. e-mail: guczi@hp.osski.hu; Reiller, P. [CEA, CE Sac lay, Nuclear Energy Division/DPC/SERC, Laboratoire de Speciation des Radionuclei des et des Molecules, F-91191 Gif-sue-Yvette (France); Bulman, R.A. [Radiation Protection Division Division, Health Protection Agency, Chilton, Didcot (United Kingdom); Geckeis, H. [FZK - Inst. fuer Nukleare Entsorgung, Karlsruhe (Germany)

2007-06-15

Interaction of plutonium with humic substances has been investigated by a batch method use of the surface bound humic acid from perchlorate solutions at pH 4-6. By using these novel solid phases, complexing capacities and interaction constants are obtained. The complexing behavior of plutonium is analyzed. Pu(IV)-humate conditional stability constants have been evaluated from data obtained from these experiments by using non-linear regression of binding isotherms. The results have been interpreted in terms of complexes of 1:1 stoichiometry.

Extraction of Eu(III) by dinonylnaphthalenesulfonic acid and synergistic effects of crown ethers and trioctylphosphine oxide

International Nuclear Information System (INIS)

Ramadan, A.; Khalifa, S.M.; Mahmoud, M.; Souka, N.

1993-01-01

The extraction of Eu(III) by dinonylnaphthalenesulfonic acid (HDNNS) in benzene from nitrate and perchlorate solutions has been investigated. For nitrate solutions the ionic strength of the aqueous phase was kept constant at 0.1M using NaNO 3 -HNO 3 mixtures. The Eu distribution was measured at different temperatures. The following stoichiometric formulae for the Eu species in benzene were derived: Eu(NO 3 )(H n-1 (DNNS) n ) 2 and Eu(H n-1 (DNNS) n )3, from the nitrate and perchlorate medium respectively (n being a small number, e.g. 1,2 or 3). The equilibrium constants were calculated and the thermodynamic parameters of the system were determined. When adding dibenzo-24-crown-8, dicyclohexyl-18-crown-6 or trioctylphosphine oxide, no synergism, but rather antagonism was observed. (author) 14 refs.; 8 figs.; 2 tabs

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

International Nuclear Information System (INIS)

Terashima, Yukio; Takeda, Kiyoshi; Honda, Makoto

2011-01-01

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

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

Science.gov (United States)

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

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

Science.gov (United States)

This method is applicable to the identification and quantitation of perchlorate in raw and finished drinking waters. The approach used is ion chromatography with suppressed conductivity and electrospray ionization mass spectrometry (IC-ESI/MS)

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

Science.gov (United States)

2006-07-31

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

Rechargeable lithium/polymer cathode batteries

Science.gov (United States)

Osaka, Tetsuya; Nakajima, Toshiki; Shiota, Koh; Owens, Boone B.

1989-06-01

Polypyrrole (PPy) and polyaniline (PAn) were investigated for cathode materials of rechargeable lithium batteries. PPy films prepared with PF6(-) anion and/or platinum substrate precoated with nitrile butadiene rubber (NBR) were excellent cathode materials because of rough and/or highly oriented film structure. PAn films were successfully prepared from non-aqueous propylene carbonate solution containing aniline, CF3COOH and lithium perchlorate. Its acidity strongly affects the anion doping-undoping behavior. The PAn cathode prepared in high acidic solution (e.g., 4:1 ratio of acid:aniline) gives the excellent battery performance.

Strong ion and weak acid analysis in severe preeclampsia: potential clinical significance.

Science.gov (United States)

Ortner, C M; Combrinck, B; Allie, S; Story, D; Landau, R; Cain, K; Dyer, R A

2015-08-01

The influence of common disturbances seen in preeclampsia, such as changes in strong ions and weak acids (particularly albumin) on acid-base status, has not been fully elucidated. The aims of this study were to provide a comprehensive acid-base analysis in severe preeclampsia and to identify potential new biological predictors of disease severity. Fifty women with severe preeclampsia, 25 healthy non-pregnant- and 46 healthy pregnant controls (26-40 weeks' gestation), were enrolled in this prospective case-control study. Acid-base analysis was performed by applying the physicochemical approach of Stewart and Gilfix. Mean [sd] base excess was similar in preeclamptic- and healthy pregnant women (-3.3 [2.3], and -2.8 [1.5] mEq/L respectively). In preeclampsia, there were greater offsetting contributions to the base excess, in the form of hyperchloraemia (BE(Cl) -2 [2.3] vs -0.4 [2.3] mEq/L, Palkalosis was associated with a non-reassuring/abnormal fetal heart tracing (Prespiratory and hypoalbuminaemic alkalosis that was metabolically offset by acidosis, secondary to unmeasured anions and dilution. While the overall base excess in severe preeclampsia is similar to that in healthy pregnancy, preeclampsia is associated with a greater imbalance offsetting hypoalbuminaemic alkalosis and hyperchloraemic acidosis. Rather than the absolute value of base excess, the magnitude of these opposing contributors may be a better indicator of the severity of this disease. Hypoalbuminaemic alkalosis may also be a predictor of fetal compromise. clinicaltrials.gov: NCT 02164370. © The Author 2015. Published by Oxford University Press on behalf of the British Journal of Anaesthesia. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Sensitive detection of strong acidic condition by a novel rhodamine-based fluorescent pH chemosensor.

Science.gov (United States)

Tan, Jia-Lian; Yang, Ting-Ting; Liu, Yu; Zhang, Xue; Cheng, Shu-Jin; Zuo, Hua; He, Huawei

2016-05-01

A novel rhodamine-based fluorescent pH probe responding to extremely low pH values has been synthesized and characterized. This probe showed an excellent photophysical response to pH on the basis that the colorless spirocyclic structure under basic conditions opened to a colored and highly fluorescent form under extreme acidity. The quantitative relationship between fluorescence intensity and pH value (1.75-2.62) was consistent with the equilibrium equation pH = pKa + log[(Imax - I)/(I - Imin)]. This sensitive pH probe was also characterized with good reversibility and no interaction with interfering metal ions, and was successfully applied to image Escherichia coli under strong acidity. Copyright © 2015 John Wiley & Sons, Ltd.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-11-01

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

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

NARCIS (Netherlands)

Menninga, Lubbertus

1976-01-01

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

The behaviour of tungsten electrodes in a mixture of acetic acid and acetic anhydride

International Nuclear Information System (INIS)

Pastor, T.J.; Vajgand, V.H.

1976-01-01

Tungsten electrodes have advantageously been used for potentiometric end-point detection in perchloric acid titration of bases in a mixture of acetic acid and acetic anhydride. They have also given good results in biamperometric detection of the equivalence point in continuous coulometric titration of small quantities of bases and acids in the same solvent. Tungsten electrodes in the presence of quinhydrone behave like platinum electrodes, but in biamperometric end-point determination in the absence of quinhydrone it is better to remove the oxide layer from their surface. Some other factors affecting their behaviour have also been studied. Errors in determination do not exceed +-2% even in titration of very small quantities of substances. (author)

Synthesis of polycrystalline Co{sub 3}O{sub 4} nanowires with excellent ammonium perchlorate catalytic decomposition property

Energy Technology Data Exchange (ETDEWEB)

Zhou, Hai [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Lv, Baoliang, E-mail: lbl604@sxicc.ac.cn [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 (China); Wu, Dong; Xu, Yao [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001 (China)

2014-12-15

Graphical abstract: Co{sub 3}O{sub 4} nanowires with excellent ammonium perchlorate catalytic decomposition property were synthesized via a methanamide-assisted hydrolysis and subsequent dissolution–recrystallization process in the presence of methanamide. - Abstract: Co{sub 3}O{sub 4} nanowires, with the length of tens of micrometers and the width of several hundred nanometers, were produced by a hydrothermal treatment and a post-anneal process. X-ray diffraction (XRD) result showed that the Co{sub 3}O{sub 4} nanowires belong to cubic crystal system. Scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) analysis indicated that the Co{sub 3}O{sub 4} nanowires, composed by single crystalline nanoparticles, were of polycrystalline nature. On the basis of time-dependent experiments, methanamide-assisted hydrolysis and subsequent dissolution–recrystallization process were used to explain the precursors' formation process of the polycrystalline Co{sub 3}O{sub 4} nanowires. The TGA experiments showed that the as-obtained Co{sub 3}O{sub 4} nanowires can catalyze the thermal decomposition of ammonium perchlorate (AP) effectively.

Photobehavior of aqueous uranyl ion and photo-oxygenation of isobutane using light from the visible region

International Nuclear Information System (INIS)

Bergfeldt, T.M.; Waltz, W.L.; Xu, X; Sedlak, P.; Dreyer, U.; Mockel, H.; Lilie, J.; Stephenson, J.W.

2003-01-01

The photochemical and photophysical behavior of the aqueous uranyl ion [UO 2 (H 2 O) 5 ] 2+ has been studied under the influence of visible light and with added perchloric acid over the range of 0.01-4 M. In the presence of 2-methylpropane (isobutane), photo-oxygenation of isobutane occurs to yield, as the major product, 2-methyl-2-propanol (tert-butyl alcohol) along with lesser amounts of 2-methyl-2-propene (isobutene) and other C1-C8 products. The quantum yield for formation of tert-butyl alcohol is independent of light intensity at the irradiation wavelength of 415 nm and of uranyl concentration, but it increases from 0.016 ± 0.001 at 0.01 M HC1O 4 (pH 2) to 0.13 ± 0.01 at 4 M HC1O 4 . The emission spectrum from the electronically excited uranyl ion and the associated quantum yields have been measured in the presence and absence of isobutane, as a function of added perchloric acid. While in both cases the shape of the spectrum remains invariant, the quantum yields increase with increasing perchloric acid concentration. The strong dependence on added perchloric acid is interpreted within the context of the presence and interconversion of two electronically excited species, an acid form, *[UO 2 (H 2 O) 5 ] 2+ , and a base form, *[UO 2 (H 2 O) n (OH)] + . It is proposed that both forms react with isobutane to give a tert-butyl radical, and that oxidation of coordinated aqua ligands occur, the latter generating a hydroxyl radical whose reaction with isobutane rapidly leads also to a tert-butyl radical. The reaction of this alkyl radical with ground-state [UO 2 (H 2 O) 5 ] 2+ then gives rise to the stable tert-butyl alcohol product and reduced forms of uranyl ion. Based upon the values of the quantum yields and of excited-state lifetime measurements reported in the literature, a comprehensive mechanism has been developed in a quantitative manner to provide calculated values of the rate constants for the individual mechanistic steps. The calculated rate constants

A Porous Perchlorate-Doped Polypyrrole Nanocoating on Nickel Nanotube Arrays for Stable Wide-Potential-Window Supercapacitors.

Science.gov (United States)

Chen, Gao-Feng; Li, Xian-Xia; Zhang, Li-Yi; Li, Nan; Ma, Tian Yi; Liu, Zhao-Qing

2016-09-01

A bottom-up synthetic strategy is developed to fabricate a highly porous wave-superposed perchlorate-doped polypyrrole nanocoating on nickel nanotube arrays. The delicate nanostructure and the unique surface chemistry synergistically endow the obtained electrode with revealable pseudocapacitance, large operating potential window, and excellent cycling stability, which are highly promising for both asymmetric and symmetric supercapacitors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2013-01-01

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

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

Science.gov (United States)

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

Extraction of some acids using aliphatic amines; Extraction de quelques acides par des amines aliphatiques

Energy Technology Data Exchange (ETDEWEB)

Matutano, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1964-06-01

Hydrochloric, nitric, sulphuric, perchloric, phosphoric, acetic and formic acids in aqueous solution (0.05 to 10 M) are extracted by amberlite LA2 and trilaurylamine in solution, 5 per cent by volume, in kerosene and xylene respectively. The extraction process consists of: neutralization of the amine salt; a 'molecular extraction', i.e. an extraction using an excess of acid with respect to the stoichiometry of the amine salt. According to the behaviour of the acid during the extraction, three groups may be distinguished: completely dissociated acids, carboxylic acids, phosphoric acid. This classification is also valid for the extraction of the water which occurs simultaneously with that of the acid. An extraction mechanism is put forward for formic acid and the formation constant of its amine salt is calculated. (author) [French] Les acides chlorhydrique, nitrique, sulfurique, perchlorique, phosphorique, acetique et formique, en solution aqueuse - 0,05 a 10 M - sont extraits par l'amberlite LA2 et la trilaurylamine en solution, a 5 pour cent en volume, dans le kerosene et le xylene respectivement. L'extraction comprend: une neutralisation de l'amine par l'acide avec formation d'un sel d'amine; une 'extraction moleculaire', c'est-a-dire une extraction d'acide en exces par rapport a la stoechiometrie du sel d'amine. Suivant le comportement des acides au cours de l'extraction nous distinguons trois groupes: acides entierement dissocies, acides carboxyliques, acide phosphorique. Cette classification est egalement valable pour l'extraction de l'eau qui est simultanee a celle de l'acide. Un mecanisme d'extraction pour l'acide formique est propose et nous calculons la constante de formation de son sel d'amine. (auteur)

Study on the adducts formation of Zr and Hf chelates

International Nuclear Information System (INIS)

Ree, Chin Taik; Jung, Young Sam; Park, Jun Kown

1986-01-01

The synergistic effect observed in Zr(IV) and Hf(IV) extraction from strong perchloric acid solutions by the mixtures of 2-Thenoyltri-fluoroacetone(TTA) and Octanols is shown to be caused by the formation of a mixed complex, M(TTA) 3 XS (M=Zr(IV), HF(IV), X=ClO 4 - , S=Octanol). One of the four TTA molecules coordinated at lower HClO 4 concentration to the metal as bidendate ligand seems to be changed to monodendate due to increasing HClO 4 concentration. The monodenate TTA ligand leaves the coordination site, finally, due to the activity of perchlorate at higher concentration and the additional coordination of an Octanol molecule seems to be allowed to the vaccant site which shows the synergistic extraction phenomena. (Author)

Investigation of REE perchlorates complexing with benzimidazole in aqua-dioxane media. Issledovanie kompleksoobrazovaniya perkhloratov RZEh s benzimidazolom v vodno-dioksanovoj srede

Energy Technology Data Exchange (ETDEWEB)

Akhrimenko, Z M; Panyushkin, V T; Ishbulatova, S K [Kubanskij Gosudarstvennyj Univ., Krasnodar (Russian Federation)

1992-01-01

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

[Health survey of plant workers for an occupational exposure to ammonium perchlorate].

