The adsorption and reaction of halogenated volatile organic compounds (VOC's) on metal oxides. 1998 annual progress report

International Nuclear Information System (INIS)

Goodman, D.W.; Haw, J.F.; Lunsford, J.

1998-01-01

'The goal of the research is to elucidate the properties of the materials responsible for the activation of halocarbons and the nature of the intermediates formed in the dissociative adsorption of this class of compounds. This information is essential for interpreting and predicting stoichiometric and catalytic pathways for the safe destruction of halocarbon pollutants. The specific objectives are: (1) to study the adsorption and reactivity of chloromethanes and chloroethanes on metal oxides; (2) to identify the reaction intermediates using spectroscopic methods; and (3) to develop kinetic models for the reaction of these halocarbons with oxide surfaces. This report summarizes work after 20 months of a 36-month project. Emphasis has been placed understanding the surfaces phases, as well as the bulk phases that are present during the reactions of chlorinated hydrocarbons with strongly basic metal oxides. Most of the research has been carried out with carbon tetrachloride.'

Matrix isolation infrared spectroscopic and theoretical study of 1,1,1-trifluoro-2-chloroethane (HCFC-133a)

Science.gov (United States)

Rodrigues, Gessenildo Pereira; Lucena, Juracy Régis; Ventura, Elizete; Andrade do Monte, Silmar; Reva, Igor; Fausto, Rui

2013-11-01

The molecular structure and infrared spectrum of the atmospheric pollutant 1,1,1-trifluoro-2-chloroethane (HCFC-133a; CF3CH2Cl) in the ground electronic state were characterized experimentally and theoretically. Excited state calculations (at the CASSCF, MR-CISD, and MR-CISD+Q levels) have also been performed in the range up to ˜9.8 eV. The theoretical calculations show the existence of one (staggered) conformer, which has been identified spectroscopically for the monomeric compound isolated in cryogenic (˜10 K) argon and xenon matrices. The observed infrared spectra of the matrix-isolated HCFC-133a were interpreted with the aid of MP2/aug-cc-pVTZ calculations and normal coordinate analysis, which allowed a detailed assignment of the observed spectra to be carried out, including identification of bands due to different isotopologues (35Cl and 37Cl containing molecules). The calculated energies of the several excited states along with the values of oscillator strengths and previous results obtained for CFCs and HCFCs suggest that the previously reported photolyses of the title compound at 147 and 123.6 nm [T. Ichimura, A. W. Kirk, and E. Tschuikow-Roux, J. Phys. Chem. 81, 1153 (1977)] are likely to be initiated in the n-4s and n-4p Rydberg states, respectively.

Use of carbon stable isotope to investigate chloromethane formation in the electrolytic dechlorination of trichloroethylene

International Nuclear Information System (INIS)

Fang Yuanxiang; Al-Abed, Souhail R.

2007-01-01

Carbon stable isotope trichloroethylene ( 13 C TCE) was used to investigate the formation of chloromethane (CM) during the electrolytic dechlorination of trichloroethylene (TCE) at a granular-graphite packed cathode. A method was developed to use a conventional GC/MS to analyze and quantify regular and 13 C TCE and their dechlorination products. The concentration of a 13 C compound can be calculated, based on the concentration of its regular counterpart, from the response ratio of two fragments of different mass per charge values from the compounds in a sample and two characteristic MS spectrum ratios: one is the response ratio of the two fragments of the regular compound, and the other is the response ratio of the corresponding fragments of the regular and 13 C compounds at the same concentrations. The method was used to analyze the regular and 13 C compounds observed in an experiment of dechlorination in an ammonium acetate solution that contained both regular TCE and 13 C TCE. Results of analysis confirmed that CM was not a direct product of TCE dechlorination at the granular graphite cathode that cis-DCE was an intermediate product of TCE dechlorination, and that 1,1-DCE was not a dechlorination product

Use of carbon stable isotope to investigate chloromethane formation in the electrolytic dechlorination of trichloroethylene

Energy Technology Data Exchange (ETDEWEB)

Fang Yuanxiang [National Risk Management Research Laboratory, USEPA 26 W. Martin Luther King Dr. Cincinnati, OH 45268 (United States); Al-Abed, Souhail R. [National Risk Management Research Laboratory, USEPA 26 W. Martin Luther King Dr. Cincinnati, OH 45268 (United States)]. E-mail: Al-Abed.Souhail@epa.gov

2007-03-22

Carbon stable isotope trichloroethylene ({sup 13}C TCE) was used to investigate the formation of chloromethane (CM) during the electrolytic dechlorination of trichloroethylene (TCE) at a granular-graphite packed cathode. A method was developed to use a conventional GC/MS to analyze and quantify regular and {sup 13}C TCE and their dechlorination products. The concentration of a {sup 13}C compound can be calculated, based on the concentration of its regular counterpart, from the response ratio of two fragments of different mass per charge values from the compounds in a sample and two characteristic MS spectrum ratios: one is the response ratio of the two fragments of the regular compound, and the other is the response ratio of the corresponding fragments of the regular and {sup 13}C compounds at the same concentrations. The method was used to analyze the regular and {sup 13}C compounds observed in an experiment of dechlorination in an ammonium acetate solution that contained both regular TCE and {sup 13}C TCE. Results of analysis confirmed that CM was not a direct product of TCE dechlorination at the granular graphite cathode that cis-DCE was an intermediate product of TCE dechlorination, and that 1,1-DCE was not a dechlorination product.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts.

Science.gov (United States)

Tsai, Wen-Tien

2017-09-21

Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH₃Cl; methylene chloride, CH₂Cl₂; chloroform, CHCl₃; and carbon tetrachloride, CCl₄) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl₂), formyl chloride (HCOCl), carbonyl chloride (COCl₂), and hydrogen peroxide (H₂O₂). Among them, COCl₂ (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride.

Fast and effective transformation of toxaphene by superreduced vitamin B12 and dicyanocobalamin

Energy Technology Data Exchange (ETDEWEB)

Recke, R. von der; Gaul, S. [Inst. of Food Chemistry, Univ. of Hohenheim, Stuttgart (Germany); Ruppe, S.; Vetter, W. [Inst. of Food and Nutrition, Friedrich-Schiller-Univ. Jena (Germany); Neumann, A. [Dept. of Technical Biology, Univ. of Karlsruhe (Germany)

2004-09-15

The chloropesticide toxaphene (Camphechlor, Melipax) has been used in high quantities since 1945. Toxaphene has been classified as a persistent organohalogen pollutant (POP) and belongs to the ''dirty dozen''. Due to its heavy use in the 1960s and 1970s, several environmental compartments were significantly contaminated with toxaphene. For instance, concentrations in polluted areas could exceed 1 mg/kg sediment. Recently, it was shown that cultures of the isolated bacterium Dehalospirillum multivorans transformed toxaphene in a similar way as anaerobic sediment and soil samples. The potential of D. multivorans for the anaerobic transformation of organohalogens was previously demonstrated for chloroethenes (PCE and TCE) 6. The reactive dehalogenase of D. multivorans contains a corrinoide co-factor. In this study two corrinoids cyanocobalamin (vitamin B12, CCA) and dicyanocobinamide (DCC) were used in their superreduced forms (i. e. those having the central atom Co in the oxidation state +I). Interestingly, a very fast transformation of toxaphene was observed with superreduced DCC. Unfortunately, the transformation occurred so fast that no transformation products could be identified. For this reason, we performed further experiments with the less reactive superreduced vitamin B12 (CCA{sub s}). CCA{sub s} has previously been used for the transformation of PCBs, hexachlorobenzene, chloroform, and chloroethanes.

Fate of Chloromethanes in the Atmospheric Environment: Implications for Human Health, Ozone Formation and Depletion, and Global Warming Impacts

Science.gov (United States)

Tsai, Wen-Tien

2017-01-01

Among the halogenated hydrocarbons, chloromethanes (i.e., methyl chloride, CH3Cl; methylene chloride, CH2Cl2; chloroform, CHCl3; and carbon tetrachloride, CCl4) play a vital role due to their extensive uses as solvents and chemical intermediates. This article aims to review their main chemical/physical properties and commercial/industrial uses, as well as the environment and health hazards posed by them and their toxic decomposition products. The environmental properties (including atmospheric lifetime, radiative efficiency, ozone depletion potential, global warming potential, photochemical ozone creation potential, and surface mixing ratio) of these chlorinated methanes are also reviewed. In addition, this paper further discusses their atmospheric fates and human health implications because they are apt to reside in the lower atmosphere when released into the environment. According to the atmospheric degradation mechanism, their toxic degradation products in the troposphere include hydrogen chloride (HCl), carbon monoxide (CO), chlorine (Cl2), formyl chloride (HCOCl), carbonyl chloride (COCl2), and hydrogen peroxide (H2O2). Among them, COCl2 (also called phosgene) is a powerful irritating gas, which is easily hydrolyzed or thermally decomposed to form hydrogen chloride. PMID:29051455

Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

Directory of Open Access Journals (Sweden)

F. Keppler

2018-05-01

Full Text Available Chloromethane (CH3Cl is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −264±45 and −280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4 as the target compound with OH and obtained a fractionation constant of −205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

The kinetics of free radical metathetical and addition reactions in silane solutions

International Nuclear Information System (INIS)

Aloni, R.

1976-12-01

In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

Metabolism of 1-fluoro-1,1,2-trichloroethane, 1,2-dichloro-1,1-difluoroethane, and 1,1,1-trifluoro-2-chloroethane.

Science.gov (United States)

Yin, H; Jones, J P; Anders, M W

1995-03-01

1-Fluoro-1,1,2-trichloroethane (HCFC-131a), 1,2-dichloro-1,1-difluoroethane (HCFC-132b), and 1,1,1-trifluoro-2-chloroethane (HCFC-133a) were chosen as models for comparative metabolism studies on 1,1,1,2-tetrahaloethanes, which are under consideration as replacements for ozone-depleting chlorofluorocarbons (CFCs). Male Fischer 344 rats were given 10 mmol/kg ip HCFC-131a or HCFC-132b or exposed by inhalation to 1% HCFC-133a for 2 h. Urine collected in the first 24 h after exposure was analyzed by 19F NMR and GC/MS and with a fluoride-selective ion electrode for the formation of fluorine-containing metabolites. Metabolites of HCFC-131a included 2,2-dichloro-2-fluoroethyl glucuronide, 2,2-dichloro-2-fluoroethyl sulfate, dichlorofluoroacetic acid, and inorganic fluoride. Metabolites of HCFC-132b were characterized as 2-chloro-2,2-difluoroethyl glucuronide, 2-chloro-2,2-difluoroethyl sulfate, chlorodifluoroacetic acid, chlorodifluoroacetaldehyde hydrate, chlorodifluoroacetaldehyde-urea adduct, and inorganic fluoride. HCFC-133a was metabolized to 2,2,2-trifluoroethyl glucuronide, trifluoroacetic acid, trifluoroacetaldehyde hydrate, trifluoroacetaldehyde-urea adduct, inorganic fluoride, and a minor, unidentified metabolite. With HCFC-131a and HCFC-132b, glucuronide conjugates of 2,2,2-trihaloethanols were the major urinary metabolites, whereas with HCFC-133a, a trifluoroacetaldehyde-urea adduct was the major urinary metabolite. Analysis of metabolite distribution in vivo indicated that aldehydic metabolites increased as fluorine substitution increased in the order HCFC-131a < HCFC-132b < HCFC-133a. With NADPH-fortified rat liver microsomes, HCFC-133a and HCFC-132b were biotransformed to trifluoroacetaldehyde and chlorodifluoroacetaldehyde, respectively, whereas HCFC-131a was converted to dichlorofluoroacetic acid. No covalently bound metabolites were detected by 19F NMR spectroscopy.(ABSTRACT TRUNCATED AT 250 WORDS)

Role of bicarbonate as a pH buffer and electron sink in microbial dechlorination of chloroethenes

Directory of Open Access Journals (Sweden)

Delgado Anca G

2012-09-01

Full Text Available Abstract Background Buffering to achieve pH control is crucial for successful trichloroethene (TCE anaerobic bioremediation. Bicarbonate (HCO3− is the natural buffer in groundwater and the buffer of choice in the laboratory and at contaminated sites undergoing biological treatment with organohalide respiring microorganisms. However, HCO3− also serves as the electron acceptor for hydrogenotrophic methanogens and hydrogenotrophic homoacetogens, two microbial groups competing with organohalide respirers for hydrogen (H2. We studied the effect of HCO3− as a buffering agent and the effect of HCO3−-consuming reactions in a range of concentrations (2.5-30 mM with an initial pH of 7.5 in H2-fed TCE reductively dechlorinating communities containing Dehalococcoides, hydrogenotrophic methanogens, and hydrogenotrophic homoacetogens. Results Rate differences in TCE dechlorination were observed as a result of added varying HCO3− concentrations due to H2-fed electrons channeled towards methanogenesis and homoacetogenesis and pH increases (up to 8.7 from biological HCO3− consumption. Significantly faster dechlorination rates were noted at all HCO3− concentrations tested when the pH buffering was improved by providing 4-(2-hydroxyethyl-1-piperazineethanesulfonic acid (HEPES as an additional buffer. Electron balances and quantitative PCR revealed that methanogenesis was the main electron sink when the initial HCO3− concentrations were 2.5 and 5 mM, while homoacetogenesis was the dominant process and sink when 10 and 30 mM HCO3− were provided initially. Conclusions Our study reveals that HCO3− is an important variable for bioremediation of chloroethenes as it has a prominent role as an electron acceptor for methanogenesis and homoacetogenesis. It also illustrates the changes in rates and extent of reductive dechlorination resulting from the combined effect of electron donor competition stimulated by HCO3− and the changes in pH exerted by

Determination of chloromethane and dichloromethane in a tropical terrestrial mangrove forest in Brazil by measurements and modelling

Science.gov (United States)

Kolusu, S. R.; Schlünzen, K. H.; Grawe, D.; Seifert, R.

2018-01-01

Chloromethane (CH3Cl) and dichloromethane (CH2Cl2) are known to have both natural and anthropogenic sources to the atmosphere. From recent studies it is known that tropical and sub tropical plants are primary sources of CH3Cl in the atmosphere. In order to quantify the biogenic emissions of CH3Cl and CH2Cl2 from mangroves, field measurement were conducted in a tropical mangrove forest on the coast of Brazil. To the best of our knowledge these field measurements were the first of its kind conducted in the tropical mangrove ecosystem of Braganca. A mesoscale atmospheric model, MEsoscale TRAnsport and fluid (Stream) model (METRAS), was used to simulate passive tracers concentrations and to study the dependency of concentrations on type of emission function and meteorology. Model simulated concentrations were normalized using the observed field data. With the help of the mesoscale model results and the observed data the mangrove emissions were estimated at the local scale. By using this bottom-up approach the global emissions of CH3Cl and CH2Cl2 from mangroves were quantified. The emission range obtained with different emission functions and different meteorology are 4-7 Gg yr-1 for CH3Cl and 1-2 Gg yr2 for CH2Cl2. Based on the present study the mangroves contribute 0.3 percent of CH2Cl2 and 0.2 percent of CH3Cl in the global emission budget. This study corroborates the study by Manley et al. (2007) which estimated that mangroves produce 0.3 percent of CH3Cl in the global emission budget. Although they contribute a small percentage in the global budget, their long lifetime enables them to contribute to the destruction of ozone in the stratosphere. From the detailed analyses of the model results it can be concluded that meteorology has a larger influence on the variability of concentrations than the temporal variability of the emission function.

Dehalogenation of chlorinated ethenes and immobilization of nickel in anaerobic sediment columns under sulfidogenic conditions

NARCIS (Netherlands)

Drzyzga, O; EL Mamouni, R; Agathos, SN; Gottschal, JC

2002-01-01

A sediment column study was carried out to demonstrate the bioremediation of chloroethene- and nickel-contaminated sediment in a single anaerobic step under sulfate-reducing conditions. Four columns (one untreated control column and three experimental columns) with sediment from a chloroethene- and

Laboratory studies of nitrate radical chemistry - application to atmospheric processes

Energy Technology Data Exchange (ETDEWEB)

Noremsaune, Ingse

1997-12-31

This thesis studies atmospheric chemistry and tries in particular to fill gaps in the data base of atmospheric reactions. It studies the nitrate radical reactions with chloroethenes and with but-2-yne (2-butyne). The mechanisms and rate coefficients for the NO{sub 3}-initiated degradation of the chloroethenes and 2-butyne were investigated by means of the static reaction chamber and the fast flow-discharge technique. The reactions between the nitrate radical and the chloroethenes were studied at atmospheric pressure in a reaction chamber with synthetic air as bath gas. FTIR (Fourier Transform InfraRed spectroscopy) spectroscopy was used to follow the reactions and to identify the products. Products were observed for the reactions with (E)-1,2-dichloroethene and tetrachloroethene, although the absorption bands are weak. The alkyl peroxynitrate and nitrate compounds form very strong and characteristic absorption bands. The rate coefficients for the reactions between NO{sub 3} and the chloroethenes were investigated at room temperature by three different methods. The results are given in tables. 132 refs., 44 figs., 21 tabs.

Henry's law constants and infinite dilution activity coefficients of cis-2-butene, dimethylether, chloroethane, and 1,1-difluoroethane in methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol

International Nuclear Information System (INIS)

Miyano, Yoshimori; Kobashi, Takahiro; Shinjo, Hiroshi; Kumada, Shinya; Watanabe, Yusuke; Niya, Wataru; Tateishi, Yoko

2006-01-01

Henry's law constants and infinite dilution activity coefficients of cis-2-butene, dimethylether, chloroethane, and 1,1-difluoroethane in methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol in the temperature range of 250 K to 330 K were measured by a gas stripping method and partial molar excess enthalpies were calculated from the activity coefficients. A rigorous formula for evaluating the Henry's law constants from the gas stripping measurements was used for the data reduction of these highly volatile mixtures. The uncertainty is about 2% for the Henry's law constants and 3% for the estimated infinite dilution activity coefficients. In the evaluation of the infinite dilution activity coefficients, the nonideality of the solute such as the fugacity coefficient and Poynting correction factor cannot be neglected, especially at higher temperatures. The estimated uncertainty of the infinite dilution activity coefficients includes 1% for nonideality

In situ TCE degradation mediated by complex dehalorespiring communities during biostimulation processes

OpenAIRE

DUGAT-BONY, ERIC; Biderre-Petit, Corinne; Jaziri, Faouzi; David, Maude M; Denonfoux, Jérémie; Lyon, Delina Y; Richard, Jean-Yves; Curvers, Cyrille; Boucher, Delphine; Vogel, Timothy M; Peyretaillade, Eric; Peyret, Pierre

2012-01-01

Summary The bioremediation of chloroethene contaminants in groundwater polluted systems is still a serious environmental challenge. Many previous studies have shown that cooperation of several dechlorinators is crucial for complete dechlorination of trichloroethene to ethene. In the present study, we used an explorative functional DNA microarray (DechloArray) to examine the composition of specific functional genes in groundwater samples in which chloroethene bioremediation was enhanced by del...

Baseline Estimation and Outlier Identification for Halocarbons

Science.gov (United States)

Wang, D.; Schuck, T.; Engel, A.; Gallman, F.

2017-12-01

The aim of this paper is to build a baseline model for halocarbons and to statistically identify the outliers under specific conditions. In this paper, time series of regional CFC-11 and Chloromethane measurements was discussed, which taken over the last 4 years at two locations, including a monitoring station at northwest of Frankfurt am Main (Germany) and Mace Head station (Ireland). In addition to analyzing time series of CFC-11 and Chloromethane, more importantly, a statistical approach of outlier identification is also introduced in this paper in order to make a better estimation of baseline. A second-order polynomial plus harmonics are fitted to CFC-11 and chloromethane mixing ratios data. Measurements with large distance to the fitting curve are regard as outliers and flagged. Under specific requirement, the routine is iteratively adopted without the flagged measurements until no additional outliers are found. Both model fitting and the proposed outlier identification method are realized with the help of a programming language, Python. During the period, CFC-11 shows a gradual downward trend. And there is a slightly upward trend in the mixing ratios of Chloromethane. The concentration of chloromethane also has a strong seasonal variation, mostly due to the seasonal cycle of OH. The usage of this statistical method has a considerable effect on the results. This method efficiently identifies a series of outliers according to the standard deviation requirements. After removing the outliers, the fitting curves and trend estimates are more reliable.

Evaluation of Metal-Organic Frameworks for the Removal of Toxic Industrial Chemicals

National Research Council Canada - National Science Library

Peterson, Gregory W; Mahle, John J; Balboa, Alex; Sewell, Tara L; Karwacki, Christopher J; Friday, David

2008-01-01

.... This report summarizes the evaluation of four MOFs using nitrogen isotherm data, temperature stability analyses, water and chloroethane adsorption equilibria, and ammonia, cyanogen chloride (CK...

Decomposition of tetrachloroethylene by ionizing radiation

International Nuclear Information System (INIS)

Hakoda, T.; Hirota, K.; Hashimoto, S.

