Science.gov

Sample records for chlorinated hydrocarbons

  1. Process for Photochemical Chlorination of Hydrocarbons

    DOEpatents

    Beanblossom, W S

    1951-08-28

    A process for chlorination of a major portion of the hydrogen atoms of paraffinic hydrocarbons of five or more carbon atoms may be replaced by subjecting the hydrocarbon to the action of chlorine under active light. The initial chlorination is begun at 25 to 30 deg C with the chlorine diluted with HCl. The later stages may be carried out with undiluted chlorine and the temperature gradually raised to about 129 deg C.

  2. Chlorinated hydrocarbons in peat

    SciTech Connect

    Rapaport, R.A.

    1985-01-01

    Concentrations (ng/g), accumulation rates (ug/m/sup 2/=yr) and burdens were determined for DDT (1,1,1-trichlorophenyl2-2'bis(p-chlorophenyl)ethane), polychlorinated biphenyls. Toxaphene, hexachlorobenzene (HCB) and a,b,g-hexachlorocyclohexanes (HCHs) in peat cores taken across the mid-latitudes of North America. Because peat bogs are ombrotrophic, thereby receiving all contaminant inputs from the atmosphere and because peat cores were dated, atmospheric input functions were constructed for all of the compounds listed above excepting the HCHs. Compound inventories (burdens) in peat cores of PCBs, HCB, HCHs, Toxaphene, DDT, Pb and Zn were compared, indicating a strong influence from areas proximate to industrial sources and the atmospheric transport from source regions. Untransformed parent DDT (p,p' and o,p'-DDT) in surface peat and in precipitation provides evidence for the long range transport of DDT from neighboring countries where use has increased over the past 10-15 years. Present accumulation rates of DDT in peat are about 10-20% of maximum levels associated with peak use in the US around 1960. The DDT input function that was developed can be used to date peat cores. Transformations of DDT and PCBs were also examined in peat cores. First order transformation rates of DDT (p,p' and o,p') to DDD in anaerobic peat core environments ranged from 0.03 to 0.09 yr/sup -1/ with differences related to temperature. Aerobic transformation of PCB congeners in peat cores and microcosms was rapid for 2,3 and several 4 chlorinated congeners (T/sub 1/2 less than or equal to 0.2 to 3 years) and declined with increasing chlorine number.

  3. [Determination of chlorinated hydrocarbons in coffee beans].

    PubMed

    Wieczorek, Jolanta; Czyrska, Regina; Wieczorek, Zbigniew; Smoczyńska, Krystyna

    2002-01-01

    Chlorinated hydrocarbons (gamma-HCH, DDT and their analogous metabolites) were determined in coffee beans. Four sorts of green coffee beans and 18 sorts of burnt coffee beans were used in the research. The method was based on extraction of fat and its destruction with concentrated sulphuric acid. Chlorinated hydrocarbons were extracted with n-hexane, separated and quantitatively determined by gas chromatography. The presence of chlorinated hydrocarbons was detected in green coffee beans and, in smaller quantities, in burnt coffee beans. The concentration of chlorinated hydrocarbons was lower in medium and darkly burnt coffee beans than lightly burnt coffee. The level of DDT and its metabolites in final product decreased after coffee burning at higher temperatures. After brewing the grind coffee beans the remains of chlorinated hydrocarbons were detected in coffee-grounds at concentration to those found in coffee beans. Drinking of natural coffee does not influence an increase of intake the chlorinated hydrocarbons by human beings.

  4. Behavioral toxicology, risk assessment, and chlorinated hydrocarbons.

    PubMed Central

    Evangelista de Duffard, A M; Duffard, R

    1996-01-01

    Behavioral end points are being used with greater frequency in neurotoxicology to detect and characterize the adverse effects of chemicals on the nervous system. Behavioral measures are particularly important for neurotoxicity risk assessment since many known neurotoxicants do not result in neuropathology. The chlorinated hydrocarbon class consists of a wide variety of chemicals including polychlorinated biphenyls, clioquinol, trichloroethylene, hexachlorophene, organochlorine insecticides (DDT, dicofol, chlordecone,dieldrin, and lindane), and phenoxyherbicides. Each of these chemicals has effects on motor, sensory, or cognitive function that are detectable using functional measures such as behavior. Furthermore, there is evidence that if exposure occurs during critical periods of development, many of the chlorinated hydrocarbons are developmental neurotoxicants. Developmental neurotoxicity is frequently expressed as alterations in motor function or cognitive abilities or changes in the ontogeny of sensorimotor reflexes. Neurotoxicity risk assessment should include assessments of the full range of possible neurotoxicological effects, including both structural and functional indicators of neurotoxicity. PMID:9182042

  5. Behavioral toxicology, risk assessment, and chlorinated hydrocarbons

    SciTech Connect

    Evangelista de Duffard, A.M.; Duffard, R.

    1996-04-01

    Behavioral end points are being used with greater frequency in neurotoxicology to detect and characterize the adverse effects of chemicals on the nervous system. Behavioral measures are particularly important for neurotoxicity risk assessment since many known neurotoxicants do not result in neuropathology. The chlorinated hydrocarbon class consists of a wide variety of chemicals including polychlorinated biphenyls, clioquinol, trichloroethylene, hexachlorophene, organochlorine insecticides (DDT, dicofol, chlordecone, dieldrin, and lindane), and phenoxyherbicides. Each of these chemicals has effects on motor, sensory, or cognitive function that are detectable using functional measures such as behavior. Furthermore, there is evidence that if exposure occurs during critical periods of development, many of the chlorinated hydrocarbons are developmental neurotoxicants. Developmental neurotoxicity is frequently expressed as alterations in motor function or cognitive abilities or charges in the ontogeny of sensorimotor reflexes. Neurotoxicity risk assessment should include assessments of the full range of possible neurotoxicological effects, including both structural and functional indicators of neurotoxicity. 121 refs., 1 tab.

  6. Hydrocarbon and chlorinated hydrocarbon-soluble magnesium dialkoxides

    SciTech Connect

    Kamienski, C.W.

    1988-05-31

    This patent describes a process for the preparation of hydrocarbon or chlorinated hydrocarbon solvent solutions of magnesium dialkoxides, which comprises reacting a suspension of magnesium metal or magnesium amide, or a solution of a dialkyimagnesium compound, in a volatile hydrocarbon or chlorinated hydrocarbon solvent with an alcohol selected from the group of (a) aliphatic, cycloaliphatic and acyclic C/sub 5/-C/sub 18/ beta- and gamma-alkyl-substituted secondary and tertiary monohydric alcohols; or (b) mixtures of the (a) alcohols with C/sub 3/-C/sub 18/ aliphatic or cycloaliphatic beta- and gamma-alkyl-unsubstituted secondary or tertiary alcohols; or (c) mixtures of the (a) alcohols with C/sub 1/-C/sub 18/ aliphatic primary unsubstituted and 2-alkyl-substituted alcohols; the mole ratios of the (a) to the (b), and the (a) to the (c), alcohols being 1 of the (a) alcohols to 0.1 to 2 of the (b) and/or the (c) alcohols.

  7. Biological monitoring of chlorinated hydrocarbon solvents

    SciTech Connect

    Monster, A.C.

    1986-08-01

    The possibility of biological monitoring of exposure to some volatile, halogenated hydrocarbons will be discussed. Most of these agents are widely used as solvents. All agents act on the nervous system as narcotics and differ widely in toxicity. Most of the solvents undergo biotransformation to metabolites. This allows biological assessment of exposure by measurement of the solvent and/or metabolites in exhaled air, blood, and/or urine. However, the same metabolites may occur with exposure to different chlorinated hydrocarbons, eg, trichloroethanol and trichloroacetic acid from exposure to trichloroethene, tetrachloroethene, and 1,1,1-trichloroethane. On the other hand, these agents differ widely in the percentage that is metabolized. There are large gaps in our knowledge, however, and much research will have to be carried out before even tentative data can be established for most of the solvents.

  8. Chlorinated hydrocarbons in women with repeated miscarriages.

    PubMed Central

    Gerhard, I; Daniel, V; Link, S; Monga, B; Runnebaum, B

    1998-01-01

    This study was conducted to investigate a possible etiological role of chlorinated hydrocarbons in the pathogenesis of repeated miscarriages. The blood levels of chlorinated hydrocarbons [CHCs: pentachlorophenol, hexachlorocyclohexane, hexachlorobenzene, the dichlorodiphenyltrichloroethane (DDT) group, polychlorinated biphenyls] were determined in 89 women with repeated miscarriages, who were referred to the University Hospital of Obstetrics and Gynecology of Heidelberg for investigations between 1989 and 1993, and compared to a previously investigated reference population. In more than 20% of the women, at least one of the CHC levels exceeded the reference range. CHC levels did not differ significantly between women with primary or secondary and early or late miscarriages; neither did they differ between women with hormonal or immunological disorders as causes of repeated miscarriages or women with idiopathic repeated miscarriages. No significant associations were detected between CHC levels and further conceptions or the outcome of further pregnancies. As significant associations were found between increasing CHC blood concentrations and immunological and hormonal changes, CHCs may have an impact on the pregnancy course in certain cases. PMID:9755145

  9. PCB's and chlorinated hydrocarbon pesticides in Antarctic atmosphere and hydrosphere

    SciTech Connect

    Tanabe, S.; Hidaka, H.; Tatsukawa, R.

    1983-01-01

    PCBs and chlorinated hydrocarbon pesticides such as DDTs and HCHs (BHCs) were measured in air, water, ice and snow samples collected around the Japanese research stations in Antarctica and adjacent oceans during December 1980 to March 1982. The atmospheric concentrations of chlorinated hydrocarbons decreased in the transport process from northern lands to Antarctica, but the compositions of PCBs, DDT compounds and HCH isomers were relatively uniform throughout this process. Regional and seasonal variations were found in aerial concentrations of these pollutants at Syowa Station and adjacent seas in Antarctica. Chlorinated hydrocarbons were also detected in snow, ice, lake water and sea water samples, in which rather high concentrations were found in snow and ice samples. This suggests that snow and ice serve as media of supply of these pollutants into Antarctic marine environment.

  10. Chlorinated hydrocarbon contaminants in arctic marine mammals.

    PubMed

    Norstrom, R J; Muir, D C

    1994-09-16

    By 1976, the presence of chlorinated hydrocarbon contaminants (CHCs) had been demonstrated in fur seal (Callorhinus ursinus), ringed seal (Phoca hispida), hooded seal (Cystophora cristata), bearded seal (Erignathus barbatus), walrus (Obdobenus rosmarus divergens), beluga (Delphinapterus leucas), porpoise (Phocoena phocoena) and polar bear (Ursus maritimus) in various parts of the Arctic. In spite of this early interest, very little subsequent research on contaminants in Arctic marine mammals was undertaken until the mid-1980s. Since that time, there has been an explosion of interest, resulting in a much expanded data base on contaminants in Arctic marine mammals. Except in the Russian Arctic, data have now been obtained on the temporospatial distribution of PCBs and other contaminants in ringed seal, beluga and polar bear. Contaminants in narwhal (Monodon monoceros) have also now been measured. On a fat weight basis, the sum of DDT-related compounds (S-DDT) and PCB levels are lowest in walrus (< 0.1 microgram/g), followed by ringed seal, (0.1-1 microgram/g range). Levels are an order of magnitude higher in beluga and narwhal (1-10 micrograms/g range). It appears that metabolism and excretion of S-DDT and PCBs may be less efficient in cetaceans, leading to greater biomagnification. Polar bears have similar levels of PCBs as cetaceans (1-10 micrograms/g), but with a much simpler congener pattern. DDE levels are lowest in polar bear, indicating rapid metabolism. Effects of age and sex on residue levels are found for all species where this was measured. Among cetaceans and ringed seal, sexually mature females have lower levels than males due to lactation. Although PCB levels in adult male polar bears are about twice as high as females, there is only a trivial age effect in either sex apart from an initial decrease from birth to sexual maturity (age 0-5). Comparison of levels of S-DDT and PCBs in Arctic beluga and ringed seal with those in beluga in the Gulf of St

  11. Shock-tube pyrolysis of chlorinated hydrocarbons - Formation of soot

    NASA Technical Reports Server (NTRS)

    Frenklach, M.; Hsu, J. P.; Miller, D. L.; Matula, R. A.

    1986-01-01

    Soot formation in pyrolysis of chlorinated methanes, their mixtures with methane, and chlorinated ethylenes were studied behind reflected shock waves by monitoring the attenuation of an He-Ne laser beam. An additional single-pulse shock-tube study was conducted for the pyrolysis of methane, methyl chloride, and dichloromethane. The experiments were performed at temperatures 1300-3000 K, pressures of 0.4-3.6 bar, and total carbon atom concentrations of 1-5 x 10 to the 17th atoms cu cm. The amounts of soot produced in the pyrolysis of chlorinated hydrocarbons are larger than that of their nonchlorinated counterparts. The sooting behavior and product distribution can be generally explained in terms of chlorine-catalyzed chemical reaction mechanisms. The pathway to soot from chlorinated methanes and ethylenes with high H:Cl ratio proceeds via the formation of C2H, C2H2, and C2H3 species. For chlorinated hydrocarbons with low H:Cl ratio, the formation of C2 and its contribution to soot formation at high temperatures becomes significant. There is evidence for the importance of CHCl radical and its reactions in the pyrolysis of dichloromethane.