Science.gov (United States)

Chen, Hong-xia; Shao, Yuan-peng; Wu, Feng-hong; Li, Yang-ping; Peng, Kai-liang

2013-01-01

To understand the occupational hazards of ammonium perchlorate dust on operating workers and to provide the basis preventive measures for protecting the workers' health. 36 workers exposed to ammonium perchlorate dust and 48 unexposed workers from one factory were selected as the exposure and control groups. Investigations on the general condition, sampling of dust in the workplaces and a special medical examination were conducted for two groups, including occupational history, clinical manifestations, blood routine test, hepatic and renal functions, indexes of thyroid hormone, spirometric test and chest X-ray. The total dust concentration of AP in the batch plant reached to 51.63 ± 43.27 mg/m(3), exceeding the U.S. Occupational Safety and Health Administration (OSHA) permission exposure limits. The systolic blood pressure in the exposure group was higher than that of the control group (146.14 ± 21.03 VS 134.67 ± 18.58), and the difference was statistically significant (P detection rates of the cumulative total symptoms, short of breath and skin itch symptoms in the exposure group were significantly higher than those in the control group (86.11% VS 66.67%; 30.56% VS 12.50%) (P detected on the left of lung door area in the control group. The systolic blood pressure of workers in the exposure group was significantly higher, which could not exclude related to the exposure to AP dust; The T(3) levels in the exposure workers were lower than those in the control group, which may due to AP exposure, suggesting that long-term chronic exposure to AP dust may affect thyroid function.

The electrochemical polishing behavior of the Inconel 718 alloy in perchloric-acetic mixed acids

International Nuclear Information System (INIS)

Huang, C.A.; Chen, Y.C.; Chang, J.H.

2008-01-01

The electropolishing behavior of the Inconel 718 alloy was studied by using rotating disc electrode (RDE) in the HClO 4 -CH 3 COOH mixed acids with different HClO 4 -concentrations. After electropolishing, surface morphologies of RDE specimens were examined with surface profiler, atomic force microscope and scanning electron microscope. According to the surface morphologies observed, three types of anodic dissolution behavior can be characterized in relation to the HClO 4 -content in mixed acids; namely, leveling without brightening of the surface in the mixed acids with 10 and 20 vol% HClO 4 , leveling and brightening of the surface in the mixed acids with 30 and 40 vol% HClO 4 , and a matt and gray surface in the mixed acids with 50 vol% or more HClO 4 . Anodic dissolution in the first and second dissolution types follows a mass-transfer controlled mechanism, in which a linear relationship between the reciprocal of limiting-current density and the reciprocal of square root of rotating speed of RDE specimen can be detected. Owing to precipitation of salt film on the polished surface of the Inconel 718 material, saturated dissolved metallic ions could be the chemical species for the mass-controlled mechanism. The salt film, in addition, could enhance the corrosion resistance of the Inconel 718 alloy

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-10-01

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

The perchlorate discharge test with {sup 123}I for the diagnosis of the Pendred syndrome in children; Der Depletionstest mit {sup 123}Iod zur Diagnose des Pendred-Syndroms bei Kindern

Energy Technology Data Exchange (ETDEWEB)

Hahn, K.; Fischer, S. [Klinik und Poliklinik fuer Nuklearmedizin, Klinikum der Ludwig-Maximilians-Univ. Muenchen (Germany)

2009-03-15

The method for the diagnosis of the Pendred Syndrome in children by the Perchlorate discharge test using {sup 123}I is described. The older child, who has the Pendred Syndrome and the obligatory hearing deficit, frequently has neither a goitre nor hypothyroidism, but other investigations (bone growth, scars and function tests) can also show changes. However a more certain diagnosis of this disorder in children is possible by the perchlorate discharge test using {sup 123}I. (orig.)

Kinetics and Mechanism of Oxidation of Aromatic Aldehydes by Imidazolium Dichromate in Aqueous Acetic Acid Medium

Directory of Open Access Journals (Sweden)

S. Sheik Mansoor

2009-01-01

Full Text Available The kinetics of oxidation of benzaldehyde (BA and para-substituted benzaldehydes by imidazolium dichromate (IDC has been studied in aqueous acetic acid medium in the presence of perchloric acid. The reaction is first order each in [IDC], [Substrate] and [H+]. The reaction rates have been determined at different temperatures and the activation parameters calculated. Electron withdrawing substituents are found to increase the reaction and electron releasing substituents are found to retard the rate of the reaction and the rate data obey the Hammett relationship. The products of the oxidation are the corresponding acids. The rate decreases with the increase in the water content of the medium. A suitable mechanism is proposed.

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

Science.gov (United States)

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

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

Science.gov (United States)

2008-10-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-02-15

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-05-10

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

MEASUREMENT OF PERCHLORATE IN WATER BY USE OF AN 18O-ENRICHED ISOTOPIC STANDARD AND ION CHROMATOGRAPHY WITH MASS SPECTROMETRIC DETECTION

Science.gov (United States)

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

Reduction Rates for Higher Americium Oxidation States in Nitric Acid

Energy Technology Data Exchange (ETDEWEB)

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

2015-09-30

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

Eight supramolecular assemblies constructed from bis(benzimidazole) and organic acids through strong classical hydrogen bonding and weak noncovalent interactions

Science.gov (United States)

Jin, Shouwen; Wang, Daqi

2014-05-01

Eight crystalline organic acid-base adducts derived from alkane bridged bis(N-benzimidazole) and organic acids (2,4,6-trinitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, 3,5-dinitrobenzoic acid, 5-sulfosalicylic acid and oxalic acid) were prepared and characterized by X-ray diffraction analysis, IR, mp, and elemental analysis. Of the eight compounds five are organic salts (1, 4, 6, 7 and 8) and the other three (2, 3, and 5) are cocrystals. In all of the adducts except 1 and 8, the ratio of the acid and the base is 2:1. All eight supramolecular assemblies involve extensive intermolecular classical hydrogen bonds as well as other noncovalent interactions. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, all the complexes displayed 3D framework structure. The results presented herein indicate that the strength and directionality of the classical N+-H⋯O-, O-H⋯O, and O-H⋯N hydrogen bonds (ionic or neutral) and other nonbonding associations between acids and ditopic benzimidazoles are sufficient to bring about the formation of cocrystals or organic salts.

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

DEFF Research Database (Denmark)

Birk, Torben; Bendix, Jesper

2010-01-01

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

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

International Nuclear Information System (INIS)

Montero, V.; Cernicchiaro, G.

2008-01-01

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

SOLVENT EFFECTS IN THE LIQUID-PHASE HYDRATION OF CYCLOHEXENE CATALYZED BY A MACROPOROUS STRONG ACID ION-EXCHANGE RESIN

NARCIS (Netherlands)

PANNEMAN, HJ; BEENACKERS, AACM

1992-01-01

The liquid-phase hydration of cyclohexene, a pseudo first order reversible reaction catalyzed by a strong acid ion exchange resin, macroporous Amberlite XE 307, was investigated in solvent mixtures of water and sulfolane. A decrease by a factor of 3 and 6 is observed in the experimentally measured

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

Science.gov (United States)

2007-07-01

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

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

Directory of Open Access Journals (Sweden)

Torben Birk

2010-02-01

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

Theoretical Investigation of Oxazine 170 Perchlorate Doped Polymeric Optical Fiber Amplifier

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Piotr Miluski

2017-01-01

Full Text Available Optical signal amplification in the waveguiding structure of optical fibers can be used for optical telecommunication systems and new light sources constructions. Organic dyes doped materials are interesting for new applications in polymeric optical fibers technology due to their benefits (efficient fluorescence, high absorption cross section, and easy processing. This article presents a numerical simulation of gain in poly(methyl methacrylate optical fiber doped by Oxazine 170 Perchlorate. The calculated gain characteristic for the used dye molar concentration (0.2·10-6–1.4·10-6 and pump power (1–10 kW is presented. The fabricated fluorescent polymeric optical fiber is also shown. The presented analysis can be used for optical amplifier construction based on dye-doped polymeric optical fiber (POF.

High-Nitrogen-Based Pyrotechnics: Longer- and Brighter-Burning, Perchlorate-Free, Red-Light Illuminants for Military and Civilian Applications

Science.gov (United States)

2011-01-01

combustion of these materials. To address the aforementioned perchlorate issues, an effort was initiated by ARDEC to remove potassium per- chlorate ...with acceptable burn times for pyrotechnic applications by using potassium nitrate– amorphous boron–crystalline boron/boron carbide–epoxy binder mixtures...3,4] Moreover, it was discovered by ARDEC that a potassium nitrate–boron carbide–epoxy binder mix- ture alone was able to generate suitable green

SUB-PPB QUANTITATION AND CONFIRMATION OF PERCHLORATE IN DRINKING WATERS CONTAINING HIGH TOTAL DISSOLVED SOLIDS USING ION CHROMATOGRAPHY WITH MASS SPECTROMETRIC DETECTION

Science.gov (United States)

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

Preliminary Study on Purification and Identification of Aromatic Acid Amino L-Dopa From Malaysia Freshwater Green Mussel Byssus

International Nuclear Information System (INIS)

Saiful Irwan Zubairi; Wan Rosmaryana Wan Musa; Syed Anuar Faua'ad Syed Mohammad

2014-01-01

L-DOPA (L-3, 4-dihydroxyphenylalanine) is a type of aromatic amino acid which can be detected by using acidic extraction and purification method involving adhesive byssus green mussel protein. The main objective of this study is to identify and purify the aromatic amino acid L-DOPA via the utilization of gel Sephadex G-200 filtration chromatography based on two types of acidic and basic mobile phase solution. The crushing and homogenizing for adhesive byssus green mussel were conducted using a mortar and a pestle with the aid of liquid nitrogen. The samples that had been crushed were then mixed and dissolved in perchloric acid 0.7 %, 1.0 % and 1.5 % (v/ v) (pre-treatment) prior to the extraction process. The extraction was carried out by centrifuging the extracts at 11,000 rpm for about 10 mins and at a temperature of 10 degree Celsius to obtain supernatant S1. The supernatant was mixed with acetone and sulphuric acid and centrifuged for the second time to produce a pellet and then it was dissolved in the respective mobile phase solutions prior to purification process. Purification was later performed using two mobile phase solutions which were acetic acid 5 % (v/ v) and NaOH 1 M. The absorbance (abs) value of each purified protein extract fractions was collected and analysed at 214 nm to 400 nm with the help of UV-spectrophotometer. The highest abs value was selected for identification and verification of amino acid L-DOPA in the purified solution. Verification was carried out by utilizing high performance liquid chromatography (HPLC) and thin layer chromatography (TLC). The results showed that the use of 0.7 % (v/ v) perchloric acid and 5 % (v/ v) acetic acid for pre-treatment process and mobile phase solution of purification process respectively, yielded the highest effluent abs profile at a wavelength of 260 nm. TLC analysis proved the existence of several important amino acids besides L-DOPA which were tyrosine and phenylalanine after 78 hrs of collection of

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

International Nuclear Information System (INIS)

Li, Ping; Zhou, Zhen; Xu, Hongbin; Zhang, Yi

2012-01-01

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

Determination of microquantities of zirconium and thorium in uranium dioxide

International Nuclear Information System (INIS)

Weber de D'Alessio, Ana; Zucal, Raquel.

1975-07-01

A method for the determination of 10 to 50 ppm of zirconium and thorium in uranium IV oxide of nuclear purity is established. Zirconium and thorium are retained in a strong cation-exchange resin Dowex 50 WX8 in 1 M HCl. Zirconium is eluted with 0,5% oxalic acid solution and thorium with 4% ammonium oxalate. The colorimetric determination of zirconium with xilenol orange is done in perchloric acid after destructtion of oxalic acid and thorium is determined with arsenazo III in 5 M HCl. 10 μg of each element were determined with a standard deviation of 2,1% for thorium and 3,4% for zirconium. (author) [es

Streptomyces clavuligerus shows a strong association between TCA cycle intermediate accumulation and clavulanic acid biosynthesis.

Science.gov (United States)

Ramirez-Malule, Howard; Junne, Stefan; Nicolás Cruz-Bournazou, Mariano; Neubauer, Peter; Ríos-Estepa, Rigoberto

2018-05-01

Clavulanic acid (CA) is produced by Streptomyces clavuligerus (S. clavuligerus) as a secondary metabolite. Knowledge about the carbon flux distribution along the various routes that supply CA precursors would certainly provide insights about metabolic performance. In order to evaluate metabolic patterns and the possible accumulation of tricarboxylic acid (TCA) cycle intermediates during CA biosynthesis, batch and subsequent continuous cultures with steadily declining feed rates were performed with glycerol as the main substrate. The data were used to in silico explore the metabolic capabilities and the accumulation of metabolic intermediates in S. clavuligerus. While clavulanic acid accumulated at glycerol excess, it steadily decreased at declining dilution rates; CA synthesis stopped when glycerol became the limiting substrate. A strong association of succinate, oxaloacetate, malate, and acetate accumulation with CA production in S. clavuligerus was observed, and flux balance analysis (FBA) was used to describe the carbon flux distribution in the network. This combined experimental and numerical approach also identified bottlenecks during the synthesis of CA in a batch and subsequent continuous cultivation and demonstrated the importance of this type of methodologies for a more advanced understanding of metabolism; this potentially derives valuable insights for future successful metabolic engineering studies in S. clavuligerus.

Complexes of Th(IV) perchlorates, nitrates and thiocyanates with some heterocyclic bases

International Nuclear Information System (INIS)

Agarwal, R.K.; Srivastava, A.K.; Srivastava, M.; Bhakru, N.; Srivastava, T.N.