1998-01-01

Decomposition of tetrachloroethylene and other chloroethenes by ionizing radiation were examined to get information on treatment of industrial off-gas. Model gases, airs containing chloroethenes, were confined in batch reactors and irradiated with electron beam and gamma ray. The G-values of decomposition were larger in the order of tetrachloro- > trichloro- > trans-dichloro- > cis-dichloro- > monochloroethylene in electron beam irradiation and tetrachloro-, trichloro-, trans-dichloro- > cis-dichloro- > monochloroethylene in gamma ray irradiation. For tetrachloro-, trichloro- and trans-dichloroethylene, G-values of decomposition in EB irradiation increased with increase of chlorine atom in a molecule, while those in gamma ray irradiation were almost kept constant. The G-value of decomposition for tetrachloroethylene in EB irradiation was the largest of those for all chloroethenes. In order to examine the effect of the initial concentration on G-value of decomposition, airs containing 300 to 1,800 ppm of tetrachloroethylene were irradiated with electron beam and gamma ray. The G-values of decomposition in both irradiation increased with the initial concentration. Those in electron beam irradiation were two times larger than those in gamma ray irradiation

40 CFR Table 8 to Subpart Ggg of... - Fraction Measured (Fm) for HAP Compounds in Wastewater Streams

Science.gov (United States)

2010-07-01

... POLLUTANTS FOR SOURCE CATEGORIES National Emission Standards for Pharmaceuticals Production Pt. 63, Subpt...) 106898 0.94 Ethyl acrylate 140885 1.00 Ethylbenzene 100414 1.00 Ethyl chloride (Chloroethane) 75003 1.00...

Physical and physicochemical factors effecting transport of chlorohydrocarbon gases from lung alveolar air to blood as measured by the causation of narcosis.

Science.gov (United States)

Holder, James W

2012-01-01

This systematic investigation examines gas transport in the lung for two sets of chlorohydrocarbons (CHCs): the chloromethanes (C1) and chloroethanes (C2). The C1 series includes chloromethane, methylene chloride, chloroform, and carbon tetrachloride, and the C2 series includes chloroethane, 1,2-dichloroethane, 1, 1, 2-trichloroethane, and 1, 1, 2, 2-tetrachloroethane. Most CHC gases cause narcosis. The comprehensive narcosis work of Lehmann and colleagues on CHCs was used as a basis for the narcosis endpoint in the present examination. The sites for narcosis are located in the brain (midline cortex and posterior parietal area), the spine, and at many peripheral nerve sites. Central nervous system (CNS) exposure executes a multisite, neural transmission set of inhibitions that promotes rapid loss of consciousness, sensory feeling, and current and stored memory while providing temporary amnesia. Absorption into the system requires dissolution into many lipid membranes and binding to lipoproteins. Lipophilicity is a CHC property shared with many anesthetics according to the Meyer-Overton Rule. Many structurally different lipid chemicals produce the narcosis response when the lipid concentration exceeds -67 mM. This suggests narcotic or anesthetic dissolution into CNS membranes until the lipid organization is disrupted or perturbed. This perturbation includes loading of Na(+)- and K(+)-channel transmembrane lipoprotein complexes and disrupting their respective channel functional organizations. The channel functions become attenuated or abrogated until the CHC exposure ceases and CHC loading reverses. This investigation demonstrates how the CHC physical and chemical properties influence the absorption of these CHCs via the lung and the alveolar system on route to the blood. Narcosis in test animals was used here as an objective biological endpoint to study the effects of the physical factors Bp, Vp, Kd (oil: gas) partition, Henry's constant (HK), and water solubility

Bacterial communities in tetrachloroethene-polluted groundwaters: A case study

Czech Academy of Sciences Publication Activity Database

Kotík, Michael; Davidová, Anna; Voříšková, Jana; Baldrian, Petr

2013-01-01

Roč. 454, JUN 2013 (2013), s. 517-527 ISSN 0048-9697 R&D Projects: GA ČR GAP504/10/0137 Institutional support: RVO:61388971 Keywords : Tetrachloroethene * Chloroethenes * Dechlorination Subject RIV: CE - Biochemistry Impact factor: 3.163, year: 2013

HYDROGEN CONCENTRATIONS IN SULFATE-REDUCING ESTUARINE SEDIMENTS DURING PCE DEHALOGENATION

Science.gov (United States)

Despite recent progress made evaluating the role of hydrogen (H2) as a key electron donor in the anaerobic remediation of chloroethenes, few studies have focused on the evaluation of hydrogen thresholds relative to reductive dehalogenation in sulfidogenic environments. Competitio...

29 CFR 1910.1017 - Vinyl chloride.

Science.gov (United States)

2010-07-01

... employee exposure to vinyl chloride (chloroethene), Chemical Abstracts Service Registry No. 75014. (2) This section applies to the manufacture, reaction, packaging, repackaging, storage, handling or use of vinyl... this section by engineering, work practice, and personal protective controls as follows: (1) Feasible...

Microreactor Technology for On-Site Production of Methyl Chloride

Czech Academy of Sciences Publication Activity Database

Schmidt, S.A.; Vajglová, Zuzana; Eränen, K.; Murzin, D.Y.; Salmi, T.

2014-01-01

Roč. 3, č. 5 (2014), s. 345-352 ISSN 2191-9542 Institutional support: RVO:67985858 Keywords : chloromethane * intensification * microreactor * product separation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.125, year: 2014

Remedial Investigation Report for USATHAMA - RATSS Lake City Army Ammunition Plant, Independence, Missouri. Volume 2

Science.gov (United States)

1990-06-01

animals, acute oral administration produces fatty infiltration and histological alterations in the liver. High doses produce irreversible liver damage...animals has produced histological or pathological changes in the liver, brain, and lungs (Troshina 1964). Chronic exposure of animals to chloroethane...ingestion include salivation, gastrointestinal irritation, nausea, vomiting, hemorrhagic gastritis , and diarrhea (ACGIH 1986). Dermal or ocular exposure of

Potential of isotope analysis (C, Cl) to identify dechlorination mechanisms

Science.gov (United States)

Cretnik, Stefan; Thoreson, Kristen; Bernstein, Anat; Ebert, Karin; Buchner, Daniel; Laskov, Christine; Haderlein, Stefan; Shouakar-Stash, Orfan; Kliegman, Sarah; McNeill, Kristopher; Elsner, Martin

2013-04-01

Chloroethenes are commonly used in industrial applications, and detected as carcinogenic contaminants in the environment. Their dehalogenation is of environmental importance in remediation processes. However, a detailed understanding frequently accounted problem is the accumulation of toxic degradation products such as cis-dichloroethylene (cis-DCE) at contaminated sites. Several studies have addressed the reductive dehalogenation reactions using biotic and abiotic model systems, but a crucial question in this context has remained open: Do environmental transformations occur by the same mechanism as in their corresponding in vitro model systems? The presented study shows the potential to close this research gap using the latest developments in compound specific chlorine isotope analysis, which make it possible to routinely measure chlorine isotope fractionation of chloroethenes in environmental samples and complex reaction mixtures.1,2 In particular, such chlorine isotope analysis enables the measurement of isotope fractionation for two elements (i.e., C and Cl) in chloroethenes. When isotope values of both elements are plotted against each other, different slopes reflect different underlying mechanisms and are remarkably insensitive towards masking. Our results suggest that different microbial strains (G. lovleyi strain SZ, D. hafniense Y51) and the isolated cofactor cobalamin employ similar mechanisms of reductive dechlorination of TCE. In contrast, evidence for a different mechanism was obtained with cobaloxime cautioning its use as a model for biodegradation. The study shows the potential of the dual isotope approach as a tool to directly compare transformation mechanisms of environmental scenarios, biotic transformations, and their putative chemical lab scale systems. Furthermore, it serves as an essential reference when using the dual isotope approach to assess the fate of chlorinated compounds in the environment.

Patrick Air Force Base Storm Water Pollution Prevention Plan.

Science.gov (United States)

1994-09-01

7758987 Cupric sulfate 77-47-4 Hexachlorocyclopentadliene 10380297 Cupric sulfate, ammoniated 67-72-1 H-exachloroethane 815827 Cupric tartrate 76-47-01...28300745 Antimony potassium 75-00-3 Chloroethane (Ethyl chlo- tartrate ride) 7789619 Antimony tribromide 67-66-3 Chloroform 10025919 Antimony...5 p-Cresol 7787475 Beryllium chloride 1319-77-3 Cresol (mixed isomers) 7787497 Beryllium fluoride 142712 Cupric acetate 7787555 Beryllium nitrate

Genomic and Transcriptomic Analysis of Growth-Supporting Dehalogenation of Chlorinated Methanes in Methylobacterium

Directory of Open Access Journals (Sweden)

Pauline Chaignaud

2017-09-01

Full Text Available Bacterial adaptation to growth with toxic halogenated chemicals was explored in the context of methylotrophic metabolism of Methylobacterium extorquens, by comparing strains CM4 and DM4, which show robust growth with chloromethane and dichloromethane, respectively. Dehalogenation of chlorinated methanes initiates growth-supporting degradation, with intracellular release of protons and chloride ions in both cases. The core, variable and strain-specific genomes of strains CM4 and DM4 were defined by comparison with genomes of non-dechlorinating strains. In terms of gene content, adaptation toward dehalogenation appears limited, strains CM4 and DM4 sharing between 75 and 85% of their genome with other strains of M. extorquens. Transcript abundance in cultures of strain CM4 grown with chloromethane and of strain DM4 grown with dichloromethane was compared to growth with methanol as a reference C1 growth substrate. Previously identified strain-specific dehalogenase-encoding genes were the most transcribed with chlorinated methanes, alongside other genes encoded by genomic islands (GEIs and plasmids involved in growth with chlorinated compounds as carbon and energy source. None of the 163 genes shared by strains CM4 and DM4 but not by other strains of M. extorquens showed higher transcript abundance in cells grown with chlorinated methanes. Among the several thousand genes of the M. extorquens core genome, 12 genes were only differentially abundant in either strain CM4 or strain DM4. Of these, 2 genes of known function were detected, for the membrane-bound proton translocating pyrophosphatase HppA and the housekeeping molecular chaperone protein DegP. This indicates that the adaptive response common to chloromethane and dichloromethane is limited at the transcriptional level, and involves aspects of the general stress response as well as of a dehalogenation-specific response to intracellular hydrochloric acid production. Core genes only differentially

Potentially bioavailable natural organic carbon and hydrolyzable amino acids in aquifer sediments

Science.gov (United States)

Thomas, Lashun K.; Widdowson, Mark A.; Novak, John T.; Chapelle, Francis H.; Benner, Ronald; Kaiser, Karl

2012-01-01

This study evaluated the relationship between concentrations of operationally defined potentially bioavailable organic -carbon (PBOC) and hydrolyzable amino acids (HAAs) in sediments collected from a diverse range of chloroethene--contaminated sites. Concentrations of PBOC and HAA were measured using aquifer sediment samples collected at six selected study sites. Average concentrations of total HAA and PBOC ranged from 1.96 ± 1.53 to 20.1 ± 25.6 mg/kg and 4.72 ± 0.72 to 443 ± 65.4 mg/kg, respectively. Results demonstrated a statistically significant positive relationship between concentrations of PBOC and total HAA present in the aquifer sediment (p amino acids are known to be readily biodegradable carbon compounds, this relationship suggests that the sequential chemical extraction procedure used to measure PBOC is a useful indicator of bioavailable carbon in aquifer sediments. This, in turn, is consistent with the interpretation that PBOC measurements can be used for estimating the amount of natural organic carbon available for driving the reductive dechlorination of chloroethenes in groundwater systems.

Evaluation of Chlorinated Hydrocarbon Concentrations in Tehran’s Districts Drinking Water

Directory of Open Access Journals (Sweden)

Alireza Pardakhti

2012-01-01

Full Text Available In this study Tehran’s drinking water was evaluated for the presence of chlorinated hydrocarbons during spring and summer of 2009. Chlorinated hydrocarbons are an important class of environmental pollutants that cause adverse health effects on human’s kidney, liver and central nervous systems. In this study six water districts were selected for taking drinking water samples in the city of Tehran as well as one location outside the city limits. The samples were analyzed by GC/MS using EPA method 8260. The average concentrations of 1,1-dichloroethylene, 1,2 Dichloromethane, Tetra chloromethane, Trichloroethylene and tetra chloroethylene were determined during a 7 month period and the results were 0.04ppb, 0.52ppb, 0.01ppb, 0.24ppb, 0.03ppb respectively. The highest concentration of chlorinated hydrocarbon observed in Tehran’s drinking water was Trichloroethylene and the lowest concentration was Tetra chloromethane. Districts 5 and 6 showed the highest concentrations of chlorinated hydrocarbons in the city of Tehran.

Halite as a Methane Sequestration Host: A Possible Explanation for Periodic Methane Release on Mars, and a Surface-accessible Source of Ancient Martian Carbon

Science.gov (United States)

Fries, M. D.; Steele, Andrew; Hynek, B. M.

2015-01-01

We present the hypothesis that halite may play a role in methane sequestration on the martian surface. In terrestrial examples, halite deposits sequester large volumes of methane and chloromethane. Also, examples of chloromethane-bearing, approximately 4.5 Ga old halite from the Monahans meteorite show that this system is very stable unless the halite is damaged. On Mars, methane may be generated from carbonaceous material trapped in ancient halite deposits and sequestered. The methane may be released by damaging its halite host; either by aqueous alteration, aeolian abrasion, heating, or impact shock. Such a scenario may help to explain the appearance of short-lived releases of methane on the martian surface. The methane may be of either biogenic or abiogenic origin. If this scenario plays a significant role on Mars, then martian halite deposits may contain samples of organic compounds dating to the ancient desiccation of the planet, accessible at the surface for future sample return missions.

A high volume sampling system for isotope determination of volatile halocarbons and hydrocarbons

Directory of Open Access Journals (Sweden)

E. Bahlmann

2011-10-01

Full Text Available The isotopic composition of volatile organic compounds (VOCs can provide valuable information on their sources and fate not deducible from mixing ratios alone. In particular the reported carbon stable isotope ratios of chloromethane and bromomethane from different sources cover a δ¹³C-range of almost 100‰ making isotope ratios a very promising tool for studying the biogeochemistry of these compounds. So far, the determination of the isotopic composition of C₁ and C₂ halocarbons others than chloromethane is hampered by their low mixing ratios.

In order to determine the carbon isotopic composition of C₁ and C₂ halocarbons with mixing ratios as low as 1 pptv (i a field suitable cryogenic high volume sampling system and (ii a chromatographic set up for processing these samples have been developed and validated. The sampling system was tested at two different sampling sites, an urban and a coastal location in Northern Germany. The average δ¹³C-values for bromomethane at the urban site were −42.9 ± 1.1‰ and agreed well with previously published results. But at the coastal site bromomethane was substantially enriched in ¹³C by almost 10‰. Less pronounced differences were observed for chlorodifluoromethane, 1,1,1-trichloroethane and chloromethane. We suggest that these differences are related to the turnover of these compounds in ocean surface waters. Furthermore we report first carbon isotope ratios for iodomethane (−40.4‰ to −79.8‰, bromoform (−13.8‰ to 22.9‰, and other halocarbons.

Quantitative structure-activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: wing spot test of Drosophila melanogaster.

Science.gov (United States)

Chroust, Karel; Pavlová, Martina; Prokop, Zbynek; Mendel, Jan; Bozková, Katerina; Kubát, Zdenek; Zajícková, Veronika; Damborský, Jiri

2007-02-01

Halogenated aliphatic compounds were evaluated for toxic and genotoxic effects in the somatic mutation and recombination test employing Drosophila melanogaster. The tested chemicals included chlorinated, brominated and iodinated; mono-, di- and tri-substituted; saturated and unsaturated alkanes: 1,2-dibromoethane, 1-bromo-2-chloroethane, 1-iodopropane, 2,3-dichloropropene, 3-bromo-1-propene, epibromohydrin, 2-iodobutane, 3-chloro-2-methylpropene, 1,2,3-trichloropropane, 1,2-dichloroethane, 1,2-dichlorobutane, 1-chloro-2-methylpropane, 1,3-dichloropropane, 1,2-dichloropropane, 2-chloroethymethylether, 1-bromo-2-methylpropane and 1-chloropentane. N-methyl-N-nitrosourea served as the positive and distilled water as the negative control. The set of chemicals for the toxicological testing was selected by the use of statistical experiment design. Group of unsaturated aliphatic hydrocarbons were generally more toxic than saturated analogues. The genotoxic effect was observed with 14 compounds in the wing spot test, while 3 substances did not show any genotoxicity by using the wing spot test at 50% lethal concentration. The highest number of wing spots was observed in genotoxicity assay with 1-bromo-2-chloroethane, 1,2-dichloroethane, 1,2-dibromoethane and 1-iodopropane. Nucleophilic superdelocalizability calculated by quantum mechanics appears to be a good parameter for prediction of both toxicity and genotoxicity effects of halogenated aliphatic compounds.

Characterization of the Fate and Biotransformation of Fluorochemicals in AFFF-Contaminated Groundwater at Fire/Crash Testing Military Sites

Science.gov (United States)

2017-04-10

reaction media was neutralized and then combined with1 mL methanol. Headspace oxygen was measured by gas chromatography flame ionization detection...materials except the mixture of perfluorinated acids. Analytical Methods. Chloroethene, methane, and hydrogen were quantified by gas chromatography...275-296. (49) Milinovic, J.; Lacorte, S.; Vidal, M.; Rigol, A. Sorption behaviour of perfluoroalkyl substances in soils. Sci Total Environ 2015, 511

Mixed Waste Management Facility (MWMF) groundwater monitoring report. Fourth quarter 1992 and 1992 summary

Energy Technology Data Exchange (ETDEWEB)

1993-03-01

During fourth quarter 1992, nine constituents exceeded final Primary Drinking Water Standards (PDWS) in one or more groundwater samples from monitoring wells at the Mixed Waste Management Facility (MWMF) and adjacent facilities. As in previous quarters, tritium and trichloroethylene were the most widespread constituents. Fifty-seven (48%) of the 120 monitoring wells, contained elevated tritium activities, and 23 (19%) contained elevated trichloroethylene concentrations. Total alpha-emitting radium, tetrachloroethylene, chloroethene, cadmium, 1,1-dichloroethylene, lead, or nonvolatile beta levels exceeded standards in one or more wells. During 1992, elevated levels of 13 constituents were found in one or more of 80 of the 120 groundwater monitoring wells (67%) at the MWMF and adjacent facilities. Tritium and trichloroethylene exceeded their final PDWS more frequently and more consistently than did other constituents. Tritium activity exceeded its final PDWS m 67 wells and trichloroethylene was. elevated in 28 wells. Lead, tetrachloroethylene, total alpha-emitting radium, gross alpha, cadmium, chloroethene, 1,1-dichloroethylene 1,2-dichloroethane, mercury, or nitrate exceeded standards in one or more wells during the year. Nonvolatile beta exceeded its drinking water screening level in 3 wells during the year.

Mixed Waste Management Facility (MWMF) groundwater monitoring report

International Nuclear Information System (INIS)

1993-03-01

During fourth quarter 1992, nine constituents exceeded final Primary Drinking Water Standards (PDWS) in one or more groundwater samples from monitoring wells at the Mixed Waste Management Facility (MWMF) and adjacent facilities. As in previous quarters, tritium and trichloroethylene were the most widespread constituents. Fifty-seven (48%) of the 120 monitoring wells, contained elevated tritium activities, and 23 (19%) contained elevated trichloroethylene concentrations. Total alpha-emitting radium, tetrachloroethylene, chloroethene, cadmium, 1,1-dichloroethylene, lead, or nonvolatile beta levels exceeded standards in one or more wells. During 1992, elevated levels of 13 constituents were found in one or more of 80 of the 120 groundwater monitoring wells (67%) at the MWMF and adjacent facilities. Tritium and trichloroethylene exceeded their final PDWS more frequently and more consistently than did other constituents. Tritium activity exceeded its final PDWS m 67 wells and trichloroethylene was. elevated in 28 wells. Lead, tetrachloroethylene, total alpha-emitting radium, gross alpha, cadmium, chloroethene, 1,1-dichloroethylene 1,2-dichloroethane, mercury, or nitrate exceeded standards in one or more wells during the year. Nonvolatile beta exceeded its drinking water screening level in 3 wells during the year

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

Science.gov (United States)

Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.;

16S rRNA gene-based detection of tetrachloroethene-dechlorinating Desulfuromonas and Dehalococcoides species

Energy Technology Data Exchange (ETDEWEB)

Loeffler, F.E.; Sun, Q.; Li, J.; Tiedje, J.M.