  12. Transformation of Chlorinated Hydrocarbons on Synthetic Green Rusts

    EPA Science Inventory

    Green rusts (GRs) are layered double hydroxides that contain both ferrous and ferric ions in their structure. GRs can potentially serve as a chemical reductant for degradation of chlorinated hydrocarbons. GRs are found in zerovalent iron based permeable reactive barriers and in c...

  13. USE OF SONOCHEMISTRY IN MONITORING CHLORINATED HYDROCARBONS IN WATER

    EPA Science Inventory

    The U.S. Environmental Protection Agency (EPA) has been examining the potential of combining sonication with available measurement technologies for monitoring chlorinated hydrocarbons in water. The chloride ion (C1-) concentration, conductivity, and pH were measured before and af...

  14. Transformation of Chlorinated Hydrocarbons on Synthetic Green Rusts

    EPA Science Inventory

    Green rusts (GRs) are layered double hydroxides that contain both ferrous and ferric ions in their structure. GRs can potentially serve as a chemical reductant for degradation of chlorinated hydrocarbons. GRs are found in zerovalent iron based permeable reactive barriers and in c...

  15. TURBULENT FLAME REACTOR STUDIES OF CHLORINATED HYDROCARBON DESTRUCTION EFFICIENCY

    EPA Science Inventory

    Four mixtures of C1 and C2 chlorinated hydrocarbons, diluted in heptane, were burned in a Turbulent Flame Reactor (TFR) under high and low oxygen conditions. Emissions of undestroyed feed, stable organic by-products, carbon monoxide, carbon dioxide and oxyg...

  16. [Electrochemical reduction characteristics and mechanism of chlorinated hydrocarbon at the copper electrode].

    PubMed

    Xu, Wen-Ying; Gao, Ting-Yao; Zhou, Rong-Feng; Ma, Lu-Ming

    2005-07-01

    The electrochemical reduction characteristics of chlorinated hydrocarbons were investigated by applying cyclic voltammetry technique. The reduction mechanism and reactivity of the chlorinated hydrocarbons at the copper electrodes were explored. The relation between the reductive reactivity at the copper electrode and the structures of this kind of compounds was discussed. The experimental results show that chlorinated paraffin hydrocarbons and a portion of chlorinated aromatic hydrocarbons could be reduced directly at the copper electrode; however, chlorinated aromatic hydrocarbons aren't easy to reduced directly at the copper electrode. The results provide a theoretical basis for the catalyzed iron inner electrolysis method.

  17. Integrated carbon and chlorine isotope modeling: applications to chlorinated aliphatic hydrocarbons dechlorination.

    PubMed

    Jin, Biao; Haderlein, Stefan B; Rolle, Massimo

    2013-02-05

    We propose a self-consistent method to predict the evolution of carbon and chlorine isotope ratios during degradation of chlorinated hydrocarbons. The method treats explicitly the cleavage of isotopically different C-Cl bonds and thus considers, simultaneously, combined carbon-chlorine isotopologues. To illustrate the proposed modeling approach we focus on the reductive dehalogenation of chlorinated ethenes. We compare our method with the currently available approach, in which carbon and chlorine isotopologues are treated separately. The new approach provides an accurate description of dual-isotope effects regardless of the extent of the isotope fractionation and physical characteristics of the experimental system. We successfully applied the new approach to published experimental results on dehalogenation of chlorinated ethenes both in well-mixed systems and in situations where mass-transfer limitations control the overall rate of biodegradation. The advantages of our self-consistent dual isotope modeling approach proved to be most evident when isotope fractionation factors of carbon and chlorine differed significantly and for systems with mass-transfer limitations, where both physical and (bio)chemical transformation processes affect the observed isotopic values.

  18. Estimating The Thermodynamics And Kinetics Of Chlorinated Hydrocarbon Degradation

    SciTech Connect

    Bylaska, Eric J.

    2006-08-01

    Many different degradation reactions of chlorinated hydrocarbons are possible in natural ground waters. In order to identify which degradation reactions are important, a large number of possible reaction pathways must be sorted out. Recent advances in ab initio electronic structure methods have the potential to help identify relevant environmental degradation reactions by characterizing the thermodynamic properties of all relevant contaminant species and intermediates for which experimental data is usually not available, as well as provide activation energies for relevant pathways. In this paper, strategies based on ab initio electronic structure methods for estimating thermochemical and kinetic properties of reactions with chlorinated hydrocarbons are presented. Particular emphasis is placed on strategies that are computationally fast and can be used for large organochlorine compounds such as 4,4?-DDT.

  19. Aerobic microorganism for the degradation of chlorinated aliphatic hydrocarbons

    DOEpatents

    Fliermans, Carl B.

    1989-01-01

    A chlorinated aliphatic hydrocarbon-degrading microorganism, having American Type Culture Collection accession numbers ATCC 53570 and 53571, in a biologically pure culture aseptically collected from a deep subsurface habitat and enhanced, mineralizes trichloroethylene and tetrachloroethylene to HCl, H.sub.2 O and Co.sub.2 under aerobic conditions stimulated by methane, acetate, methanol, tryptone-yeast extract, propane and propane-methane.

  20. Atmospheric chlorinated polycyclic aromatic hydrocarbons in East Asia.

    PubMed

    Kakimoto, Kensaku; Nagayoshi, Haruna; Konishi, Yoshimasa; Kajimura, Keiji; Ohura, Takeshi; Hayakawa, Kazuichi; Toriba, Akira

    2014-09-01

    This study estimates atmospheric concentrations of chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and polycyclic aromatic hydrocarbons (PAHs) in East Asia using a Gas Chromatograph with High Resolution Mass Spectrometer (GC-HRMS). ClPAHs are ubiquitously generated from PAHs through substitution, and some ClPAHs show higher aryl hydrocarbon receptor (AhR)-mediated activities than their parent PAHs. Atmospheric particles were collected using a high-volume air sampler equipped with a quartz-fiber filter. We determined the ClPAH concentrations of atmospheric particles collected in Japan (Sapporo, Sagamihara, Kanazawa, and Kitakyushu), Korea (Busan), and China (Beijing). The concentrations of ClPAHs were highest in the winter Beijing sample, where the total mean concentration was approximately 15-70 times higher than in the winter samples from Japan and Korea. The concentrations of Σ19ClPAHs and Σ9PAHs were significantly correlated in the Kanazawa and the Busan samples. This indicates that within those cities ClPAHs and PAHs share the same origin, implying direct chlorination of parent PAHs. Toxic equivalent concentrations (TEQs) of the total ClPAHs and PAHs were lowest in Kanazawa in the summer, reaching 1.18 and 2610fg-TEQm(-3) respectively, and highest in Beijing in the winter, reaching 627 and 4240000fg-TEQm(-3) respectively.

  1. Chlorinated hydrocarbons in flatfishes from the Southern California, USA, Bight

    SciTech Connect

    Schiff, K.; Allen, M.J.

    2000-06-01

    Although inputs of chlorinated hydrocarbon compounds to the Southern California Bight (SCB) are presently low, historical deposits represent a source of bioaccumulation potential to sediment-associated fauna. To assess this bioaccumulation potential, 14 chlorinated hydrocarbon classes were measured in livers of three species of flatfish collected from 63 randomly selected sites on the coastal shelf between Point Conception and the United States-Mexico international border. Tissue contamination was widespread throughout the SCB, but was limited to just two chlorinated hydrocarbon classes. Virtually 100% of Pacific sanddab (Citharichthys sordidus) and longfin sanddab (Citharichthys xanthostigma) populations were estimated to be contaminated with dichlorodiphenyltrichloroethane (total DDT = sum of o.p{prime} and p,p{prime} isomers of DDT + dichlorodiphenyldichloroethylene [DDE] + dichlorodiphenyldichloroethane [DDD]) and/or polychlorinated biphenyls (total PCBs). Total DDT also contaminated the majority (64%) of the Dover sole (Microstomus pacificus) population in the SCB. Total PCB measurements in tissues of SCB flatfish were dominated by 12 congeners (52, 66, 87, 101, 105, 118, 128, 138, 153, 170, 180, and 187), which averaged 95% of the combined mass of the 27 congeners analyzed. Sediment concentrations accounted for most of the variability observed in tissue concentrations for 8 of these 12 congeners and total PCBs. Normalized sediment concentrations were also significantly correlated to normalized tissue concentrations for total DDT and p,p{prime}-DDE. Tissue concentrations measured in this study from reference areas of the SCB were compared to tissue concentrations measured form reference areas in studies conducted in 1977 and 1985. Total DDT and total PCB liver concentrations were found to have decreased one to two orders of magnitude in pacific and longfin sanddabs between 1985 and 1994. Total DDT and total PCB liver concentrations decreased 5- to 35-fold in

  2. Predicting the distribution of contamination from a chlorinated hydrocarbon release

    SciTech Connect

    Lupo, M.J.; Moridis, G.J.

    1995-03-01

    The T2VOC model with the T2CG1 conjugate gradient package was used to simulate the motion of a dense chlorinated hydrocarbon plume released from an industrial plant. The release involved thousands of kilograms of trichloroethylene (TCE) and other chemicals that were disposed of onsite over a period of nearly twenty years. After the disposal practice ceased, an elongated plume was discovered. Because much of the plume underlies a developed area, it was of interest to study the migration history of the plume to determine the distribution of the contamination.

  3. Occurrence of chlorinated polynuclear aromatic hydrocarbons in tap water

    SciTech Connect

    Shiraishi, H.; Pilkington, N.H.; Otsuki, A.; Fuwa, K.

    1985-07-01

    Organic compounds in tap waters were extracted by a modified continuous liquid-liquid extractor and analyzed by computerized gas chromatography/mass spectrometry using a fused silica capillary column. The results indicate the presence of monochlorinated derivatives of naphthalene, dibenzofuran, fluorene, fluorenone, phenanthrene, and fluoranthene and dichlorinated derivatives of naphthalene, phenanthrene, and fluoranthene. The parent polynuclear aromatic hydrocarbons (PAHs) and their oxygenated derivatives such as fluorenone and anthraquinone were also found. It was demonstrated that chlorinated PAHs (Cl-PAHs) were really present in tap waters at 10/sup -1/-10/sup -2/ ng/L levels.

  4. Electron beam degradation of chlorinated hydrocarbons in air

    NASA Astrophysics Data System (ADS)

    Prager, L.; Langguth, H.; Rummel, S.; Mehnert, R.

    1995-09-01

    Using a low-energy electron accelerator (180 keV, 3 kW) synthetic air polluted with chlorinated hydrocarbons such as cis-dichloro-, trichloro- and perchloroethene was irradiated in a flow system. Already at doses of 2.5 kGy, more than 90 vol% of the initial pollutant concentration (2-50 ppm) could be removed. As main products HCl, CO, chloromethanes, chloroacetyl chlorides and phosgene were identified. After hydrolysis of phosgene and chloroacteyl chlorides in a wet scrubbing system, the chlorine balance shows nearly complete mineralization of the pollutants to HCl, CO and CO2. Less than 5 vol% of chloromethanes and about 0.1 vol% chloroacetic acids were detected after irradiation and hydrolysis. An attempt is made to describe the degradation mechanism as OH radical induced chain reaction. The OH radical adds to the ethene double bond. The resulting adduct releases a chlorine radical. In presence of oxygen a chain reaction is initiated by this radical, which leads to decomposition of the chloroethenes.