1980-01-01

Some Th(IV) perchlorate complexes of heterocyclic bases have been reported previously. Adducts of Th(IV) nitrates and thiocyanates with some heterocyclic N-oxides have been prepared and physico-chemical properties investigated. Comparatively little is known about the complexes of Th(IV) ion with the ligands containing nitrogen atom acting as electron donating centres. In view of this, the adducts of Th(IV) ion with certain nitrogen heterocyclic bases such as pyridine (Py), α-picoline (Pic), 2-amino pyridine (NH 2 Py), 2:4-lutidine (2,4LN), 2:6-lutidine, (2,6LN), quinoline (Q), isoquinoline (Isoq), 2,2'-bipyridine (Bipy) and 1,10-phenanthroline (Phen) were synthesised and characterised by analysis and IR absorption spectra. The results are presented and discussed. (author)

Fabrication of porous MgCo2O4 with rod-like morphology and its superb catalytic activity towards ammonium perchlorate thermal decomposition

Science.gov (United States)

Li, Gang; Liu, Xiaoli; Bai, Weiyang

2018-03-01

In this paper, porous MgCo2O4 with rod-like morphology was successfully synthesized through the thermal treatment of metal oxalates precursor originated by the reaction of metal sulfates and oxalic acid, without the addition of other additives. The porous rod-like MgCo2O4, with a diameter of several hundred nanometers and a length of several micrometers, was formed through the agglomeration of numerous crystalline grains sized in 10–25 nm. Its catalytic effect on ammonium perchlorate (AP) thermal decomposition was evaluated using differential scanning calorimetry (DSC) techniques. It was found that the pyrolysis temperature of AP reduced by 129 °C and the heat release increased more than 3.19-fold with a 2 wt% addition of MgCo2O4. Meanwhile, the addition of MgCo2O4 resulted in an AP decomposition activation energy reduction from 216 kJ mol‑1 to 155 kJ mol‑1, calculated using the Kissinger correlation. This study provides new insights into the design and development of high performance catalysts for AP thermal decomposition.

Kinetics of uranium (4) oxidation with nitrous acid in the presence of oxalate-ions in nitric and perchloric acid solutions

International Nuclear Information System (INIS)

Nikitenko, S.I.; Astafurova, L.N.

1991-01-01

Kinetics of uranium (4) oxidation with nitrous acid in the presence of oxalate-ions are studied spectrometrically. It is shown that even at small oxalate concentrations a notable effect of tetravalent uranium stabilization is observed relatively to the oxidation with nitrous acid. In case of a significant excess of oxalate-ions the oxidation rate will be considerably slower as a result of the formation of U(4) bisoxalate complex

Size-tunable silver nanoparticles synthesized by using aminopolycarboxylic acids at ambient-temperature

International Nuclear Information System (INIS)

Malkar, Vishwabharati V.; Chadha, R.; Biswas, N.; Mukherjee, T.; Kapoor, S.

2009-01-01

Full text: Stable aqueous sols of silver nanoparticles are prepared by using various aminopolycarboxylic acids as stabilizing agents at ambient temperature. The precursor silver perchlorate is reduced using γ radiations. Interestingly, it was observed that size of silver nanoparticles obtained could be tuned using various aminopolycarboxylic acids of varying carboxylic acid groups The silver sols synthesized by this method were stable for months and particles obtained were monodisperse in almost all cases. Particle formation was observed at equimolar concentration of silver and aminopolycarboxylic acids. The stabilization of particles even in the absence of any polymer indicates that the adsorption of aminopolycarboxylic acids on silver particle is a spontaneous process. The adsorbed aminopolycarboxylic acids can saturate the residual valence force of the silver atom on the particle surface by coordinating with unoccupied orbital. Adsorption of aminopolycarboxylic acids does not lead to any change in surface plasmon band of silver nanoparticles; this indicates that anions in the double layer on the colloidal particle have different chemical properties from the free anions. Synthesized silver nanoparticles were characterized by UV-visible spectrophotometer, X-ray Diffraction, Dynamic Light Scattering and Transmission Electron Microscope

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

Directory of Open Access Journals (Sweden)

Greg A. Brewer

2008-01-01

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

Kinetics of phosphotungstic acid catalyzed oxidation of propan-1,3-diol and butan-1,4-diol by N-chlorosaccharin

Directory of Open Access Journals (Sweden)

Sanjay Kumar Singh

2011-09-01

Full Text Available The kinetic studies of N-chlorosaccharin (NCSA oxidation of propan-1,3-diol and butan-1,4-diol have been reported in presence of phophotungstic acid and in aqueous acetic acid medium. The reactions follow first-order in NCSA and one to zero order with respect to substrate and phosphotungstic acid. Increase in the concentration of added perchloric acid increases the rate of oxidation. A negative effect on the oxidation rate is observed for solvent whereas the ionic strength does not influence the rate of reaction. Addition of the reaction product, saccharin, exhibited retarding effect. Various activation parameters have been evaluated. The products of the reactions were identified as the corresponding aldehydes. A suitable scheme of mechanism consistent with the experimental results has been proposed.

Single-step electrochemical method for producing very sharp Au scanning tunneling microscopy tips

International Nuclear Information System (INIS)

Gingery, David; Buehlmann, Philippe

2007-01-01

A single-step electrochemical method for making sharp gold scanning tunneling microscopy tips is described. 3.0M NaCl in 1% perchloric acid is compared to several previously reported etchants. The addition of perchloric acid to sodium chloride solutions drastically shortens etching times and is shown by transmission electron microscopy to produce very sharp tips with a mean radius of curvature of 15 nm

Characteristics of polyaniline electrosynthesized in propylene carbonate medium in the presence of di- and trichloroacetic acids

Directory of Open Access Journals (Sweden)

Venancio Everaldo C.

2001-01-01

Full Text Available In the present work the characterization of polyaniline electrosynthesized in propylene carbonate medium in the presence of di- and trichloroacetic acids was performed using different techniques. The electrochemical response by cyclic voltammetry showed redox processes due to the formation of polaron and bipolaron and polymer degradation. The characterization by infrared and UV-visible spectroscopies indicated that the polymers are in the emeraldine salt form with perchlorate anions incorporated. The films produced with both acids in propylene carbonate media presented a compact morphology as observed by scanning electron microscopy. By testing the polyaniline film produced in selected conditions in a lithium battery environment it was found that it presents a high coulombic efficiency, promising for battery applications.

The tricarboxylic acid cycle activity in cultured primary astrocytes is strongly accelerated by the protein tyrosine kinase inhibitor tyrphostin 23

DEFF Research Database (Denmark)

Hohnholt, Michaela C; Blumrich, Eva-Maria; Waagepetersen, Helle S

2017-01-01

production. In addition, T23-treatment strongly increased the molecular carbon labeling of the TCA cycle intermediates citrate, succinate, fumarate and malate, and significantly increased the incorporation of (13)C-labelling into the amino acids glutamate, glutamine and aspartate. These results clearly......Tyrphostin 23 (T23) is a well-known inhibitor of protein tyrosine kinases and has been considered as potential anti-cancer drug. T23 was recently reported to acutely stimulate the glycolytic flux in primary cultured astrocytes. To investigate whether T23 also affects the tricarboxylic acid (TCA...

Optimized methods to measure acetoacetate, 3-hydroxybutyrate, glycerol, alanine, pyruvate, lactate and glucose in human blood using a centrifugal analyser with a fluorimetric attachment.

Science.gov (United States)

Stappenbeck, R; Hodson, A W; Skillen, A W; Agius, L; Alberti, K G

1990-01-01

Optimized methods are described for the analysis of glucose, lactate, pyruvate, alanine, glycerol, D-3-hydroxybutyrate and acetoacetate in perchloric acid extracts of human blood using the Cobas Bio centrifugal analyser. Glucose and lactate are measured using the photometric mode and other metabolites using the fluorimetric mode. The intra-assay coefficients of variation ranged from 0.7 to 4.1%, except with very low levels of pyruvate and acetoacetate where the coefficients of variation were 7.1 and 12% respectively. All seven metabolites can be measured in a perchloric acid extract of 20 mul of blood. The methods have been optimized with regard to variation in the perchloric acid content of the samples. These variations arise from the method of sample preparation used to minimize changes occurring in metabolite concentration after venepuncture.

Thermodynamics of the complexation of ciprofloxacin with calcium and magnesium perchlorate

Energy Technology Data Exchange (ETDEWEB)

Al-Mustafa, Jamil, E-mail: malkawi@just.edu.jo [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid (Jordan); Taha, Ziyad A. [Department of Applied Chemistry, Faculty of Arts and Sciences, Jordan University of Science and Technology, P.O. Box 3030, Irbid (Jordan)

2011-07-10

Highlights: {yields} The thermodynamics of the reactions of ciprofloxacin (CIP) with Ca(ClO{sub 4}){sub 2} and Mg(ClO{sub 4}){sub 2} were investigated by conductometric titration. {yields} The reactions of CIP with each ion produce two ionic complexes with the formulas M(CIP){sup 2+} and M(CIP){sub 2}{sup 2+}. {yields} The change in enthalpy and entropy were negative which indicate that the complexation is driven by the enthalpy change. - Abstract: The thermodynamics of the reactions of ciprofloxacin (CIP) with calcium perchlorate (Ca(ClO{sub 4}){sub 2}) and magnesium perchlorate (Mg(ClO{sub 4}){sub 2}) have been investigated in water-methanol solvent using conductometric titration. The reactions of CIP with each ion produce two ionic complexes with the general formulas M(CIP){sup 2+} and M(CIP){sub 2}{sup 2+}. The stability constants K{sub 1} and K{sub 2} at 25 {sup o}C for the complexes formed from the reaction with Ca(ClO{sub 4}){sub 2} were 8.84 x 10{sup 4} and 3.62 x 10{sup 4}, respectively. For the reaction with Mg(ClO{sub 4}){sub 2}K{sub 1} and K{sub 2} were 1.72 x 10{sup 5} and 2.50 x 10{sup 3}, respectively. The enthalpy ({Delta}H{sub 1}, {Delta}H{sub 2}, {Delta}H{sub 12}) and entropy ({Delta}S{sub 1}, {Delta}S{sub 2}, {Delta}S{sub 12}) of complexation reactions were determined from the temperature dependence of the complexation constants. The reactions of CIP with both ions are accompanied by a decrease in entropy ({Delta}S{sub 12} = -468.12 and -478.89 J/K mol for complexation with Ca(ClO{sub 4}){sub 2} and Mg(ClO{sub 4}){sub 2}, respectively) and enthalpy ({Delta}H{sub 12} = -193.09 and -192.01 kJ/mol for complexation with Ca(ClO{sub 4}){sub 2} and Mg(ClO{sub 4}){sub 2}, respectively), which indicate that the reactions are driven by the enthalpy change.

Hirshfeld surface analysis of the 1,1´-(ethane-1,2-diyl)dipyridinium dication in two new salts: perchlorate and peroxodisulfate

Czech Academy of Sciences Publication Activity Database

Gholizadeh, M.; Pourayoubi, M.; Farimaneh, M.; Tarahhomi, A.; Dušek, Michal; Eigner, Václav

2014-01-01

Roč. 70, FEB (2014), s. 230-235 ISSN 0108-2701 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : crystal structure * Hirshfeld surface analysis * fingerprint plots * perchlorate salt * peroxodisulfate salt * 1,1'-( ethane -1,2-diyl)dipyridinium dication Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.326, year: 2014

Perchlorate remediation using packed-bed bioreactors and electricity generation in microbial fuel cells (MFCs)

Science.gov (United States)

Min, Booki

Two pilot-scale fixed bed bioreactors were operated in continuous mode in order to treat groundwater contaminated by perchlorate. The bioreactors were constructed and operated side-by-side at the Texas Street Well Facility in Redlands, California. Each reactor was packed with either sand or plastic media. A perchlorate-reducing bacterium, Dechlorosoma sp. KJ, was used to inoculate the bioreactors. Perchlorate was successfully removed down to a non-detectable level (microbial fuel cells (MFCs), which were run either in batch or continuous mode. In batch experiments, both a pure culture (Geobactor metallireducens) and a mixed culture (wastewater inoculum) were used as the biocatalyst, and acetate was added as substrate in the anode chamber of the MFC. Power output in a membrane MFC with either inoculum was essentially the same, with 40 +/- 1 mW/m2 for G. metallireducens and 38 +/- 1 mW/m2 for mixed culture. A different type of the MFC containing a salt bridge instead of a membrane system was examined to generate power using the same substrate and pure culture as used in the membrane MFC. Power output in the salt bridge MFC was 2.2 mW/m 2. It was found that the lower power output was directly attributed to the higher internal resistance of the salt bridge system (19920 +/- 50 O) in comparison with that of the membrane system (1286 +/- 1 O). Continuous electricity generation was examined in a flat plate microbial fuel cell (FPMFC) using domestic wastewater and specific organic substrates. The FPMFC, containing a combined electrode/proton exchange membrane (PEM), was initially acclimated for one month to domestic wastewater, and then was operated as a plug flow reactor system. Power density using domestic wastewater as a substrate was 72 +/- 1 mW/m2 at a liquid flow rate of 0.39 mL/min (1.1 hr hydraulic retention time, HRT), and COD removal was 42%. At a longer HRT of 4.0 hr, the COD removal increased to 79%, and power density was 43 mW/m2. Several organic compounds

Chlorine-36 abundance in natural and synthetic perchlorate

Energy Technology Data Exchange (ETDEWEB)

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

2009-01-01

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

Chromatographic retention prediction and octanol-water partition coefficient determination of monobasic weak acidic compounds in ion-suppression reversed-phase liquid chromatography using acids as ion-suppressors.