2000-03-01

Members of the genera Desulfuromonas and Dehalococcoides reductively dechlorinate tetrachloroethene (PCE) and trichloroethene. Two primer pairs specific to hypervariable regions of the 16S rRNA genes of the Dehalococcoides group (comprising Dehalococcoides ethenogenes and Dehalococcoides sp. strain FL2) and the acetate-oxidizing, PCE-dechlorinating Desulfuromonas group (comprising Desulfuromonas sp. strain BB1 and Desulfuromonas chloroethenica) were designed. The detection threshold of a nested PCR approach using universal bacterial primers followed by a second PCR with the Desulfuromonas dechlorinator-targeted primer pair was 1 x 10{sup 3} BB1 cells added per gram (wet weight) of sandy aquifer material. Total community DNA isolated from sediments of three Michigan rivers and six different chloroethene-contaminated aquifer samples was used as template in nested PCR. All river sediment samples yielded positive signals with the BB1- and the Dehalococcoides-targeted primers. One chloroethene-contaminated aquifer tested positive with the Dehalococcoides-targeted primers, and another contaminated aquifer tested positive with the Desulfuromonas dechlorinator-targeted primer pair. Restriction fragment analysis of the amplicons could discriminate strain BB1 from other known Desulfuromonas species. Microcosm studies confirmed the presence of PCE-dechlorinating, acetate-oxidizing Desulfuromonas and hydrogenotrophic Dehalococcoides species in samples yielding positive PCR signals with the specific primers.

Evaluation of Anaerobic Biodegradation of Organic Carbon Extracted from Aquifer Sediment

OpenAIRE

Kelly, Catherine Aileen

2006-01-01

In conjunction with ongoing studies to develop a method for quantifying potentially biodegradable organic carbon (Rectanus et al 2005), this research was conducted to evaluate the extent to which organic carbon extracted using this method will biodegrade in anaerobic environments. The ultimate goal is to use this method for the evaluation of chloroethene contaminated sites in order to estimate the long-term sustainability of monitored natural attenuation (MNA) as a remediation strategy. Alt...

The Search for Organic Compounds of Martian Origin in Gale Crater by the Sample Analysis at Mars (SAM) Instrument on Curiosity

Science.gov (United States)

Glavin, Daniel; Freissinet, Caroline; Mahaffy, Paul; Miller, Kristen; Eigenbrode, Jennifer; Summons, Roger; Archer, Douglas, Jr.; Brunner, Anna; Martin, Mildred; Buch, Arrnaud;

Improved dechlorinating performance of upflow anaerobic sludge blanket reactors by incorporation of Dehalospirillum multivorans into granular sludge

DEFF Research Database (Denmark)

Hörber, Christine; Christiansen, Nina; Arvin, Erik

1998-01-01

.5 mM acetate and were operated under sterile conditions. In the test reactor, an average of 93% (mole/mole) of the effluent chloroethenes was dichloroethene (DCE), compared to 99% (mole/mole) in the Ri reactor. The R2 reactor, with no inoculation, produced only trichloroethene (TCE), averaging 43...... to DCE, even at HRTs much lower than the reciprocal maximum specific growth rate of D. multivorans, indicating that this bacterium was immobilized in the living and autoclaved granular sludge. In contrast, the R2 reactor, with no inoculation of D. multivorans, only converted PCE to TCE under the same...

Dehalogenation of chloroalkanes by nickel(i) porphyrin derivatives, a computational study.

Science.gov (United States)

Szatkowski, L; Hall, M B

2016-11-14

The nickel(i) octaethylisobacteriochlorin anion ([OEiBCh-Ni (I) ] - ) is commonly used as a synthetic model of cofactor F 430 from Methyl-Coenzyme M Reductase. In this regard, experimental studies show that [OEiBCh-Ni (I) ] - can catalyze dehalogenation of aliphatic halides in DMF solution by a highly efficient S N 2 reaction. To better understand this process, we constructed theoretical models of the dehalogenation of chloromethane by a simple nickel(i) isobacteriochlorin anion and compared its reactivity with that of similar Ni (I) complexes with other porphyrin-derived ligands: porphyrin, chlorin, bactreriochlorin, hexahydroporphyrin and octahydroporphyrin. Our calculations predict that all of the porphyrin derivative's model reactions proceed through low-spin complexes. Relative to the energy of the separate reactants the theoretical activation energies (free-energy barriers with solvation corrections) for the dehalogenation of chloromethane are similar for all of the porphyrin derivatives and range for the different functionals from 10-15 kcal mol -1 for B3LYP to 5-10 kcal mol -1 for M06-L and to 13-18 kcal mol -1 for ωB97X-D. The relative free energies of the products of the dehalogenation step, L-Ni-Me adducts, have a range from -5 to -40 kcal mol -1 for all functionals; generally becoming more negative with increasing saturation of the porphyrin ligand. Moreover, no significant differences in the theoretical chlorine kinetic isotope effect were discernable with change of porphyrin ligand.

Electrocarboxylation of benzyl chlorides at silver cathode at the preparative scale level

Energy Technology Data Exchange (ETDEWEB)

Scialdone, Onofrio [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy)], E-mail: scialdone@dicpm.unipa.it; Galia, Alessandro; Errante, Giuseppina [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy); Isse, Abdirisak Ahmed; Gennaro, Armando [Dipartimento di Scienze Chimiche, Universita di Padova, Via Marzolo 1, 35131 Padova (Italy); Filardo, Giuseppe [Dipartimento di Ingegneria Chimica dei Processi e dei Materiali, Universita di Palermo, Viale delle Scienze, 90128 Palermo (Italy)

2008-01-01

The electrocarboxylation of benzyl chlorides to the corresponding carboxylic acids performed at silver cathodes was investigated both theoretically and experimentally in order to find the influence of the operative parameters on the selectivity and on the Faradic efficiency of the process. Theoretical considerations were confirmed by the electrocarboxylation of 1-phenyl-1-chloroethane performed in undivided cells equipped with sacrificial anodes both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel plate electrochemical cell. Selectivity and Faradic yields higher than 80% and 70%, respectively, were obtained by working under anhydrous conditions both under amperostatic and potentiostatic alimentation at appropriate values of either current density or applied potential.

Stimulation of reductive dechlorination of tetrachloroethane in anaerobic aquifer microcosms by addition of short-chain organic acids or alcohols

International Nuclear Information System (INIS)

Gibson, S.A.; Sewell, G.W.

1992-01-01

Although the ecological and public health risk associated with tetrachloroethene (PCE) contamination may be the most severe when spills affect groundwater, little is known about the environmental conditions necessary to initiate and sustain dehalogenation activity in contaminated aquifers. This study was done with core material collected from a site impacted by both aviation gasoline and chloroethenes at a Coast Guard Air Station at Traverse City, Michigan. The effect of the addition of common fermentation products on the dehalogenation of tetrachloroethene was studied in methanogenic slurries made with aquifer solids. Lactate, propionate, crotonate, butyrate, and ethanol stimulated dehalogenation activity, while acetate, methanol, and isopropanol did not

Pollutant plume delineation from tree core sampling using standardized ranks

DEFF Research Database (Denmark)

Wahyudi, Agung; Bogaert, Patrick; Trapp, Stefan

2012-01-01

There are currently contradicting results in the literature about the way chloroethene (CE) concentrations from tree core sampling correlate with those from groundwater measurements. This paper addresses this issue by focusing on groundwater and tree core datasets in CE contaminated site, Czech...... Republic. Preliminary analyses revealed strongly and positively skewed distributions for the tree core dataset, with an intra-tree variability accounting for more than 80% of the total variability, while the spatial analyses based on variograms indicated no obvious spatial pattern for CE concentration...... groundwater and tree core measurements. Nonetheless, tree core sampling and analysis proved to be a quick and inexpensive semi-quantitative method and a useful tool....

Variational Flooding Study of a SN2 Reaction.

Science.gov (United States)

Piccini, GiovanniMaria; McCarty, James J; Valsson, Omar; Parrinello, Michele

2017-02-02

We have studied the reaction dynamics of a prototypical organic reaction using a variationally optimized truncated bias to accelerate transitions between educt and product reactant states. The asymmetric S N 2 nucleophilic substitution reaction of fluoromethane and chloromethane CH 3 F + Cl - ⇌ CH 3 Cl + F - is considered, and many independent biased molecular dynamics simulations have been performed at 600, 900, and 1200 K, collecting several hundred transitions at each temperature. The transition times and relative rate constants have been obtained for both reaction directions. The activation energies extracted from an Arrhenius plot compare well with standard static calculations.

Improved Dechlorinating Performance of Upflow Anaerobic Sludge Blanket Reactors by Incorporation of Dehalospirillum multivorans into Granular Sludge

Science.gov (United States)

Hörber, Christine; Christiansen, Nina; Arvin, Erik; Ahring, Birgitte K.

1998-01-01

Dechlorination of tetrachloroethene, also known as perchloroethylene (PCE), was investigated in an upflow anaerobic sludge blanket (UASB) reactor after incorporation of the strictly anaerobic, reductively dechlorinating bacterium Dehalospirillum multivorans into granular sludge. This reactor was compared to the reference 1 (R1) reactor, where the granules were autoclaved to remove all dechlorinating abilities before inoculation, and to the reference 2 (R2) reactor, containing only living granular sludge. All three reactors were fed mineral medium containing 3 to 57 μM PCE, 2 mM formate, and 0.5 mM acetate and were operated under sterile conditions. In the test reactor, an average of 93% (mole/mole) of the effluent chloroethenes was dichloroethene (DCE), compared to 99% (mole/mole) in the R1 reactor. The R2 reactor, with no inoculation, produced only trichloroethene (TCE), averaging 43% (mole/mole) of the effluent chloroethenes. No dechlorination of PCE was observed in an abiotic control consisting of sterile granules without inoculum. During continuous operation with stepwise-reduced hydraulic retention times (HRTs), both the test reactor and the R1 reactor showed conversion of PCE to DCE, even at HRTs much lower than the reciprocal maximum specific growth rate of D. multivorans, indicating that this bacterium was immobilized in the living and autoclaved granular sludge. In contrast, the R2 reactor, with no inoculation of D. multivorans, only converted PCE to TCE under the same conditions. Immobilization could be confirmed by using fluorescein-labeled antibody probes raised against D. multivorans. In granules obtained from the R1 reactor, D. multivorans grew mainly in microcolonies located in the centers of the granules, while in the test reactor, the bacterium mainly covered the surfaces of granules. PMID:9572963

Sanitary Landfill groundwater monitoring report. Fourth quarterly report and summary 1993

Energy Technology Data Exchange (ETDEWEB)

1994-02-01

Fifty-seven wells of the LFW series monitor groundwater quality in Steed Pond Aquifer (Water Table) beneath the Sanitary Landfill at the Savannah River Site (SRS). These wells are sampled quarterly to comply with the South Carolina Department of Health and Environmental Control Domestic Waste Permit DWP-087A and as part of the SRS Groundwater Monitoring Program. Dichloromethane a common laboratory contaminant, and trichloroethylene were the most widespread constituents exceeding standards during 1993. Benzene, chlorobenzene, chloroethene 1,2 dichloroethane, 1,1-dichloroethylene, 1,2-dichloropropane, gross alpha, lindane, mercury, tetrachloroethylene, and tritium also exceeded standards in one or more wells. No groundwater contaminants were observed in wells screened in the lower section of Steed Pond Aquifer.

Mixed waste management facility groundwater monitoring report. Fourth quarter 1995 and 1995 summary

International Nuclear Information System (INIS)

1996-03-01

During fourth quarter 1995, seven constituents exceeded final Primary Drinking Water Standards (PDWS) in groundwater samples from downgradient monitoring wells at the Mixed Waste Management Facility. No constituents exceeded final PDWS in samples from the upgradient monitoring wells. As in previous quarters, tritium and trichloroethylene were the most widespread elevated constituents. Chloroethene, gross alpha, lead, mercury, and tetrachloroethylene also exceeded final PDWS in one or more wells. Elevated constituents were found in numerous Aquifer Zone IIB 2 (Water Table) and Aquifer Zone IIB 1 (Barnwell/McBean) wells and in three Aquifer Unit IIA (Congaree) wells. The groundwater flow directions and rates in the three hydrostratigraphic units were similar to those of previous quarters

Poly-benzyl domains grown on porous silicon and their I-V rectification

International Nuclear Information System (INIS)

Chao Jie; Han Huanmei; Xia Bing; Ba Long; Liu Hongbo; Xiao Shoujun

2007-01-01

Microwave-irradiated polymerization of benzyl chloride and triphenyl chloromethane on hydride-terminated porous silicon (PS) was achieved through the use of Zn powder as a catalyst. Transmission infrared Fourier-transform spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses confirmed the poly-benzyl membranes grafted on PS. Topographical images by AFM revealed crystal-like domains rather than homogenous monolayers on the surface. The current-voltage measurements in nano-scale by current sensing atomic force microscopy (CS-AFM) showed the rectification behavior of this polymer membrane. Finally, mechanism of a radical initiation on the surface and a following Friedel-Crafts alkylation was proposed for the covalent assembly of poly-benzyl domains

Mixed Waste Management Facility (MWMF) groundwater monitoring report. Fourth quarter 1993 and 1993 summary

Energy Technology Data Exchange (ETDEWEB)

Butler, C.T.

1994-03-01

During fourth quarter 1993, 10 constituents exceeded final Primary Drinking Water Standards in groundwater samples from downgradient monitoring wells at the Mixed Waste Management Facility, the Old Burial Ground, the E-Area Vaults, and the proposed Hazardous Waste/Mixed Waste Disposal Vaults. As in previous quarters, tritium and trichloroethylene were the most widespread elevated constituents. Carbon tetrachloride, chloroform, chloroethane (vinyl chloride), 1,1-dichloroethylene, dichloromethane (methylene chloride), lead, mercury, or tetrachloroethylene also exceeded standards in one or more wells. Elevated constituents were found in numerous Aquifer Zone 2B{sub 2} (Water Table) and Aquifer Zone 2B{sub 1}, (Barnwell/McBean) wells and in two Aquifer Unit 2A (Congaree) wells. The groundwater flow direction and rates in the three hydrostratigraphic units were similar to those of previous quarters.

Use of Cometabolic Air Sparging to Remediate Chloroethene-Contaminated Groundwater Aquifers

National Research Council Canada - National Science Library

Magar, Victor

2001-01-01

...) process at the McClellan National Test Site, California. The purpose of the demonstration was to evaluate the effectiveness of and costs associated with CAS for removal of chlorinated aromatic hydrocarbons (CAHs) from groundwater...

Mixed Waste Management Facility (MWMF) groundwater monitoring report: Third quarter 1993

Energy Technology Data Exchange (ETDEWEB)

1993-12-01

During third quarter 1993, eight constituents exceeded final Primary Drinking Water Standards in groundwater samples from downgradient monitoring wells at the Mixed Waste Management Facility, the Old Burial Ground, the E-Area Vaults, and the proposed Hazardous Waste/Mixed Waste Disposal Vaults. As in previous quarters, tritium and trichloroethylene were the most widespread constituents Chloroethene (vinyl chloride), 1,1-dichloroethylene, dichloromethane (methylene chloride), lead, mercury, or tetrachloroethylene also exceeded standards in one or more wells. The elevated constituents were found in Aquifer Zone IIB{sub 2} (Water Table) and Aquifer Zone IIB{sub 1} (Barnwell/McBean) wells. No elevated constituents were exhibited in Aquifer Unit IIA (Congaree) wells. The groundwater flow directions and rates in the three hydrostratigraphic units were similar to those of previous quarters.

Mixed Waste Management Facility (MWMF) groundwater monitoring report. First quarter 1993

Energy Technology Data Exchange (ETDEWEB)

1993-06-01

During first quarter 1993, eight constituents exceeded final Primary Drinking Water Standards in groundwater samples from downgradient monitoring wells at the Mixed Waste anagement Facility, the Old Burial Ground, the E-Area Vaults, and the proposed Hazardous Waste/Mixed Waste Disposal Vaults (HWMWDV). As in previous quarters, tritium and trichloroethylene were the most widespread constituents. Tetrachloroethylene, chloroethene, 1,1-dichloroethylene, gross alpha, lead, or nonvolatile beta levels also exceeded standards in one or more wells. The elevated constituents were found primarily in Aquifer Zone IIB{sub 2} (Water Table) and Aquifer Zone IIB{sub 1}, (Barnwell/McBean) wells. However, several Aquifer Unit IIA (Congaree) wells also contained elevated constituent levels. The groundwater flow directions and rates in the three hydrostratigraphic units were similar to previous quarters.

Mixed waste management facility groundwater monitoring report. Fourth quarter 1996 and 1996 summary

International Nuclear Information System (INIS)

1997-03-01

During fourth quarter 1996, nine constituents exceeded final Primary Drinking Water Standards (PDWS) in groundwater samples from downgradient monitoring wells at the Mixed Waste Management Facility. No constituents exceeded final PDWS in samples from the upgradient monitoring wells. As in previous quarters, tritium and trichloroethylene were the most widespread elevated constituents. Carbon tetrachloride, chloroethene, chloroform, 1,1-dichloroethylene, dichloromethane, gross alpha, and tetrachloroethylene also exceeded final PDWS in one or more wells. Elevated constituents were found in numerous Aquifer Zone llB2 (Water Table) and Aquifer Zone llB1 (Barnwell/McBean) wells and in six Aquifer Unit IIA (Congaree) wells. The groundwater flow directions and rates in the three hydrostratigraphic units were similar to those of previous quarters

Mixed Waste Management Facility (MWMF) groundwater monitoring report

International Nuclear Information System (INIS)

1993-06-01

During first quarter 1993, eight constituents exceeded final Primary Drinking Water Standards in groundwater samples from downgradient monitoring wells at the Mixed Waste anagement Facility, the Old Burial Ground, the E-Area Vaults, and the proposed Hazardous Waste/Mixed Waste Disposal Vaults (HWMWDV). As in previous quarters, tritium and trichloroethylene were the most widespread constituents. Tetrachloroethylene, chloroethene, 1,1-dichloroethylene, gross alpha, lead, or nonvolatile beta levels also exceeded standards in one or more wells. The elevated constituents were found primarily in Aquifer Zone IIB 2 (Water Table) and Aquifer Zone IIB 1 , (Barnwell/McBean) wells. However, several Aquifer Unit IIA (Congaree) wells also contained elevated constituent levels. The groundwater flow directions and rates in the three hydrostratigraphic units were similar to previous quarters

LCA of contaminated site remediation - integration of site-specific impact assessment of local toxic impacts

DEFF Research Database (Denmark)

Lemming, Gitte; Hauschild, Michael Zwicky; Chambon, Julie Claire Claudia

2011-01-01

impacts have typically been assessed using site-generic characterization models representing a continental scale and excluding the groundwater compartment. Soil contaminants have therefore generally been assigned as emissions to surface soil or surface water compartments. However, such site-generic...... assessments poorly reflect the fate of frequent soil contaminants such as chloroethenes as they exclude the groundwater compartment and assume that the main part escapes to the atmosphere. Another important limitation of the generic impact assessment models is that they do not include the formation......The environmental impacts from remediation can be divided into primary and secondary impacts. Primary impacts cover the local impacts associated with the on-site contamination, whereas the secondary impacts are impacts on the local, regional and global scale generated by the remediation activities...

Migration of chlorinated hydrocarbons in multilayer unconsolidated porous media: a case study from the Po Plain, Italy

Directory of Open Access Journals (Sweden)

Maria Filippini

2017-12-01

Full Text Available Chlorinated solvents are the most ubiquitous organic contaminants found in groundwater since the last six decades. Due to their high degree of carcinogenicity/toxicity and the relatively high mobility and persistence, they represent a serious threat against the human health and the environment. These contaminants generally reach groundwater as Dense Non-Aqueous Phase Liquid (DNAPL that can migrate through aquifers easier than aqueous contaminants. The complex phase partitioning to which chlorinated solvent DNAPLs can undergo (i.e. to the dissolved, vapor or sorbed phase, as well as their transformations (e.g. degradation, depend on the physico-chemical properties of the contaminants and on the features of the hydrogeological system in which they migrate. The hydrogeologic setting below the city of Ferrara (Po plain, northern Italy, which is affected by scattered contamination by chlorinated solvents, has been investigated. In particular, a limited-inspace high-resolution investigation was performed in one selected contaminated test-site, known as “Caretti site”. Here, high-resolution vertical profiling of different kind of data (i.e. stratigraphic data, hydraulic heads, hydrochemical composition of water, stable isotopes of water and contaminants were collected by means of multilevel monitoring systems and other innovative sampling and analytical techniques. The main goals of the research were to assess the intrinsic vulnerability of the aquifers and to identify the dynamics of migration and transformation of the chloroethene contaminants in relationship to the features of the hosting porous medium. The confined aquifers turned out to be more vulnerable to DNAPLs than aqueous contaminants due to the occurrence of microfractures in the overlying clayey aquitards. The presence of organic-rich deposits in the local stratigraphy enhanced the biodegradation of chloroethenes causing accumulation of Vinyl Chloride. The results are useful at the

Comparison of Laboratory Experiments of Chemical, Biological, and Thermal Methods for Treatment of Chlorinated Solvent DNAPL at Kærgård Plantage in Denmark

DEFF Research Database (Denmark)

Christophersen, Mette; Christensen, Jørgen Fjeldsø; Jørgensen, Torben H.