  5. Iron-carbon composites for the remediation of chlorinated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Sunkara, Bhanu Kiran

    This research is focused on engineering submicron spherical carbon particles as effective carriers/supports for nanoscale zerovalent iron (NZVI) particles to address the in situ remediation of soil and groundwater chlorinated contaminants. Chlorinated hydrocarbons such as trichloroethylene (TCE) and tetrachloroethylene (PCE) form a class of dense non-aqueous phase liquid (DNAPL) toxic contaminants in soil and groundwater. The in situ injection of NZVI particles to reduce DNAPLs is a potentially simple, cost-effective, and environmentally benign technology that has become a preferred method in the remediation of these compounds. However, unsupported NZVI particles exhibit ferromagnetism leading to particle aggregation and loss in mobility through the subsurface. This work demonstrates two approaches to prepare carbon supported NZVI (iron-carbon composites) particles. The objective is to establish these iron-carbon composites as extremely useful materials for the environmental remediation of chlorinated hydrocarbons and suitable materials for the in situ injection technology. This research also demonstrates that it is possible to vary the placement of iron nanoparticles either on the external surface or within the interior of carbon microspheres using a one-step aerosol-based process. The simple process of modifying iron placement has significant potential applications in heterogeneous catalysis as both the iron and carbon are widely used catalysts and catalyst supports. Furthermore, the aerosol-based process is applied to prepare new class of supported catalytic materials such as carbon-supported palladium nanoparticles for ex situ remediation of contaminated water. The iron-carbon composites developed in this research have multiple functionalities (a) they are reactive and function effectively in reductive dehalogenation (b) they are highly adsorptive thereby bringing the chlorinated compound to the proximity of the reactive sites and also serving as adsorption

  6. Chlorinated hydrocarbons in the Sargasso sea atmosphere and surface water.

    PubMed

    Bidleman, T F; Olney, C E

    1974-02-08

    Polychlorinated biphenyls (PCB), DDT, and chlordane concentrations were measured in air sampled from a tower on the south shore of Bermuda and in Sargasso Sea surface water approximately 80 to 320 kilometers south of Bermuda. The atmospheric chlorinated hydrocarbons appeared to be gaseous, and the DDT concentration was two orders of magnitude higher than previously reported particulate values. The PCB and DDT were enriched in the surface microlayer (150 micrometers) relative to their concentrations in water at a depth of 30 centimeters. Atmospheric residence times for PCB and DDT of 40 to 50 days, calculated from the concentrations in the air and water, are 20 times shorter than values previously estimated for DDT from rainfall and DDT production data.

  7. Aqueous phase microemulsions employing alkyl glucamide surfactants with chlorinated hydrocarbons

    SciTech Connect

    Arenas, E.; Baran, J.R. Jr.; Pope, G.A.

    1995-12-31

    This paper summarizes experiments on nonionic surfactants for electrolyte-free aquifer remediation of chlorocarbon contaminants. Various combinations of linear and branched alkylglucamides succeeded in producing Winsor Type I and III microemulsions at room temperature with various chlorinated hydrocarbons with little or no added electrolyte. Solubilization parameters at 0 and 0.1% NaCl were determined for the surfactant solutions. In comparing these two values, the solubilization parameter shows no definite trend of increasing as had been previously noted. There is no apparent explanation for this anomaly, except that operating at 0% NaCl may not be governed by the same rules that apply to systems with an electrolyte. A class of nonionic surfactants that produce aqueous phase microemulsions with no electrolyte and Winsor III middle phase microemulsions was identified.

  8. Effects of chlorinated hydrocarbon insecticides upon quail and pheasants

    USGS Publications Warehouse

    DeWitt, J.B.

    1955-01-01

    Previous studies had shown that heavy or repeated applications of DDT resulted in decreases.in bird populations, but long-range effects of this and other chlorinated hydrocarbon insecticides had not been fully evaluated. Experiments were conducted to determine toxiCitY to quail and pheasants of aldrin, dieldrin, endrin, and strobane, and to determine effects of these compounds upon survival, growth, and reproduction....Feeding of diets containing 0.02% DDT to breeding quail resulted in significant decreases in hatchability of eggs and in viability of chiCks. Similar results were obtained by feeding 0.001% dieldrin, but effects upon reproduct.ion of short-term feeding of aldrin and endrin could not be determined....Aldrin, dieldrin, and endrin were lethal to both male and female quail when fed at levels of 0.0005% in the diets. Female pheasants appeared more resistant than males to the effects of these compounds.

  9. Occurrence of chlorinated hydrocarbon insecticides, southern Florida--1968-72.

    PubMed

    Mattraw, H C

    1975-09-01

    The frequency with which chlorinated hydrocarbon insecticides appear in samples of southern Florida surface waters decreased sharply between 1968 and 1972. Sediment analyses attest to the earlier widespread use of chlordane, DDT, and dieldrin. Insecticide residues are more frequently detected in southern Florida than in other U.S. cropland soils. Transport of DDT, DDD, and DDE from the Everglades agricultural area into water conservation areas and undeveloped parts of the Everglades of southeastern Florida is facilitated by a system of water-management canals. Canal sediments within the urban area of southern Florida have high DDD, DDE, and dieldrin residue concentrations which may reflect local use of insecticides rather than their transport from adjacent agricultural areas.

  10. A New, Rapid, Precise and Sensitive Method for Chlorine Stable Isotope Analysis of Chlorinated Aliphatic Hydrocarbons

    NASA Astrophysics Data System (ADS)

    van Acker, M. R.; Shahar, A.; Young, E. D.; Coleman, M. L.

    2005-12-01

    Chlorinated aliphatic hydrocarbons (CAH) are recognized common groundwater contaminants. Because of their physico-chemical properties, their lifespan in groundwater is in the order of decades (Pankow and Cherry, 1996). Stable isotopes can play a role in determining the rate and extent of CAH attenuation (Slater, 2003). The use of chlorine has been hampered by the current time consuming and insensitive analytical methods. We present a new analytical procedure to measure chlorine stable isotope values using a gas chromatograph coupled to a multi-collector inductively coupled mass spectrometer (GC-MC-ICP-MS). The GC has a Porapack Q packed column. The carrier gas was helium and the temperature was constant at 160°C. The GC was coupled to the MC-ICP-MS by heated stainless steel tubing. Our high resolution spectra showed that 37Cl is free of its main interference 36Ar-H over a range of 0.004 amu. Two pure CAH, trichloroethene (TCE) and tetrachloroethene (PCE), were used for zero enrichment (sample relative to itself) and standard-sample difference measurements. Integrations and background corrections of transient signals were performed using Microsoft Excel after import of the raw data from the MC-ICPMS acquisition software. Zero enrichment tests with TCE and PCE yielded δ37Cl of -0.04±0.16‰ and -0.03±0.17‰, respectively, results for sample injections of 0.12 to 0.02 microliters. Accuracy was tested by injecting 0.24 microliters of a 50/50 mixture of TCE and PCE of known isotopic compositions as the difference between the two solvents was of paramount interest. The δ37Cl(TCE) value of PCE was -1.99±0.16‰. A highly satisfactory comparison with the conventional method is shown by published values for TCE and PCE, -2.04±0.12‰ and -0.30±0.14‰, respectively (Jendrzejewski et al., 2001), giving a δ37Cl(TCE) value for PCE of -2.34±0.18‰. These tests of the GC-MC-ICP-MS method showed that we can obtain reproducible and accurate Cl isotope values using an

  11. Remedial evaluation of a UST site impacted with chlorinated hydrocarbons

    SciTech Connect

    Ilgner, B.; Rainey, E. ); Ball, M.; Schutt, M.

    1993-10-01

    During assessment and remedial planning of an underground storage tank (UST) site, it was discovered that chlorinated hydrocarbons were present. A network of selected wells were sampled for analysis of halogenated volatile organics and volatile organic compounds to determine the extent of constituents not traditionally associated with refined petroleum motor fuel products. The constituents detected included vinyl chloride, tetrachloroethylene (PCE), bromodichloromethane, and 2-chloroethylvinyl ether. These analytical data were evaluated as to what effect the nonpetroleum hydrocarbon constituents may have on the remedial approach utilized the site hydrogeologic properties to its advantage and took into consideration the residential nature of the impacted area. The geometry of the dissolved plume is very flat and broad, emanating from the site and extending downgradient under a residential area situated in a transmissive sand unit. Ground-water pumping was proposed from two areas of the dissolved plume including five wells pumping at a combined rate of 55 gallons per minute (gpm) at a downgradient position, and two wells on-site to remove free product and highly impacted ground water. Also, to assist in remediation of the dissolved plume and to control vapors, a bioventing system was proposed throughout the plume area.

  12. Hydrous pyrolysis/oxidation process for in situ destruction of chlorinated hydrocarbon and fuel hydrocarbon contaminants in water and soil

    DOEpatents

    Knauss, Kevin G.; Copenhaver, Sally C.; Aines, Roger D.

    2000-01-01

    In situ hydrous pyrolysis/oxidation process is useful for in situ degradation of hydrocarbon water and soil contaminants. Fuel hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, petroleum distillates and other organic contaminants present in the soil and water are degraded by the process involving hydrous pyrolysis/oxidation into non-toxic products of the degradation. The process uses heat which is distributed through soils and water, optionally combined with oxygen and/or hydrocarbon degradation catalysts, and is particularly useful for remediation of solvent, fuel or other industrially contaminated sites.

  13. RELATIONSHIPS BETWEEN LABORATORY AND PILOT-SCALE COMBUSTION OF SOME CHLORINATED HYDROCARBONS

    EPA Science Inventory

    Factors governing the occurence of trace amounts of residual organic substance emmissions (ROSEs) in full-scale incierators are not fully understood. Pilot-scale spray combustion expereiments involving some liquid chlorinated hydrocarbons (CHCs) and their dilute mixtures with hy...

  14. Considerations concerning the murine hepatocarcinogenicity of selected chlorinated hydrocarbons.

    PubMed

    Maronpot, R R; Anna, C H; Devereux, T R; Lucier, G W; Butterworth, B E; Anderson, M W

    1995-01-01

    Of the chlorinated hydrocarbons discussed above, all six are associated with induction of hepatocellular neoplasia in mice. None of the six is considered to be potent mutagen and most are without any significant genotoxic activity as assessed by conventional in vitro testing schemes. Although some of the agents have biological effects in common (see Figure 4), there is no single biological response (mode of action) that they all share to provide a mechanistic basis for the observed murine hepatocarcinogenicity. Based upon the information currently available for each of the chlorinated hydrocarbons discussed above, it is probable that some modes of action may be more contributory to the rodent carcinogenic response than others; however, no mode of action, pathway, or mechanism should be considered to be mutually exclusive. The murine hepatocarcinogenic effect of TriCE is most probably contingent upon its species-specific metabolism to trichloroacetic acid and DCA. There is fairly consistent evidence that cytotoxicity and reparative hyperplasia are associated with doses of TriCE that cause induction of liver neoplasms. The possibility that peroxisome proliferation is playing a role in the induction of mouse hepatocellular neoplasia remains a tempting explanation, since higher intracellular steady states of H2O2 production would be consistent with observed enhanced cellular proliferation as well as the possibility of in vivo DNA damage. The mouse hepatocarcinogenicity associated with TetCE most probably is associated with species-specific metabolic production of trichloroacetic acid. As with TriCE, cytotoxicity and reparative hyperplasia may represent a potential mode of action for the observed hepatocarcinogenicity. Once again, the potential for enhanced peroxisome proliferation is consistent with enhanced cell proliferation and oxygen radical damage would help explain the random point mutations in ras proto-oncogenes documented in DNA from TetCE-induced mouse liver

  15. [Advances in degradation of chlorinated hydrocarbons by obligate and facultative methanotrophs].

    PubMed

    Xing, Zhilin; Zhang, Lijie; Zhao, Tiantao

    2014-04-01

    Bioremediation is one of the most effective ways to treat and dispose of chlorinated hydrocarbons, and methanotrophs are potentially useful to do so. Recent studies found that facultative methanotrophs can use compounds containing C-C bond as sources of carbon and energy, thus overcoming the limitation that obligate methanotrophsone uses only C1 compounds for this process. This is a unique metabolic approach that is becoming increasingly attractive in the field of contaminant biodegradation. Here, we summarized the bioremediation of chlorinated hydrocarbons by obligate and facultative methanotrophs. This process involves the degradation of various chlorinated hydrocarbons by diverse strains, including pure cultures and mixed cultures. We also compare the activity expression and catalytic properties of different types of methane monooxygenases in various substrates. We furthermore summarize the kinetic characteristics of the degradation of chlorinated hydrocarbons using the model strain Methylosinus trichosporium OB3b, and outline the degradation and potential of chlorinated hydrocarbons by facultative methanotrophs. Lastly, we discuss current problems and future research directions for degradation of chlorinated hydrocarbons by methanotrophs.

  16. Persistence of chlorinated hydrocarbon contamination in a California marine ecosystem

    SciTech Connect

    Young, D.R.; Gossett, R.W.; Heesen, T.C.

    1989-01-01

    Despite major reductions in the dominant DDT and polychlorinated biphenyls (PCB) input off Los Angeles (California, U.S.A.) in the early 1970s, the levels of these pollutants decreased only slightly from 1972 to 1975 both in surficial bottom sediments and in a flatfish bioindicator (Dover sole, Microstomus pacificus) collected near the submarine outfall. Concentrations of these pollutants in the soft tissues of the mussel Mytilus californianus, collected intertidally well inshore of the highly contaminated bottom sediments, followed much more closely the decreases in the outfall discharges. These observations suggest that contaminated sediments on the seafloor were the principal (although not necessarily direct) cause of the relatively high and persistent concentrations of DDT and PCB residues in tissues. The study indicated that residues of the higher-molecular-weight chlorinated hydrocarbons, such as DDT and PCB, can be highly persistent once released to coastal marine ecosystems and that their accumulation in surficial bottom sediments is the most likely cause of this persistence observed in the biota of the discharge zone.

  17. Accumulation and diagenesis of chlorinated hydrocarbons in lacustrine sediments

    USGS Publications Warehouse

    Elsenreich, S.J.; Capel, P.D.; Robbins, J.A.; Bourbonniere, R.