Science.gov (United States)

Ming, Xin; Han, Shu-ying; Qi, Zheng-chun; Sheng, Dong; Lian, Hong-zhen

2009-08-15

Although simple acids, replacing buffers, have been widely applied to suppress the ionization of weakly ionizable acidic analytes in reversed-phase liquid chromatography (RPLC), none of the previously reported works focused on the systematic studies about the retention behavior of the acidic solutes in this ion-suppression RPLC mode. The subject of this paper was therefore to investigate the retention behavior of monobasic weak acidic compounds using acetic, perchloric and phosphoric acids as the ion-suppressors. The apparent octanol-water partition coefficient (K" ow) was proposed to calibrate the octanol-water partition coefficient (K(ow)) of these weak acidic compounds, which resulted in a better linear correlation with log k(w), the logarithm of the hypothetical retention factor corresponding to neat aqueous fraction of hydroorganic mobile phase. This log K" ow-log k w linear correlation was successfully validated by the results of monocarboxylic acids and monohydrating phenols, and moreover by the results under diverse experimental conditions for the same solutes. This straightforward relationship not only can be used to effectively predict the retention values of weak acidic solutes combined with Snyder-Soczewinski equation, but also can offer a promising medium for directly measuring K(ow) data of these compounds via Collander equation. In addition, the influence of the different ion-suppressors on the retention of weak acidic compounds was also compared in this RPLC mode.

ANALYSIS OF THE KINETICS OF SOLVOLYSIS OF P-NITROPHENYLSULFONYLMETHYL PERCHLORATE IN BINARY ALCOHOLIC MIXTURES IN TERMS OF THE THERMODYNAMIC PROPERTIES OF THE SOLVENT MIXTURES

NARCIS (Netherlands)

Wijnen, J W; Engberts, J B F N; Blandamer, Michael J

Rate constants are reported for the solvolysis of p-nitrophenylsulfonylmethyl perchlorate in binary ethanolic and methanolic mixtures at 298.2 K. Co-solvents include hydrocarbons, chlorinated hydrocarbons and 1,4-dioxane. The kinetic data are examined in terms of the effect of decreasing mole

A summary of recent developments in transportation hazard classification activities for ammonium perchlorate

Science.gov (United States)

Koller, A. M., Jr.; Hannum, J. A. E.

1983-01-01

The transportation hazard classification of Ammonium Perchlorate is discussed. A test program was completed and data were forwarded to retain a Class 5.1 designation (oxidizer) for AP which is shipped internationally. As a follow-on to the initial team effort to conduct AP tests existing data were examined and a matrix which catalogs test parameters and findings was compiled. A collection of test protocols is developed to standardize test methods for energetic materials of all types. The actions to date are summarized; the participating organizations and their roles as presently understood; specific findings on AP (matrix); and issues, lessons learned, and potential actions of particular interest to the propulsion community which may evolve as a result of future U.N. propellant transportation classification activities.

Redox reactions of neptunium in tributyl phosphate-dodecane mixtures

International Nuclear Information System (INIS)

Wehrey, F.

1989-01-01

In relation with the reprocessing of irradiated fuels, disproportionation and oxidation by nitric acid of pentavalent neptunium in tributyl phosphate-dodecane mixtures have been studied. The experimental part of this work is based on spectrophotometric measurements. The disproportionation of pentavalent neptunium in organic perchloric medium is a second order reaction with respect to neptunium V. The reaction rate is strongly influenced by the perchloric acid concentration and has a higher value than in an aqueous medium. The reverse reaction in nitric media is a first order with respect to tetravalent and hexavalent ions. The reaction rate is a function of the reverse of the square of the nitric acid concentration. The energy of activation is the same than in aqueous medium. The oxidation rate of pentavalent neptunium by nitric acid is increased by nitrous acid. When no nitrous acid is added to the mixture, the reaction revealed to be autocatalytic, possesses an induction period. When nitrous and nitric acids are in excess to neptunium the reaction is first order with respect to neptunium. The reaction rate depends on the concentration of nitric acid and is a linear function of the concentration of nitrous acid. In tributyl phosphate dodecane mixtures the reaction occurs spontaneously. It is not the case in aqueous media. The values of thermodynamical and kinetical constants determined in this work could be used in a modelization of the behavior of neptunium in the reprocessing of irradiated fuels, which has to eliminate this element among its tasks [fr

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

Science.gov (United States)

2010-08-01

presents a meaningful opportunity for reducing health risks for persons served by public water systems. History of EPA’s Investigation and Study...Colorado River region reported perchlorate in milk and various fruits and vegetables, including lettuce , but researchers concluded that few...installations. Of the 361 installations that reported not sampling, the primary reason cited for not sampling was that there was no history , record, or

3,4,5-trihydroxybenzoic acid as chelating agent

International Nuclear Information System (INIS)

Agrawal, M.D.; Bhandari, C.S.; Dixit, M.K.; Sogani, N.C.

1976-01-01

Stability constants of praseodymium chelates of 3,4,5-trihydroxy sodium benzoate are determined by using Bjerrum-Calvin pH titration techniques at constant ionic strength 0.1M-sodium perchlorate and at 28+-0.1 0 C. Values calculated by different methods are in good agreement. The study reveals that during complexation only one proton of the ligand molecule is replaced by the metal and oxygen of adjacent phenolic group acts as a coordinating atom. IR and NMR spectral studies of the ligand reveal that one of the OH groups (in meta position to carboxylic group) remains free while two other phenolic groups are involved in intramolecular hydrogen bonding. One water molecule is found attached in crystalline gallic acid. (author)

Nectar sugars and amino acids in day- and night-flowering Nicotiana species are more strongly shaped by pollinators' preferences than organic acids and inorganic ions.

Science.gov (United States)

Tiedge, Kira; Lohaus, Gertrud

2017-01-01

acids are more strongly correlated with the preferences of predominant pollinators than organic acids and inorganic ions.

Nectar sugars and amino acids in day- and night-flowering Nicotiana species are more strongly shaped by pollinators’ preferences than organic acids and inorganic ions

Science.gov (United States)

Tiedge, Kira; Lohaus, Gertrud

2017-01-01

acids are more strongly correlated with the preferences of predominant pollinators than organic acids and inorganic ions. PMID:28467507

Nectar sugars and amino acids in day- and night-flowering Nicotiana species are more strongly shaped by pollinators' preferences than organic acids and inorganic ions.

Directory of Open Access Journals (Sweden)

Kira Tiedge

, nectar sugars and amino acids are more strongly correlated with the preferences of predominant pollinators than organic acids and inorganic ions.

Performance of a pilot-scale packed bed reactor for perchlorate reduction using a sulfur oxidizing bacterial consortium.

Science.gov (United States)

Boles, Amber R; Conneely, Teresa; McKeever, Robert; Nixon, Paul; Nüsslein, Klaus R; Ergas, Sarina J

2012-03-01

A novel sulfur-utilizing perchlorate reducing bacterial consortium successfully treated perchlorate (ClO₄⁻) in prior batch and bench-scale packed bed reactor (PBR) studies. This study examined the scale up of this process for treatment of water from a ClO ₄⁻ and RDX contaminated aquifer in Cape Cod Massachusetts. A pilot-scale upflow PBR (∼250-L) was constructed with elemental sulfur and crushed oyster shell packing media. The reactor was inoculated with sulfur oxidizing ClO₄⁻ reducing cultures enriched from a wastewater seed. Sodium sulfite provided a good method of dissolved oxygen removal in batch cultures, but was found to promote the growth of bacteria that carry out sulfur disproportionation and sulfate reduction, which inhibited ClO₄⁻ reduction in the pilot system. After terminating sulfite addition, the PBR successfully removed 96% of the influent ClO₄⁻ in the groundwater at an empty bed contact time (EBCT) of 12 h (effluent ClO₄⁻ of 4.2 µg L(-1)). Simultaneous ClO₄⁻ and NO₃⁻ reduction was observed in the lower half of the reactor before reactions shifted to sulfur disproportionation and sulfate reduction. Analyses of water quality profiles were supported by molecular analysis, which showed distinct groupings of ClO₄⁻ and NO₃⁻ degrading organisms at the inlet of the PBR, while sulfur disproportionation was the primary biological process occurring in the top potion of the reactor. Copyright © 2011 Wiley Periodicals, Inc.

Estimation of free acid content in lanthanide salt solution used for pH-potentiometric determination of their stability constants with organic ligands

International Nuclear Information System (INIS)

Zheltvaj, I.I.; Tishchenko, M.A.

1985-01-01

To improve the pH-potentiometric method for determining complex stability constants the possibility of alkalimetric titration of a free acid in the lanthanide perchlorate solution after binding metal ions by disodium salt of ethylene-diamine-tetraacetic acid is studied. The stability constants were determined from the difference between the total acid content after complexon addition and doubled metal cation content in the solution which has been preliminarily determined by the complexonometric method. It is shown that the alkaline (NaOH) equivalent quantities spent for free acid titration either in the absence or presence of the complexon is different. With increase of free acid content in the solution the difference in determinations with complexon and without it is somewhat reduced. Thus, the use of complexon contributes to a higher accuracy in determining the free acid, and in the first place in case of minor contents

Biological perchlorate reduction in packed bed reactors using elemental sulfur.

Science.gov (United States)

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

2009-06-15

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

Solvent extraction of thorium(IV) with dibutyldithiophosphoric acid in various organic solvents

International Nuclear Information System (INIS)

Curtui, M.; Haiduc, I.

1994-01-01

The extraction of thorium(IV) from perchlorate solutions with di-n-butyldithiophosphoric acid (HBudtp) in various organic solvents occurs through an ion exchange mechanism. The extracted species in the organic phase is an eight-coordinate complex Th(Budtp) 4 . The higher values of the distribution ratio obtained in HBudtp-benzene-water system than in HBudtp-n-butanol-water system are explained by higher solubility of the complex species in nonpolar solvents. The position of the extraction curves in the pH-range lower than 0.7 reduces the complexation of thorium(IV) with Budtp - in the aqueous phase and also the hydrolysis process. (author) 8 refs.; 4 figs.; 1 tab

The interaction between Otto fuel II and aqueous hydroxylammonium perchlorate (HAP). Pt. 3: depletion of components within the reacting liquids

Energy Technology Data Exchange (ETDEWEB)

Bellerby, John M.; Blackman, Christopher S. [Department of Environmental and Ordnance Systems, Cranfield University, Defence College of Management and Technology, Shrivenham, Swindon SN6 8LA (United Kingdom)

2007-06-15

Gas chromatography (GC) with a Flame Ionisation Detector (FID) has been used to determine changes in the concentrations of the components of Otto Fuel II (OF) in contact with an 82% aqueous solution of hydroxylammonium perchlorate (HAP) in sealed vials at 31.7 C during the period leading up to auto-ignition of the two liquids. The concentration of hydroxylamine in HAP was monitored over the same period using a titration method. It was found that 2-nitrodiphenylamine (2NDPA), the stabiliser in the OF, is completely consumed after about 65-70 h and that the concentration of hydroxylamine begins to fall at this point. 1,2-Propanediol dinitrate (propylene glycol dinitrate, PGDN), the energetic component in the OF, is not depleted significantly until after about 90 h. The evolution of nitrous oxide (N{sub 2}O) between 65 and 90 h is attributed to the reaction of the hydroxylammonium ion with nitrous acids produced by PGDN decomposition at the liquid-liquid interface. Carbon dioxide (CO{sub 2}) is evolved after 90 h and is attributed to PGDN decomposition. HAP and PGDN are each thought to contribute to N{sub 2}O evolution after 90 h. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

Comparison of digestion procedures used for the determination of boron in biological tissues by ICP-AES [inductively-coupled, plasma-atomic emission spectroscopy

International Nuclear Information System (INIS)

Bauer, W.F.; Miller, D.L.; Steele, S.M.

1988-01-01

A study was designed to identify the most accurate and reliable procedures for the digestion of biological tissues prior to the determination of boron by inductively-coupled, plasma-atomic emission spectroscopy (ICP-AES). The four procedures used in this study were an acid bomb digestion and digestions performed in test tubes using perchloric acid and hydrogen peroxide, nitric acid and hydrogen peroxide, and nitric acid alone. Digestions using nitric acid and hydrogen peroxide and nitric acid alone were performed in a manner analogous to the perchloric acid/hydrogen peroxide procedure. The tissues used in the study were from dogs that had been administered a boron compound (Na 2 B 12 H 11 SH) and included two brain tissues, a liver and a tongue. These tissues were selected in order to eliminate results that may be due to surface spiking only. None of the test tube procedures were successful in completely dissolving the samples, as was evidenced by residual color and a coagulated precipitate. The amount of precipitate was much larger for the brain tissues in all cases. The acid bomb digestion and the perchloric acid/hydrogen peroxide procedures gave comparable boron concentrations for all of the tissues in this study. 2 refs., 1 tab

"JCE" Classroom Activity #109: My Acid Can Beat Up Your Acid!

Science.gov (United States)

Putti, Alice

2011-01-01

In this guided-inquiry activity, students investigate the ionization of strong and weak acids. Bead models are used to study acid ionization on a particulate level. Students analyze seven strong and weak acid models and make generalizations about the relationship between acid strength and dissociation. (Contains 1 table and 2 figures.)

Rapid determination of amino acids in biological samples using a monolithic silica column.

Science.gov (United States)

Song, Yanting; Funatsu, Takashi; Tsunoda, Makoto

2012-05-01

A high-performance liquid chromatography method in which fluorescence detection is used for the simultaneous determination of 21 amino acids is proposed. Amino acids were derivatized with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) and then separated on a monolithic silica column (MonoClad C18-HS, 150 mm×3 mm i.d.). A mixture of 25 mM citrate buffer containing 25 mM sodium perchlorate (pH 5.5) and acetonitrile was used as the mobile phase. We found that the most significant factor in the separation was temperature, and a linear temperature gradient from 30 to 49°C was used to control the column temperature. The limits of detection and quantification for all amino acids ranged from 3.2 to 57.2 fmol and 10.8 to 191 fmol, respectively. The calibration curves for the NBD-amino acid had good linearity within the range of 40 fmol to 40 pmol when 6-aminocaproic acid was used as an internal standard. Using only conventional instruments, the 21 amino acids could be analyzed within 10 min. This method was found to be suitable for the quantification of the contents of amino acids in mouse plasma and adrenal gland samples.