2010-01-01

The Kærgård Plantage megasite on the western coast of Denmark represents one of the most difficult remediation challenges in Scandinavia. Disposal of an estimated 280,000 m3 of pharmaceutical wastes at the site from 1956 to 1973 resulted in the development of a complex mixture of contaminants...... in soil and groundwater, including sulfonamides, barbiturates, aniline, pyridine, chlorinated solvents (chloroethenes), fuel hydrocarbons, mercury, cyanide, lithium and many other compounds.  Wastes were disposed in six pits that continue to leach contaminants to groundwater. Contaminants in groundwater...... technologies for remediation of the residual wastes below the water table - first in the laboratory and then in pilot tests. Given the complex and highly concentrated mixture of contaminants, implementation of multiple or sequenced remediation technologies may be required to achieve cleanup goals.  An...

Identification of volatiles by headspace gas chromatography with simultaneous flame ionization and mass spectrometric detection.

Science.gov (United States)

Tiscione, Nicholas B; Yeatman, Dustin Tate; Shan, Xiaoqin; Kahl, Joseph H

2013-10-01

Volatiles are frequently abused as inhalants. The methods used for identification are generally nonspecific if analyzed concurrently with ethanol or require an additional analytical procedure that employs mass spectrometry. A previously published technique utilizing a capillary flow technology splitter to simultaneously quantitate and confirm ethyl alcohol by flame ionization and mass spectrometric detection after headspace sampling and gas chromatographic separation was evaluated for the detection of inhalants. Methanol, isopropanol, acetone, acetaldehyde, toluene, methyl ethyl ketone, isoamyl alcohol, isobutyl alcohol, n-butyl alcohol, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane (Norflurane, HFC-134a), chloroethane, trichlorofluoromethane (Freon®-11), dichlorodifluoromethane (Freon®-12), dichlorofluoromethane (Freon®-21), chlorodifluoromethane (Freon®-22) and 1,2-dichlorotetrafluoroethane (Freon®-114) were validated for qualitative identification by this method. The validation for qualitative identification included evaluation of matrix effects, sensitivity, carryover, specificity, repeatability and ruggedness/robustness.

Public health assessment for Munisport landfill, North Miami, Dade County, Florida, Region 4. CERCLIS No. FLD084535442. Final report

International Nuclear Information System (INIS)

1993-01-01

The Munisport Landfill site is an inactive landfill in, and owned by, the City of North Miami, Florida. The site is an urban area adjacent to the Oleta River Recreational Area, a state mangrove preserve, and Biscayne Bay. Soil, sediments, surface water, and ground water are contaminated. The authors selected ammonia, benzene, di(2-ethylhexyl)phthalate, cadmium, carbon disulfide, chloromethane, coliform bacteria, dieldrin, lead, methylene chloride, pentachlorophenol, polychlorinated biphenyls (PCBs), styrene, vanadium, and zinc as contaminants of concern. Accidentally ingesting contaminated soil and surface water, and breathing contaminated smoke are completed human exposure pathways. Children who swam in the landfill lakes risked bacterial and viral infections. Based on the available data, the authors categorize the Munisport Landfill site as an indeterminate public health hazard

Environmental assessment of contaminated site remediation in a life cycle perspective

DEFF Research Database (Denmark)

Lemming, Gitte

is an environmental assessment tool that compiles a very wide array of environmental exchanges (emissions to air, water, and soil, and resource consumption) associated with the life cycle of a product or service .and translates them to impacts (global warming, acidification, human toxicity, ecotoxicity, etc...... fate and transport models. This made it possible to account for important processes, such as the formation of chlorinated degradation products and to include the site-specific exposure of humans via ingestion of groundwater used for drinking water. The inclusion of primary impacts in the environmental......-cleaning and industries. Chloroethenes are dense non-aqueous phase liquids (DNAPLs) with high density and viscosity and low solubility in water. These characteristics allow a spill to migrate deep into the subsurface, where it can act as long-term source of dissolved-phase groundwater contamination. Due to the longevity...

Abiotic and biotic transformations of 1,1,1-trichloroethane under methanogenic conditions

International Nuclear Information System (INIS)

Vogel, T.M.; McCarty, P.L.

1987-01-01

A common industrial solvent, 1,1,1-trichloroethane (TCA), is one of the most frequently found contaminants in ground water. The fate of TCA in ground water is complicated by the different possible abiotic and biotic transformations that it may undergo. Abiotic transformation of TCA can result in a mixture of 1,1-dichloro-ethylene (1,1-DCE) and acetic acid, as shown by others. This study confirms that TCA can be biotransformed by reductive dehalogenation to 1,1-dichloroethane (1,1-DCA) and chloroethane (CA) under methanogenic conditions. Also, reductive dehalogenation of 1,1-DCE to vinyl chloride (VC) is confirmed. This study demonstrates that these transformations can occur stoichiometrically. In addition, [ 14 C]TCA, [ 14 C]-1,1-DCA, [ 14 C]-1,1-DCE, [ 14 C]CA, and [ 14 C]VC were at least partially mineralized to 14 CO 2 under similar methanogenic conditions.23 references, 3 figures, 4 tables

THE USE OF CHLOROSULFONIC ACID ON SULFONATION OF cPTFE FILM GRAFTED STYRENE FOR PROTON EXCHANGE MEMBRANE

Directory of Open Access Journals (Sweden)

Yohan Yohan

2010-06-01

Full Text Available Sulfonation of g-ray iradiated and styrene-grafted crosslinked polytetrafluoro ethylene film (cPTFE-g-S film have been done. The aim of the research was to make hydrophyl membrane as proton exchange membrane fuel cell. Sulfonation was prepared by using chlorosulfonic acid in chloroethane under various conditions. The impact of the percentage of grafting, the concentration of chlorosulfonic acid, the reaction time,and the reaction temperature on the properties of sulfonated film were examined. The results show that sulfonation of surface-grafted films was incomplete at room temperature. Increasing concentration of chlorosulfonic acid and reaction temperature accelerate the reaction but they also favor side reactions. These lead to the decrease of the ion-exchange capacity, water uptake, and proton conductivity but the increase of the resistance to oxidation in a perhydrol solution. The resulted cPTFE-g-SS membraneis stabile in a H2O2 30% solution for 20 h.   Keywords: Chorosulfonic acid, sulfonation, PTFE film, proton excange membrane.

Sulfonation of cPTFE Film grafted Styrene for Proton Exchange Membrane Fuel Cell

Directory of Open Access Journals (Sweden)

Yohan Yohan

2010-10-01

Full Text Available Sulfonation of γ-ray iradiated and styrene-grafted crosslinked polytetrafluoroethylene film (cPTFE-g-S film have been done. The aim of the research is to make hydropyl membrane as proton exchange membrane fuel cell. Sulfonation was prepared with chlorosulfonic acid in chloroethane under various conditions. The impact of the percent of grafting, the concentration of chlorosulfonic acid, the reaction time,and the reaction temperature on the properties of sulfonated film is examinated. The results show that sulfonation of surface-grafted films is incomplete at room  temperature. The increasing of concentration of chlorosulfonic acid and reaction temperature accelerates the reaction but they also add favor side reactions. These will lead to decreasing of the ion-exchange capacity, water uptake, and proton conductivity but increasing the resistance to oxidation in a perhidrol solution. The cPTFE-g-SS membrane which is resulted has stability in a H2O2 30% solution for 20 hours.

Bioremediation in Fractured Rock: 2. Mobilization of Chloroethene Compounds from the Rock Matrix.

Science.gov (United States)

Shapiro, Allen M; Tiedeman, Claire R; Imbrigiotta, Thomas E; Goode, Daniel J; Hsieh, Paul A; Lacombe, Pierre J; DeFlaun, Mary F; Drew, Scott R; Curtis, Gary P

2018-03-01

A mass balance is formulated to evaluate the mobilization of chlorinated ethene compounds (CE) from the rock matrix of a fractured mudstone aquifer under pre- and postbioremediation conditions. The analysis relies on a sparse number of monitoring locations and is constrained by a detailed description of the groundwater flow regime. Groundwater flow modeling developed under the site characterization identified groundwater fluxes to formulate the CE mass balance in the rock volume exposed to the injected remediation amendments. Differences in the CE fluxes into and out of the rock volume identify the total CE mobilized from diffusion, desorption, and nonaqueous phase liquid dissolution under pre- and postinjection conditions. The initial CE mass in the rock matrix prior to remediation is estimated using analyses of CE in rock core. The CE mass mobilized per year under preinjection conditions is small relative to the total CE mass in the rock, indicating that current pump-and-treat and natural attenuation conditions are likely to require hundreds of years to achieve groundwater concentrations that meet regulatory guidelines. The postinjection CE mobilization rate increased by approximately an order of magnitude over the 5 years of monitoring after the amendment injection. This rate is likely to decrease and additional remediation applications over several decades would still be needed to reduce CE mass in the rock matrix to levels where groundwater concentrations in fractures achieve regulatory standards. © 2017, National Ground Water Association.

Bioremediation in fractured rock: 2. Mobilization of chloroethene compounds from the rock matrix

Science.gov (United States)

Shapiro, Allen M.; Tiedeman, Claire; Imbrigiotta, Thomas; Goode, Daniel J.; Hsieh, Paul A.; Lacombe, Pierre; DeFlaun, Mary F.; Drew, Scott R.; Curtis, Gary P.

2018-01-01

A mass balance is formulated to evaluate the mobilization of chlorinated ethene compounds (CE) from the rock matrix of a fractured mudstone aquifer under pre- and postbioremediation conditions. The analysis relies on a sparse number of monitoring locations and is constrained by a detailed description of the groundwater flow regime. Groundwater flow modeling developed under the site characterization identified groundwater fluxes to formulate the CE mass balance in the rock volume exposed to the injected remediation amendments. Differences in the CE fluxes into and out of the rock volume identify the total CE mobilized from diffusion, desorption, and nonaqueous phase liquid dissolution under pre- and postinjection conditions. The initial CE mass in the rock matrix prior to remediation is estimated using analyses of CE in rock core. The CE mass mobilized per year under preinjection conditions is small relative to the total CE mass in the rock, indicating that current pump-and-treat and natural attenuation conditions are likely to require hundreds of years to achieve groundwater concentrations that meet regulatory guidelines. The postinjection CE mobilization rate increased by approximately an order of magnitude over the 5 years of monitoring after the amendment injection. This rate is likely to decrease and additional remediation applications over several decades would still be needed to reduce CE mass in the rock matrix to levels where groundwater concentrations in fractures achieve regulatory standards.

Sanitary landfill groundwater monitoring report. Fourth quarter 1994 and 1994 summary

International Nuclear Information System (INIS)

1995-02-01

Eighty-nine wells of the LFW series monitor groundwater quality in the Steed Pond Aquifer (Water Table) beneath the Sanitary Landfill at the Savannah River Site (SRS). These wells are sampled quarterly to comply with the South Carolina Department of Health and Environmental Control Domestic Waste Permit DWP-087A and as part of the SRS Groundwater Monitoring Program. Dichloromethane, a common laboratory contaminant, and trichloroethylene were the most widespread constituents exceeding standards during 1994. Benzene, chloroethene (vinyl chloride), 1,2-dichloroethane, 1,1-dichloroethylene, 1,2-dichloropropane, gross alpha, mercury, nonvolatile beta, tetrachloroethylene, and tritium also exceeded standards in one or more wells. The groundwater flow direction in the Steed Pond Aquifer (Water Table) beneath the Sanitary Landfill was to the southeast (universal transverse Mercator coordinates). The flow rate in this unit was approximately 140 ft/year during first and fourth quarters 1994

Design and Performance of an Enhanced Bioremediation Pilot Test in a Tidal Wetland Seep, West Branch Canal Creek, Aberdeen Proving Ground, Maryland

Science.gov (United States)

Majcher, Emily H.; Lorah, Michelle M.; Phelan, Daniel J.; McGinty, Angela L.

2009-01-01

unconsolidated sediments between 1.5 and 6 years following installation of the reactive mat. To ensure hydraulic compatibility in the mat design, mat materials that had a hydraulic conductivity greater than the surrounding wetland sediments were selected, and the mixture was optimized to consist of 1.5 parts compost, 1.5 parts peat and 1 part sand as a safeguard against fluidization. Sediment and matrix properties also indicated that a nonwoven geotextile with a cross-plane flow greater than that of the native sediments was suitable as the base of the reactive mat. Another nonwoven geotextile was selected for installation between the iron mix and organic zones of the mat to create more laminar flow conditions within the mat. Total metals and sequential extraction procedure analyses of mat materials, which were conducted to evaluate water-quality compatibility of the mat materials, showed that concentrations of metals in the compost ranged from one-half to one order of magnitude below consensus-based probable effect concentrations in sediment. A 22-inch-thick reactive mat, containing 0.5 percent WBC-2 by volume, was constructed at seep area 3-4W and monitored from October 2004 through October 2005 for the pilot test. No local, immediate failure of the mat or of wetland sediments was observed during mat installation, indicating that design estimates of bearing capacity and geotextile textile selection ensured the integrity of the mat and wetland sediments during and following installation. Measurements of surface elevation of the mat showed an average settlement of the mat surface of approximately 0.25 feet after 10 months, which was near the predicted settlement for unconsolidated sediment. Monitoring showed rapid establishment and sustainment throughout the year of methanogenic conditions conducive to anaerobic biodegradation and efficient dechlorination activity by WBC-2. The median mass removal of chloromethanes and total chloroethenes and ethane during the

A NEW GAS CELL FOR HIGH-PRECISION DOPPLER MEASUREMENTS IN THE NEAR-INFRARED

International Nuclear Information System (INIS)

Valdivielso, L.; Esparza, P.; MartIn, E. L.; Maukonen, D.; Peale, R. E.

2010-01-01

High-resolution spectroscopy in the near-infrared could become the leading method for discovering extra-solar planets around very low mass stars and brown dwarfs. In order to help to achieve an accuracy of ∼m s -1 , we are developing a gas cell which consists of a mixture of gases whose absorption spectral lines span all over the near-infrared region. We present the most promising mixture, made of acetylene, nitrous oxide, ammonia, chloromethanes, and hydrocarbons. The mixture is contained in a small size 13 cm long gas cell and covers most of the H and K bands. It also shows small absorptions in the J band, but they are few and not sharp enough for near-infrared wavelength calibration. We describe the working method and experiments, and compare our results with the state of the art for near-infrared gas cells.

BIOMASS, OLEATE, AND OTHER POSSIBLE SUBSTRATES FOR CHLOROETHENE REDUCTIVE DEHALOGENATION. (R825689C084)

Science.gov (United States)

AbstractComparative studies were conducted with benzoate, propionate, oleate, tetrabutyl orthosilicate (TBOS), and biomass as substrates for dehalogenation of cis-1,2-dichloroethene (cDCE). All five substrates supported dehalogenation. Sufficient calcium was re...

Mixed Waste Management Facility groundwater monitoring report: Third quarter 1994

International Nuclear Information System (INIS)

1994-12-01

Currently, 125 wells monitor groundwater quality in the uppermost aquifer beneath the Mixed Waste Management Facility (MWMF) at the Savannah River Site. Samples from the wells are analyzed for selected heavy metals, herbicides/pesticides, indicator parameters, radionuclides, volatile organic compounds, and other constituents. As in previous quarters, tritium and trichloroethylene were the most widespread elevated constituents during third quarter 1994. Sixty-four (51%) of the 125 monitoring wells contained elevated tritium activities. Trichloroethylene concentrations exceeded the final PDWS in 22 (18%) wells. Chloroethene, 1,1-dichloroethylene, and tetrachloroethylene, elevated in one or more wells during third quarter 1994, also occurred in elevated levels during second quarter 1994. These constituents generally were elevated in the same wells during both quarters. Gross alpha, which was elevated in only one well during second quarter 1994, was elevated again during third quarter. Mercury, which was elevated during first quarter 1994, was elevated again in one well. Dichloromethane was elevated in two wells for the first time in several quarters

Hydrogen production profiles using furans in microbial electrolysis cells.

Science.gov (United States)

Catal, Tunc; Gover, Tansu; Yaman, Bugra; Droguetti, Jessica; Yilancioglu, Kaan

2017-06-01

Microbial electrochemical cells including microbial fuel cells (MFCs) and microbial electrolysis cells (MECs) are novel biotechnological tools that can convert organic substances in wastewater or biomass into electricity or hydrogen. Electroactive microbial biofilms used in this technology have ability to transfer electrons from organic compounds to anodes. Evaluation of biofilm formation on anode is crucial for enhancing our understanding of hydrogen generation in terms of substrate utilization by microorganisms. In this study, furfural and hydroxymethylfurfural (HMF) were analyzed for hydrogen generation using single chamber membrane-free MECs (17 mL), and anode biofilms were also examined. MECs were inoculated with mixed bacterial culture enriched using chloroethane sulphonate. Hydrogen was succesfully produced in the presence of HMF, but not furfural. MECs generated similar current densities (5.9 and 6 mA/cm 2 furfural and HMF, respectively). Biofilm samples obtained on the 24th and 40th day of cultivation using aromatic compounds were evaluated by using epi-fluorescent microscope. Our results show a correlation between biofilm density and hydrogen generation in single chamber MECs.

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 remediation performance model for enhanced metabolic reductive dechlorination of chloroethenes in fractured clay till

Science.gov (United States)

Manoli, Gabriele; Chambon, Julie C.; Bjerg, Poul L.; Scheutz, Charlotte; Binning, Philip J.; Broholm, Mette M.

2012-04-01

A numerical model of metabolic reductive dechlorination is used to describe the performance of enhanced bioremediation in fractured clay till. The model is developed to simulate field observations of a full scale bioremediation scheme in a fractured clay till and thereby to assess remediation efficiency and timeframe. A relatively simple approach is used to link the fermentation of the electron donor soybean oil to the sequential dechlorination of trichloroethene (TCE) while considering redox conditions and the heterogeneous clay till system (clay till matrix, fractures and sand stringers). The model is tested on lab batch experiments and applied to describe sediment core samples from a TCE-contaminated site. Model simulations compare favorably to field observations and demonstrate that dechlorination may be limited to narrow bioactive zones in the clay matrix around fractures and sand stringers. Field scale simulations show that the injected donor is expected to be depleted after 5 years, and that without donor re-injection contaminant rebound will occur in the high permeability zones and the mass removal will stall at 18%. Long remediation timeframes, if dechlorination is limited to narrow bioactive zones, and the need for additional donor injections to maintain dechlorination activity may limit the efficiency of ERD in low-permeability media. Future work should address the dynamics of the bioactive zones, which is essential to understand for predictions of long term mass removal.

Cost and Performance Report - Use of Cometabolic Air Sparging to Remediate Chloroethene-Contaminated Groundwater Aquifers

National Research Council Canada - National Science Library

Magar, Victor

2001-01-01

...) process at the McClellan National Test Site, California. The purpose of the demonstration was to evaluate the effectiveness of and costs associated with CAS for removal of chlorinated aromatic hydrocarbons (CAHs) from groundwater...

Assessment of chloroethene degradation rates based on ratios of daughter/parent compounds in groundwater plumes

Science.gov (United States)

Höhener, Patrick

2014-05-01

Chlorinated solvent spills at industrial and urban sites create groundwater plumes where tetrachloro- and trichloroethene may degrade to their daughter compounds, dichloroethenes, vinyl chloride and ethane. The assessment of degradation and natural attenuation at such sites may be based on the analysis and inverse modelling of concentration data, on the calculation of mass fluxes in transsects, and/or on the analysis of stable isotope ratios in the ethenes. Relatively few work has investigated the possibility of using ratio of concentrations for gaining information on degradation rates. The use of ratios bears the advantage that dilution of a single sample with contaminant-free water does not matter. It will be shown that molar ratios of daughter to parent compounds measured along a plume streamline are a rapid and robust mean of determining whether degradation rates increase or decrease along the degradation chain, and allow furthermore a quantitation of the relative magnitude of degradation rates compared to the rate of the parent compound. Furthermore, ratios of concentration will become constant in zones where degradation is absent, and this allows to sketching the extension of actively degrading zones. The assessment is possible for pure sources and also for mixed sources. A quantification method is proposed in order to estimate first-order degradation rates in zones of constant degradation activity. This quantification method includes corrections that are needed due to longitudinal and transversal dispersivity. The method was tested on a number of real field sites from literature. At the majority of these sites, the first-order degradation rates were decreasing along the degradation chain from tetrachloroethene to vinyl chloride, meaning that the latter was often reaching important concentrations. This is bad news for site owners due to the increased toxicity of vinyl chloride compared to its parent compounds.

A remediation performance model for enhanced metabolic reductive dechlorination of chloroethenes in fractured clay till

DEFF Research Database (Denmark)

Manoli, Gabriele; Chambon, Julie C.; Bjerg, Poul L.

2012-01-01

A numerical model of metabolic reductive dechlorination is used to describe the performance of enhanced bioremediation in fractured clay till. The model is developed to simulate field observations of a full scale bioremediation scheme in a fractured clay till and thereby to assess remediation...

Sampling and analysis of soil from the old F-Area effluent ditch and its surrounding wetlands

International Nuclear Information System (INIS)

Dixon, K.L.