    1989-01-01

    Two sediment cores were taken from the Rochester Basin of eastern Lake Ontario and analyzed for the radionuclides 210Pb and 137Cs and several high molecular weight chlorinated hydrocarbons (CHs). The two sites are geographically proximate but differ in sedimentation rate, permitting sedimentation-dependent processes to be factored out. The 210Pb chronology showed a mixed depth of 3-5 cm and an intrinsic time resolution of 11-14 years. Vertically integrated numbers of deposit-feeding oligochaete worms and burrowing organisms are insufficient to homogenize the sediment on the time scale of CH inputs, which are non steady state. U.S. production and sales of polychlorinated biphenyls (PCBs), DDT, Mirex, and hexachlorobenzene (HCB), as determinants of the shape of the input function, adequately predict the overall shape and, in many cases, details in the sedimentary profile. Sediment focusing factors (FF) inferred from 137Cs and 210Pb inventories averaged 1.17 and 1.74 for cores E-30 and G-32, respectively. This permitted CH accumulation rates to be corrected for focusing. Apparent molecular diffusion coefficients modeled for many of the CHs were about (1-3) ?? 10-9 cm2/s.

  18. Assimilation of chlorinated alkanes by hydrocarbon-utilizing fungi

    SciTech Connect

    Murphy, G.L.; Perry, J.J.

    1984-12-01

    The fatty acid compositions of two filamentous fungi (Cunninghamella elegans and Penicillium zonatum) and a yeast (Candida lipolytica) were determined after the organisms were grown on 1-chlorohexadecane or 1-chlorooctadecane. These organisms utilized the chlorinated alkanes as sole sources of carbon and energy. Analyses of the fatty acids present after growth on the chlorinated alkanes indicated that 60 to 70% of the total fatty acids in C. elegans were chlorinated. Approximately 50% of the fatty acids in C. lipolytica were also chlorinated. P. zonatum contained 20% 1-chlorohexadecanoic acid after growth on either substrate but did not incorporate C/sub 18/ chlorinated fatty acids.

  19. Method for removing chlorine compounds from hydrocarbon mixtures

    DOEpatents

    Janoski, Edward J.; Hollstein, Elmer J.

    1985-12-31

    A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.

  20. Method for removing chlorine compounds from hydrocarbon mixtures

    DOEpatents

    Janoski, E.J.; Hollstein, E.J.

    1984-09-29

    A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.

  1. Persistent pollutants: a brief history of the discovery of the widespread toxicity of chlorinated hydrocarbons.

    PubMed

    Rosner, David; Markowitz, Gerald

    2013-01-01

    Rachel Carson's Silent Spring is often depicted as the beginning of a broad societal concern about the dangers of DDT and other pesticides. Attention to the other chlorinated hydrocarbons, specifically PCBs, is seen as an outgrowth of the late 1960s environmental movement. Carson's work was clearly critical in broadening the history to include the environmental impact and set the stage for the path breaking work decades later by Theo Colburn and others on endocrine disruptions associated with other synthetic chemicals. This article reviews the development of the understanding the dangers of the chlorinated hydrocarbons in the decades preceding Carson's book. Although little noticed, Rachel Carson makes this observation herself.

  2. Polychlorinated biphenyl and other chlorinated hydrocarbon residues in adipose tissue of Canadians

    SciTech Connect

    Mes, J.; Davies, D.J.; Turton, D.

    1982-01-01

    The data reported in this paper are part of a continuing monitoring program of chlorinated hydrocarbons in adipose tissue of Canadians in order to determine a possible trend in both the disappearance of restricted OC pesticides, such as p,p,-DDT, as well as the appearance of new environmental contaminants, such as hexachloro-1,3-butadiene (HCBD).

  3. Chlorinated Hydrocarbon Degradation in Plants: Mechanisms and Enhancement of Phytoremediation of Groundwater Contamination

    SciTech Connect

    Strand, Stuart E.

    2003-06-01

    Our research objectives are as follows: (1) Transform poplar and other tree species to extend and optimize chlorinated hydrocarbon (CHC) oxidative activities. (2) Determine the mechanisms of CHC oxidation in plants. (3) Isolate the genes responsible for CHC oxidation in plants.

  4. Modeling the national chlorinated hydrocarbon supply chain and effects of disruption.

    SciTech Connect

    Sun, Amy Cha-Tien; Downes, Paula Sue; Blair, Angela S.; Welk, Margaret Ellen

    2010-03-01

    Chlorinated hydrocarbons represent the precursors for products ranging from PVC and refrigerants to pharmaceuticals. Natural or manmade disruptions that affect the availability of these products nationally have the potential to affect a wide range of markets, from healthcare to construction. Sandia National Laboratories (Sandia) has developed datasets and models that allow the analysis of the interdependencies within the chlorine chemical supply chain and consequences of disruptions. Combining data on plant locations, transportation, utilities, and the chemical supply chain itself, with modeling tools such as N-ABLE, a Sandia-developed agent based modeling system, allows Sandia to model this complex system dynamically. Sandia has used the N-ABLE technology to simulate a disruption to the chlorinated hydrocarbon supply chain caused by a hurricane striking the Louisiana coast. This paper presents results and conclusions from this analysis.

  5. Oxidative destruction of chlorinated hydrocarbons on Pt-containing fiber-glass catalysts.

    PubMed

    Paukshtis, E A; Simonova, L G; Zagoruiko, A N; Balzhinimaev, B S

    2010-03-01

    Novel catalysts comprising noble metals (Pt), supported on fiber-glass woven materials demonstrated efficient oxidation of different chlorinated hydrocarbons (chlorobenzene, dichloroethane, dichloropropane,butyl chloride) and industrial mixed chlorinated organic wastes into HCl, CO2 and H2O at moderate temperatures without formation of highly toxic by-products (dioxins, phosgene, polychlorinated hydrocarbons,elemental chlorine). The highest oxidation activity and selectivity was observed for the platinum catalysts produced from fiber-glass supports with increased acidity and with additional introduction of promoting elements (such as Co, Mn and Cu). Long-term tests (more than 100 h) have shown no deactivation of the said catalysts. In combination with competitive catalyst price (due to the extra-low content of Pt--below 0.05% mass) it opens the way for development of highly efficient and feasible technology for utilization and detoxication of various chloro-organic wastes.

  6. Determination of chlorinated polycyclic aromatic hydrocarbons in water by solid-phase extraction coupled with gas chromatography and mass spectrometry.

    PubMed

    Wang, Xianli; Kang, Haiyan; Wu, Junfeng

    2016-05-01

    Given the potential risks of chlorinated polycyclic aromatic hydrocarbons, the analysis of their presence in water is very urgent. We have developed a novel procedure for determining chlorinated polycyclic aromatic hydrocarbons in water based on solid-phase extraction coupled with gas chromatography and mass spectrometry. The extraction parameters of solid-phase extraction were optimized in detail. Under the optimal conditions, the proposed method showed wide linear ranges (1.0-1000 ng/L) with correlation coefficients ranging from 0.9952 to 0.9998. The limits of detection and the limits of quantification were in the range of 0.015-0.591 and 0.045-1.502 ng/L, respectively. Recoveries ranged from 82.5 to 102.6% with relative standard deviations below 9.2%. The obtained method was applied successfully to the determination of chlorinated polycyclic aromatic hydrocarbons in real water samples. Most of the chlorinated polycyclic aromatic hydrocarbons were detected and 1-monochloropyrene was predominant in the studied water samples. This is the first report of chlorinated polycyclic aromatic hydrocarbons in water samples in China. The toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in the studied tap water were 9.95 ng the toxic equivalency quotient m(-3) . 9,10-Dichloroanthracene and 1-monochloropyrene accounted for the majority of the total toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in tap water.

  7. Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

    PubMed

    Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

    2016-05-15

    This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided.

  8. Biodegradation of individual and multiple chlorinated aliphatic hydrocarbons by methane-oxidizing cultures.

    PubMed Central

    Chang, H L; Alvarez-Cohen, L

    1996-01-01

    The microbial degradation of chlorinated and nonchlorinated methanes, ethanes, and ethanes by a mixed methane-oxidizing culture grown under chemostat and batch conditions is evaluated and compared with that by two pure methanotrophic strains: CAC1 (isolated from the mixed culture) and Methylosinus trichosporium OB3b. With the exception of 1,1-dichloroethylene, the transformation capacity (Tc) for each chlorinated aliphatic hydrocarbon was generally found to be in inverse proportion to its chlorine content within each aliphatic group (i.e., methanes, ethanes, and ethenes), whereas similar trends were not observed for degradation rate constants. Tc trends were similar for all methane-oxidizing cultures tested. None of the cultures were able to degrade the fully chlorinated aliphatics such as perchloroethylene and carbon tetrachloride. Of the four cultures tested, the chemostat-grown mixed culture exhibited the highest Tc for trichloroethylene, cis-1,2-dichloroethylene, tetrachloroethane, 1,1,1-trichloroethane, and 1,2-dichloroethane, whereas the pure batch-grown OB3b culture exhibited the highest Tc for all other compounds tested. The product toxicity of chlorinated aliphatic hydrocarbons in a mixture containing multiple compounds was cumulative and predictable when using parameters measured from the degradation of individual compounds. The Tc for each chlorinated aliphatic hydrocarbon in a mixture (Tcmix) and the total Tc for the mixture (sigma Tcmix) are functions of the individual Tc, the initial substrate concentration (S0), and the first-order rate constant (k/Ks) of each compound in the mixture, indicating the importance of identifying the properties and compositions of all potentially degradable compounds in a contaminant mixture. PMID:8795228

  9. CROWTM PROCESS APPLICATION FOR SITES CONTAMINATED WITH LIGHT NON-AQUEOUS PHASE LIQUIDS AND CHLORINATED HYDROCARBONS

    SciTech Connect

    L.A. Johnson, Jr.

    2003-06-30

    Western Research Institute (WRI) has successfully applied the CROWTM (Contained Recovery of Oily Wastes) process at two former manufactured gas plants (MGPs), and a large wood treatment site. The three CROW process applications have all occurred at sites contaminated with coal tars or fuel oil and pentachlorophenol (PCP) mixtures, which are generally denser than water and are classified as dense non-aqueous phase liquids (DNAPLs). While these types of sites are abundant, there are also many sites contaminated with gasoline, diesel fuel, or fuel oil, which are lighter than water and lie on top of an aquifer. A third site type occurs where chlorinated hydrocarbons have contaminated the aquifer. Unlike the DNAPLs found at MGP and wood treatment sites, chlorinated hydrocarbons are approximately one and a half times more dense than water and have fairly low viscosities. These contaminants tend to accumulate very rapidly at the bottom of an aquifer. Trichloroethylene (TCE) and perchloroethylene, or tetrachloroethylene (PCE), are the major industrial chlorinated solvents that have been found contaminating soils and aquifers. The objective of this program was to demonstrate the effectiveness of applying the CROW process to sites contaminated with light non-aqueous phase liquids (LNAPLs) and chlorinated hydrocarbons. Individual objectives were to determine a range of operating conditions necessary to optimize LNAPL and chlorinated hydrocarbon recovery, to conduct numerical simulations to match the laboratory experiments and determine field-scale recoveries, and determine if chemical addition will increase the process efficiency for LNAPLs. The testing consisted of twelve TCE tests; eight tests with PCE, diesel, and wood treatment waste; and four tests with a fuel oil-diesel blend. Testing was conducted with both vertical and horizontal orientations and with ambient to 211 F (99 C) water or steam. Residual saturations for the horizontal tests ranged from 23.6% PV to 0.3% PV

  10. A theoretical study of the interference from chlorine in the oxidative coulometric method for trace determination of sulphur in hydrocarbons.

    PubMed

    Cedergren, A

    1975-12-01

    A theoretical investigation has been made of the interference from chlorine in the oxidative coulometric method for trace sulphur determinations. A computer program (SOLGAS), based on the free-energy minimization principle, has been used to predict equilibrium compositions of the products resulting from combustion of a hydrocarbon sample containing sulphur and chlorine. The theoretical possibilities of overcoming the interference from chlorine and maintaining a high recovery of sulphur are described.

  11. Mild Aliphatic and Benzylic Hydrocarbon C-H Bond Chlorination Using Trichloroisocyanuric Acid.

    PubMed

    Combe, Sascha H; Hosseini, Abolfazl; Parra, Alejandro; Schreiner, Peter R

    2017-03-03

    We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25-30 °C using N-hydroxyphthalimide (NHPI) as radical initiator and commercially available trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic amounts of CBr4 reduced the reaction times considerably due to the formation of chain-carrying ·CBr3 radicals. Benzylic C-H chlorination affords moderate to good yields for arenes carrying electron-withdrawing (50-85%) or weakly electron-donating groups (31-73%); cyclic aliphatic substrates provide low yields (24-38%). The products could be synthesized on a gram scale followed by simple purification via distillation. We report the first direct side-chain chlorination of 3-methylbenzoate affording methyl 3-(chloromethyl)benzoate, which is an important building block for the synthesis of vasodilator taprostene.