A Systematic Approach to In Situ Bioremediation in Groundwater Including Decision Trees on In Situ Bioremediation for Nitrates, Carbon Tetrachloride, and Perchlorate

Science.gov (United States)

2002-08-01

and waste, phytoremediation , aboveground denitrification, and, of course, EISBD. Please refer to this document for more details. 8.6 Applicability...facility also had associated seed treatment operations that may have contributed mercury compounds to the subsurface. The time of the releases will...the receptor community is essential. 10.8.2 Phytoremediation Bench-scale perchlorate phytoremediation studies have been conducted using parrot

Synthesis and thermal characterization of xylan-graft-polyacrylonitrile.

Science.gov (United States)

Ünlü, Cüneyt H; Öztekin, N Simge; Atıcı, Oya Galioğlu

2012-10-01

In this study emulsion polymerization of acrylonitrile using xylan from agricultural waste material (corn cob) and cerium ammonium nitrate was investigated in terms of catalyst acid. Stock ceric solutions were prepared using either nitric or perchloric acid as catalyst. Optimum conditions were determined using different parameters such as reaction time, temperature, and component concentrations. Nitric acid catalyzed reactions resulted in maximum conversion ratio (96%) at 50°C, 1 h where ceric ion, acrylonitrile, xylan, and catalyst concentrations were 21.7 mmol l(-1), 0.5 mol l(-1), 0.2% (w/v), and 0.1 mol l(-1), respectively. However, 83% conversion was obtained with perchloric acid catalysis at 27 °C, 1 h where concentrations were 5.4 mmol l(-1), 0.8 mol l(-1), 0.5% (w/v), and 0.2 mol l(-1), respectively. Copolymer synthesis using perchloric acid was realized at milder conditions than using nitric acid. Thermal analyses of obtained polymers were conducted to characterize copolymers. Results showed that calculated activation energy, maximum degradation temperature, and heat of thermal decomposition changed relying mainly on molecular weight. Copyright © 2012 Elsevier Ltd. All rights reserved.

Widespread occurrence of (per)chlorate in the Solar System

Science.gov (United States)

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

2015-01-01

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

Electrolytic nature of aqueous sulfuric acid. 2. Acidity.

Science.gov (United States)

Fraenkel, Dan

2012-09-27

In part 1 of this study, I reported that the Debye-Hückel limiting law and the smaller-ion shell (SiS) model of strong electrolyte solutions fit nicely with the experimental mean ionic activity coefficient (γ(±)) of aqueous sulfuric acid as a function of concentration and of temperature when the acid is assumed to be a strong 1-3 electrolyte. Here, I report that the SiS-derived activity coefficient of H(+), γ(H(+)), of the 1-3 acid is comparable to that of aqueous HCl. This agrees with titration curves showing, as well-known, that sulfuric acid in water is parallel in strength to aqueous HCl. The calculated pH is in good accord with the Hammett acidity function, H(0), of aqueous sulfuric acid at low concentration, and differences between the two functions at high concentration are discussed and explained. This pH-H(0) relation is consistent with the literature showing that the H(0) of sulfuric acid (in the 1-9 M range) is similar to those of HCl and the other strong mineral monoprotic acids. The titration of aqueous sulfuric acid with NaOH does not agree with the known second dissociation constant of 0.010 23; rather, the constant is found to be ~0.32 and the acid behaves upon neutralization as a strong diprotic acid practically dissociating in one step. A plausible reaction pathway is offered to explain how the acid may transform, upon base neutralization, from a dissociated H(4)SO(5) (as 3H(+) and HSO(5)(3-)) to a dissociated H(2)SO(4) even though the equilibrium constant of the reaction H(+) + HSO(5)(3-) ↔ SO(4)(2-) + H(2)O, at 25 °C, is 10(-37) (part 1).

Calculation of the total plasma concentration of nonvolatile weak acids and the effective dissociation constant of nonvolatile buffers in plasma for use in the strong ion approach to acid-base balance in cats.

Science.gov (United States)

McCullough, Sheila M; Constable, Peter D

2003-08-01

To determine values for the total concentration of nonvolatile weak acids (Atot) and effective dissociation constant of nonvolatile weak acids (Ka) in plasma of cats. Convenience plasma samples of 5 male and 5 female healthy adult cats. Cats were sedated, and 20 mL of blood was obtained from the jugular vein. Plasma was tonometered at 37 degrees C to systematically vary PCO2 from 8 to 156 mm Hg, thereby altering plasma pH from 6.90 to 7.97. Plasma pH, PCO2, and concentrations of quantitatively important strong cations (Na+, K+, and Ca2+), strong anions (Cl-, lactate), and buffer ions (total protein, albumin, and phosphate) were determined. Strong ion difference was estimated from the measured strong ion concentrations and nonlinear regression used to calculate Atot and Ka from the measured pH and PCO2 and estimated strong ion difference. Mean (+/- SD) values were as follows: Atot = 24.3 +/- 4.6 mmol/L (equivalent to 0.35 mmol/g of protein or 0.76 mmol/g of albumin); Ka = 0.67 +/- 0.40 x 10(-7); and the negative logarithm (base 10) of Ka (pKa) = 7.17. At 37 degrees C, pH of 7.35, and a partial pressure of CO2 (PCO2) of 30 mm Hg, the calculated venous strong ion difference was 30 mEq/L. These results indicate that at a plasma pH of 7.35, a 1 mEq/L decrease in strong ion difference will decrease pH by 0.020, a 1 mm Hg decrease in PCO2 will increase plasma pH by 0.011, and a 1 g/dL decrease in albumin concentration will increase plasma pH by 0.093.

Multicomponent synthesis of imidazo [1,2-a] pyridines using catalytic zinc chloride

CSIR Research Space (South Africa)

Rousseau, AL

2007-06-01

Full Text Available HN R1 R2 Scheme 1. Tetrahedron Letters 48 (2007) 4079–4082 chloride,12 acetic acid,10a perchloric acid,10e or Montmo- rillonite clay K1013 to catalyze the reaction. The use of solid supports with a range of acid catalysts in the 3CC reaction... tempera- ture (for reactions catalyzed by scandium triflate, acetic acid, toluenesulfonic acid or perchloric acid) or using N X N 1 X=CH 2 X=N N N 3 R1=R2=Cl, R3=R4=C3H7 4 R1=R2=R3=R4=CH3 R1 R2 O N R3 R4 N N SO2Me antagonists.9 Drug...

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

Energy Technology Data Exchange (ETDEWEB)

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

2009-08-15

Nanocrystalline transition metal oxides (NTMOs) have been successfully prepared by three different methods: novel quick precipitation method (Cr{sub 2}O{sub 3} and Fe{sub 2}O{sub 3}); surfactant mediated method (CuO), and reduction of metal complexes with hydrazine as reducing agent (Mn{sub 2}O{sub 3}). The nano particles have been characterized by X-ray diffraction (XRD) which shows an average particle diameter of 35-54 nm. Their catalytic activity was measured in the thermal decomposition of ammonium perchlorate (AP). AP decomposition undergoes a two step process where the addition of metal oxide nanocrystals led to a shifting of the high temperature decomposition peak toward lower temperature. The kinetics of the thermal decomposition of AP and catalyzed AP has also been evaluated using model fitting and isoconversional method. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

Kinetics and Mechanism of Electron Transfer Reaction: Oxidation of Sulfanilic Acid by N-Chloro-p-Toluene Sulfonamide in Acid Perchlorate Medium

Energy Technology Data Exchange (ETDEWEB)

Sailani, Riya; Bhasin, Meneka; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

2014-01-15

The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be (61.67 ± 0.47) kJ mol{sup -1} and (-62.71 ± 2.48) JK{sup -1}mol{sup -1} respectively employing Eyring equation.

Modification of surface of zirconium diphosphate in solution; Modificacion de la superficie del difosfato de circonio en solucion

Energy Technology Data Exchange (ETDEWEB)

Garcia G, N.; Ordonez R, E. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Barrera D, C. E. [Universidad Autonoma del Estado de Mexico, Facultad de Quimica, Paseo Colon y Paseo Tollocan, Toluca 50120, Estado de Mexico (Mexico); Simoni, E. [Universite de Paris-Sud-XI, Institut de Physique Nucleaire d' Orsay, Bat 100, 91406 Orsay (France)], e-mail: eduardo.ordonez@inin.gob.mx

2009-10-15

The hydration process of ZrP{sub 2}O{sub 7}, forms active places in the surface of material that depend on the time and of nature of means in that it is immersed. The objective of this work is to study the influence that affect the active places of ZrP{sub 2}O{sub 7} for the action of poly carboxylic acid solutions during the hydration process. The experimentation was realized hydrating the ZrP{sub 2}O{sub 7} with solutions of sodium perchlorate, citric acid/sodium perchlorate and oxalic acid/sodium perchlorate during 24 hours, subsequently it is evaluated if some change exists in active places density formed by area unit. The organic acids action also modifies the acidity constants of surface, evaluated by means of titration acid-base technique. With these results the distribution diagrams of amphoteric species were modeled for each studied system. The results of this study phase showed that places density of hydrated material with NaClO{sub 4} was of 5.3 s/nm{sup 2}, with citric acid 13.7 s/nm{sup 2} and oxalic acid 7.3 s/nm{sup 2}. We can conclude that when solutions are used with organic acids a significant change takes place in the acidity constants and of the species distribution in surface that are discussed along this work. (Auth0008.

SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .3. EFFECT OF SULFOLANE ON THE EQUILIBRIUM CONVERSION

NARCIS (Netherlands)

PANNEMAN, HJ; BEENACKERS, AACM

The liquid-phase hydration of cyclohexene, a pseudo-first-order reversible reaction catalyzed by a strong acid ion-exchange resin, was investigated in solvent mixtures of water and sulfolane. Macroporous Amberlite XE 307 was used because of its superior catalytic activity. Chemical equilibrium

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

International Nuclear Information System (INIS)

Foulks, J.G.; Morishita, L.

1985-01-01

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

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

International Nuclear Information System (INIS)

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

2011-01-01

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

Synthesis, characterization and antitumour activity of copper(II) 6-(4-chlorobenzylamino)purine complexes. X-ray structure of 6-(4-chloro-benzylamino)purinium perchlorate

Czech Academy of Sciences Publication Activity Database

Maloň, M.; Trávníček, Z.; Maryško, Miroslav; Marek, J.; Doležal, Karel; Rolčík, Jakub; Strnad, Miroslav

2002-01-01

Roč. 27, č. 6 (2002), s. 580-586 ISSN 0340-4285 R&D Projects: GA ČR GA522/01/0275; GA MŠk OC 844.10; GA ČR GA301/02/0475 Institutional research plan: CEZ:AV0Z5038910 Keywords : Copper complexes * human malignant melanoma * purinium perchlorate Subject RIV: CE - Biochemistry Impact factor: 0.949, year: 2002

Synthesis, Structure and Spectroscopy of Two Structurally Related Hydrogen Bonded Compounds in the dpma/HClO4 System; dpma (dimethylphosphorylmethanamine

Directory of Open Access Journals (Sweden)

Guido J. Reiss

2013-06-01

Full Text Available The new phosphine oxide compound, (dimethylphosphorylmethanaminium perchlorate, dpmaHClO4 (1, was synthesized by the reaction of (dimethylphosphoryl methanamine (dpma with concentrated perchloric acid. (Dimethylphosphorylmethanaminium perchlorate (dimethylphosphorylmethanamine solvate, dpmaHClO4•dpma (2 was obtained by the slow evaporation of an equimolar methanolic solution of 1 and dpma at room temperature. For both compounds, single-crystal X-ray structures, IR and Raman spectra are reported. The assignment of the spectroscopic data were supported by quantum chemical calculations at the B3LYP/6-311G(2d,p level of theory. In 1, the dpmaH cations form polymeric, polar double-strands along [010] by head to tail connections via N–H∙∙∙O hydrogen bonds. The perchlorate anions are located between these strands attached by one medium strong and two weaker un-bifurcated hydrogen bonds (monoclinic, centrosymmetric space group C2/c, a = 17.8796(5 Å, b = 5.66867(14 Å, c = 17.0106(5 Å, β = 104.788(3°, V = 1666.9(1 Å3, Z = 8, T = 293 K, R(F [I > 2σ(I] = 0.0391, wR(F2 [all] = 0.1113. In 2, besides the N–H∙∙∙O hydrogen bonds, medium strong N–H∙∙∙N hydrogen bonds are present. One dpmaH cation and the neutral dpma molecule are connected head to tail by two N–H∙∙∙O hydrogen bonds forming a monocationic cyclic unit. These cyclic units are further connected by N–H∙∙∙O and N–H∙∙∙N hydrogen bonds forming polymeric, polar double-strands along [001]. The perchlorate anions fill the gaps between these strands, and each [ClO4]− anion is weakly connected to the NH2 group by one N–H∙∙∙O hydrogen bond (orthorhombic, non-centrosymmetric space group Pca21 (No. 29, a = 18.5821(5 Å, b = 11.4320(3 Å, c = 6.89400(17 Å, V = 1464.50(6 Å3, Z = 4, T = 100 K, R(F [I > 2σ(I] = 0.0234, wR(F2 [all] = 0.0575. Both structures are structurally related, and their commonalities are discussed in terms of a graph

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-03-15

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

The Acid-Base Titration of a Very Weak Acid: Boric Acid

Science.gov (United States)

Celeste, M.; Azevedo, C.; Cavaleiro, Ana M. V.