1994-06-01

Four surface soil samples were collected from the wetlands at the old F-Area effluent ditch. All samples were collected near shallow well point locations except FHB012, which was collected from the effluent ditch stream sediment. Samples were analyzed for metals, Target Compound List volatile organic compounds, and gross radiological indicators. Barium, beryllium, and zinc were detected in all four samples and antimony was detected in three of four samples. These metals occur naturally in the wetland soils at the SRS. Comparisons of metals concentrations were male to concentration ranges taken from background wetland soil samples. These comparison, showed that barium and beryllium concentrations were within expected ranges while zinc and antimony concentrations were elevated above expected concentration ranges. Volatile organic compounds were detected in all four samples. Detected compounds included acetone, 2-butanone, chloromethane, cis-1,2-dichloroethene, and toluene. The only radionuclide detected in a significant quantities was tritium which was detected in all four samples

Development and validation of an universal interface for compound-specific stable isotope analysis of chlorine (37Cl/35Cl) by GC-high-temperature conversion (HTC)-MS/IRMS.

Science.gov (United States)

Renpenning, Julian; Hitzfeld, Kristina L; Gilevska, Tetyana; Nijenhuis, Ivonne; Gehre, Matthias; Richnow, Hans-Hermann

2015-03-03

A universal application of compound-specific isotope analysis of chlorine was thus far limited by the availability of suitable analysis techniques. In this study, gas chromatography in combination with a high-temperature conversion interface (GC-HTC), converting organic chlorine in the presence of H2 to gaseous HCl, was coupled to a dual-detection system, combining an ion trap mass spectrometer (MS) and isotope-ratio mass spectrometer (IRMS). The combination of the MS/IRMS detection enabled a detailed characterization, optimization, and online monitoring of the high-temperature conversion process via ion trap MS as well as a simultaneous chlorine isotope analysis by the IRMS. Using GC-HTC-MS/IRMS, chlorine isotope analysis at optimized conversion conditions resulted in very accurate isotope values (δ(37)Cl(SMOC)) for measured reference material with known isotope composition, including chlorinated ethylene, chloromethane, hexachlorocyclohexane, and trichloroacetic acids methyl ester. Respective detection limits were determined to be <15 nmol Cl on column with achieved precision of <0.3‰.

Current sources of carbon tetrachloride (CCl4) in our atmosphere

Science.gov (United States)

Sherry, David; McCulloch, Archie; Liang, Qing; Reimann, Stefan; Newman, Paul A.

2018-02-01

Carbon tetrachloride (CCl4 or CTC) is an ozone-depleting substance whose emissive uses are controlled and practically banned by the Montreal Protocol (MP). Nevertheless, previous work estimated ongoing emissions of 35 Gg year-1 of CCl4 into the atmosphere from observation-based methods, in stark contrast to emissions estimates of 3 (0-8) Gg year-1 from reported numbers to UNEP under the MP. Here we combine information on sources from industrial production processes and legacy emissions from contaminated sites to provide an updated bottom-up estimate on current CTC global emissions of 15-25 Gg year-1. We now propose 13 Gg year-1 of global emissions from unreported non-feedstock emissions from chloromethane and perchloroethylene plants as the most significant CCl4 source. Additionally, 2 Gg year-1 are estimated as fugitive emissions from the usage of CTC as feedstock and possibly up to 10 Gg year-1 from legacy emissions and chlor-alkali plants.

Sanitary Landfill Groundwater Monitoring Report, Fourth Quarter 1999 and 1999 Summary

International Nuclear Information System (INIS)

Chase, J.

2000-01-01

A maximum of thirty eight-wells of the LFW series monitor groundwater quality in the Steed Pond Aquifer (Water Table) beneath the Sanitary Landfill Area at the Savannah River Site (SRS). These wells are sampled quarterly to comply with the South Carolina Department of Health and Environmental Control Domestic Water Permit DWP-087A and as part of the SRS Groundwater Monitoring Program. Iron (Total Recoverable), Chloroethene (Vinyl Chloride) and 1,1-Dichloroethane were the most widespread constituents exceeding the Final Primary Drinking Water Standards during 1999. Trichloroethylene, 1,1-Dichloroethylene, 1,2-Dichloroethane, 1,4-Dichlorobenzene, Aluminum (Total Recoverable), Benzene, cis-1,2-Dichloroethylene, Dichlorodifluoromethane, Dichloromethane (Methylene Chloride), Gross Alpha, Mercury (Total Recoverable), Nonvolatile Beta, Tetrachloroethylene, Total Organic Halogens, Trichlorofluoromethane, Tritium also exceeded standards in one or more wells. The groundwater flow direction in the Steed Pond Aquifer (Water Table) beneath the Sanitary Landfill is to the southeast (universal transverse Mercator coordinates). The flow rate in this unit was approximately 144.175 ft/year during first quarter 1999 and 145.27 ft/year during fourth quarter 1999

Chlorinated organic compound removal by gas phase pulsed streamer corona electrical discharge with reticulated vitreous carbon electrodes

International Nuclear Information System (INIS)

Kirkpatrick, M.J.; Finney, W.C.; Locke, B. R.

2002-01-01

Trichloroethylene (TCE) and vinyl chloride removal by pulsed corona discharge was investigated with attention to energy efficiency and byproduct identification. Approximately, 50 to 95 percent removal of TCE and vinyl chloride was observed depending on the energy density applied to the gas. Water vapor had no significant effect on TCE removal. Evidence was found for post-corona reactions leading to removal of vinyl chloride downstream of the plasma discharge. Energy efficiencies of 100-900 g/kw-hr in the case of 1000 ppm feed of TCE and efficiencies of 2-24 g/kw-hr for a 100 ppm feed of vinyl chloride were found. In TCE experiments, the formation of dichloroacetyl chloride was observed, while chloro-ethane formation was found for vinyl chloride. In both cases, Cl- was measured downstream of the pulsed corona reactor in a water trap using an ion-selective electrode, although measured amounts varied widely due to condensation in the gas lines between the reactor and the water trap. The addition of a platinum-rhodium coated electrode was found only to reduce the downstream removal of vinyl chloride at low energy density. (author)

Induction of prophage lambda by chlorinated organics: Detection of some single-species/single-site carcinogens

Energy Technology Data Exchange (ETDEWEB)

DeMarini, D.M.; Brooks, H.G. (Environmental Protection Agency, Research Triangle Park, NC (United States))

1992-01-01

Twenty-eight chlorinated organic compounds were evaluated for their ability to induce DNA damage using the Microscreen prophage-induction assay in Escherichia coli. Comparison of the performance characteristics of the prophage-induction and Salmonella assays to rodent carcinogenicity assays showed that the prophage-induction assay had a somewhat higher specificity than did the Salmonella assay (70% vs. 50%); sensitivity, concordance, and positive and negative predictivity were similar for the two microbial assays. The Microscreen prophage-induction assay failed to detect eight carcinogens, perhaps due to toxicity or other unknown factors; five of these eight carcinogens were detected by the Salmonella assay. However, the prophage-induction assay did detect six carcinogens that were not detected by the Salmonella assay, and five of these were single-species, single-site carcinogens, mostly mouse liver carcinogens. Some of these carcinogens, such as the chloroethanes, produce free radicals, which may be the basis for their carcinogenicity and ability to induce prophage. The prophage-induction (or other SOS) assay may be useful in identifying some genotoxic chlorinated carcinogens that induce DNA damage that do not revert the standard Salmonella tester strains.

Occurrence and Assessment of Chemical Contaminants in Drinking Water in Tunceli, Turkey

Directory of Open Access Journals (Sweden)

Veysel Demir

2013-01-01

Full Text Available The objective of this study was to analyze drinking water samples from 21 sites in the city center and seven municipalities of Tunceli, Turkey, in order to determine the presence of nitrate, nitrite, fluoride, bromate, pesticides, polycyclic aromatic hydrocarbons (PAHs, trihalomethanes (THMs, and some other chemicals. In all locations, the concentrations of chemicals investigated were below the permissible limits set by local and international organizations for drinking water. Low levels of nitrate (4.79 ± 4.20 mg/L, fluoride (0.11 ± 0.08 mg/L, and THMs (6.63 ± 5.14 μg/L were detected in all locations. A low level of tetra, chloroethane, which is suspected to be a human carcinogen, was also detected in 8 locations in the range of 0.26–0.43 μg/L. These contaminants may pose adverse health effects or minimum hazard due to long-term exposure. In all locations, bromate, benzene, total PAH, 1-2 dichloroethane, vinyl chloride, acrylamide, and epichloridine levels in drinking water samples were under detection limits.

Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong.

Science.gov (United States)

Guo, H; Lee, S C; Louie, P K K; Ho, K F

2004-12-01

Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas

Determination of volatile organic compounds (VOCs) using tedlar bag/solid-phase microextraction/gas chromatography/mass spectrometry (SPME/GC/MS) in ambient and workplace air

Energy Technology Data Exchange (ETDEWEB)

Lee, Jae Hwan; Lee, Dai Woon [Yonsei Univ., Seoul (Korea, Republic of); Hwang, Seung Man; Heo, Gwi Suk [Korea Research Institute of Standards and Science, Taejon (Korea, Republic of)

2002-03-01

SPME techniques have proven to be very useful tools in the analysis of wide VOCs in the air. In this study, we estimated VOCs in ambient and workplace air using a Tedlar ba/SPME/GC/MS system. The calibration curve was set to be linear over the range of 1-30 ppbv. The detection limits ranged from 10 pptv 0.93 ppbv for all VOCs. Reproducibility of TO-14 target gas mixtures by SPME/GC/MS averaged at 8.8 R.S.D (%). Air toxic VOCs (hazardous air pollutants, HAPs) containing a total of forty halohydrocarbons, aromatics, and haloaro-matic carbons could be analyzed with significant accuracy, detection limit and linearity at low ppbv level. Only reactive VOCs with low molecular weight, such as chloromethane, vinylchloride, ethylchloride and 1,2-dichloro-ethane, yielded relatively poor results using this technique. In ambient air samples, ten VOCs were identified and quantified after external calibration. VOC concentration in ambient and workplace air ranged from 0.04 to 1.85 ppbv. The overall process was successfully applied to identify and quantify VOCs in ambient/workplace air.

Application of B{sub 12}N{sub 12} and B{sub 12}P{sub 12} as two fullerene-like semiconductors for adsorption of halomethane: Density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Rad, Ali Shokuhi, E-mail: a.shokuhi@gmail.com [Islamic Azad University, Department of Chemical Engineering, Qaemshahr Branch (Iran, Islamic Republic of)

2017-01-15

We examined and discussed the interaction of two halomethanes (mono-chloromethane (MCM), and mono-fluoromethane (MFM)) with B{sub 12}N{sub 12} and B{sub 12}P{sub 12} fullerene-like nanocages as semiconductor based on density functional theory (DFT). We calculated adsorption energies and followed the changes in the electronic structure of semiconductors upon adsorption of MCM and MFM. We found that the adsorption on the B{sub 12}N{sub 12} nano-cluster is energetically more favorable compared to B{sub 12}P{sub 12} nano-cluster. Also for both systems we found higher values of adsorption energy for MFM than for MCM. We found that upon adsorption of above-mentioned species on these two fullerene-like semiconductors, the HOMO–LUMO distributions and also the gap energy for each system did not change significantly, which correspond to the physisorption process. As a result, B{sub 12}N{sub 12} is a more appropriate nano-cluster to be used as a selective sensor for halomethanes, especially for MFM.

Determination of volatile organic compounds (VOCs) using tedlar bag/solid-phase microextraction/gas chromatography/mass spectrometry (SPME/GC/MS) in ambient and workplace air

International Nuclear Information System (INIS)

Lee, Jae Hwan; Lee, Dai Woon; Hwang, Seung Man; Heo, Gwi Suk

2002-01-01

SPME techniques have proven to be very useful tools in the analysis of wide VOCs in the air. In this study, we estimated VOCs in ambient and workplace air using a Tedlar ba/SPME/GC/MS system. The calibration curve was set to be linear over the range of 1-30 ppbv. The detection limits ranged from 10 pptv 0.93 ppbv for all VOCs. Reproducibility of TO-14 target gas mixtures by SPME/GC/MS averaged at 8.8 R.S.D (%). Air toxic VOCs (hazardous air pollutants, HAPs) containing a total of forty halohydrocarbons, aromatics, and haloaro-matic carbons could be analyzed with significant accuracy, detection limit and linearity at low ppbv level. Only reactive VOCs with low molecular weight, such as chloromethane, vinylchloride, ethylchloride and 1,2-dichloro-ethane, yielded relatively poor results using this technique. In ambient air samples, ten VOCs were identified and quantified after external calibration. VOC concentration in ambient and workplace air ranged from 0.04 to 1.85 ppbv. The overall process was successfully applied to identify and quantify VOCs in ambient/workplace air

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

Science.gov (United States)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Electrochemical peroxidation of PCBs and VOCs in superfund site water and sediments

Energy Technology Data Exchange (ETDEWEB)

Scrudato, R.J.; Chiarenzelli, J.R. [SUNY, Oswego, NY (United States)

1996-12-31

An electrochemical peroxidation (ECP) process has been developed and used to degrade polychlorinated biphenyls (PCB) and volatile organic compounds (VOC)-contaminated water, sludge, and sediments at a New York State Federal and State Superfund Site. The process involves passing an oscillating low-amperage (<10 amps) current through steel electrodes immersed in an acidified water or sediment slurry into which hydrogen peroxide (<1,000 ppm) is added. The generated free radicals attack organic compounds, including organo-metallic complexes and refractory compounds including PCBs. PCB degradation ranged from about 30% to 80% in experiments involving Federal Superfund Site sediments; total PCBs were reduced by {approximately}97% to 68%, respectively, in water and slurry collected from a State Superfund subsurface storage tank. VOC bench-scale experiments involved chloroethane, 1,1-dichloroethane, dichloromethane, 1,1,1-trichloroethane, and acetone and after a 3-min ECP treatment, degradation ranged from >94% to about 99.9%. Results indicate the ECP is a viable process to degrade organic contaminants in water and sediment suspensions. Because the treated water suspensions are acidified, select trace metal sorbed to the particulates is solubilized and therefore can be segregated from the particulates, offering a process that simultaneously degrades organic contaminants and separates trace metals. 19 refs., 1 fig., 4 tabs.

Hydrogen/Chlorine exchange reactions of gaseous carbanions.

Science.gov (United States)

Chen, Hao; Cooks, R Graham; Meurer, Eduardo C; Eberlin, Marcos N

2005-12-01

Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.

Fragranced consumer products and undisclosed ingredients

International Nuclear Information System (INIS)

Steinemann, Anne C.

2009-01-01

Fragranced consumer products-such as air fresheners, laundry supplies, personal care products, and cleaners-are widely used in homes, businesses, institutions, and public places. While prevalent, these products can contain chemicals that are not disclosed to the public through product labels or material safety data sheets (MSDSs). What are some of these chemicals and what limits their disclosure? This article investigates these questions, and brings new pieces of evidence to the science, health, and policy puzzle. Results from a regulatory analysis, coupled with a chemical analysis of six best-selling products (three air fresheners and three laundry supplies), provide several findings. First, no law in the U.S. requires disclosure of all chemical ingredients in consumer products or in fragrances. Second, in these six products, nearly 100 volatile organic compounds (VOCs) were identified, but none of the VOCs were listed on any product label, and one was listed on one MSDS. Third, of these identified VOCs, ten are regulated as toxic or hazardous under federal laws, with three (acetaldehyde, chloromethane, and 1,4-dioxane) classified as Hazardous Air Pollutants (HAPs). Results point to a need for improved understanding of product constituents and mechanisms between exposures and effects

A stable isotope approach for source apportionment of chlorinated ethene plumes at a complex multi-contamination events urban site

Science.gov (United States)

Nijenhuis, Ivonne; Schmidt, Marie; Pellegatti, Eleonora; Paramatti, Enrico; Richnow, Hans Hermann; Gargini, Alessandro

2013-10-01

The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50 years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in 13C (-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, 13C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas.

Triticonazole enantiomers: Separation by supercritical fluid chromatography and the effect of the chromatographic conditions.

Science.gov (United States)

He, Jianfeng; Fan, Jun; Yan, Yilun; Chen, Xiaodong; Wang, Tai; Zhang, Yaomou; Zhang, Weiguang

2016-11-01

Enantiomeric pairs of triticonazole have been successfully separated by supercritical fluid chromatography coupled with a tris(3,5-dimethylphenylcarbamoyl) cellulose-coated chiral stationary phase in this work. The effects of co-solvent, dissolution solvent, flow rate, backpressure, and column temperature have been studied in detail with respect to retention, selectivity, and resolution of triticonazole. As indicated, the co-solvents mostly affected the retention factors and resolution, due to the different molecular structure and polarity. In addition, the dissolution solvents, namely, chloromethanes and alcohols, have been also important for enantioseparation because of the different interaction with stationary phase. Higher flow rate and backpressure led to faster elution of the triticonazole molecules, and the change of column temperature showed slight effect on the resolution of triticonazole racemate. Moreover, a comparative separation experiment between supercritical fluid chromatography and high performance liquid chromatography revealed that chiral supercritical fluid chromatography gave the 3.5 times value of R s /t R2 than high performance liquid chromatography, which demonstrated that supercritical fluid chromatography had much higher separation efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impacts of Residual Surfactant on Tetrachloroethene (PCE) Degradation Following Pilot-Scale SEAR Treatment at a Chloroethene-Impacted Site

Science.gov (United States)

Ramsburg, C. A.; Abriola, L. M.; Pennell, K. D.; Löffler, F. E.; Gamache, M.; Petrovskis, E. A.

2003-04-01

A pilot-scale surfactant-enhanced aquifer remediation (SEAR) demonstration was completed during the summer of 2000 at the Bachman Road site (Oscoda, MI USA). For this test, an aqueous solution of 60 g/L Tween 80 (polyoxyethylene (20) sorbitan monooleate) was used to recover tetrachloroethene (PCE) from a suspected source zone, located underneath a former dry-cleaning facility. Tween 80 was selected for use based upon its demonstrated capacity to solubilize PCE, “food-grade” status, and biodegradative potential. Hydraulic control was maintained throughout the test, with 95% of the injected surfactant mass recovered by a single extraction well. Source-zone monitoring conducted 15 months after SEAR treatment revealed the presence of previously undetected volatile fatty acids (acetate and formate) and PCE degradation products (trichloroethene, cis-1,2-dichloroethene, trans-1,2-dichlorethene, and vinyl chloride), in conjunction with PCE concentration reductions of approximately two orders-of-magnitude. The detection of volatile fatty acids is relevant, as they are likely fermentation products of residual Tween 80. Microbial reductive dechlorination is limited by available electron donors, and microcosm studies demonstrated that both acetate and formate support reductively dechlorinating populations present at the oligotrophic Bachman Road site aquifer. Surfactant transport simulations, using a regional flow model developed for the site, were employed to determine appropriate down-gradient monitoring locations. Drive point samples taken 15 months post-treatment in the vicinity of the simulated residual surfactant plume, contained elevated concentrations of acetate and PCE daughter products. Ongoing efforts include continued site-monitoring, and microcosm studies to corroborate a causal relationship between Tween 80 fermentation and PCE dechlorination.

One-year measurements of chloroethenes in tree cores and groundwater at the SAP Mimoň Site, Northern Bohemia

DEFF Research Database (Denmark)

Wittlingerova, Z.; Machackova, J.; Petruzelkova, A.

2013-01-01

Chlorinated ethenes (CE) are among the most frequent contaminants of soil and groundwater in the Czech Republic. Because conventional methods of subsurface contamination investigation are costly and technically complicated, attention is directed on alternative and innovative field sampling methods...... documented that the results of tree core analyses can be used to indicate the presence of CE in the subsurface. The results may also be helpful to identify the best sampling period for tree coring and to learn about the time it takes until tree core concentrations react to changes in groundwater conditions....... One promising method is sampling of tree cores (plugs of woody tissue extracted from a host tree). Volatile organic compounds can enter into the trunks and other tissues of trees through their root systems. An analysis of the tree core can thus serve as an indicator of the subsurface contamination...

One-year measurements of chloroethenes in tree cores and groundwater at the SAP Mimoň Site, Northern Bohemia.

Science.gov (United States)

Wittlingerova, Z; Machackova, J; Petruzelkova, A; Trapp, S; Vlk, K; Zima, J

2013-02-01

Chlorinated ethenes (CE) are among the most frequent contaminants of soil and groundwater in the Czech Republic. Because conventional methods of subsurface contamination investigation are costly and technically complicated, attention is directed on alternative and innovative field sampling methods. One promising method is sampling of tree cores (plugs of woody tissue extracted from a host tree). Volatile organic compounds can enter into the trunks and other tissues of trees through their root systems. An analysis of the tree core can thus serve as an indicator of the subsurface contamination. Four areas of interest were chosen at the experimental site with CE groundwater contamination and observed fluctuations in groundwater concentrations. CE concentrations in groundwater and tree cores were observed for a 1-year period. The aim was to determine how the CE concentrations in obtained tree core samples correlate with the level of contamination of groundwater. Other factors which can affect the transfer of contaminants from groundwater to wood were also monitored and evaluated (e.g., tree species and age, level of groundwater table, river flow in the nearby Ploučnice River, seasonal effects, and the effect of the remediation technology operation). Factors that may affect the concentration of CE in wood were identified. The groundwater table level, tree species, and the intensity of transpiration appeared to be the main factors within the framework of the experiment. Obtained values documented that the results of tree core analyses can be used to indicate the presence of CE in the subsurface. The results may also be helpful to identify the best sampling period for tree coring and to learn about the time it takes until tree core concentrations react to changes in groundwater conditions. Interval sampling of tree cores revealed possible preservation of the contaminant in the wood of trees.