  12. Radiation induced dechlorination of some chlorinated hydrocarbons in aqueous suspensions of various solid particles

    NASA Astrophysics Data System (ADS)

    Múčka, V.; Buňata, M.; Čuba, V.; Silber, R.; Juha, L.

    2015-07-01

    Radiation induced dechlorination of trichloroethylene (TCE) and tetrachloroethylene (PCE) in aqueous solutions containing the active carbon (AC) or cupric oxide (CuO) as the modifiers was studied. The obtained results were compared to the previously studied dechlorination of polychlorinated biphenyls (PCBs). Both modifiers were found to decrease the efficiency of dechlorination. The AC modifier acts mainly via adsorption of the aliphatic (unlike the aromatic) hydrocarbons and the CuO oxide mainly inhibits the mineralization of the perchloroethylene. The results presented in this paper will be also helpful for the studies of the impact of chlorinated hydrocarbons on the membrane permeability of living cells.

  13. Evaluated Enthalpies of Formation of the Stable Closed Shell C1 and C2 Chlorinated Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Manion, Jeffrey A.

    2002-03-01

    Experimental data on the enthalpies of formation of chloromethanes, chloroethynes, chloroethenes, and chloroethanes are critically reviewed. Enthalpy of formation values for the C1 and C2 chlorinated hydrocarbons are highly cross-linked by various measured reaction equilibria and currently available sets of values are not internally self-consistent. It is shown that the early static bomb combustion calorimetry studies on highly chlorinated compounds generally give enthalpies of formation that are systematically more positive than later values derivable from rotating bomb combustion or equilibria studies. Those previously recommended values which were based mainly on the early static bomb work therefore need substantial revision. On the basis of more recent literature data obtained with rotating bomb combustion calorimetry, together with analyses of literature data on other reaction enthalpies and equilibria involving chlorinated hydrocarbons, an updated self-consistent set of ΔfHo[298.15 K] values for closed shell chlorinated C1 and C2 hydrocarbons (25 compounds) is recommended. Data on the enthalpies of vaporization are also reviewed and values of ΔvapH[298.15 K] and ΔvapHo[298.15 K] are recommended. The presently suggested enthalpies of formation for highly chlorinated alkenes and alkanes (particularly C2Cl4, C2HCl3, C2HCl5, and C2Cl6) are significantly (8-15 kJ mol-1) more negative than given by most previous evaluators. Values for the chloroethynes are 10-25 kJ mol-1 more positive than given in previous reviews and more limited changes are suggested for other compounds in the series.

  14. Using trees to remediate groundwaters contaminated with chlorinated hydrocarbons. 1997 annual progress report

    SciTech Connect

    Gordon, M.P.; Newman, L.A.; Strand, S.E.

    1997-01-01

    'Metabolism of Chlorinated Hydrocarbons Laboratory and field tests with poplar in tissue culture, bioreactors, and field sites have shown that, unlike bacteria, these plants are able to carry out complete degradation of fully chlorinated alkanes and alkenes to carbon dioxide and chloride. Carbon dioxide was produced as a product of the degradation of trichloroethylene (TCE), carbon tetrachloride (CT), and perchloroethylene (PCE) when axenic tissue cultures of poplar cells were exposed to radiolabelled compounds. The apparent degradation of PCE and CT, fully chlorinated hydrocarbons, in these aerobic plants is remarkable when contrasted to the lack of comparable aerobic degradation by bacteria. Oxidized metabolites, such as trichloroethanol, and di- and trichloroacetic acid, were detected in cell cultures exposed to TCE, suggesting the involvement of cytochrome P450s or other monooxygenase activities. Mass balance experiments with small poplar plants in laboratory reactors showed that significant TCE and CT was volatilized from the leaves, while a similar fraction of radiolabeled carbon from these chlorinated solvents was retained in the plant tissue.'

  15. Membrane-Extraction Ion Mobility Spectrometry for In-Situ Detection of Chlorinated Hydrocarbons in Water

    SciTech Connect

    Du, Yongzhai; Zhang, Wei; Whitten, William B; Li, Haiyang; Watson, David B; Xu, Jun

    2010-01-01

    Membrane-extraction ion mobility spectrometry (ME-IMS) has been developed for in-situ sampling and analysis of trace chlorinated hydrocarbons in water in a single procedure. The sampling is configured so that aqueous contaminants permeate through a spiral hollow polydimethylsiloxane (PDMS) membrane and are carried away by a vapor flow through the membrane tube. The extracted analyte flows into an atmospheric pressure chemical ionization (APCI) chamber and is analyzed in a home-made IMS analyzer. PDMS membrane is found to effectively extract chlorinated hydrocarbon solvents from liquid phase to vapor. The specialized IMS analyzer has been found to have resolutions of R=33 and 41, respectively, for negative- and positive-modes and is capable of detecting aqueous tetrachloroethylene (PCE) and trichloroethylene (TCE) as low as 80 g/L and 74 g/L in negative ion mode, respectively. The time-dependent characteristics of sampling and detection of TCE are both experimentally and theoretically studied for various concentrations, membrane lengths, and flow rates. These characteristics demonstrate that membrane-extraction IMS is feasible for the continuous monitoring of chlorinated hydrocarbons in water.

  16. Natural attenuation of chlorinated hydrocarbons in a freshwater wetland

    USGS Publications Warehouse

    Lora, Michelle M.; Olsen, Lisa D.; Smith, Barrett L.; Alleman, Bruce C.; Leeson, Andrea

    1997-01-01

    Natural attenuation of chlorinated volatile organic compounds (VOC's) occurs as ground water discharges from a sand aquifer to a freshwater wetland at Aberdeen Proving Ground, Md. Field and laboratory results indicate that biotransformation in the anaerobic wetland sediments is an important attenuation process. Relatively high concentrations of the parent compounds trichloroethylene (TCE) and 1,1,2,2-tetrachloroethane (PCA) and low or undetectable concentrations of daughter products were measured in the aquifer. In contrast, relatively high concentrations of the daughter products cis- and trans-1,2-dichloroethylene (12DCE); vinyl chloride (VC); 1,1,2-trichloroethane (112TCA); and 1,2-dichloroethane (12DCA) were measured in ground water in the wetland sediments, although total VOC concentrations decreased upward from about 1 mu mol/L (micromoles per liter) at the base of the wetland sediments to less than 0.2 near the surface. Microcosm experiments showed that 12DCE and VC are produced from anaerobic degradation of both TCE and PCA; PCA degradation also produced 112TCA and 12DCA.

  17. Determination of the Possible Source of Chlorinated Hydrocarbons Detected By SAM during MSL Mission

    NASA Astrophysics Data System (ADS)

    Buch, A.; Belmahdi, I.; Szopa, C.; Freissinet, C.; Glavin, D. P.; Francois, P.; Coll, P. J.; Miller, K.; Eigenbrode, J. L.; Stern, J. C.; Navarro-Gonzalez, R.; McAdam, A.; Teinturier, S.; Bonnet, J. Y.; Summons, R. E.; Millan, M.; Dequaire, T.; Cabane, M.; Mahaffy, P. R.

    2014-12-01

    The SAM GC-MS instrument on the Curiosity rover allows to analyze volatile compounds from the atmosphere or volatile compounds from the Martian regolith and refractory compounds in the regolith after sample treatment using wet chemistry. One portion of the wet chemistry experiment is composed of MTBSTFA (N-methyl-N-tert-butyldimethylsilyltrifluoroacetamide) / DMF (dimethylformamide). Abundant chlorinated hydrocarbons have been detected with SAM when analyzing samples collected in several sites explored by Curiosity rover. Some of these chlorohydrocarbons are produced during pyrolysis by the reaction of Martian oxychlorine compounds in the samples with terrestrial carbon from a derivatization agent (MTBSTFA) used in SAM (1, 2). Chlorobenzene cannot be formed by the direct reaction of MTBSTFA and DMF when heated in the presence of fused silica and perchlorates under SAM-like conditions (1)) therefore two other reaction pathways for chlorobenzene were proposed : (1) reactions between the volatile thermal degradation products of perchlorates (e.g. O2, Cl2 and HCl) and Tenax® and (2) the interaction of perchlorates with organic material from the martian regolith such as benzenecarboxylates (3, 4). This study investigates several propositions for chlorinated hydrocarbon formation by looking for: (1) all products coming from the interaction of Tenax® (which is part of the SAM hydrocarbon trap) and perchlorates, (2) also between some soil sample and perchlorates in the presence or absence of MTBSTFA and (c) sources of chlorinated hydrocarbon precursors. References: 1. D. P. Glavin et al.(2013) JGR 118, 1955-1973. 2. L. a Leshin et al. (2013) Science 341, 1238937. 3. C. Freissinet et al. (2014) LPSC XXXXV Abstract 2796. 4. D. Glavin et al. (2014) LPSC XXXV Abstract #1157.

  18. Polychlorinated biphenyls (PCB), chlorinated pesticides, and polycyclic aromatic hydrocarbons (PAHs) in environmental standard reference materials

    SciTech Connect

    Poster, D.L.; Schantz, M.M.; Parris, R.M.; Benner, B.A. Jr.; Wise, S.A.

    1995-12-31

    Standard reference materials (SRMs) are certified reference materials issued by the National Institute of Standards and Technology (NIST). Natural matrix environmental sample SRMs have been developed the Analytical Chemistry Division to assist in validating measurements for organic contaminants in the environment. Many of these are well characterized for contaminants such as polychlorinated biphenyls (PCBs), chlorinated pesticides, and polycyclic aromatic hydrocarbons (PAHs). SRM 1649, Organics in Urban Dust, is currently available with certified concentrations for 5 PAHs but because of the widespread use of this material in air pollution monitoring programs and to expand the usefulness of this material, the authors are further characterizing the material for a larger number of PAHs as well as PCBs and chlorinated pesticides. They will also soon issue a diesel particulate extract (SRM 1975) that is well characterized for PAHS, including many nitrogen substituted compounds. In addition to natural matrix materials, solutions useful for calibrating chromatographic detector response factors and retention times, and spiking sample blanks for determination of analyte recoveries, are also available. Solution SRMs currently available contain PCS congeners, chlorinated pesticides, and PAHs. New solution SRMs in preparation will contain additional chlorinated pesticides, PCB congeners (e.g., non-ortho substituted chlorobiphenyls), and perdeuterated PAHs. Recent SRM work will be presented with particular attention on the methods used for determining organic contaminant concentrations in the urban dust material and in the diesel particulate extract.

  19. A modified oxidative microcoulometric method for determination of sulphur in hydrocarbons containing large amounts of chlorine.

    PubMed

    Cedergren, A

    1977-01-01

    The oxidative coulometric method for trace sulphur determinations has been modified and a procedure is described which includes the elimination of the interferences caused by chlorine whilst retaining a high recovery of sulphur. The liquid hydrocarbon sample is combusted in an excess of oxygen at 1000 K followed by dilution with a proper flow of carbon monoxide at 1300 K. In this way the partial pressure of oxygen is kept small and the interfering chlorine compounds are effectively converted into hydrogen chloride which does not interfere with the coulometric titration. A recovery of sulphur of 96 +/- 1% was found for thiophene in mixtures of chlorobenzene (0-10%) and cyclohexane, thus indicating the absence of significant interference.

  20. Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

    NASA Technical Reports Server (NTRS)

    Singh, H. B.; Kasting, J. F.

    1988-01-01

    The role of chlorine atoms in the oxidation of methane and nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere was investigated using a one-dimensional photochemical model that incorporated the chemistry of CH4, NMHCs, NO(x), O(x), and HO(x), as well as organic and inorganic halogens in the troposphere and lower stratosphere. The model predicted that chlorine atoms are present in the marine troposphere at the concentrations of about 1000/cu cm, mostly as a product of the reaction between OH and HCl released from sea spray. The results indicate that Cl atoms cause 20 to 40 percent of NMHC oxidation in the troposphere and 40 to 90 percent in the lower stratosphere. At 15 km, the NMHC-Cl reactions account for nearly 80 percent of the PAN produced. Where available, experimental data confirmed the model predictions.

  1. Effect of reduced iron on the degradation of chlorinated hydrocarbons in contaminated soil and ground water: A review of publications

    NASA Astrophysics Data System (ADS)

    Vodyanitskii, Yu. N.

    2014-02-01

    Chlorinated hydrocarbons are among the most hazardous organic pollutants. The traditional remediation technologies, i.e., pumping of contaminated soil- and groundwater and its purification appear to be costly and not very efficient as applied to these pollutants. In the last years, a cheaper method of destroying chlorine-replaced hydrocarbons has been used based on the construction of an artificial permeable barrier, where the process develops with the participation of in situ bacteria activated by zerovalent iron. The forced significant decrease in the redox potential (Eh) down to -750 mV provides the concentration of electrons necessary for the reduction of chlorinated hydrocarbons. A rise in the pH drastically accelerates the dechlorination process. In addition to chlorine-organic compounds, ground water is often contaminated with heavy metals. The influence of the latter on the effect of zerovalent iron may be different: both accelerating its degradation (Cu) and inhibiting it (Cr). Most of the products of zerovalent iron corrosion, i.e., green rust, magnetite, ferrihydrite, hematite, and goethite, weaken the efficiency of the Fe0 barrier by mitigating the dechlorination and complicating the water filtration. However, pyrrhotite FeS, on the contrary, accelerates the dechlorination of chlorine hydrocarbons.