2012-01-01

A laboratory experiment based on the titration of boric acid with strong base in the presence of d-mannitol is described. Boric acid is a very weak acid and direct titration with NaOH is not possible. An auxiliary reagent that contributes to the release of protons in a known stoichiometry facilitates the acid-base titration. Students obtain the…

Solubility and solvation of alkali metal perchlorates, tetramethyl and tetraethylammonium in aqua-ketone solvents

International Nuclear Information System (INIS)

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

1998-01-01

The KClO 4 , RbClO 4 , CsClO 4 , (CH 3 ) 4 NClO 4 , (C 2 H 5 ) 4 NClO 4 solubility in water and water-acetone, water-methylethylketone mixtures is determined through the method of isothermal saturation at 298.15 K. Dissociation constants of alkali metals perchlorates in acetone and its 90% mixtures (by volume) are determined conductometrically. Solubility products and standard energies of the Gibbs transfer of the studied electrolytes from water into water-acetone and water-methylethylketone solvents. It is established that the Gibbs standard energies of Na + , K + , Rb + and Cs + cations transfer from water to water-ketone solvents are close to each other. It is shown that the effect of acetone and methylethylketone on solvation of the studied electrolytes is practically similar

Limited overshooting of NH{sub 4}{sup +} ions in ammonium perchlorate; Ograniczene przeskoki jonow NH{sub 4}{sup +} w nadchloranie amonowym

Energy Technology Data Exchange (ETDEWEB)

Birczynski, A.; Lalowicz, Z.T. [Inst. of Nuclear Physics, Cracow (Poland); Ingman, L.P.; Punkkinen, M.; Ylinen, E.E. [Wihuri Physical Lab., Turku Univ., Turku (Finland)

1995-12-31

The interpretation of NMR spectra for polycrystalline sample of ammonium perchlorate in helium temperature assumes the tunneling of NH{sub 4}{sup +}. Such interpretation does not agree with experimental data. The hypothesis of additional motion (fast rotation around one of C3 axis) has been checked and discussed on the base of NMR spectra of NH{sub 4}ClO{sub 4} monocrystal for the temperature range 2.1-25 K. 9 refs, 1 fig.

Limited overshooting of NH{sub 4}{sup +} ions in ammonium perchlorate; Ograniczene przeskoki jonow NH{sub 4}{sup +} w nadchloranie amonowym

Energy Technology Data Exchange (ETDEWEB)

Birczynski, A; Lalowicz, Z T [Inst. of Nuclear Physics, Cracow (Poland); Ingman, L P; Punkkinen, M; Ylinen, E E [Wihuri Physical Lab., Turku Univ., Turku (Finland)

1996-12-31

The interpretation of NMR spectra for polycrystalline sample of ammonium perchlorate in helium temperature assumes the tunneling of NH{sub 4}{sup +}. Such interpretation does not agree with experimental data. The hypothesis of additional motion (fast rotation around one of C3 axis) has been checked and discussed on the base of NMR spectra of NH{sub 4}ClO{sub 4} monocrystal for the temperature range 2.1-25 K. 9 refs, 1 fig.

Adsorption of pertechnetate ion on various active carbons from mineral acid solutions

International Nuclear Information System (INIS)

Ito, K.

1991-01-01

The adsorption behavior of pertechnetate ion (TcO 4 - ) on active carbon has been studied for various acid solutions, taking as indicative value the distribution coefficient K d of Tc between active carbon surface and solution. In a system where the total anion concentration of the acid and its sodium salt was maintained constant, modifying the pH of the solution proved distinctly to influence the Tc adsorption behavior of active carbon: taking the case of active carbon derived from coconut shell, increasing the acidity raised K d ; around neutrality there occurred a level stage; in the alkali region, K d declined. The rise of K d in the acid region, however, was observed only with active carbon derived from coconut shell, from oil pitch or from saw dust; it failed to occur when the active carbon was derived from coal or from bone. With a hydrochloric acid system, the rise of K d started around 1 M (mol dm -1 ) HCl. Beyond 3 M, on the other hand, a breakthrough occurred, and K d declined with increasing acidity. With a nitric acid system, K d rose from 1 M, and the breakthrough occurred at 2 M. When the adsorption was left to equilibrate beyond 4 h, desorption displacement of TcO 4 - by a coexisting other anion was observed in the case of perchloric acid solutions of concentration above 0.1 M and with sulfuric acid solutions above 0.5 M. (author)

Acidizing reservoirs while chelating iron with sulfosalicylic acid

Energy Technology Data Exchange (ETDEWEB)

McLaughlin, W A; Berkshire, D C

1980-09-30

A well treating process is described in which an aqueous solution of a strong acid capable of dissolving solids in a manner increasing the permeability of a subterranean earth formation is injected into a subterranean reservoir that contains an asphaltenic oil. At least the first injected portion of the aqueous acid and a solution or homogeneous dispersion of at least enough 5-sulfosalicylic acid to chelate with and prevent the formation of iron-asphaltene solids are included with substantially all of the ferric ions that become dissolved within the strong acid solution that enters the earth formation. 10 claims.

Removing hydrochloric acid exhaust products from high performance solid rocket propellant using aluminum-lithium alloy

Energy Technology Data Exchange (ETDEWEB)

Terry, Brandon C., E-mail: terry13@purdue.edu [School of Aeronautics and Astronautics, Purdue University, Zucrow Laboratories, 500 Allison Rd, West Lafayette, IN 47907 (United States); Sippel, Travis R. [Department of Mechanical Engineering, Iowa State University, 2025 Black Engineering, Ames, IA 50011 (United States); Pfeil, Mark A. [School of Aeronautics and Astronautics, Purdue University, Zucrow Laboratories, 500 Allison Rd, West Lafayette, IN 47907 (United States); Gunduz, I.Emre; Son, Steven F. [School of Mechanical Engineering, Purdue University, Zucrow Laboratories, 500 Allison Rd, West Lafayette, IN 47907 (United States)

2016-11-05

Highlights: • Al-Li alloy propellant has increased ideal specific impulse over neat aluminum. • Al-Li alloy propellant has a near complete reduction in HCl acid formation. • Reduction in HCl was verified with wet bomb experiments and DSC/TGA-MS/FTIR. - Abstract: Hydrochloric acid (HCl) pollution from perchlorate based propellants is well known for both launch site contamination, as well as the possible ozone layer depletion effects. Past efforts in developing environmentally cleaner solid propellants by scavenging the chlorine ion have focused on replacing a portion of the chorine-containing oxidant (i.e., ammonium perchlorate) with an alkali metal nitrate. The alkali metal (e.g., Li or Na) in the nitrate reacts with the chlorine ion to form an alkali metal chloride (i.e., a salt instead of HCl). While this technique can potentially reduce HCl formation, it also results in reduced ideal specific impulse (I{sub SP}). Here, we show using thermochemical calculations that using aluminum-lithium (Al-Li) alloy can reduce HCl formation by more than 95% (with lithium contents ≥15 mass%) and increase the ideal I{sub SP} by ∼7 s compared to neat aluminum (using 80/20 mass% Al-Li alloy). Two solid propellants were formulated using 80/20 Al-Li alloy or neat aluminum as fuel additives. The halide scavenging effect of Al-Li propellants was verified using wet bomb combustion experiments (75.5 ± 4.8% reduction in pH, ∝ [HCl], when compared to neat aluminum). Additionally, no measurable HCl evolution was detected using differential scanning calorimetry coupled with thermogravimetric analysis, mass spectrometry, and Fourier transform infrared absorption.

Removing hydrochloric acid exhaust products from high performance solid rocket propellant using aluminum-lithium alloy

International Nuclear Information System (INIS)

Terry, Brandon C.; Sippel, Travis R.; Pfeil, Mark A.; Gunduz, I.Emre; Son, Steven F.

2016-01-01

Highlights: • Al-Li alloy propellant has increased ideal specific impulse over neat aluminum. • Al-Li alloy propellant has a near complete reduction in HCl acid formation. • Reduction in HCl was verified with wet bomb experiments and DSC/TGA-MS/FTIR. - Abstract: Hydrochloric acid (HCl) pollution from perchlorate based propellants is well known for both launch site contamination, as well as the possible ozone layer depletion effects. Past efforts in developing environmentally cleaner solid propellants by scavenging the chlorine ion have focused on replacing a portion of the chorine-containing oxidant (i.e., ammonium perchlorate) with an alkali metal nitrate. The alkali metal (e.g., Li or Na) in the nitrate reacts with the chlorine ion to form an alkali metal chloride (i.e., a salt instead of HCl). While this technique can potentially reduce HCl formation, it also results in reduced ideal specific impulse (I_S_P). Here, we show using thermochemical calculations that using aluminum-lithium (Al-Li) alloy can reduce HCl formation by more than 95% (with lithium contents ≥15 mass%) and increase the ideal I_S_P by ∼7 s compared to neat aluminum (using 80/20 mass% Al-Li alloy). Two solid propellants were formulated using 80/20 Al-Li alloy or neat aluminum as fuel additives. The halide scavenging effect of Al-Li propellants was verified using wet bomb combustion experiments (75.5 ± 4.8% reduction in pH, ∝ [HCl], when compared to neat aluminum). Additionally, no measurable HCl evolution was detected using differential scanning calorimetry coupled with thermogravimetric analysis, mass spectrometry, and Fourier transform infrared absorption.

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

Directory of Open Access Journals (Sweden)

Abdelhakim Laachir

2017-03-01

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

New Organic Semiconductor Materials Applied in Organic Photovoltaic and Optical Devices

Directory of Open Access Journals (Sweden)

Andre F. S. Guedes

2015-04-01

Full Text Available The development of flexible organic photovoltaic solar cells, using an optically transparent substrate material and organic semiconductor materials, has been widely utilized by the electronic industry when producing new technological products. The flexible organic photovoltaic solar cells are the base Poly (3,4-ethylenedioxythiophene, PEDOT, Poly(3-hexyl thiophene, P3HT, Phenyl-C61-butyric acid methyl ester, PCBM and Polyaniline, PANI, were deposited in Indium Tin Oxide, ITO, and characterized by Electrical Measurements and Scanning Electron Microscopy (SEM. In addition, the thin film obtained by the deposition of PANI, prepared in perchloric acid solution, was identified through PANI-X1. The result obtained by electrical Measurements has demonstrated that the PET/ITO/PEDOT/P3HT:PCBM Blend/PANI-X1 layer presents the characteristic curve of standard solar cell after spin-coating and electrodeposition. The Thin film obtained by electrodeposition of PANI-X1 on P3HT/PCBM Blend was prepared in perchloric acid solution. These flexible organic photovoltaic solar cells presented power conversion efficiency of 12%. The inclusion of the PANI-X1 layer reduced the effects of degradation these organic photovoltaic panels induced for solar irradiation. In Scanning Electron Microscopy (SEM these studies reveal that the surface of PANI-X1 layers is strongly conditioned by the surface morphology of the dielectric.

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

Energy Technology Data Exchange (ETDEWEB)

Terashima, Yukio [Department of Natural Science Education, Joint Graduate School, Hyogo University of Teacher Education (Japan); Takeda, Kiyoshi, E-mail: takeda@naruto-u.ac.j [Department of Chemistry, Naruto University of Education, 748 Nakajima, Takashima Naruto-cho, Naruto, Tokushima 772-8502 (Japan); Honda, Makoto [Department of Physics, Naruto University of Education (Japan)

2011-03-15

The phase and glass transition behaviour in a binary mixture of sodium perchlorate and 1,2-propanediamine {l_brace}(NaClO{sub 4}){sub x}(12PDA){sub 1-x}, x < 0.40{r_brace} was investigated by differential scanning calorimetry and Raman scattering measurements. A eutectic point and a peritectic point were found at x = 0.17 and 0.19, respectively. The phase diagram indicates the existence of solvated compounds of (NaClO{sub 4}){sub 1}(12PDA){sub 4} and (NaClO{sub 4}){sub 2}(12PDA){sub 5}. The concentration dependence of the glass transition point shows a sigmoid curve implying an underlying anomaly.

Oxidation of phenyl alanine by pyridinium chlorochromate in acidic DMF–water medium: A kinetic study

Directory of Open Access Journals (Sweden)

B.L. Hiran

2016-11-01

Full Text Available The kinetics of oxidation of phenyl alanine by pyridinium chlorochromate in DMF–water (70:30% mixture in presence of perchloric acid leads to the formation of corresponding aldehyde. The reaction is of first order each in [PCC], [HClO4] and [AA]. Michaelis–Menten type kinetics was observed with phenyl alanine. The reaction rates were determined at different temperatures [25, 30, 35, 40, 45, 50 °C] and the activation parameters were calculated. The reaction does not induce polymerization of acrylonitrile. With an increase in the amount of DMF in its aqueous mixture, the rate increases. A suitable mechanism for the reaction was postulated.

Picosecond laser fabricated Ag, Au and Ag-Au nanoparticles for detecting ammonium perchlorate using a portable Raman spectrometer

Science.gov (United States)

Byram, Chandu; Moram, Sree Sathya Bharathi; Soma, Venugopal Rao

2018-04-01

In this paper, we present the results from fabrication studies of Ag, Au, and Ag-Au alloy nanoparticles (NPs) using picosecond laser ablation technique in the presence of liquid media. The alloy formation in the NPs was confirmed from UV-Visible measurements. The shape and crystallinity of NPs were investigated by using high resolution transmission electron microscopy (HRTEM), selected area diffraction pattern (SAED) and energy dispersive spectroscopy (EDS). The SERS effect of fabricated NPs was tested with methylene blue and an explosive molecule (ammonium perchlorate) using a portable Raman spectrometer and achieved EFs of ˜106.

Electrochemistry and analytical determination of lysergic acid diethylamide (LSD) via adsorptive stripping voltammetry.

Science.gov (United States)

Merli, Daniele; Zamboni, Daniele; Protti, Stefano; Pesavento, Maria; Profumo, Antonella

2014-12-01

Lysergic acid diethylamide (LSD) is hardly detectable and quantifiable in biological samples because of its low active dose. Although several analytical tests are available, routine analysis of this drug is rarely performed. In this article, we report a simple and accurate method for the determination of LSD, based on adsorptive stripping voltammetry in DMF/tetrabutylammonium perchlorate, with a linear range of 1-90 ng L(-1) for deposition times of 50s. LOD of 1.4 ng L(-1) and LOQ of 4.3 ng L(-1) were found. The method can be also applied to biological samples after a simple extraction with 1-chlorobutane. Copyright © 2014 Elsevier B.V. All rights reserved.