Evaluating fugacity models for trace components in landfill gas

Energy Technology Data Exchange (ETDEWEB)

Shafi, Sophie [Integrated Waste Management Centre, Sustainable Systems Department, Building 61, School of Industrial and Manufacturing Science, Cranfield University, Cranfield, Bedfordshire MK43 0AL (United Kingdom); Sweetman, Andrew [Department of Environmental Science, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Hough, Rupert L. [Integrated Waste Management Centre, Sustainable Systems Department, Building 61, School of Industrial and Manufacturing Science, Cranfield University, Cranfield, Bedfordshire MK43 0AL (United Kingdom); Smith, Richard [Integrated Waste Management Centre, Sustainable Systems Department, Building 61, School of Industrial and Manufacturing Science, Cranfield University, Cranfield, Bedfordshire MK43 0AL (United Kingdom); Rosevear, Alan [Science Group - Waste and Remediation, Environment Agency, Reading RG1 8DQ (United Kingdom); Pollard, Simon J.T. [Integrated Waste Management Centre, Sustainable Systems Department, Building 61, School of Industrial and Manufacturing Science, Cranfield University, Cranfield, Bedfordshire MK43 0AL (United Kingdom)]. E-mail: s.pollard@cranfield.ac.uk

2006-12-15

A fugacity approach was evaluated to reconcile loadings of vinyl chloride (chloroethene), benzene, 1,3-butadiene and trichloroethylene in waste with concentrations observed in landfill gas monitoring studies. An evaluative environment derived from fictitious but realistic properties such as volume, composition, and temperature, constructed with data from the Brogborough landfill (UK) test cells was used to test a fugacity approach to generating the source term for use in landfill gas risk assessment models (e.g. GasSim). SOILVE, a dynamic Level II model adapted here for landfills, showed greatest utility for benzene and 1,3-butadiene, modelled under anaerobic conditions over a 10 year simulation. Modelled concentrations of these components (95 300 {mu}g m{sup -3}; 43 {mu}g m{sup -3}) fell within measured ranges observed in gas from landfills (24 300-180 000 {mu}g m{sup -3}; 20-70 {mu}g m{sup -3}). This study highlights the need (i) for representative and time-referenced biotransformation data; (ii) to evaluate the partitioning characteristics of organic matter within waste systems and (iii) for a better understanding of the role that gas extraction rate (flux) plays in producing trace component concentrations in landfill gas. - Fugacity for trace component in landfill gas.

Characterization of the Aerobic Oxidation of cis-Dichloroethene and Vinyl Chloride in Support of Bioremediation of Chloroethene-Contaminated Sites

National Research Council Canada - National Science Library

Gossett, James M; Mattes, Timothy E; Sills, Deborah L; Spain, Jim C; Nishino, Shirley F; Coleman, Nicholas V

2004-01-01

...) and trichloroethene (TCE). Accumulation of VC and cDCE under anaerobic conditions limits the application of natural attenuation and enhanced reductive anaerobic biological in-situ treatment technologies (RABITT...

[The biology of aerobic methylobacteria capable of degrading halomethanes].

Science.gov (United States)

Trotsenko, Iu A; Doronina, N V

2003-01-01

Recent data on the biology of aerobic methylotrophic bacteria capable of utilizing toxic halogenated methane derivatives as sources of carbon and energy are reviewed, with particular emphasis on the taxonomic, physiological, and biochemical diversity of mono- and dihalomethane-degrading methylobacteria and the enzymatic and genetic aspects of their primary metabolism. The initial steps of chloromethane dehalogenation to formate and HCl through a methylated corrinoid and methyletrahydrofolate are catalyzed by inducible cobalamin methyl transferase, made up of two proteins (CmuA and CmuB) encoded by the cmuA and cmuB genes. At the same time, the primary dehalogenation of dichloromethane to formaldehyde and HCl is catalyzed by cytosolic glutathione transferase with S-chloromethylglutathione as an intermediate. The latter enzyme is encoded by the structural dcmA gene and is under the negative control of the regulatory dcmR gene. In spite of considerable progress in the study of halomethane dehalogenation, some aspects concerning the structural and functional organization of this process and its regulation remain unknown, including the mechanisms of halomethane transport, the release of toxic dehalogenation products (S-chloromethylglutathione, CH2O, and HCl) from cells, and the maintenance of intracellular pH. Of particular interest is quantitative evaluation of the ecophysiological role of aerobic methylobacteria in the mineralization of halomethanes and protection of the biosphere from these toxic pollutants.

Bioremediation of 1,2-dichloroethane contaminated groundwater: Microcosm and microbial diversity studies

International Nuclear Information System (INIS)

Wang, S.Y.; Kuo, Y.C.; Huang, Y.Z.; Huang, C.W.; Kao, C.M.

2015-01-01

In this study, the effectiveness of bioremediating 1,2-dichloroethane (DCA)-contaminated groundwater under different oxidation–reduction processes was evaluated. Microcosms were constructed using indigenous bacteria and activated sludge as the inocula and cane molasses and a slow polycolloid-releasing substrate (SPRS) as the primary substrates. Complete DCA removal was obtained within 30 days under aerobic and reductive dechlorinating conditions. In anaerobic microcosms with sludge and substrate addition, chloroethane, vinyl chloride, and ethene were produced. The microbial communities and DCA-degrading bacteria in microcosms were characterized by 16S rRNA-based denatured-gradient-gel electrophoresis profiling and nucleotide sequence analyses. Real-time polymerase chain reaction was applied to evaluate the variations in Dehalococcoides spp. and Desulfitobacterium spp. Increase in Desulfitobacterium spp. indicates that the growth of Desulfitobacterium might be induced by DCA. Results indicate that DCA could be used as the primary substrate under aerobic conditions. The increased ethene concentrations imply that dihaloelimination was the dominate mechanism for DCA biodegradation. - Highlights: • DCA can be used as the primary substrate and degraded by the indigenous microbial consortia. • Reductive dechlorination of DCA can be enhanced by the supplement of substrates and sludge. • Dihaloelimination is the dominant mechanism for DCA dechlorination and ethene is the end product. • SPRS can serve as the primary substrate and creates anaerobic conditions for DCA dechlorination. • Reductive dechlorination is a feasible option for DCA-contaminated groundwater remediation. - DCA can serve as the primary substrate and degraded by indigenous bacteria aerobically. Dihaloelimination is the dominant mechanism and ethene is the end product via dechlorination

Integration of organohalide-respiring bacteria and nanoscale zero-valent iron (Bio-nZVI-RD): A perfect marriage for the remediation of organohalide pollutants?

Science.gov (United States)

Wang, Shanquan; Chen, Siyuan; Wang, Yu; Low, Adrian; Lu, Qihong; Qiu, Rongliang

2016-12-01

Due to massive production and improper handling, organohalide compounds are widely distributed in subsurface environments, primarily in anoxic groundwater, soil and sediment. Compared to traditional pump-and-treat or dredging-and-disposal treatments, in situ remediation employing abiotic or biotic reductive dehalogenation represents a sustainable and economic solution for the removal of organohalide pollutants. Both nanoscale zero-valent iron (nZVI) and organohalide-respiring bacteria remove halogens through reductive dehalogenation and have been extensively studied and successfully applied for the in situ remediation of chloroethenes and other organohalide pollutants. nZVI and microbial reductive dehalogenation (Bio-RD) complement each other to boost reductive dehalogenation efficiency, suggesting that the integration of nZVI with Bio-RD (Bio-nZVI-RD) may constitute an even more promising strategy for the in situ remediation of organohalide pollutants. In this review, we first provide an overview of the current literature pertaining to nZVI- and organohalide-respiring bacteria-mediated reductive dehalogenation of organohalide pollutants and compare the pros and cons of individual treatment methods. We then highlight recent studies investigating the implementation of Bio-nZVI-RD to achieve rapid and complete dehalogenation and discuss the halogen removal mechanism of Bio-nZVI-RD and its prospects for future remediation applications. In summary, the use of Bio-nZVI-RD facilitates opportunities for the effective in situ remediation of a wide range of organohalide pollutants. Copyright © 2016 Elsevier Inc. All rights reserved.

STIMULATION OF REDUCTIVE DECHLORINATION OF TETRA- CHLOROETHENE (PCE) IN ANAEROBIC AQUIFER MICROCOSMS BY ADDITION OF SHORT-CHAIN ORGANIC ACIDS OR ALCOHOLS

Science.gov (United States)

The effect of the addition of common fermentation products on the dehalogenation of tetrachloroethene was studied in methanogenic slurries made with aquifer solids. Lactate, propionate, crotonate, butyrate, and ethanol stimulated dehalogenation activity, while acetate, methanol, ...

Organic Compounds in Clackamas River Water Used for Public Supply near Portland, Oregon, 2003-05

Science.gov (United States)

Carpenter, Kurt D.; McGhee, Gordon

2009-01-01

Organic compounds studied in this U.S. Geological Survey (USGS) assessment generally are man-made, including pesticides, gasoline hydrocarbons, solvents, personal care and domestic-use products, disinfection by-products, and manufacturing additives. In all, 56 compounds were detected in samples collected approximately monthly during 2003-05 at the intake for the Clackamas River Water plant, one of four community water systems on the lower Clackamas River. The diversity of compounds detected suggests a variety of different sources and uses (including wastewater discharges, industrial, agricultural, domestic, and others) and different pathways to drinking-water supplies (point sources, precipitation, overland runoff, ground-water discharge, and formation during water treatment). A total of 20 organic compounds were commonly detected (in at least 20 percent of the samples) in source water and (or) finished water. Fifteen compounds were commonly detected in source water, and five of these compounds (benzene, m- and p-xylene, diuron, simazine, and chloroform) also were commonly detected in finished water. With the exception of gasoline hydrocarbons, disinfection by-products, chloromethane, and the herbicide diuron, concentrations in source and finished water were less than 0.1 microgram per liter and always less than human-health benchmarks, which are available for about 60 percent of the compounds detected. On the basis of this screening-level assessment, adverse effects to human health are assumed to be negligible (subject to limitations of available human-health benchmarks).

Mixed quantum-classical studies of energy partitioning in unimolecular chemical reactions

Science.gov (United States)

Bladow, Landon Lowell

A mixed quantum-classical reaction path Hamiltonian method is utilized to study the dynamics of unimolecular reactions. The method treats motion along the reaction path classically and treats the transverse vibrations quantum mechanically. The theory leads to equations that predict the disposai of the exit-channel potential energy to product translation and vibration. In addition, vibrational state distributions are obtained for the product normal modes. Vibrational excitation results from the curvature of the minimum energy reaction path. The method is applied to six unimolecular reactions: HF elimination from fluoroethane, 1,1-difluoroethane, 1,1-difluoroethene, and trifluoromethane; and HCl elimination from chloroethane and acetyl chloride. The minimum energy paths were calculated at either the MP2 or B3LYP level of theory. In all cases, the majority of the vibrational excitation of the products occurs in the HX fragment. The results are compared to experimental data and other theoretical results, where available. The best agreement between the experimental and calculated HX vibrational distributions is found for the halogenated ethanes, and the experimental deduction that the majority of the HX vibrational excitation arises from the potential energy release is supported. It is believed that the excess energy provided in experiments contributes to the poorer agreement between experiment and theory observed for HF elimination from 1,1-difluoroethene and trifluoromethane. An attempt is described to incorporate a treatment of the excess energy into the present method. However, the sign of the curvature coupling elements is then found to affect the dynamics. Overall, the method appears to be an efficient dynamical tool for modeling the disposal of the exit-channel potential energy in unimolecular reactions.

Synthesis of some glycoside analogs and related compounds from 9-amino-6-(methylthio)-9H-purine.

Science.gov (United States)

Temple, C; Kussner, C L; Montgomery, J A

1975-12-01

Additional information on the anticancer activity of 9-amino-9H-purine-6(1H)-thione and its derivatives was sought by the synthesis of some 9-(substituted amino)-6-(methylthio)-9H-purines in which the 9-substituent contained functional groups capable of either reversible or irreversible binding with an enzymatic site. Condensation of 9-amino-6-(methylthio)-9H-purine (1) with some carbonyl compounds followed by hydride reduction of the azomethine linkage in the intermediates leads to the 2-pyrrolylmethyl (8), 2,3,4-trihydroxybutyl (10), and the 1,5-dihydroxy-2- and 3-pentyl (11 and 12) compounds. A 4-hydroxybutyl derivative (13) was obtained by alkylation of 18, the 9-acetyl derivative of 1, with 4-chlorobutyl acetate followed by saponification. The cyclization of 13 and 11 with a sulfonyl chloride gave the 9-pyrrolidin-1-yl (27) and the 9-[2-(tosyloxymethyl)pyrrolidin-1-yl] (28), respectively. Acylation of 1 with ethyl L-2-pyrrolidine-5-carboxylate and ethyl 1-methyl-5-pyrrolidone-3-carboxylate, respectively, in Me2SO containing NaH gave the corresponding amides 15 and 17. Alkylation of 18 with 1-bromo-2-chloroethane and epichlorohydrin gave the N-(2-chloroethyl) and N-(1,2-epoxy-3-propyl) derivatives 19 and 20. The chloro group of the chlorobutyl derivative of 18 was displaced with KSCN and NaN3, respectively, to give the thiocyanate and azido derivatives 23 and 24. Hydrogenation of the latter gave the amine (25), which was acylated with ethyl chloroformate to give the (ethoxycarbonyl)amino compound 26. None of these compounds showed activity against L1210 leukemia cells implanted ip in mice on a single-dose schedule, suggesting that the activity observed in the simpler 9-aminopurines resulted from cleavage of the hydrazino linkage to give pH-purine-6(1H)-thione.

Potential Precursor Compounds for Chlorohydrocarbons Detected in Gale Crater, Mars, by the SAM Instrument Suite on the Curiosity Rover

Science.gov (United States)

Miller, Kristen E.; Eigenbrode, Jennifer L.; Freissinet, Caroline; Glavin, Daniel P.; Kotrc, Benjamin; Francois, Pascaline; Summons, Roger E.

2016-01-01

The detection of chlorinated organic compounds in near-surface sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite aboard the Mars Science Laboratory Curiosity rover represents an important step toward characterizing habitable environments on Mars. However, this discovery also raises questions about the identity and source of their precursor compounds and the processes by which they become chlorinated. Here we present the results of analog experiments, conducted under conditions similar to SAM gas chromatography-mass spectrometry analyses, in which we pyrolyzed potential precursor compounds in the presence of various Cl salts and Fe oxides that have been identified in Martian sediments. While chloromethanes could not be unambiguously identified, 1,2-dichloropropane (1,2-DCP), which is one of the chlorinated compounds identified in SAM data, is formed from the chlorination of aliphatic precursors. Additionally, propanol produced more 1,2-DCP than nonfunctionalized aliphatics such as propane or hexanes. Chlorinated benzenes ranging from chlorobenzene to hexachlorobenzene were identified in experiments with benzene carboxylic acids but not with benzene or toluene. Lastly, the distribution of chlorinated benzenes depended on both the substrate species and the nature and concentration of the Cl salt. Ca and Mg perchlorate, both of which release O2 in addition to Cl2 and HCl upon pyrolysis, formed less chlorobenzene relative to the sum of all chlorinated benzenes than in experiments with ferric chloride. FeCl3, a Lewis acid, catalyzes chlorination but does not aid combustion. Accordingly, both the precursor chemistry and sample mineralogy exert important controls on the distribution of chlorinated organics.

Impact of biomass burning on urban air quality estimated by organic tracers: Guangzhou and Beijing as cases

International Nuclear Information System (INIS)

Qiaoqiao Wang; Min Shao; Ying Liu; Kuster, William; Goldan, Paul; Xiaohua Li; Yuan Liu; Sihua Lu

2007-01-01

The impacts of biomass burning have not been adequately studied in China. In this work, chemical compositions of volatile organic compounds and particulate organic matters were measured in August 2005 in Beijing and in October 2004 in Guangzhou city. The performance of several possible tracers for biomass burning is compared by using acetonitrile as a reference compound. The correlations between the possible tracers and acetonitrile show that the use of K + as a tracer could result in bias because of the existence of other K+ sources in urban areas, while chloromethane is not reliable due to its wide use as industrial chemical. The impact of biomass burning on air quality is estimated using acetonitrile and levoglucosan as tracers. The results show that the impact of biomass burning is ubiquitous in both suburban and urban Guangzhou, and the frequencies of air pollution episodes significantly influenced by biomass burning were 100% for Xinken and 58% for downtown Guangzhou city. Fortunately, the air quality in only 2 out of 22 days was partly impacted by biomass burning in August in Beijing, the month that 2008 Olympic games will take place. The quantitative contribution of biomass burning to ambient PM 2.5 concentrations in Guangzhou city was also estimated by the ratio of levoglocusan to PM 2.5 in both the ambient air and biomass burning plumes. The results show that biomass burning contributes 3.02013;16.8% and 4.02013;19.0% of PM 2.5 concentrations in Xinken and Guangzhou downtown, respectively. (Author)

Impact of biomass burning on urban air quality estimated by organic tracers: Guangzhou and Beijing as cases

Energy Technology Data Exchange (ETDEWEB)

Qiaoqiao Wang; Min Shao; Ying Liu [State Joint Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences, Peking University, Beijing 100871, (China); Kuster, William; Goldan, Paul [Earth System Research Laboratory, U.S. Department of Commerce, Boulder, CO 80305, (United States); Xiaohua Li; Yuan Liu; Sihua Lu [State Joint Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences, Peking University, Beijing 100871, (China)

2007-12-15

The impacts of biomass burning have not been adequately studied in China. In this work, chemical compositions of volatile organic compounds and particulate organic matters were measured in August 2005 in Beijing and in October 2004 in Guangzhou city. The performance of several possible tracers for biomass burning is compared by using acetonitrile as a reference compound. The correlations between the possible tracers and acetonitrile show that the use of K{sup +} as a tracer could result in bias because of the existence of other K+ sources in urban areas, while chloromethane is not reliable due to its wide use as industrial chemical. The impact of biomass burning on air quality is estimated using acetonitrile and levoglucosan as tracers. The results show that the impact of biomass burning is ubiquitous in both suburban and urban Guangzhou, and the frequencies of air pollution episodes significantly influenced by biomass burning were 100% for Xinken and 58% for downtown Guangzhou city. Fortunately, the air quality in only 2 out of 22 days was partly impacted by biomass burning in August in Beijing, the month that 2008 Olympic games will take place. The quantitative contribution of biomass burning to ambient PM{sub 2.5} concentrations in Guangzhou city was also estimated by the ratio of levoglocusan to PM{sub 2.5} in both the ambient air and biomass burning plumes. The results show that biomass burning contributes 3.02013;16.8% and 4.02013;19.0% of PM{sub 2.5} concentrations in Xinken and Guangzhou downtown, respectively. (Author)

Impact of biomass burning on urban air quality estimated by organic tracers: Guangzhou and Beijing as cases

Energy Technology Data Exchange (ETDEWEB)

Qiaoqiao Wang; Min Shao; Ying Liu [State Joint Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences, Peking University, Beijing 100871, (China); Kuster, William; Goldan, Paul [Earth System Research Laboratory, U.S. Department of Commerce, Boulder, CO 80305, (United States); Xiaohua Li; Yuan Liu; Sihua Lu [State Joint Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences, Peking University, Beijing 100871, (China)

2007-12-15

The impacts of biomass burning have not been adequately studied in China. In this work, chemical compositions of volatile organic compounds and particulate organic matters were measured in August 2005 in Beijing and in October 2004 in Guangzhou city. The performance of several possible tracers for biomass burning is compared by using acetonitrile as a reference compound. The correlations between the possible tracers and acetonitrile show that the use of K{sup +} as a tracer could result in bias because of the existence of other K+ sources in urban areas, while chloromethane is not reliable due to its wide use as industrial chemical. The impact of biomass burning on air quality is estimated using acetonitrile and levoglucosan as tracers. The results show that the impact of biomass burning is ubiquitous in both suburban and urban Guangzhou, and the frequencies of air pollution episodes significantly influenced by biomass burning were 100% for Xinken and 58% for downtown Guangzhou city. Fortunately, the air quality in only 2 out of 22 days was partly impacted by biomass burning in August in Beijing, the month that 2008 Olympic games will take place. The quantitative contribution of biomass burning to ambient PM{sub 2.5} concentrations in Guangzhou city was also estimated by the ratio of levoglocusan to PM{sub 2.5} in both the ambient air and biomass burning plumes. The results show that biomass burning contributes 3.02013;16.8% and 4.02013;19.0% of PM{sub 2.5} concentrations in Xinken and Guangzhou downtown, respectively. (Author).