  2. Biotransformation of monoaromatic and chlorinated hydrocarbons at an aviation-gasoline spill site

    SciTech Connect

    Wilson, B.H.; Wilson, J.T.; Kampbell, D.H.; Bledsoe, B.E.; Armstrong, J.M.

    1991-01-01

    Loss of petroleum products from underground storage tanks, pipelines, and accidental spills are major sources of contamination of unsaturated soils, aquifer solids, and a shallow water table aquifer under the U.S. Coast Guard Air Station at Traverse City, MI, has acclimated to the aerobic and anaerobic transformation of monoaromatic hydrocarbons (BTX) released from an aviation gasoline spill. The aquifer also exhibits reductive dechlorination of a chlorinated solvent spill adjacent to the aviation gasoline spill. The groundwater is buffered near neutrality. The aviation gasoline plume is methanogenic and the aquifer contains enough iron minerals to support significant iron solubilization. Field evidence of both aerobic and anaerobic biotransformation of monoaromatics was confirmed by laboratory studies of aquifer material obtained from the site. In the laboratory studies, the removal of the monoaromatics in the anaerobic material was rapid and compared favorable with removal in the aerobic material. The kinetics of anaerobic removal of monoaromatics in the laboratory were similar to the kinetics at field scale in the aquifer. Biotransformation of the chlorinated solvents was not observed until late in the study, when daughter products from reductive dechlorination of the chlorinated solvents were identified by GC/MS.

  3. Determination of chlorinated hydrocarbons in water using highly sensitive mid-infrared sensor technology.

    PubMed

    Lu, Rui; Mizaikoff, Boris; Li, Wen-Wei; Qian, Chen; Katzir, Abraham; Raichlin, Yosef; Sheng, Guo-Ping; Yu, Han-Qing

    2013-01-01

    Chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons (CHCs) are toxic and carcinogenic contaminants commonly found in environmental samples, and efficient online detection of these contaminants is still challenging at the present stage. Here, we report an advanced Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) sensor for in-situ and simultaneous detection of multiple CHCs, including monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, trichloroethylene, perchloroethylene, and chloroform. The polycrystalline silver halide sensor fiber had a unique integrated planar-cylindric geometry, and was coated with an ethylene/propylene copolymer membrane to act as a solid phase extractor, which greatly amplified the analytical signal and contributed to a higher detection sensitivity compared to the previously reported sensors. This system exhibited a high detection sensitivity towards the CHCs mixture at a wide concentration range of 5~700 ppb. The FTIR-ATR sensor described in this study has a high potential to be utilized as a trace-sensitive on-line device for water contamination monitoring.

  4. Determination of Chlorinated Hydrocarbons in Water Using Highly Sensitive Mid-Infrared Sensor Technology

    PubMed Central

    Lu, Rui; Mizaikoff, Boris; Li, Wen-Wei; Qian, Chen; Katzir, Abraham; Raichlin, Yosef; Sheng, Guo-Ping; Yu, Han-Qing

    2013-01-01

    Chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons (CHCs) are toxic and carcinogenic contaminants commonly found in environmental samples, and efficient online detection of these contaminants is still challenging at the present stage. Here, we report an advanced Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) sensor for in-situ and simultaneous detection of multiple CHCs, including monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, trichloroethylene, perchloroethylene, and chloroform. The polycrystalline silver halide sensor fiber had a unique integrated planar-cylindric geometry, and was coated with an ethylene/propylene copolymer membrane to act as a solid phase extractor, which greatly amplified the analytical signal and contributed to a higher detection sensitivity compared to the previously reported sensors. This system exhibited a high detection sensitivity towards the CHCs mixture at a wide concentration range of 5~700 ppb. The FTIR-ATR sensor described in this study has a high potential to be utilized as a trace-sensitive on-line device for water contamination monitoring. PMID:23982222

  5. Chlorinated and polycyclic aromatic hydrocarbons in riverine and estuarine sediments from Pearl River Delta, China.

    PubMed

    Mai, Bi-Xian; Fu, Jia-Mo; Sheng, Guo-Ying; Kang, Yue-Hui; Lin, Zheng; Zhang, Gan; Min, Yu-Shuan; Zeng, Eddy Y

    2002-01-01

    Spatial distribution of chlorinated hydrocarbons [chlorinated pesticides (CPs) and polychlorinated biphenyls (PCBs)] and polycyclic aromatic hydrocarbons (PAHs) was measured in riverine and estuarine sediment samples from Pearl River Delta, China, collected in 1997. Concentrations of CPs of the riverine sediment samples range from 12 to 158 ng/g, dry weight, while those of PCBs range from 11 to 486 ng/g. The CPs concentrations of the estuarine sediment samples are in the range 6-1658 ng/g, while concentrations of PCBs are in the range 10-339 ng/g. Total PAH concentration ranges from 1168 to 21,329 ng/g in the riverine sediment samples, whereas the PAH concentration ranges from 323 to 14,812 ng/g in the sediment samples of the Estuary. Sediment samples of the Zhujiang River and Macao harbor around the Estuary show the highest concentrations of CPs, PCBs, and PAHs. Possible factors affecting the distribution patterns are also discussed based on the usage history of the chemicals, hydrologic condition, and land erosion due to urbanization processes. The composition of PAHs is investigated and used to assess petrogenic, combustion and naturally derived PAHs of the sediment samples of the Pearl River Delta. In addition, the concentrations of a number of organic compounds of the Pearl River Delta samples indicate that sediments of the Zhujiang river and Macao harbor are most likely to pose biological impairment.

  6. Determination of Chlorinated Hydrocarbons in Water Using Highly Sensitive Mid-Infrared Sensor Technology

    NASA Astrophysics Data System (ADS)

    Lu, Rui; Mizaikoff, Boris; Li, Wen-Wei; Qian, Chen; Katzir, Abraham; Raichlin, Yosef; Sheng, Guo-Ping; Yu, Han-Qing

    2013-08-01

    Chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons (CHCs) are toxic and carcinogenic contaminants commonly found in environmental samples, and efficient online detection of these contaminants is still challenging at the present stage. Here, we report an advanced Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) sensor for in-situ and simultaneous detection of multiple CHCs, including monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, trichloroethylene, perchloroethylene, and chloroform. The polycrystalline silver halide sensor fiber had a unique integrated planar-cylindric geometry, and was coated with an ethylene/propylene copolymer membrane to act as a solid phase extractor, which greatly amplified the analytical signal and contributed to a higher detection sensitivity compared to the previously reported sensors. This system exhibited a high detection sensitivity towards the CHCs mixture at a wide concentration range of 5~700 ppb. The FTIR-ATR sensor described in this study has a high potential to be utilized as a trace-sensitive on-line device for water contamination monitoring.

  7. Transport Modeling of Membrane Extraction of Chlorinated Hydrocarbon from Water for Ion Mobility Spectrometry

    SciTech Connect

    Zhang, Wei; Du, Yongzhai; Feng, Zhili; Xu, Jun

    2010-01-01

    Membrane-extraction Ion Mobility Spectrometry (ME-IMS) is a feasible technique for the continuous monitoring of chlorinated hydrocarbons in water. This work studies theoretically the time-dependent characteristics of sampling and detection of trichloroethylene (TCE). The sampling is configured so that aqueous contaminants permeate through a hollow polydimethylsiloxane (PDMS) membrane and are carried away by a transport gas flowing through the membrane tube into IMS analyzer. The theoretical study is based on a two-dimensional transient fluid flow and mass transport model. The model describes the TCE mixing in the water, permeation through the membrane layer, and convective diffusion in the air flow inside membrane tube. The effect of various transport gas flow rates on temporal profiles of IMS signal intensity is investigated. The results show that fast time response and high transport yield can be achieved for ME-IMS by controlling the flow rate in the extraction membrane tube. These modeled time-response profiles are important for determining duty cycles of field-deployable sensors for monitoring chlorinated hydrocarbons in water.

  8. Chemical Fate of Contaminants in the Environment: Chlorinated Hydrocarbons in the Groundwater

    SciTech Connect

    Truhlar, Donald G.; Cramer, Christopher; Gao, Jiali; Garrett, Bruce C.; Dupuis, Michel; Straatsma, TP; Morokuma, Keiji; Dunning, Thomas H.; Borisov, Yurii A.; Arcia, Edgar E.; Thompson, Jacob S.

    2006-09-21

    Chlorinated hydrocarbons (CHCs) are the most common contaminant found at hazardous waste sites and are the most prevalent contaminants on U.S. Department of Energy (DOE) weapons production sites. Many of the CHCs are either known or suspected carcinogens and thus pose health risks to the public and/or site workers. Unlike simple hydrocarbons, CHCs are resistant to biodegradation, but can degrade by abiotic processes such as hydrolysis, nucleophilic substitution, and dehydrochlorination. Unfortunately, few studies of the reactions of chlorinated hydrocarbons have been reported in literature, and disagreement still exists about the mechanisms and rates of many of the key reactions. In this work, we modeled the reactions involved in the degradation of CHCs in the groundwater. The goals of the research proposed are: • development of a computational approach that will allow reaction pathways and rate constants to be accurately calculated • development of more approximate approaches, evaluated against the more accurate approach, which will lay the groundwork for exploratory studies of more complex CHCs • application of these approaches to study the degradation pathways of CHCs in aqueous liquids • application of the more approximate approaches to study the mechanism of forming complex CHC polychlorinated benzene compounds and dioxins. We examined elementary reactions involved in the aqueous-phase chemistry of chlorinated methanes and ethylenes in an attempt to obtain a detailed understanding of the abiotic processes involved in the degradation of this important class of contaminants. We began by studying the reactions of CHnCl(4-n) and C2HnCl(4-n) with OH¯, as these are thought to be the dominant processes involved in the degradation of these chlorinated species. We used state-of-the-art theoretical techniques to model the elementary reactions of CHCs important in the groundwater. We employed high-accuracy electronic structure methods (e.g., perturbation theory

  9. Analysis of dechlorination kinetics of chlorinated aliphatic hydrocarbons by Fe(II) in cement slurries.

    PubMed

    Jung, Bahngmi; Batchelor, Bill

    2008-03-21

    Degradative solidification/stabilization with ferrous iron (DS/S-Fe(II)) has been found to be effective in degrading a number of chlorinated aliphatic hydrocarbons including 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), tetrachloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), carbon tetrachloride (CT) and chloroform (CF). Previous studies have characterized degradation kinetics in DS/S-Fe(II) systems as affected by Fe(II) dose, pH and initial target organic concentration. The goal of this study is to investigate the importance of various chemical properties on degradation kinetics of DS/S-Fe(II). This was accomplished by first measuring rate constants for degradation of 1,1,1-TCA, 1,1,2,2-TeCA and 1,2-dichloroethane (1,2-DCA) in individual batch experiments. Rate constants developed in these experiments and those obtained from the literature were related to thermodynamic parameters including one-electron reduction potential, two-electron reduction potential, bond dissociation energy and lowest unoccupied molecular orbital energies. Degradation kinetics by Fe(II) in cement slurries were generally represented by a pseudo-first-order rate law. The results showed that the rate constants for chlorinated methanes (e.g. CT, CF) and chlorinated ethanes (e.g. 1,1,1-TCA) were higher than those for chlorinated ethylenes (e.g. PCE, TCE, 1,1-DCE and VC) under similar experimental conditions. The log of the pseudo-first-order rate constant (k) was found to correlate better with lowest unoccupied molecular orbital energies (E(LUMO)) (R2=0.874) than with other thermodynamic parameter descriptors.

  10. Differential action of chlorinated polycyclic aromatic hydrocarbons on aryl hydrocarbon receptor-mediated signaling in breast cancer cells.