Mechanism of Oxidation of (p-Substituted Phenylthioacetic Acids with N-Bromophthalimide

Directory of Open Access Journals (Sweden)

N. M. I. Alhaji

2011-01-01

Full Text Available The kinetics of oxidation of (phenylthioacetic acid (PTAA by N-Bromophthalimide (NBP in acetonitrile-water solvent mixture at 298 K in the presence of perchloric acid has been followed potentiometrically. The reaction is first-order each in NBP and PTAA and inverse fractional-order in H+. Also, it has been found that the reaction rate is not affected by changes in ionic strength of the reaction medium or by the addition of chemicals such as phthalimide, acrylonitrile and potassium bromide. However, an increase in the water content of the solvent mixture causes an increase in the rate of reaction. These observations have been well analyzed in favour of a SN2-type mechanism, involving NBP itself as the reactive species. Effect of substituents on the reaction rate has been analysed by employing various (p-sustituted phenylthioacetic acids. The electron-releasing substituent in the phenyl ring of PTAA accelerates the reaction rate while the electron-withdrawing substituent retards the rate. The excellently linear Hammett plot yields a large negative ρ value, supporting the involvement a bromosulphonium ion intermediate in the rate-determining step.

Deactivation kinetics of acid-sensing ion channel 1a are strongly pH-sensitive.

Science.gov (United States)

MacLean, David M; Jayaraman, Vasanthi

2017-03-21

Acid-sensing ion channels (ASICs) are trimeric cation-selective ion channels activated by protons in the physiological range. Recent reports have revealed that postsynaptically localized ASICs contribute to the excitatory postsynaptic current by responding to the transient acidification of the synaptic cleft that accompanies neurotransmission. In response to such brief acidic transients, both recombinant and native ASICs show extremely rapid deactivation in outside-out patches when jumping from a pH 5 stimulus to a single resting pH of 8. Given that the resting pH of the synaptic cleft is highly dynamic and depends on recent synaptic activity, we explored the kinetics of ASIC1a and 1a/2a heteromers to such brief pH transients over a wider [H + ] range to approximate neuronal conditions better. Surprisingly, the deactivation of ASICs was steeply dependent on the pH, spanning nearly three orders of magnitude from extremely fast (pH 8 to very slow (>300 ms) at pH 7. This study provides an example of a ligand-gated ion channel whose deactivation is sensitive to agonist concentrations that do not directly activate the receptor. Kinetic simulations and further mutagenesis provide evidence that ASICs show such steeply agonist-dependent deactivation because of strong cooperativity in proton binding. This capacity to signal across such a large synaptically relevant bandwidth enhances the response to small-amplitude acidifications likely to occur at the cleft and may provide ASICs with the ability to shape activity in response to the recent history of the synapse.

Application of lanthanide complexes for the purification of di-isobutyl-sulfoxide

International Nuclear Information System (INIS)

Osorio, V.K.L.; Martinez, S.A.Q.; Silva, R.M.X. da

1984-01-01

A new procedure for the purification of sulfoxides based on the selective precipitation of their complexes with class (a) metallic ions is reported. A commercial sample of di-isobutylsulfoxide containing about 5 - 10% of the corresponding sulfone was purified by precipitation with lanthanide perchlorates from alcoholic solutions. The recovery of the sulfoxide from the solid complex was accomplished by dissolving the complex in water and extracting the sulfoxide with chloroform. Alternatively the aqueous solution of the complex was passed successively through columns containing strongly acidic cation-exchanger resin in the H-cycle and strongly basic anionic-exchanger in the OH-cycle. T.L.C. homogeneous sulfoxide was obtained simply by evaporation of the solvent at reduced pressure. (Author) [pt

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

Energy Technology Data Exchange (ETDEWEB)

Kim, Jaemin [Department; Shih, Pei-Chieh [Department; Tsao, Kai-Chieh [Department; Pan, Yung-Tin [Department; Yin, Xi [Department; Sun, Cheng-Jun [X-ray; Yang, Hong [Department

2017-08-17

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap between Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.

Average formation number n-barOH of colloid-type indium hydroxide

International Nuclear Information System (INIS)

Stefanowicz, T.; Szent-Kirallyine Gajda, J.

1983-01-01

Indium perchlorate in perchloric acid solution was titrated with sodium hydroxide solution to various pH values. Indium hydroxide colloid was removed by ultracentrifugation and supernatant solution was titrated with base to neutral pH. The two-stage titration data were used to calculate the formation number of indium hydroxide colloid, which was found to equal n-bar OH = 2.8. (author)

SOLVENT EFFECTS ON THE HYDRATION OF CYCLOHEXENE CATALYZED BY A STRONG ACID ION-EXCHANGE RESIN .2. EFFECT OF SULFOLANE ON THE REACTION-KINETICS

NARCIS (Netherlands)

PANNEMAN, HJ; BEENACKERS, AACM

The kinetics of the' hydration of cyclohexene, catalyzed by a strong acid ion-exchange resin, have been studied in a packed bed reactor at temperatures between 353 and 413 K and a pressure of 20 bar. The kinetic rate constants were measured as a function of temperature and solvent composition (0-90

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

KAUST Repository

Ma, He

2016-04-10

The weak bond energy and large anisotropic domain wall energy induce many special characteristics of the domain nucleation, growth, and polarization switch in triglycine sulfate (TGS) and imidazolium perchlorate (IM), two typical molecular ferroelectrics. Their domain nucleation and polarization switch are rather slower than those of conventional oxide ferroelectrics, which may be due to the weaker bond energy of hydrogen bond or van der Waals bond than that of ionic bond. These chemical bonds dominate the elastic energy, with the latter being an important component of domain wall energy and playing an important role in domain nucleation and domain growth. The ratio of anisotropic domain wall energy to Gibbs free energy is large in TGS and IM, which allows a favorable domain shape and a special domain evolution under a certain electric field. Therefore, this study not only sheds light on the physical nature but also indicates the application direction for molecular ferroelectrics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A comparison of prognostic significance of strong ion gap (SIG) with other acid-base markers in the critically ill: a cohort study.

Science.gov (United States)

Ho, Kwok M; Lan, Norris S H; Williams, Teresa A; Harahsheh, Yusra; Chapman, Andrew R; Dobb, Geoffrey J; Magder, Sheldon

2016-01-01

This cohort study compared the prognostic significance of strong ion gap (SIG) with other acid-base markers in the critically ill. The relationships between SIG, lactate, anion gap (AG), anion gap albumin-corrected (AG-corrected), base excess or strong ion difference-effective (SIDe), all obtained within the first hour of intensive care unit (ICU) admission, and the hospital mortality of 6878 patients were analysed. The prognostic significance of each acid-base marker, both alone and in combination with the Admission Mortality Prediction Model (MPM0 III) predicted mortality, were assessed by the area under the receiver operating characteristic curve (AUROC). Of the 6878 patients included in the study, 924 patients (13.4 %) died after ICU admission. Except for plasma chloride concentrations, all acid-base markers were significantly different between the survivors and non-survivors. SIG (with lactate: AUROC 0.631, confidence interval [CI] 0.611-0.652; without lactate: AUROC 0.521, 95 % CI 0.500-0.542) only had a modest ability to predict hospital mortality, and this was no better than using lactate concentration alone (AUROC 0.701, 95 % 0.682-0.721). Adding AG-corrected or SIG to a combination of lactate and MPM0 III predicted risks also did not substantially improve the latter's ability to differentiate between survivors and non-survivors. Arterial lactate concentrations explained about 11 % of the variability in the observed mortality, and it was more important than SIG (0.6 %) and SIDe (0.9 %) in predicting hospital mortality after adjusting for MPM0 III predicted risks. Lactate remained as the strongest predictor for mortality in a sensitivity multivariate analysis, allowing for non-linearity of all acid-base markers. The prognostic significance of SIG was modest and inferior to arterial lactate concentration for the critically ill. Lactate concentration should always be considered regardless whether physiological, base excess or physical-chemical approach

Shock wave response of ammonium perchlorate single crystals to 6 GPa

International Nuclear Information System (INIS)

Yuan, G.; Feng, R.; Gupta, Y. M.; Zimmerman, K.

2000-01-01

Plane shock wave experiments were carried out on ammonium perchlorate single crystals compressed along [210] and [001] orientations to peak stresses ranging from 1.2 to 6.2 GPa. Quartz gauge and velocity interferometer techniques were used to measure the elastic and plastic shock wave velocities, and stress and particle velocity histories in the shocked samples. The measured Hugoniot elastic limit (HEL) was 0.48±0.09 GPa. Above the HEL and up to about 6 GPa, the data show a clear two-wave structure, indicating an elastic-plastic response. Time-dependent elastic precursor decay and plastic wave ramping are discernable and orientation dependent in the low stress data. However, the orientation dependence of the peak state response is small. Hence, data for both orientations were summarized into a single isotropic, elastic-plastic-stress relaxation model. Reasonable agreement was obtained between the numerical simulations using this model and the measured wave profiles. At a shock stress of about 6 GPa and for the time duration and crystal orientations examined, we did not observe any features that may be identified as a sustained chemical reaction or a phase transformation. (c) 2000 American Institute of Physics

Removing hydrochloric acid exhaust products from high performance solid rocket propellant using aluminum-lithium alloy.

Science.gov (United States)

Terry, Brandon C; Sippel, Travis R; Pfeil, Mark A; Gunduz, I Emre; Son, Steven F

2016-11-05

Hydrochloric acid (HCl) pollution from perchlorate based propellants is well known for both launch site contamination, as well as the possible ozone layer depletion effects. Past efforts in developing environmentally cleaner solid propellants by scavenging the chlorine ion have focused on replacing a portion of the chorine-containing oxidant (i.e., ammonium perchlorate) with an alkali metal nitrate. The alkali metal (e.g., Li or Na) in the nitrate reacts with the chlorine ion to form an alkali metal chloride (i.e., a salt instead of HCl). While this technique can potentially reduce HCl formation, it also results in reduced ideal specific impulse (ISP). Here, we show using thermochemical calculations that using aluminum-lithium (Al-Li) alloy can reduce HCl formation by more than 95% (with lithium contents ≥15 mass%) and increase the ideal ISP by ∼7s compared to neat aluminum (using 80/20 mass% Al-Li alloy). Two solid propellants were formulated using 80/20 Al-Li alloy or neat aluminum as fuel additives. The halide scavenging effect of Al-Li propellants was verified using wet bomb combustion experiments (75.5±4.8% reduction in pH, ∝ [HCl], when compared to neat aluminum). Additionally, no measurable HCl evolution was detected using differential scanning calorimetry coupled with thermogravimetric analysis, mass spectrometry, and Fourier transform infrared absorption. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of CNTs/CuO and its catalytic performance on the thermal decomposition of ammonium perchlorate

Directory of Open Access Journals (Sweden)

Ping Cui

2016-05-01

Full Text Available Copper oxide (CuO nanoparticles were successfully deposited on carbon nanotubes’ (CNTs surface via complex-precipitation method, the nanocomposite was characterized by transmission electron microscopy (TEM, scanning electron microscopy (SEM, X-ray photoelectron spectroscopy (XPS, X-ray powder diffraction (XRD, Raman spectroscopy, Fourier transform infrared (FT-IR and Brunauer–Emmett–Teller (BET. The catalytic performance of CNTs/CuO on ammonium perchlorate (AP decomposition was analyzed by differential thermal analyzer (DTA, the DTA results showed its excellent catalytic effect on AP decomposition, as 8 wt.% CNTs/CuO was added in AP, the second exothermic peak temperature decreased by 158 °C. Such composite may be a promising candidate for catalyzing the AP thermal decomposition.

Oxidation of formic acid by oxyanions of chlorine and its implications to the Viking Labeled Release experiment

Science.gov (United States)

Martinez, P.; Navarro-gonzalez, R.

2013-05-01

The Viking Landers that arrived on Mars in 1976 carried out three biological experiments designed to investigate if there was microbial life. These were the Gas-Exchange, Pyrolitic Release and Labeled Release experiments. The three experiments yielded positive responses but the Labeled Release experiment had a kinetic response indicative of microbial activity. The experiment consisted of adding a broth of nutrients (formic acid, glycolic acid, glycine, D- and L-alanine and D- and L-lactic acid uniformly marked with 14C) to martian soil samples. The results were surprising; the nutrients were consumed releasing radioactive gases in a manner that is compatible by terrestrial microorganisms. The existence of Martian life was contradicted by soil chemical analysis that indicated the absence of organic compounds above the detection limits of parts per billion (ppb). Instead the positive response of the Labeled Release Experiment was attributed to the existence of peroxides and/or superoxides in the Martian soils that destroyed the nutrients upon contact. Recently, the Phoenix mission that landed in the Martian Arctic in 2008 revealed the presence of a highly oxidized form of the element chlorine in the soil: perchlorate. Perchlorate is thought to have formed in the Martian atmosphere by the oxidation of chloride from volcanic sources with ozone. Therefore perchlorate is formed by the stepwise oxidation of hypochlorite, chlorite and chlorate. These oxyanions of chlorine are powerful oxidizers that may exist in the Martian soil and may have reacted with the nutrients of the Labeled Release Experiment. This paper aims to better understand these results by designing experiments to determine the kinetics of decomposition of formic acid to carbon dioxide with different oxidized forms of chlorine by headspace technique in gas chromatography coupled to mass spectrometry (GC / MS). Previous studies done in the laboratory showed that only hypochlorite quantitatively reacted with

Perchlorate in Lake Water from an Operating Diamond Mine.

Science.gov (United States)

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

2015-07-07

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

The application of hydrogen-palladium electrode for potentiometric acid-base determinations in tetrahydrofuran

Directory of Open Access Journals (Sweden)

Jokić Anja B.