Identification of Multiple Dehalogenase Genes Involved in Tetrachloroethene-to-Ethene Dechlorination in a Dehalococcoides-Dominated Enrichment Culture

Directory of Open Access Journals (Sweden)

Mohamed Ismaeil

2017-01-01

Full Text Available Chloroethenes (CEs are widespread groundwater toxicants that are reductively dechlorinated to nontoxic ethene (ETH by members of Dehalococcoides. This study established a Dehalococcoides-dominated enrichment culture (designated “YN3” that dechlorinates tetrachloroethene (PCE to ETH with high dechlorination activity, that is, complete dechlorination of 800 μM PCE to ETH within 14 days in the presence of Dehalococcoides species at 5.7±1.9×107 copies of 16S rRNA gene/mL. The metagenome of YN3 harbored 18 rdhA genes (designated YN3rdhA1–18 encoding the catalytic subunit of reductive dehalogenase (RdhA, four of which were suggested to be involved in PCE-to-ETH dechlorination based on significant increases in their transcription in response to CE addition. The predicted proteins for two of these four genes, YN3RdhA8 and YN3RdhA16, showed 94% and 97% of amino acid similarity with PceA and VcrA, which are well known to dechlorinate PCE to trichloroethene (TCE and TCE to ETH, respectively. The other two rdhAs, YN3rdhA6 and YN3rdhA12, which were never proved as rdhA for CEs, showed particularly high transcription upon addition of vinyl chloride (VC, with 75±38 and 16±8.6 mRNA copies per gene, respectively, suggesting their possible functions as novel VC-reductive dehalogenases. Moreover, metagenome data indicated the presence of three coexisting bacterial species, including novel species of the genus Bacteroides, which might promote CE dechlorination by Dehalococcoides.

Draft Technical Protocol: A Treatability Test for Evaluating the Potential Applicability of the Reductive Anaerobic Biological in Situ Treatment Technology (Rabitt) to Remediate Chloroethenes

National Research Council Canada - National Science Library

Morse, Jeff

1998-01-01

This draft, unvalidated protocol describes a comprehensive approach for conducting a phased treatability test to determine the potential for employing the Reductive Anaerobic Biological In Situ Treatment Technology (RABITT...

Origin of VC-only plumes from naturally enhanced dechlorination in a peat-rich hydrogeologic setting

Science.gov (United States)

Filippini, Maria; Amorosi, Alessandro; Campo, Bruno; Herrero-Martìn, Sara; Nijenhuis, Ivonne; Parker, Beth L.; Gargini, Alessandro

2016-09-01

The occurrence of vinyl chloride (VC) is often a main concern at sites contaminated with chlorinated solvents due to its high degree of toxicity and carcinogenicity. VC occurrence in aquifers is most often related to the degradation of higher chlorinated ethenes or ethanes and it is generally detected in plumes along with parent contaminants. However, specific combination of stratigraphic, hydrogeologic and geochemical conditions can enhance the degradation of parents and lead to the formation of plumes almost entirely composed of VC (i.e. VC-only plumes). This paper investigates the causes of VC-only plumes in the aquifers below the city of Ferrara (northern Italy) by combining multiple lines of evidence. The City of Ferrara is located on an alluvial lowland, built by the River Po, and is made up of alternating unconsolidated sandy aquifer and silt-clay aquitard deposits of fluvial origin. This region has been strongly impacted by prior industrial activities, with the occurrence of chlorinated compounds at several sites. VC-only plumes with uncertain source location were found at two contaminated sites. The source zone of a third plume composed of chloroethenes from PCE to VC was investigated for high resolution depositional facies architecture and contaminant distribution (contaminant concentration and Compound Specific Isotope Analysis - CSIA). The investigation suggested that degradation of PCE and TCE takes place during contaminant migration through peat-rich (swamp) layers related to the Holocene transgression, which locally act as a ;reactor; for stimulating degradation with the accumulation of VC in the strongly reducing environment of the peat. Regional-scale stratigraphic architecture showed the ubiquitous occurrence of swamp layers at distinct stratigraphic levels in the investigated system and their apparent linkage to the in situ creation of the VC-only plumes.

Microbial Mineralization of cis-Dichloroethene and Vinyl Chloride as a Component of Natural Attenuation of Chloroethene Contaminants under Conditions Identified in the Field as Anoxic

Science.gov (United States)

2012-01-01

16 2. cis-DCE mineralization kinetics under hypoxic and anoxic conditions .............................17 Conversion Factors Inch/Pound...situ conditions. Vmax is influenced by micro- bial biomass , metabolic activity, and the availability of nutri- ents and substrates that support...were incapable of growth at atmospheric oxygen levels (Morris 1976). Enzymatic defenses against oxygen radicals have been documented 20 Microbial

Synthesis, chemical and biological properties of the new mono- and bis-derivatives of imidazoles

Directory of Open Access Journals (Sweden)

E. V. Welchinska

2014-12-01

Full Text Available The aim of research. The problem of finding effective antitumour medical preparation with low toxicity is an important issue of medical and pharmaceutical chemistry. Knowledge of cancer cell features and its metabolism enables to predict the direction of chemical and biological research, to conduct a targeted synthesis of potential drugs, and to assess their applicability in oncological practice as antitumor agents. The purpose of work is to explain preformed heterocycles as purines, its synthesis and investigation of chemical and biological properties. After construction of the potential active structures we proposed the new method of original derivatives synthesis which are received on the base of imidazole, from one side, and fluorocontaining common anesthetic halothane (2-bromo-1,1,1-trifluoro-2-chloroethane from other side. Molecular complex of more perspective biologically active bis-imidazole with antitumour bacterial lectine has been received. With the purpose to synthesize potential antitumour compounds on the base of halothane and imidazole, new convenient methods for the preparation of original heterocyclic derivatives of imidazole have been described. The structure and composition of synthesized compound has been confirmed by the methods of elemental analysis, IR- and NMRІН-spectra. Materials and methods. The majority of the absolute organic solvents (benzene, dimethylformamide, ethyl ester employed in the present studies were distilled before their use. Organic solvents were dried over anhydrous magnesium sulfate or metallic sodium. Gas-liquid chromatography was carried out by Perkin Elmer chromatograph with UV-detector ("Perkin", Germany. IR spectra were recorded in a UR-20 spectrometer ("Charles Ceise Hena", Germany. The 1HNMR spectra were recorded in DMSO-d6 on a 200 MHz BrakerWP-200 ("Braker", Switzerland or Varian T-60 spectrometer ("Varian", USA. Investigation of critical toxicity of new compounds was carried out at

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

Science.gov (United States)

Millan, M.; Szopa, C.; Buch, A.; Belmahdi, I.; Glavin, D. P.; Freissinet, C.; Eigenbrode, J. L.; Archer, P. D., Jr,; Sutter, B.; Mahaffy, P.

2017-01-01

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Muonium formation and the 'missing fraction' in vapors

International Nuclear Information System (INIS)

Fleming, D.G.; Arseneau, D.J.; Garner, D.M.; Senba, M.; Mikula, R.J.

1983-06-01

The vapor phase fractional polarizations of positive muons thermalizing as the muonium atom (Psub(M)) and in diamagnetic environments (Psub(D)) has been measured in H 2 O, CH 3 OH, C 6 H 14 , C 6 H 12 , CCl 4 , CHCl 3 , CH 2 Cl 2 and TMS, in order to compare with the corresponding fractions measured in the condensed phases. There is a marked contrast in every case, with the vapor phase results being largely understandable in terms of a charge exchange/hot atom model. Unlike the situation in the corresponding liquids, there is no permanent lost fraction in the vapor phase in the limit of even moderately high pressures (approximately 1 atm); at lower pressures, depolarization is due to hyperfine mixing and is believed to be well understood. For vapor phase CH 3 OH, C 6 H 14 , C 6 H 12 , and TMS the relative fractions are found to be pressure dependent, suggesting the importance of termolecular hot atom (or ion) reactions in the slowing-down process. For vapor phase H 2 O and the chloromethanes, the relative fractions are pressure independent. For CCl 4 , Psub(M) = Psub(D) approximately 0.5 in the vapor phase vs. Psub(D) = 1.0 in the liquid phase; fast thermal reactions of Mu likely contribute significantly to this difference in the liquid phase. For H 2 O, Psub(M) approximately 0.9 and Psub(D) approximately 0.1 in the vapor phase vs. Psub(D) approximately 0.6 and Psub(M) approximately 0.2 in the liquid phase. Water appears to be the one unequivocal case where the basic charge exchange/hot atom model is inappropriate in the condensed phase, suggesting, therefore, that radiation-induced 'spur' effects play a major role

Ozone-depleting substances and the greenhouse gases HFCs, PFCs and SF6. Danish consumption and emissions, 2004

Energy Technology Data Exchange (ETDEWEB)

Sander Poulsen, T. [PlanMiljoe (Denmark)

2006-05-19

The objective of this project was to map the 2004 consumption of newly produced industrial ozone-depleting substances and the consumption and actual emissions of HFCs, PFCs, and SF6. The evaluation was made in accordance with the IPCC guidelines, and following the method employed in previous evaluations and it covers the net consumption of ozone-depleting substances. The term 'net consumption' is understood as the amount of imported goods in bulk or drums, less any re-export of substances as raw materials. Ozone-depleting substances contained in finished products that are imported and exported are not included in the evaluation. This delimitation is in full compliance with international guidelines. The evaluation does not account for the consumption of ozone-depleting substances used as raw material in the production of other substances, such as tetra chloromethane, and which are not subsequently emitted to the atmosphere. The information on consumption has been gathered from importers, suppliers and enterprise end-users (usually purchasing departments), and Statistics Denmark. This method of data gathering means that the information gathered is about the quantities of substances traded. Purchase and sales figures are used as an expression of consumption. This approach is considered to be suitable and adequate for the present purpose, since experience from previous projects shows that a levelling out occurs with time and that the substances sold/purchased are consumed within a relatively small time horizon. None of the substances covered here are produced in Denmark. Furthermore, ozone-depleting substances are treated at chemical waste processing plants in Denmark. Treatment and destruction data was gathered for the evaluation, but in line with all previous evaluations it has not been accounted for in the consumption figures. (BA)

Epoxyalkane:Coenzyme M Transferase Gene Diversity and Distribution in Groundwater Samples from Chlorinated-Ethene-Contaminated Sites

Science.gov (United States)

Liu, Xikun

2016-01-01

ABSTRACT Epoxyalkane:coenzyme M transferase (EaCoMT) plays a critical role in the aerobic biodegradation and assimilation of alkenes, including ethene, propene, and the toxic chloroethene vinyl chloride (VC). To improve our understanding of the diversity and distribution of EaCoMT genes in the environment, novel EaCoMT-specific terminal-restriction fragment length polymorphism (T-RFLP) and nested-PCR methods were developed and applied to groundwater samples from six different contaminated sites. T-RFLP analysis revealed 192 different EaCoMT T-RFs. Using clone libraries, we retrieved 139 EaCoMT gene sequences from these samples. Phylogenetic analysis revealed that a majority of the sequences (78.4%) grouped with EaCoMT genes found in VC- and ethene-assimilating Mycobacterium strains and Nocardioides sp. strain JS614. The four most-abundant T-RFs were also matched with EaCoMT clone sequences related to Mycobacterium and Nocardioides strains. The remaining EaCoMT sequences clustered within two emergent EaCoMT gene subgroups represented by sequences found in propene-assimilating Gordonia rubripertincta strain B-276 and Xanthobacter autotrophicus strain Py2. EaCoMT gene abundance was positively correlated with VC and ethene concentrations at the sites studied. IMPORTANCE The EaCoMT gene plays a critical role in assimilation of short-chain alkenes, such as ethene, VC, and propene. An improved understanding of EaCoMT gene diversity and distribution is significant to the field of bioremediation in several ways. The expansion of the EaCoMT gene database and identification of incorrectly annotated EaCoMT genes currently in the database will facilitate improved design of environmental molecular diagnostic tools and high-throughput sequencing approaches for future bioremediation studies. Our results further suggest that potentially significant aerobic VC degraders in the environment are not well represented in pure culture. Future research should aim to isolate and

Enhanced reductive de-chlorination of a solvent contaminated aquifer through addition and apparent fermentation of cyclodextrin

Science.gov (United States)

Blanford, William James; Pecoraro, Michael Philip; Heinrichs, Rebecca; Boving, Thomas Bernhard

2018-01-01

In a field study, aqueous cyclodextrin (CD) was investigated for its ability to extract chlorinated volatile organic compounds (cVOC), such as trichloroethylene (TCE), 1,1,1-trichloroethane (TCA), and dichloroethene (DCE) through in-situ flushing of a sandy aquifer. After cessation of aquifer flushing, a plume of CD was left. Changes in CD, cVOC, and inorganic terminal electron acceptors (TEAs) (DO, nitrate, sulfate, iron) were monitored in four rounds of wellwater sampling (20, 210, 342, and 425 days after cessation of active pumping). Post-CD flushing VOC levels rebounded (850% for TCE, 190% for TCA, and 53% for DCE) between the first two sampling rounds, apparently due to rate-limited desorption from aquifer media and dissolution from remaining NAPL. However, substantial reduction in the mass of TCE (6.3 to 0.11 mol: 98%) and TCA (2.8 to 0.73 mol: 74%) in groundwater was observed between 210 and 425 days. DCE should primarily be produced from the degradation of TCE and is expected to subsequently degrade to chloroethene. Since DCE levels decreased only slightly (0.23 to 0.17 mol: 26%), its degradation rate should be similar to that produced from the decaying TCE. Cyclodextrin was monitored starting from day 210. The mass of residual CD (as measured by Total Organic Carbon) decreased from 150 mol (day 210) to 66 (day 425) (56% decrease). The naturally anaerobic zone within the aquifer where residual CD mass decreased coincided with a loss of other major potential TEAs: nitrate (97% loss), sulfate (31%) and iron (31%). In other studies, TCE and 1,1,1-TCA have been found to be more energetically favorable TEAs than sulfate and iron and their degradation via reductive dechlorination has been found to be enhanced by the fermentation of carbohydrates. Such processes can explain these observations, but more investigation is needed to evaluate whether residual levels of CD can facilitate the anaerobic degradation of chlorinated VOCs.

Biochemistry, physiology and biotechnology of sulfate-reducing bacteria.

Science.gov (United States)

Barton, Larry L; Fauque, Guy D

2009-01-01

Chemolithotrophic bacteria that use sulfate as terminal electron acceptor (sulfate-reducing bacteria) constitute a unique physiological group of microorganisms that couple anaerobic electron transport to ATP synthesis. These bacteria (220 species of 60 genera) can use a large variety of compounds as electron donors and to mediate electron flow they have a vast array of proteins with redox active metal groups. This chapter deals with the distribution in the environment and the major physiological and metabolic characteristics of sulfate-reducing bacteria (SRB). This chapter presents our current knowledge of soluble electron transfer proteins and transmembrane redox complexes that are playing an essential role in the dissimilatory sulfate reduction pathway of SRB of the genus Desulfovibrio. Environmentally important activities displayed by SRB are a consequence of the unique electron transport components or the production of high levels of H(2)S. The capability of SRB to utilize hydrocarbons in pure cultures and consortia has resulted in using these bacteria for bioremediation of BTEX (benzene, toluene, ethylbenzene and xylene) compounds in contaminated soils. Specific strains of SRB are capable of reducing 3-chlorobenzoate, chloroethenes, or nitroaromatic compounds and this has resulted in proposals to use SRB for bioremediation of environments containing trinitrotoluene and polychloroethenes. Since SRB have displayed dissimilatory reduction of U(VI) and Cr(VI), several biotechnology procedures have been proposed for using SRB in bioremediation of toxic metals. Additional non-specific metal reductase activity has resulted in using SRB for recovery of precious metals (e.g. platinum, palladium and gold) from waste streams. Since bacterially produced sulfide contributes to the souring of oil fields, corrosion of concrete, and discoloration of stonework is a serious problem, there is considerable interest in controlling the sulfidogenic activity of the SRB. The

An aircraft gas chromatograph–mass spectrometer System for Organic Fast Identification Analysis (SOFIA: design, performance and a case study of Asian monsoon pollution outflow

Directory of Open Access Journals (Sweden)

E. Bourtsoukidis

2017-12-01

Full Text Available Volatile organic compounds (VOCs are important for global air quality and oxidation processes in the troposphere. In addition to ground-based measurements, the chemical evolution of such species during transport can be studied by performing in situ airborne measurements. Generally, aircraft instrumentation needs to be sensitive, robust and sample at higher frequency than ground-based systems while their construction must comply with rigorous mechanical and electrical safety standards. Here, we present a new System for Organic Fast Identification Analysis (SOFIA, which is a custom-built fast gas chromatography–mass spectrometry (GC-MS system with a time resolution of 2–3 min and the ability to quantify atmospheric mixing ratios of halocarbons (e.g. chloromethanes, hydrocarbons (e.g isoprene, oxygenated VOCs (acetone, propanal, butanone and aromatics (e.g. benzene, toluene from sub-ppt to ppb levels. The relatively high time resolution is the result of a novel cryogenic pre-concentration unit which rapidly cools (∼ 6 °C s−1 the sample enrichment traps to −140 °C, and a new chromatographic oven designed for rapid cooling rates (∼ 30 °C s−1 and subsequent thermal stabilization. SOFIA was installed in the High Altitude and Long Range Research Aircraft (HALO for the Oxidation Mechanism Observations (OMO campaign in August 2015, aimed at investigating the Asian monsoon pollution outflow in the tropical upper troposphere. In addition to a comprehensive instrument characterization we present an example monsoon plume crossing flight as a case study to demonstrate the instrument capability. Hydrocarbon, halocarbon and oxygenated VOC data from SOFIA are compared with mixing ratios of carbon monoxide (CO and methane (CH4, used to define the pollution plume. By using excess (ExMR and normalized excess mixing ratios (NEMRs the pollution could be attributed to two air masses of distinctly different origin, identified by back

An aircraft gas chromatograph-mass spectrometer System for Organic Fast Identification Analysis (SOFIA): design, performance and a case study of Asian monsoon pollution outflow

Science.gov (United States)

Bourtsoukidis, Efstratios; Helleis, Frank; Tomsche, Laura; Fischer, Horst; Hofmann, Rolf; Lelieveld, Jos; Williams, Jonathan

2017-12-01

Volatile organic compounds (VOCs) are important for global air quality and oxidation processes in the troposphere. In addition to ground-based measurements, the chemical evolution of such species during transport can be studied by performing in situ airborne measurements. Generally, aircraft instrumentation needs to be sensitive, robust and sample at higher frequency than ground-based systems while their construction must comply with rigorous mechanical and electrical safety standards. Here, we present a new System for Organic Fast Identification Analysis (SOFIA), which is a custom-built fast gas chromatography-mass spectrometry (GC-MS) system with a time resolution of 2-3 min and the ability to quantify atmospheric mixing ratios of halocarbons (e.g. chloromethanes), hydrocarbons (e.g isoprene), oxygenated VOCs (acetone, propanal, butanone) and aromatics (e.g. benzene, toluene) from sub-ppt to ppb levels. The relatively high time resolution is the result of a novel cryogenic pre-concentration unit which rapidly cools (˜ 6 °C s-1) the sample enrichment traps to -140 °C, and a new chromatographic oven designed for rapid cooling rates (˜ 30 °C s-1) and subsequent thermal stabilization. SOFIA was installed in the High Altitude and Long Range Research Aircraft (HALO) for the Oxidation Mechanism Observations (OMO) campaign in August 2015, aimed at investigating the Asian monsoon pollution outflow in the tropical upper troposphere. In addition to a comprehensive instrument characterization we present an example monsoon plume crossing flight as a case study to demonstrate the instrument capability. Hydrocarbon, halocarbon and oxygenated VOC data from SOFIA are compared with mixing ratios of carbon monoxide (CO) and methane (CH4), used to define the pollution plume. By using excess (ExMR) and normalized excess mixing ratios (NEMRs) the pollution could be attributed to two air masses of distinctly different origin, identified by back-trajectory analysis. This work

Occurrence of organohalogens at the Dead Sea Basin

Science.gov (United States)

Tubbesing, Christoph; Kotte, Karsten; Keppler, Frank; Krause, Torsten; Bahlmann, Enno; Schöler, Heinfried

2013-04-01

Most arid and semi-arid regions are characterized by evaporites, which are assured sources for volatile organohalogens (VOX) [1]. These compounds play an important role in tropospheric and stratospheric chemistry. The Dead Sea between Israel and Jordan is the world's most famous and biggest all-season water covered salt lake. In both countries chemical plants like the Dead Sea Works and the Arab Potash Company are located at the southern part of the Dead Sea and mine various elements such as bromine and magnesium. Conveying sea water through constructed evaporation pans multifarious salts are enriched and precipitated. In contrast, the Northern basin and main part of the Dead Sea has remained almost untouched by industrial salt production. Its fresh water supply from the Jordan River is constantly decreasing, leading to further increased salinity. During a HALOPROC campaign (Natural Halogenation Processes in the Environment) we collected various samples including air, soils, sediments, halophytic plants, ground- and seawater from the Northern and Southern basin of the Israeli side of the Dead Sea. These samples were investigated for the occurrence of halocarbons using different analytical techniques. Most samples were analyzed for volatile organohalogens such as haloalkanes using gas chromatography- mass spectrometry (GC-MS). Interestingly, there is a strong enrichment of trihalomethanes (THM), especially all chlorinated and brominated ones and also the iodinated compound dichloroiodomethane were found in the Southern basin. In addition, volatile organic carbons (VOC) such as ethene and some other alkenes were analyzed by a gas chromatography-flame ionisation detector (GC-FID) to obtain further information about potential precursors of halogenated compounds. Halophytic plants were investigated for their potential to release chloromethane and bromomethane but also for their stable carbon and hydrogen isotope composition. For this purpose, a plant chamber was

Determination of a wide range of volatile organic compounds in ambient air using multisorbent adsorption/thermal desorption and gas chromatography/mass spectrometry

Science.gov (United States)

Pankow, J.F.; Luo, W.; Isabelle, L.M.; Bender, D.A.; Baker, R.J.