    PubMed

    Ohura, Takeshi; Morita, Maki; Kuruto-Niwa, Ryoko; Amagai, Takashi; Sakakibara, Hiroyuki; Shimoi, Kayoko

    2010-04-01

    Chlorinated polycyclic aromatic hydrocarbons (ClPAHs), which are a series of halogenated aromatic hydrocarbons, have been found in the environment. The primary step in their metabolic activation seems to be associated with aryl hydrocarbon receptor (AhR)-mediated induction of the cytochrome P450 (CYP) 1 family, although the evidence remains unclear. In this study, we first investigated the effects of five ClPAHs with three to five rings and the corresponding parent PAHs on the expression of CYP1A1 and 1B1 in human breast cancer MCF-7 cells. For the targeted ClPAHs, Western blot analysis of ClPAH-induced CYP1A1 and 1B1 showed an enhancement in activities in comparison with induction by the corresponding parent PAHs, and the effects of chlorination were especially prominent in phenanthrene. In a further study, using 6-chlorobenzo[a]pyrene (6-ClBaP), cotreatment with 17beta-estradiol showed an increase in the expression of CYP1B1 mRNA but not CYP1A1 mRNA. Since the AhR ligand has been reported to induce formation of an AhR-estrogen receptor (ER) complex, which stimulates transcription of ER target genes, the effects of ClPAHs in MCF-7 cells transfected with estrogen response elements-regulated green fluorescent protein (GFP) reporter genes were also investigated in this study. 6-ClBaP induced a dose-dependent increase in GFP expression related to ER signaling through AhR activation in the cells, but 3,9,10-trichlorophenanthrene (3,9,10-Cl(3)ClPhe) did not, despite its ability to activate AhR. Furthermore, we investigated the effect of ClPAHs on the expression of the endogenous ER-responsive genes, cathepsin D, in MCF-7 cells. 6-ClBaP stimulated expression of the ER-responsive genes but 3,9,10-Cl(3)ClPhe did not, as in the GFP expression system. These results suggest that estrogenic action mediated ER signaling through AhR activation does not necessarily occur for every ligand that can activate AhR.

  11. Determination of the Sources of Chlorinated Hydrocarbons Detected During MSL Missions

    NASA Astrophysics Data System (ADS)

    Buch, Arnaud; Belmahdi, Imène; Szopa, Cyril; Freissinet, Caroline; Glavin, Danny P.; Miller, Kirsten; Summons, Roger; Francois, Pascaline; Coll, Patrice; Eigenbrode, Jennifer; Teinturier, Samuel; Navarro-Gonzalez, Rafael; Stern, Jennifer; McAdam, Amy; Dequaire, Tristan; Millan, Maeva; Bonnet, Jean Yves; Coscia, David; Cabane, Michel; Mahaffy, Paul

    2015-04-01

    Sample Analysis at Mars (SAM) is one of the instruments of the MSL mission. Three analytical instruments composed SAM: the Tunable Laser Spectrometer (TLS), the Gas Chromatography (GC) and the Mass Spectrometer (QMS). It includes a sample preparation and gas processing system implemented with a pyrolysis system, wet chemistry (MTBSTFA and TMAH) and the hydrocarbon trap (silica beads, Tenax® TA and Carbosieve G), employed to concentrate volatiles released from the sample prior to GC-MS analysis [1]. This study investigates several propositions for chlorinated hydrocarbon formation, detected by SAM. Here we report on the detection of chlorohydrocarbon compounds and their potential origin. To date, SAM has detected a range of diverse chlorinated hydrocarbons from GCMS analysis of samples collected at the several locations explored by Curiosity (Rocknest, John Klein, Cumberland and Confidence Hill). Some of these chlorohydrocarbons are produced during pyrolysis by the reaction of Martian oxychlorine compounds in the samples with terrestrial carbon from a derivatization agent (MTBSTFA) present in SAM [2, 3]. Chlorobenzene cannot be formed by the reaction of MTBSTFA and perchlorates (2) and two other reaction pathways were therefore proposed : (i) reactions between the volatile thermal degradation products of perchlorates (e.g. O2, Cl2 and HCl) and Tenax® and (ii) the interaction of perchlorates (T > 200 °C) with OM from Martian soil such as benzenecarboxylates [4, 5]. References: 1. P. R. Mahaffy et al. (2012) Space Sci. Rev. 170, 401-478. 2. D. P. Glavin et al.(2013) JGR 118, 1955-1973. 3. L. a Leshin et al. (2013) Science 341, 1238937. 4. C. Freissinet et al. (2014) LPSC XXXXV Abstract 2796. 5. H. Steininger et al. (2012) Planet. Space Sci. 71, 9-17.

  12. The Influence of Silica on the Reactivity of Iron Towards Chlorinated Hydrocarbons

    NASA Astrophysics Data System (ADS)

    Kohn, T.; Himmelheber, D. W.; Vikesland, P. J.; Fairbrother, D.; Roberts, A.

    2001-12-01

    Previous work has illustrated that dissolved silica present in groundwater can adsorb onto the iron media of a permeable reactive barrier. To date, little is known about the effect of adsorbed silica on the reactivity of iron towards chlorinated contaminants. Silica is a known corrosion inhibitor, and therefore silica sorption may affect the reactivity of cast iron towards redox-active species such as chlorinated ethanes. To determine the effect of silica sorption on iron reactivity towards chlorinated hydrocarbons, it is necessary to examine contaminant degradation rates under conditions where silica adsorption has been carefully accounted for. In this study we couple measurements of chlorinated hydrocarbon (CHC) (either trichloroethane (TCA) or trichloroethene) degradation rates with measurements of silica surface content. Both batch and columns studies were conducted as part of this effort. Batch studies were performed using electrolytic iron powder or iron coupons (1 cm2) in solutions containing sodium metasilicate and TCA. To evaluate the potential long-term effect of silica sorption, columns packed with untreated sieved Master Builder's iron were fed with simulated groundwater containing low levels of sodium metasilicate and chlorinated hydrocarbons (CHCs). Batch studies showed that at pH 8.5 the rate of TCA degradation decreased significantly with increasing silica concentration. Silica concentrations of 50 mg/L or more led to a two-fold decrease in the reaction rate, and a shift in the distribution of the reaction products towards less chlorinated compounds was observed. This shift could also be discerned at pH 7.5, even though the overall reaction rates were unaffected by the presence of silica. We ascribe the loss of reactivity at pH 8.5 but not at pH 7.5 to the fact that silica adsorbs onto iron more readily at higher pH. A decrease in iron reactivity towards CHCs was also observed in column experiments. Addition of silica to the feed resulted in

  13. Chlorinated hydrocarbons in the seawater and surface sediments of Blanca Bay, Argentina

    NASA Astrophysics Data System (ADS)

    Sericano, JoséLuis; Pucci, Adan E.

    1984-07-01

    In order to characterize our study area and to provide reference values to be used in the future to measure the changes produced by an increase in contamination, the concentrations of chlorinated hydrocarbons have been investigated in fifty-one samples of seawater, taken at four different depths: air-sea interface, surface, one metre and bottom waters, and in twenty-three samples of surface sediments from Blanca Bay, Argentina. Of eleven organochlorine compounds we were looking for (α BHC, lindane, heptachlor, δ BHC. aldrin, heptachlor epoxide, dieldrin, o-p'DDD, p-p'DDD, o-p'DDT and p-p'DDT), seven could be detected in seawater and three in surface sediments with the following mean concentrations: α-BHC=48·2 ng l -1; lindane=54·2 ng l -1; heptachlor=45·0 ng l -1; δ BHC=12·5 ng l -1; aldrin=61·8 ng l -1 and ΣDDT=67·0 ng l -1; and δ BHC=3·2 ng g -1; lindane=4·2 ng g -1 and heptachlor=1·0 ng g -1 for seawater, regarding the surface waters, and sediment samples, respectively. Concentration factors among the different water layers were also studied to see if there was any correlation between chlorinated hydrocarbon contents and the water depths from which the samples were taken. As a mean value, the air-sea interface water contains 18 times more of these compounds than that of the water near the bottom. A comparison of the values corresponding to seawater and surface sediments from our study area with those levels measured in samples from other geographic locations is also presented. With the purpose to detect a relationship between chlorinated hydrocarbon concentrations and the contents of particulate matter (PM) on the one hand, and particulate organic material (POM) on the other hand, four groups of samples containing different amounts of PM and POM, respectively were formed. From a comparison of the results obtained, lindane, heptachlor and δ BHC showed a tendency to lower concentrations in those samples containing little PM whereas α BHC and

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

    NASA Technical Reports Server (NTRS)

    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.; hide

    2013-01-01

    A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the

  15. Evidence for perchlorates and the origin of chlorinated hydrocarbons detected by SAM at the Rocknest aeolian deposit in Gale Crater

    NASA Astrophysics Data System (ADS)

    Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas; Atreya, Sushil K.; Brinckerhoff, William B.; Cabane, Michel; Coll, Patrice; Conrad, Pamela G.; Coscia, David; Dworkin, Jason P.; Franz, Heather B.; Grotzinger, John P.; Leshin, Laurie A.; Martin, Mildred G.; McKay, Christopher; Ming, Douglas W.; Navarro-González, Rafael; Pavlov, Alexander; Steele, Andrew; Summons, Roger E.; Szopa, Cyril; Teinturier, Samuel; Mahaffy, Paul R.

    2013-10-01

    A single scoop of the Rocknest aeolian deposit was sieved (< 150 µm), and four separate sample portions, each with a mass of ~50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of ~0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.

  16. Chlorinated Hydrocarbon Insecticides: Recent Animal Data of Potential Significance for Man

    PubMed Central

    Ecobichon, D. J.

    1970-01-01

    The environmental persistence of chlorinated hydrocarbon insecticides is posing a serious threat to the survival of several wildlife species. Sublethal effects, completely unrelated to the insecticidal properties of these chemicals, have contributed markedly to impaired reproduction in many species and to toxicity in neonatal animals. Considering the insecticide levels found in man, are these chemicals potentially dangerous to human infants and adults? Of special concern are the potential long-term, subtle effects of low concentrations of insecticides to which many persons are ordinarily exposed. These agents affect both the peripheral and central nervous systems. They markedly elevate hepatic enzyme levels, enhancing the biotransformation of many pharmacological agents as well as interfering with endogenous steroid biosynthesis and degradation. The DDT-like insecticides are potent estrogenic agents and some have shown teratogenic and carcinogenic activity. These aspects are discussed in relation to present levels found in humans and to possible adverse effects on perinatal and adult individuals. PMID:4096932

  17. Chlorinated Hydrocarbon Degradation in Plants: Mechanisms and Enhancement of Phytoremediation of Groundwater Contamination

    SciTech Connect

    Strand, Stuart E.

    2002-06-01

    Several varieties of transgenic poplar containing cytochrome P-450 2E1 have been constructed and are undergoing tests. Strategies for improving public acceptance and safety of transgenic poplar for chlorinated hydrocarbon phytoremediation are being developed. We have discovered a unique rhizobium species that lives within the stems of poplar and we are investigating whether this bacterium contributes nitrogen fixed from the air to the plant and whether this endophyte could be used to introduce genes into poplar. Studies of the production of chloride ion from TCE have shown that our present P-450 constructs did not produce chloride more rapidly than wild type plants. Follow-up studies will determine if there are other rate limiting downstream steps in TCE metabolism in plants. Studies of the metabolism of carbon tetrachloride in poplar cells have provided evidence that the native plant metabolism is due to the activity of oxidative enzymes similar to the mammalian cytochrome P-450 2E1.

  18. Role of plant biomass in the global environmental partitioning of chlorinated hydrocarbons

    SciTech Connect

    Calamari, D.; Morosini, M.; Vighi, M. ); Bacci, E.; Focardi, S.; Gaggi, C. )

    1991-08-01

    Plant biomass plays a significant role in the global environmental partitioning phenomena and plants are good indicators of tropospheric contamination levels by chlorinated hydrocarbons. In the present research 300 samples of plants were collected in 265 areas distributed worldwide and analyzed for HCB (hexachlorobenzene), {alpha}-HCH (hexachlorocyclohexane), {gamma}-HCH, p,p{prime}-DDT,o,p{prime}-DDT, and p,p{prime}-DDE (degradation product of DDT). Global HCB distribution is strongly dependent on the temperature, the HCB being present mainly in samples from cold areas. The sum of DDTs show higher concentrations in samples from topical areas, while the sum of HCHs is higher in the plants from the Northern Hemisphere. These results are discussed, taking into account the role of physicochemical properties in determining the global distribution as well as the air age of the contamination.

  19. Petroleum and chlorinated hydrocarbons in water from Lake Manzala and associated canals

    SciTech Connect

    Badawy, M.I.; Wahaab, R.A.; Abou Waly, H.F.

    1995-08-01

    Lake Manzala is located at the north eastern edge of Nile Delta in Egypt. It is separated from the Mediterranean sea by a sandy beach ridge. However, the lake is in connection with the sea through three opening nearby Port Said. The area of the lake is about 769 Km{sup 2} and relatively shallow with an average depth of 1.3 m. The lake is of high economic value as a natural resource, for fishery, reacreation and for migratory birds. The lake is highly polluted as it receives wastewaters discharged by several canal. The present investigation aimed to assess the residue levels of petroleum hydrocarbons, chlorinated insecticides and polychlorinated biphenyls in the lake water as well as in Hadous canal, Fariskur canal and Bahr-El-Baqar canal. 9 refs., 1 fig., 3 tabs.

  20. Using trees to remediate groundwaters contaminated with chlorinated hydrocarbons. 1998 annual progress report

    SciTech Connect

    Strand, S.E.; Gordon, M.P.