2013-01-01

Full Text Available The application of the hydrogen-palladium electrode (H2/Pd as the indicator electrode for the determination of relative acidity scale (Es, mV of tetrahydrofuran (THF and the potentiometric titrations of acids in this solvent was investigated. The relative acidity scale tetrahydrofuran was determined from the difference half-neutralization potentials of perchloric acid and tetrabutylammonium hydroxide (TBAH, which were measured by using both H2/Pd-SCE and glass-SCE electrode pairs. The experimentally obtained value of Es scale THF with a H2/Pd-SCE electrode pair was 1155 mV, and those obtained with glass-SCE electrode pair 880 mV. By using a H2/Pd indicator electrode, the individual acids (benzoic acid, palmitic acid, maleic acid, acetyl acetone, α-naphthol and two component acid mixtures (benzoic acid + α-naphthol, palmitic acid + α-naphthol, maleic acid + α-naphthol and maleic acid + ftalic acid were titrated with a standard solution of TBAH. In addition, sodium methylate and potassium hydroxide proved to be very suitable titrating agents for titrating of the individual acids and the acids in mixtures, respectively. The relative error of the determination of acids in mixture was less than 3%. The results are in agreement with those obtained by a conventional glass electrode. The advantages of H2/Pd electrode over a glass electrode in potentiometric acid-base determinations in tetrahydrofuran lie in the following: this electrode gives wider relative acidity scale THF, higher the potential jumps at the titration end-point and relatively fast response time; furthermore, it is very durable, simple to prepare and can be used in the titrations of small volumes. [Projekat Ministarstva nauke Republike Srbije, br.172051

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

International Nuclear Information System (INIS)

Chapman, Pippa J.; Clark, Joanna M.; Reynolds, Brian; Adamson, John K.

2008-01-01

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer. - Seasonal variations in soil solution ANC is controlled by seasonal variations in seasalt deposition and production of dissolved organic acids

In-situ methylation of strongly polar organic acids in natural waters supported by ion-pairing agents for headspace GC-MSD analysis

Energy Technology Data Exchange (ETDEWEB)

Neitzel, P.L.; Walther, W. [Dresden University of Technology, Institute for Groundwater Managemant, Dresden (Germany); Nestler, W. [Institute for Technology and Economics, Department of Civil Engineering and Architecture, Dresden (Germany)

1998-06-01

Strongly polar organic substances like halogenated acetic acids have been analyzed in surface water and groundwater in the catchment area of the upper Elbe river in Saxony since 1992. Coming directly from anthropogenic sources like industry, agriculture and indirectly by rainfall, their concentrations can increase up to 100 {mu}g/L in the aquatic environment of this catchment area. A new static headspace GC-MSD method without a manual pre-concentration step is presented to analyze the chlorinated acetic acids relevant to the Elbe river as their volatile methyl esters. Using an ion-pairing agent as modifier for the in-situ methylation of the analytes by dimethylsulfate, a minimal detection limit of 1 {mu}g/L can be achieved. Problems like the thermal degradation of chlorinated acetic acids to halogenated hydrocarbons and changing reaction yields during the headspace methylation, could be effectively reduced. The method has been successfully applied to monitoring bank infiltrate, surface water, groundwater and water works pumped raw water according to health provision principles. (orig.) With 3 figs., 2 tabs., 29 refs.

2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

DEFF Research Database (Denmark)

Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.

2005-01-01

A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X-ray struct......A bis-hydroxo-bridged diiron(III) complex and a bis-mu-oxo-bis-mu-hydroxo-bridged tetrairon( III) complex are isolated from the reaction of 2,6-bis((N, N'-bis-(2-picolyl) amino) methyl)-4-tert-butylphenol (Hbpbp) with iron perchlorate in acidic and neutral solutions respectively. The X...

Tranexamic acid--an old drug still going strong and making a revival.

Science.gov (United States)

Tengborn, Lilian; Blombäck, Margareta; Berntorp, Erik

2015-02-01

Experience with tranexamic acid, an indirect fibrinolytic inhibitor, started as soon as it was released from Shosuke Okamoto's lab in the early 1960s. It was first prescribed to females with heavy menstrual blood loss and to patients with hereditary bleeding disorders. Soon the indications were widened to elective surgery because of its blood saving effects. Contraindications are few, most important is ongoing venous or arterial thrombosis and allergy to tranexamic acid, and the doses has to be reduced in renal insufficiency. In randomized controlled trials, however, patients with other risk factors are excluded as well (patients with history of cardiovascular disease, thromboembolism, bleeding diathesis, renal failure with creatinine >250μmol/L, pregnancy, and patients on treatment with anticoagulants). Recent meta-analyses of several randomized controlled trials in orthopedic arthroplasty have shown that tranexamic acid reduces peri- and postoperative blood loss, blood transfusion requirements and reoperations caused by bleedings. In general, the preoperative dose was 10-15mg/kg i.v. (or 1g), followed or not, by one or two doses, some as continuous infusion i.v. To validate relationship between dose and effect more data are needed. No evidence was found of increased thromboembolic accidents or other adverse events in the patients on tranexamic acid compared to the control groups. In major cardiac surgery tranexamic acid has been used in a large number of controlled trials with various dosing schemes in which the highest dosages seem to be associated with neurotoxicity; therefore a maximum total dose of 100mg/kg especially in patients over 50years of age is recommended by ISMICS (International Society for Minimally Invasive Cardiothoracic Surgery). Other indications for tranexamic acid are reviewed here as well. In recent years the extensive trial in severe trauma with massive bleedings using tranexamic acid was presented, CRASH-2 (Clinical Randomisation of an

Determination of phosphorous in cannabis by neutron activation analysis - measurement of 32P Cerenkov radiation by liquid scintillaton spectrometer

International Nuclear Information System (INIS)

Shinogi, M.; Mori, I.

1977-05-01

Thermal neutron activaton analysis with measurement of 32 P Cerenkov radiation by liquid scintillation spectrometer was used to determine phosphorus in cannabis. After irradiation of the sample, wet ashing was carried out with conc. nitric acid and 70% perchloric acid. The solution in l M perchloric acid transferred to an inorganic ion-exchange column containing acid aluminium oxide and phosphorus was quantitatively eluted with 1M hydrofluoric acid. The 32 P radioactivity of each fraction of the eluate was counted with Cerenkov radiation by a liquid scintillation spectrometer from 2 to 7 weeks after the irradiation. The activity curve decayed with 32 P half-life. The isotope channel ratio technique was applied for the quench correction. The optimal experimental conditions for chemical separation of phosphorus and for measuring the 32 P Cerenkov radiation were also examined. (Author)

Process for the preparation of lactic acid and glyceric acid

Science.gov (United States)

Jackson, James E [Haslett, MI; Miller, Dennis J [Okemos, MI; Marincean, Simona [Dewitt, MI

2008-12-02

Hexose and pentose monosaccharides are degraded to lactic acid and glyceric acid in an aqueous solution in the presence of an excess of a strongly anionic exchange resin, such as AMBERLITE IRN78 and AMBERLITE IRA400. The glyceric acid and lactic acid can be separated from the aqueous solution. Lactic acid and glyceric acid are staple articles of commerce.

Study of molybdenum (VI) complexation and precipitation by zirconium (IV) in strongly acid medium. Application to nuclear spent fuel dissolution; Etude de la complexation et de la precipitation du molybdene (VI) par le zirconium (IV) en milieu tres acide. Application a la dissolution du combustible nucleaire irradie

Energy Technology Data Exchange (ETDEWEB)

Esbelin, E

1999-07-01

These last years the formation of solid deposits has been observed in the dissolution workshops of the La Hague plant. A sample of the solid was withdrawn for expertise: molybdenum and zirconium are the two major components of the solid, identified as zirconium molybdate. This thesis consisted in the approach of the mechanisms in solution liable to induce precipitate formation. After a bibliographical overview on the chemistry of Mo(VI) in highly acidic solution, this system was studied by absorption spectrophotometry in perchloric medium. The implication of two major forms of Mo(VI) in a dimerization equilibrium was confirmed by this way and by {sup 95}Mo NMR. The principal parameters governing this equilibrium were identified. It is thus shown that the molybdenum dimerization reaction is exothermic. Disturbance of the Mo(VI) system in highly acidic solution by Zr(IV) was also studied. In a restricted experimental field, for which 'conventional' exploitation methodologies had to be adapted to the system, a main complex of stoichiometry 1:1 between Mo(VI) and Zr(IV) was found. The precipitation study of Mo(VI) by Zr(IV) under conditions close to those of the dissolution medium of nuclear spent fuel was undertaken. The main parameters which control precipitation kinetics were identified. The results obtained reveal that precipitation is controlled by a single macroscopic process and therefore can be described by a single equation. The solid obtained is composed of only one phase presenting a Mo:Zr non-stoichiometry when compared to the theoretical formula ZrMo{sub 2}O{sub 7}(OH){sub 2},2H{sub 2}O. At last, on the basis of the research results, a descriptive mechanism of the system is proposed in which intervenes a 1:1 intermediate complex, much more soluble than a probable 2:1 precipitation precursor. (author)

Bacterial growth on ion exchange resin - investigations with a strong cationic exchanger. Pt. 3. Disinfection with peracetic acid

Energy Technology Data Exchange (ETDEWEB)

Flemming, H.C.

1984-12-01

The suitability of peracetic acid (PAA) for the disinfection of ion exchangers was investigated. 0.02% PAA is suitable for satisfactory disinfection. In this way corrosive effects are strongly reduced. Ca/sup 2+/-ions seem to protect the bacteria, therefore the disinfection should be done with the Na/sup +/-form. The disinfection has no remanent effect and therefore is not suitable for preventing bacterial aftergrowth during off-periods. A combination of silver and disinfectant can accomplish this, until a new, silver-tolerant microflora has evolved. In this case the use of 0.02% PAA is imperative, because higher concentrations will dissolve the silver. As a principle the effectiveness of disinfection procedure should be monitored bacteriologically.

Kinetics of thermal decomposition of ammonium perchlorate with nanocrystals of binary transition metal ferrites

Energy Technology Data Exchange (ETDEWEB)

Singh, Gurdip; Kapoor, Inder Pal Singh; Dubey, Shalini [Department of Chemistry, D. D. U. Gorakhpur University, Gorakhpur (India); Siril, Prem Felix [Laboratoire de Chimie Physique (LCP), Universite de Paris Sud, Orsay (France)

2009-02-15

Binary transition metal ferrite (BTMF) nanocrystals of formula MFe{sub 2}O{sub 4}(M=Cu,Co,Ni) were prepared by the coprecipitation method and characterized by X-ray diffraction (XRD). XRD patterns gave average particle size by using Scherrer's equation for CuFe{sub 2}O{sub 4}(CuF), CoFe{sub 2}O{sub 4}(CoF), and NiFe{sub 2}O{sub 4} (NiF) as 39.9, 27.3, and 43.8 nm, respectively. The catalytic activity measurements on the thermal decomposition of ammonium perchlorate (AP) were carried out by using thermogravimetry (TG), differential thermal analysis (DTA), and ignition delay studies. Isothermal TG data up to a mass loss of 45% have been used to evaluate kinetic parameters by using model fitting as well as isoconversional method. The order of catalytic activity was found to be: CoFe{sub 2}O{sub 4}>NiFe{sub 2}O{sub 4}. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

Phenotypic and genotypic description of Sedimenticola selenatireducens strain CUZ, a marine (per)chlorate-respiring gammaproteobacterium, and its close relative the chlorate-respiring Sedimenticola strain NSS.

Science.gov (United States)

Carlström, Charlotte I; Loutey, Dana E; Wang, Ouwei; Engelbrektson, Anna; Clark, Iain; Lucas, Lauren N; Somasekhar, Pranav Y; Coates, John D

2015-04-01

Two (per)chlorate-reducing bacteria, strains CUZ and NSS, were isolated from marine sediments in Berkeley and San Diego, CA, respectively. Strain CUZ respired both perchlorate and chlorate [collectively designated (per)chlorate], while strain NSS respired only chlorate. Phylogenetic analysis classified both strains as close relatives of the gammaproteobacterium Sedimenticola selenatireducens. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) preparations showed the presence of rod-shaped, motile cells containing one polar flagellum. Optimum growth for strain CUZ was observed at 25 to 30 °C, pH 7, and 4% NaCl, while strain NSS grew optimally at 37 to 42 °C, pH 7.5 to 8, and 1.5 to 2.5% NaCl. Both strains oxidized hydrogen, sulfide, various organic acids, and aromatics, such as benzoate and phenylacetate, as electron donors coupled to oxygen, nitrate, and (per)chlorate or chlorate as electron acceptors. The draft genome of strain CUZ carried the requisite (per)chlorate reduction island (PRI) for (per)chlorate respiration, while that of strain NSS carried the composite chlorate reduction transposon responsible for chlorate metabolism. The PRI of strain CUZ encoded a perchlorate reductase (Pcr), which reduced both perchlorate and chlorate, while the genome of strain NSS included a gene for a distinct chlorate reductase (Clr) that reduced only chlorate. When both (per)chlorate and nitrate were present, (per)chlorate was preferentially utilized if the inoculum was pregrown on (per)chlorate. Historically, (per)chlorate-reducing bacteria (PRB) and chlorate-reducing bacteria (CRB) have been isolated primarily from freshwater, mesophilic environments. This study describes the isolation and characterization of two highly related marine halophiles, one a PRB and the other a CRB, and thus broadens the known phylogenetic and physiological diversity of these unusual metabolisms. Copyright © 2015, American Society for Microbiology. All Rights

Extraction of molybdenum by the di-n-butyl 2.2.N.hydroxyhexanamide (tri-n-butylacetohydroxamic acid) from aqueous acidic media

International Nuclear Information System (INIS)

Landesman, C.

1991-11-01

The design of a new industrial process for the production of the fission product 99 Mo, led to study of the extraction of 99 Mo(VI) by the tri-n-butylacetohydroxamic acid (TBAH). Due to the large affinity of TBAH for Mo(VI), the study was conducted with unusual experimental conditions : the concentrations of the extracting molecule and metallic ion were very low, typically CTBAH = 10 -5 M and CMo(VI) = 10 -8 M. The overall extraction system was described using a mathematical model quite simple, which, in particular, takes into account all the Mo(VI) species present in the aqueous phase. When the extractions were carried out from a perchloric acid medium, two different extraction mechanisms of Mo(VI) were identified : for C HC10 4 3 , the extraction of Mo(VI) corresponds to a cationic exchange, whereas for C HC10 4 > 3 mol/dm 3 , a neutral Mo(VI) compound is extracted. Moreover it was found that the extracting system Mo(VI)/TBAH is extremely sensitive to the temperature. It is thus possible to change the way of the transfer of Mo(VI) between the two phases, by control of the temperature of the mixture : the extraction is carried out at room temperature and the back-extraction at elevated temperature