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;

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.

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.

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

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

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.

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;

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.'

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.

RT3D Reaction Modules for Natural and Enhanced Attenuation of Chloroethanes, Chloroethenes, Chloromethanes, and Daughter Products

Energy Technology Data Exchange (ETDEWEB)

Johnson, Christian D.; Truex, Michael J.

2006-07-25

This document describes a suite of MNA/EA reaction modules that were developed for addressing complex chlorinated solvent reactions using RT3D. As an introduction, an overview of these MNA/EA reaction modules is presented, including discussions of similarities between reaction modules, the purpose of key reaction parameters, and important considerations for using the reaction modules. Subsequent sections provide the details of the reaction kinetics (conceptual model and equations), data input requirements, and example (batch reactor) results for each reaction module. This document does not discuss reaction module implementation or validation; such information will accompany the software in the form of release notes or a supplement to the RT3D manual.

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.

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.

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)

[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.

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).

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).

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)

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

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

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

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

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