1998-01-01

Adsorption/thermal desorption with multisorbent air-sampling cartridges was developed for the determination of 87 method analytes including halogenated alkanes, halogenated alkenes, ethers, alcohols, nitriles, esters, ketones, aromatics, a disulfide, and a furan. The volatilities of the compounds ranged from that of dichlorofluoromethane (CFC12) to that of 1,2,3- trichlorobenzene. The eight most volatile compounds were determined using a 1.5-L air sample and a sample cartridge containing 50 mg of Carbotrap B and 280 mg of Carboxen 1000; the remaining 79 compounds were determined using a 5-L air sample and a cartridge containing 180 mg of Carbotrap B and 70 mg of Carboxen 1000. Analysis and detection were by gas chromatography/mass spectrometry. The minimum detectable level (MDL) concentration values ranged from 0.01 parts per billion by volume (ppbv) for chlorobenzene to 0.4 ppbv for bromomethane; most of the MDL values were in the range 0.02-0.06 ppbv. No breakthrough was detected with the prescribed sample volumes. Analyte stability on the cartridges was very good. Excellent recoveries were obtained with independent check standards. Travel spike recoveries ranged from 90 to 110% for 72 of the 87 compounds. The recoveries were less than 70% for bromomethane and chloroethene and for a few compounds such as methyl acetate that are subject to losses by hydrolysis; the lowest travel spike recovery was obtained for bromomethane (62%). Blank values for all compounds were either below detection or very low. Ambient atmospheric sampling was conducted in New Jersey from April to December, 1997. Three sites characterized by low, moderate, and high densities of urbanization/traffic were sampled. The median detected concentrations of the compounds were either similar at all three sites (as with the chlorofluorocarbon compounds) or increased with the density of urbanization/traffic (as with dichloromethane, MTBE, benzene, and toluene). For toluene, the median detected

Evaluation of Long-term Performance of Enhanced Anaerobic Source Zone Bioremediation using mass flux

Science.gov (United States)

Haluska, A.; Cho, J.; Hatzinger, P.; Annable, M. D.

2017-12-01

Chlorinated ethene DNAPL source zones in groundwater act as potential long term sources of contamination as they dissolve yielding concentrations well above MCLs, posing an on-going public health risk. Enhanced bioremediation has been applied to treat many source zones with significant promise, but long-term sustainability of this technology has not been thoroughly assessed. This study evaluated the long-term effectiveness of enhanced anaerobic source zone bioremediation at chloroethene contaminated sites to determine if the treatment prevented contaminant rebound and removed NAPL from the source zone. Long-term performance was evaluated based on achieving MCL-based contaminant mass fluxes in parent compound concentrations during different monitoring periods. Groundwater concertation versus time data was compiled for 6-sites and post-remedial contaminant mass flux data was then measured using passive flux meters at wells both within and down-gradient of the source zone. Post-remedial mass flux data was then combined with pre-remedial water quality data to estimate pre-remedial mass flux. This information was used to characterize a DNAPL dissolution source strength function, such as the Power Law Model and the Equilibrium Stream tube model. The six-sites characterized for this study were (1) Former Charleston Air Force Base, Charleston, SC; (2) Dover Air Force Base, Dover, DE; (3) Treasure Island Naval Station, San Francisco, CA; (4) Former Raritan Arsenal, Edison, NJ; (5) Naval Air Station, Jacksonville, FL; and, (6) Former Naval Air Station, Alameda, CA. Contaminant mass fluxes decreased for all the sites by the end of the post-treatment monitoring period and rebound was limited within the source zone. Post remedial source strength function estimates suggest that decreases in contaminant mass flux will continue to occur at these sites, but a mass flux based on MCL levels may never be exceeded. Thus, site clean-up goals should be evaluated as order

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

Metagenomic and Metatranscriptomic Analyses Reveal the Structure and Dynamics of a Dechlorinating Community Containing Dehalococcoides mccartyi and Corrinoid-Providing Microorganisms under Cobalamin-Limited Conditions

Energy Technology Data Exchange (ETDEWEB)

Men, Yujie; Yu, Ke; Bælum, Jacob; Gao, Ying; Tremblay, Julien; Prestat, Emmanuel; Stenuit, Ben; Tringe, Susannah G.; Jansson, Janet; Zhang, Tong; Alvarez-Cohen, Lisa; Liu, Shuang-Jiang

2017-02-10

chloroethene-dechlorinating bacteriumDehalococcoides mccartyiis a cobalamin auxotroph, thus acquiring corrinoids from other community members. Therefore, it is important to investigate the microbe-microbe interactions betweenDehalococcoidesand the corrinoid-providing microorganisms in a community. This study provides systems-level information, i.e., taxonomic and functional compositions and dynamics of the supportive microorganisms in dechlorinating communities under different cobalamin conditions. The findings shed light on the important roles ofVeillonellaceaespecies in the communities compared to other coexisting community members in producing and providing corrinoids forDehalococcoidesspecies under cobalamin-limited conditions.

In situ remediation of chlorinated solvent-contaminated groundwater using ZVI/organic carbon amendment in China: field pilot test and full-scale application.

Science.gov (United States)

Yang, Jie; Meng, Liang; Guo, Lin

2018-02-01

Chlorinated solvents in groundwater pose threats to human health and the environment due to their carcinogenesis and bioaccumulation. These problems are often more severe in developing countries such as China. Thus, methods for chlorinated solvent-contaminated groundwater remediation are urgently needed. This study presents a technique of in situ remediation via the direct-push amendment injection that enhances the reductive dechlorination of chlorinated solvents in groundwater in the low-permeability aquifer. A field-based pilot test and a following real-world, full-scale application were conducted at an active manufacturing facility in Shanghai, China. The chlorinated solvents found at the clay till site included 1,1,1-trichloroethane (1,1,1-TCA), 1,1-dichloroethane (1,1-DCA), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), and chloroethane (CA). A commercially available amendment (EHC ® , Peroxychem, Philadelphia, PA) combining zero-valent iron and organic carbon was used to treat the above pollutants. Pilot test results showed that direct-push EHC injection efficiently facilitated the in situ reductive remediation of groundwater contaminated with chlorinated solvents. The mean removal rates of 1,1,1-TCA, 1,1-DCA, and 1,1-DCE at 270 days post-injection were 99.6, 99.3, and 73.3%, respectively, which were obviously higher than those of VC and CA (42.3 and 37.1%, respectively). Clear decreases in oxidation-reduction potential and dissolved oxygen concentration, and increases in Fe 2+ and total organic carbon concentration, were also observed during the monitoring period. These indicate that EHC promotes the anaerobic degradation of chlorinated hydrocarbons primarily via long-term biological reductive dechlorination, with instant chemical reductive dechlorination acting as a secondary pathway. The optimal effective time of EHC injection was 0-90 days, and its radius of influence was 1.5 m. In full-scale application, the maximum concentrations of 1,1,1-TCA

Progress Report on the ISCR Pilot Test Conducted at the Former CCC/USDA Grain Storage Facility in Montgomery City, Missouri, as of April 2013

Energy Technology Data Exchange (ETDEWEB)

LaFreniere, Lorraine M. [Argonne National Lab. (ANL), Argonne, IL (United States). Environmental Science Division. Applied Geoscience and Environmental Restoration Program

2013-06-01

The Commodity Credit Corporation of the U.S. Department of Agriculture (CCC/USDA) is conducting an environmental investigation at the former CCC/USDA grain storage facility on the county fairgrounds in Montgomery City, Missouri, to evaluate contamination associated with the former use of grain fumigants containing carbon tetrachloride at the site. The CCC/USDA studies have identified carbon tetrachloride in the soils (primarily unconsolidated glacial tills) at concentrations that exceed the U.S. Environmental Protection Agency (EPA) regional screening level (RSL) values for this compound in residential soils (610 μg/kg) but are below the corresponding RSL for industrial soils (3,000 μg/kg). Concentrations of carbon tetrachloride greater than the EPA maximum contaminant level (MCL; 5.0 μg/L) for this contaminant in drinking water were also identified in the shallow groundwater (Argonne 2012). On the basis of these findings, remedial actions are considered necessary to mitigate the present and potential future impacts of the contamination. In cooperation with the Missouri Department of Natural Resources (MDNR), the CCC/USDA has initiated a field-scale pilot test to evaluate an in situ technology for treatment of the carbon tetrachloride contamination. In this approach, a chemical amendment consisting primarily of slow-release organic matter and zero-valent iron is employed to induce oxygen-depleted, chemically reducing conditions in the subsurface. These conditions foster the in situ chemical reduction (ISCR) of carbon tetrachloride and its degradation products (chloroform, methylene chloride, and chloromethane) via both inorganic and biologically mediated processes. The chemical amendment being used, EHC™, was developed by the Adventus Group, Freeport, Illinois, and is now manufactured and distributed by FMC Environmental Solutions, Philadelphia, Pennsylvania. With the approval of the MDNR (2012), the ISCR technology is being tested in two target areas

Salt lakes of Western Australia - Natural abiotic formation of volatile organic compounds

Science.gov (United States)

Krause, T.; Studenroth, S.; Mulder, I.; Tubbesing, C.; Kotte, K.; Ofner, J.; Junkermann, W.; Schöler, H. F.

2012-04-01

/MS. Especially the acidic lakes are sources for trihalomethanes in agreement with laboratory studies on model compounds like catechol [3]. Other compounds that are formed are chloromethane, -butane, -hexane and heptane as well as monocyclic terpenes and furan derivatives. Additionally, there are different sulphur compounds such as thiophene derivatives, carbon disulfide and dimethyl sulfide. Western Australia offers a variety of hypersaline environments with various hydrogeochemical parameters that will help to understand the abiotic formation of different volatile organic compounds. The field of research includes the complex relationships between agriculture, secondary salinisation and particle formation from volatile organic compounds emitted from the salt lakes. [1] Williams, 2001, Hydrobiologia, 466, 329-337. [2] Junkermann et al., 2009, Atmos. Chem. Phys., 9, 6531-6539. [3] Huber et al., 2009, Environ. Sci. Technol., 43 (13), 4934-4939.

Simultaneous anaerobic transformation of carbon tetrachloride to carbon dioxide and tetrachloroethene to ethene in a continuous flow column.

Science.gov (United States)

Azizian, Mohammad F; Semprini, Lewis

2017-08-01

The simultaneous anaerobic transformation of tetrachloroethene (PCE) and carbon tetrachloride (CT) was evaluated in a continuous flow column. The column was packed with quartz sand and bioaugmented with the Evanite culture (EV) that is capable of transforming PCE to ethene. Azizian and Semprini (2016) reported that PCE and CT could be simultaneously transformed in the column, with PCE (0.1mM) transformed mainly to ethene and CT (0.015mM) to chloroform (CF) (20%) and an unknown transformation product, likely carbon dioxide (CO 2 ). The fermentation of propionate, formed from lactate fermentation, was inhibited after the transformation of CT, likely from the exposure to CF. Reported here is the second phase of that study where a second bioaugmentation of the EV culture was made to reintroduce a lactate and propionate fermenting population to the column. Effective lactate and propionate fermentation were restored with a H 2 concentration of ~25nM maintained in the column effluent. PCE (0.1mM) was effectively transformed to ethene (~98%) and vinyl chloride (VC) (~2%). Unlabeled CT (0.015 to 0.03mM) was completely transformed with a transient build-up of CF and chloromethane (CM), which were subsequently removed below their detection limits. A series of transient tests were initiated through the addition of carbon-13 labeled CT ( 13 CT), with concentrations gradually increased from 0.03 to 0.10mM. GC-MS analysis of the column effluent showed that 13 C labeled CO 2 ( 13 CO 2 ) was formed, ranging from 82 to 93% of the 13 CT transformed, with the transient increases in 13 CO 2 associated with the increased concentration of 13 CT. A modified COD analysis indicated a lesser amount of 13 CT (18%) was transformed to soluble products, while 13 CO 2 represented 82% the 13 CT transformed. In a final transient test, the influent lactate concentration was decreased from 1.1 to 0.67mM. The transformation of both CT and PCE changed dramatically. Only 59% of the 13 CT was transformed

Emission of Volatile OrganoHalogens by Southern African Solar Salt Works

Science.gov (United States)

Kotte, Karsten; Weissflog, Ludwig; Lange, Christian Albert; Huber, Stefan; Pienaar, Jacobus J.

2010-05-01

Volatile organic compounds containing halogens - especially chlorine - have been considered for a long time of industrial origin only, and it was assumed that the production and emission of these compounds can easily be controlled by humans in case they will cause a threat for life on Earth. Since the middle of the 80ies of the last century it became clear that the biologically active organohalogens isolated by chemists are purposefully produced by nature as antibiotics or as antifeedant etc. To date more than 3800 organohalogens are known to be naturally produced by bio-geochemical processes. The global budgets of many such species are poorly understood and only now with the emergence of better analytical techniques being discovered. For example the compound chloromethane nature's production (5 GT) outdates the anthropogenic production (50 KT) by a factor of 100. Thus organohalogens are an interesting recent case in point since they can influence the ozone budget of the boundary layer, play a role in the production of aerosols and the climate change discussion. An intriguing observation is that most of the atmospheric CH3Cl and CH3Br are of terrestrial rather than of marine origin and that a number of halogenated small organic molecules are produced in soils. The high concentrations of halides in salt soils point to a possibly higher importance of natural halogenation processes as a source of volatile organohalogens. Terrestrial biota, such as fungi, plants, animals and insects, as well as marine algea, bacteria and archaea are known or suspected to be de-novo producers of volatile organohalogens. In recent years we revealed the possibility for VOX to form actively in water and bottom sediments of hyper-saline environments in the course of studying aridization processes during climatic warming. Due to the nature of their production process solar salt works, as to be found along-side the Southern African coast line but also upcountry, combine a variety of semi- and

Survival of Organic Materials in Ancient Cryovolcanically-Produced Halite Crystals

Science.gov (United States)

Zolensky, M.; Fries, M.; Chan, Q. H.-S.; Kebukawa, Y.; Bodnar, R.; Burton, A.; Callahan, M.; Steele, A.; Sandford, S.

2015-01-01

also far from equilibrium. Cryovolcanoes on Ceres are a potential source of our halite, however the processes that form halite should also be operating within Europa. Dissolution of Monahans halite grains has revealed a remarkable variety of organics, which dominate the population of solid inclusions. Thermal alteration of this macromolecular carbon (measured by Raman spectroscopy) shows remarkable diversity. We have identified highly-condensed aromatics, diamond, carbonates and chloromethane. Light organic compounds like methane tend to be water soluble and require cold formation temperatures at high hydrogen fugacity - i.e. require water ice. Another indication that these halites have not been heated is that light organics readily volatilize or aromaticize into PAHs. We are currently analyzing the organics by Raman and C-XANES, and measuring the content and exploring the potential chirality of amino acids in the halite. Implications for Europa Plumes: Organic materials and structures erupted by a Europa cryovolcano should be similarly preserved within halite, and other salts, which will be a convenient form for capture and analysis, since halite will serve to encapsulate and protect the organics from spacecraft contamination. Also, being transparent at many wavelengths halite will permit analysis by spacecraft-mounted spectroscopic techniques. In addition, halite is readily dissolved, permitting further analysis of entrained organics.

A Review of Semivolatile and Volatile Organic Compounds in Highway Runoff and Urban Stormwater

Science.gov (United States)

Lopes, Thomas J.; Dionne, Shannon G.

1998-01-01

, the most significant factors affecting SVOC concentrations are organic carbon content and distance from sources such as highways and power plants. Petroleum hydrocarbons, oil and grease, and polycyclic aromatic hydrocarbons (PAHs) in crankcase oil and vehicle emissions are the major SVOCs detected in highway runoff and urban stormwater. The few loading factors and regression equations that were developed in the 1970's and 1980's have limited use in estimating current (1998) loads of SVOCs on a national scale. These factors and equations are based on few data and use inconsistent units, and some are independent of rainfall. Also, more cars on the road today have catalytic converters, and fuels that were used in 1998 are cleaner than when loading factors and regression equations were developed. Comparisons to water-quality and sedimentquality criteria and guidelines indicate that PAHs, phenolic compounds, and phthalates in runoff and sediment exceeded U.S. Environmental Protection Agency drinking-water and aquatic-life standards and guidelines. PAHs in stream sediments adjacent to highways have the highest potential for adverse effects on receiving streams. Few data exist on VOCs in highway runoff. VOCs were detected in precipitation adjacent to a highway in England, and chloromethane, toluene, xylenes, 1,2,4-trimethylbenzene, and 1,2,3-trichloropropane were detected in runoff from a highway in Texas. In urban stormwater, gasoline-related compounds were detected in as many as 23 percent of the samples. Land use could be the most significant factor affecting the occurrence of VOCs, with highest concentrations of VOCs found in industrial areas. Temperature is another factor affecting the occurrence and concentrations of VOCs. Urban land surfaces are the primary nonpoint source of VOCs in stormwater. However, the atmosphere is a potential source of hydrophilic VOCs in stormwater, especially during cold seasons when partitioning of VOCs from air into water i

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

Science.gov (United States)

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

2014-02-01

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

Selected Natural Attenuation Monitoring Data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, 2007 and 2008

Science.gov (United States)

Dinicola, R.S.; Huffman, R.L.

2009-01-01

chlorinated VOCs. For the upper aquifer beneath the northern phytoremediation plantation, chlorinated VOC concentrations in 2007 and 2008 at most piezometers were similar to or slightly less than chlorinated VOC concentrations measured in previous years. The only chlorinated VOC positively detected at piezometers P1-1 and P1-5 was cis-1,2-dichloroethene (cis-DCE); most chlorinated VOC concentrations at piezometer P1-3 were at the lowest levels since monitoring began in 1999. Most VOC concentrations at piezometer P1-4 were similar to VOC concentrations measured in previous years except that vinyl chloride (VC) concentrations inexplicably increased from 280 micrograms per liter (ug/L) in June 2007 to 750 ug/L in June 2008. In 2008, measurement of the sum of concentrations of ethane and ethene, reductive dechlorination byproducts, was at the highest level at most northern plantation wells and piezometers, which is evidence of reductive dechlorination of chlorinated VOCs. For the upper aquifer beneath the southern phytoremediation plantation, chlorinated VOC concentrations in 2007 and 2008 at the piezometers were most often extremely high and they continued to vary considerable over space and between years. At piezometer P1-6, the total chlorinated VOC concentration increased from 380 ug/L in 2007 to more than 20,000 ug/L in 2008. At piezometer P1-7 in 2008, the concentrations of trichloroethene, cis-DCE, and VC were the highest to date, but total chlorinated VOC concentrations at piezometers P1-8, P1-9, and P1-10 in 2008 were relatively low compared to historical levels. The magnitude and persistence of chlorinated VOC concentrations indicate that non-aqueous phase liquid chloroethenes likely are beneath the southern plantation, and the temporal variability in concentrations likely is a result of variations in precipitation and groundwater levels interacting with the non-aqueous phase liquid. The reductive dechlorination byproducts ethane and ethene were detected at

Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

Science.gov (United States)

Scheeren, H. A.

2003-09-01

The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons are present at relatively low quantities in our atmosphere (10-12 10-9 mol mol-1 of air). Nevertheless, they play a key role in atmospheric photochemistry. For example, the oxidation of NMHC plays a dominant role in the formation of ozone in the troposphere, while the photolysis of chlorocarbons contributes to enhanced ozone depletion in the stratosphere. In spite of their important role, however, their global source and sinks budgets are still poorly understood. Hence, this study aims at improving our understanding of the sources, distribution, and chemical role of reactive NMHC and chlorocarbons in the troposphere and lower stratosphere. To meet this aim, a comprehensive data set of selected C2 C7 NMHC and chlorocarbons has been analyzed, derived from six aircraft measurement campaigns with two different jet aircrafts (the Dutch TUD/NLR Cessna Citation PH-LAB, and the German DLR Falcon) conducted between 1995 and 2001 (STREAM 1995 and 1997 and 1998, LBA-CLAIRE 1998, INDOEX 1999, MINOS 2001). The NMHC and chlorocarbons have been detected by gas-chromatography (GC-FID/ECD) in pre-concentrated whole air samples collected in stainless steel canister on-board the measurement aircrafts. The measurement locations include tropical (Maldives/Indian Ocean and Surinam), midlatitude (Western Europe and Canada) and polar regions (Lapland/northern Sweden) between the equator to about 70ºN, covering different seasons and pollution levels in the troposphere and lower stratosphere. Of