    1998-06-01

    'Industrial practices in the past have resulted in contamination of groundwater with chlorinated hydrocarbons (CHCs) at many DOE sites, such as Hanford and Savannah River. Such contamination is a major problem because existing groundwater remediation technologies are expensive and difficult. An inexpensive method for groundwater remediation is greatly needed. Trees could be used to remediate CHC polluted groundwater at minimal cost (phytoremediation). Before phytoremediation can be extensively applied, the authors must determine the range of compounds that are attacked, the effects of metabolic products on the plants and the environment, and the effect of transpiration and concentration of CHC on uptake and metabolism. They will test the ability of hybrid poplar to take up and transform the chlorinated methanes, ethanes and ethylenes. The rate of uptake and transformation by poplar of TCE as a function of concentration in the soil, transpiration rate and illumination level will be determined. Methods will be developed to permit rapid testing of plants from contaminated sites for species able to oxidize and sequester chlorinated compounds. They will identify the nature of the bound residues of TCE metabolism in poplar. They will identify the mechanisms involved in CHC oxidation in poplar and use genetic manipulations to enhance that activity. They will introduce the genes for mammalian cytochrome P-450-IIE1, known to oxidize light CHCs such as TCE to attempt to increase the CHC metabolism capacity of poplar. The results of this research will place phytoremediation of CHCs on a firm scientific footing, allowing a rational assessment of its application to groundwater contamination. This report summarizes the results of the first 1.5 years of work on a three-year project.'

  1. Chlorinated hydrocarbons and PAH decomposition in dry and humid air by electron beam irradiation

    NASA Astrophysics Data System (ADS)

    Nichipor, H.; Dashouk, E.; Yacko, S.; Chmielewski, A. G.; Zimek, Z.; Sun, Y.

    2002-11-01

    The mechanism and kinetics of CCl 4; CH 2Cl 2; C 2HCl 3; C 2H 2Cl 2; C 2H 5Cl and polycyclic aromatic hydrocarbons (PAH), e.g. naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and benzo(a)pyrene, decomposition have been investigated in dry and humid air under the influence of electron beam irradiation, by computer simulation based on established theoretical models. The experimental data published in the literature and the results of calculations confirmed an assumption that thermalized electron dissociative attachment reactions are an important part of the chlorinated VOCs decomposition process. The exception is CH 2Cl 2 where the decomposition process is initiated by nitrogen atoms and N 2+ ions. A chain reaction was observed in the case of C 2HCl 3 and C 2H 2Cl 2 decomposition, where the dose necessary for 90% reduction is below 10 kGy. In contrast to the chlorinated VOC's, PAHs in humid air were primarily decomposed by OH radical's interactions. When initial PAH concentration was ⩽100 ppm the dose necessary for 90% reduction was below 10 kGy.

  2. Comparative bioaccumulation of chlorinated hydrocarbons from sediment by two infaunal invertebrates

    SciTech Connect

    Meador, J.P.; Adams, N.G.; Casillas, E.; Bolton, J.L.

    1995-12-31

    Bioaccumulation of chlorinated hydrocarbons (CHs) from field-contaminated sediments by two infaunal invertebrates, Rhepoxynius abronius and Armandia brevis was examined in the laboratory. Sediments were selected over a large geographical area of an urban estuary, the Hudson-Raritan, to assess the potential for bioaccumulation. Amphipod and polychaete tissue burdens were highly correlated over sites; however, concentrations of the trichlorobiphenyls in the polychaete were about twice that found in the amphipod and 4 to 8 times higher for the more hydrophobic PCBs. Unlike PAHs from these sediments, concentrations of CHs in IW and sediment indicated that partition coefficients (K{sub oc}) were generally as predicted. K{sub oc} values determined with non-sorbed interstitial water concentrations (IW{sub free}) were much closer to predicted values compared to those based on the total chlorinated compound. As expected, BAF values were highly variable among sites and increased greatly with declining TOC content. The BAF{sub loc} (lipid/organic carbon normalized bioaccumulation factor) for trichlorobiphenyls in the polychaete was similar to that for the amphipod; however the polychaete BAF{sub loc} increased with increasing hydrophobicity and was maximum for the pentachlorobiphenyls and close to the expected maximum. Some evidence for site-specific BAF{sub loc} values was found because of a strong correlation between BAF{sub loc} and sediment concentration; however for some PCBs, this correlation was weak.

  3. Chlorine

    Integrated Risk Information System (IRIS)

    Chlorine ; CASRN 7782 - 50 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects

  4. Chlorine

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical chlorine, produced in small quantities in the laboratory, is presented. The profile summarizes physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  5. Chlorine

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical chlorine, produced in small quantities in the laboratory, is presented. The profile summarizes physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  6. Chlorine

    SciTech Connect

    Talmage, Sylvia Smith

    2009-01-01

    Following a brief description of the use of chlorine as a chemical warfare agent in World War I, this chapter summarizes physical and chemical data and recent clinical and controlled laboratory studies on the irritant and lethal effects of chlorine. The mechanism of toxicity for both irritation and lethal effects is described. The mathematical relationship between concentration and exposure duration for a set endpoint is given for both an irritancy response and mortality. This information can be used to assist in time-scaling for the set endpoint to other exposure durations. Risk assessment addresses the potential for greater effects in sensitive populations such as asthmatics. A concentration of 0.5 ppm for up to 8 hours is a no-adverse-effect concentration in most sensitive subjects; whereas, a concentration of 1.0 ppm induces some sensory irritation and transient changes in respiratory tract airflow parameters. Treatment and intervention of exposed individuals is dependent upon symptoms

  7. An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

    NASA Astrophysics Data System (ADS)

    Skubal, Karen L.; Barcelona, Michael J.; Adriaens, Peter

    2001-05-01

    Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 μmol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH 4 and CO 2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation

  8. Chlorinated hydrocarbons in North Sea whiting ( Merlangius merlangus L.), and effects on reproduction. I. Tissue burden and hatching success

    NASA Astrophysics Data System (ADS)

    v. Westernhagen, H.; Cameron, P.; Dethlefsen, V.; Janssen, D.

    1989-03-01

    Artificially inseminated eggs of feral North Sea whiting ( Merlangius merlangus) were incubated in the laboratory in order to determine reproductive success. After incubation, two measures for reproductive success, total hatch and viable hatch, were determined and correlated with chlorinated hydrocarbon residues in the respective ovaries. From their specific toxicities and the sum of all determined chlorinated hydrocarbon contaminants, a contamination factor (CF) was calculated. Significant negative correlations were found between total hatch and DDT, including its metabolites (ΣDDT), dieldrin and the CF. ΣDDT and the CF were also negatively correlated with viable hatch. A threshold value of ovary contamination above which impairment of reproductive success was likely to occur was set at > 200 μg kg-1 wet wt. for ΣPCB, > 20 μg kg-1 wet wt. for ΣDDT and > 10 μg kg-1 wet wt. for dieldrin.

  9. Contamination of urban, industrial and continental waters by chlorinated hydrocarbon pesticides along the Mediterranean coast of Morocco.

    PubMed

    Kessabi, M; Elhraiki, A; Nader, B

    1988-05-01

    Residual waters (urban, industrial and continental) of the Moroccan Mediterranean coast situated between Tangier and Al Hoceima were found to be contaminated by chlorinated hydrocarbon pesticides. Hexachlorobenzene, lindane, aldrin and heptachlor were frequently encountered. The contamination was relatively low for endrin and dieldrin and irregular for DDT and its derivatives. The levels detected differed from traces to 0.5 ppm. The areas of high urban density showed the highest contamination, with some seasonal variation.

  10. Use of standards and reference materials in the measurement of chlorinated hydrocarbon residues: Chemistry workbook. Technical memo

    SciTech Connect

    Wade, T.L.; Cantillo, A.Y.

    1994-03-01

    The document is a workbook on the use of standards and reference materials for a quality assurance/quality control (QA/QC) program for marine pollution studies of chlorinated hydrocarbons. The first sections of this workbook give details of sample collection, archival, extraction, instrumental analyses, and data reduction under proper QA/QC procedures. The last sections give examples of how the calculations and procedures are actually applied in a laboratory.

  11. Microbial diversity in a hydrocarbon- and chlorinated-solvent- contaminated aquifer undergoing intrinsic bioremediation

    USGS Publications Warehouse

    Dojka, M.A.; Hugenholtz, P.; Haack, S.K.; Pace, N.R.

    1998-01-01

    A culture-independent molecular phylogenetic approach was used to survey constituents of microbial communities associated with an aquifer contaminated with hydrocarbons (mainly jet fuel) and chlorinated solvents undergoing intrinsic bioremediation. Samples were obtained from three redox zones: methanogenic, methanogenic-sulfate reducing, and iron or sulfate reducing. Small-subunit rRNA genes were amplified directly from aquifer material DNA by PCR with universally conserved or Bacteria- or Archaea-specific primers and were cloned. A total of 812 clones were screened by restriction fragment length polymorphisms (RFLP), approximately 50% of which were unique. All RFLP types that occurred more than once in the libraries, as well as many of the unique types, were sequenced. A total of 104 (94 bacterial and 10 archaeal) sequence types were determined. Of the 94 bacterial sequence types, 10 have no phylogenetic association with known taxonomic divisions and are phylogenetically grouped in six novel division level groups (candidate divisions WS1 to WS6); 21 belong to four recently described candidate divisions with no cultivated representatives (OPS, OP8, OP10, and OP11); and 63 are phylogenetically associated with 10 well-recognized divisions. The physiology of two particularly abundant sequence types obtained from the methanogenic zone could be inferred from their phylogenetic association with groups of microorganisms with a consistent phenotype. One of these sequence types is associated with the genus Syntrophus; Syntrophus spp. produce energy from the anaerobic oxidation of organic acids, with the production of acetate and hydrogen. The organism represented by the other sequence type is closely related to Methanosaeta spp., which are known to be capable of energy generation only through aceticlastic methanogenesis. We hypothesize, therefore, that the terminal step of hydrocarbon degradation in the methanogenic zone of the aquifer is aceticlastic methanogenesis and

  12. [Applicability of an electronic nose for detection of volatile chlorinated hydrocarbons in soil].

    PubMed

    Bu, Fan-Yang; Wen, Xiao-Gang; Wan, Mei; Liu, Rui; Cai, Qiang; Chen, Lü-Jun; Zhang, Yong-Ming

    2011-12-01

    An electronic nose principally composed of a photo ionization detector (PID) was developed for rapid detection of volatile chlorinated hydrocarbons (VCHs) in contaminated soil. Removal of interference gas such as benzene homologues with a pre-filtration tube was analyzed with gas chromatography (GC). A standard gas generator was applied to generate different concentrations of perchloroethylene (PCE) and trichloroethylene (TCE) gas, with which the determine precision and reproducibility of the electronic nose were evaluated by comparison with GC. Finally, simulated contamination soil with three typical paddy soils in Yangtze river delta region were used for ventilation purification experiments, the change of VCHs concentrations in the ventilation gas was monitored, based on which the applicability of the electronic nose was evaluated for on-line detection of the on-going of the ventilation purification process. Results showed that a halogenated hydrocarbon RAE-SEP tube was effective to remove interference gas, with 80%-97% of benzene homologues such as benzene and ethyl benzene being removed while more than 90% of VCHs passed through. With PCE or TCE gas, a linear dependence was derived between the data determined with the electronic nose and GC, the linear slope being 1.012 and R2 > 0.99. The electronic nose showed data consistent with GC (R2 > 0.99, n = 47) when applied for monitoring the remediation progress in a soil ventilation process. The electronic nose is therefore possibly applicable for rapid determination of soil pollution by VCHs, improving the efficiency of pollution diagnosis and remediation.

  13. Residential exposure to chlorinated hydrocarbons from groundwater contamination and the impairment of renal function-An ecological study

    NASA Astrophysics Data System (ADS)

    Chen, Hui-Ming; Wu, Ming-Tsang

    2017-01-01

    Groundwater pollution from the petrochemical industry causes serious deterioration of soil and groundwater quality and impacts on human health worldwide. However, few studies have examined the effect of residential exposure to petrochemical chlorinated hydrocarbon-contaminated groundwater on renal function impairment in humans. We conducted an ecological study to investigate the two. A polyvinyl chloride (PVC) plant was located in one of the six villages, the study area, in Kaohsiung city of southwestern Taiwan. Based on the direction of groundwater flow and previous groundwater measurements of chlorinated hydrocarbons from Taiwan Environmental Protection Bureau, we divided the six villages into highly-polluted villages, moderately-polluted villages, and a non-polluted village. All inhabitants in those six villages were invited to receive free health examinations between May-June, 2010. In total, 4,432 study subjects ≥18 yrs old were analyzed. Compared to those in the non-polluted village, subjects in highly-polluted villages had 1.89- and 1.46-fold the risk of impaired estimated glomerular filtration rate (eGFR) and proteinuria (95% CI = 1.15–1.85 and 1.09–3.28, respectively) after adjusting for other covariates. Given this relative large sample size, we found that groundwater chlorinated hydrocarbon pollution can cause kidney damage in adults.

  14. Residential exposure to chlorinated hydrocarbons from groundwater contamination and the impairment of renal function-An ecological study

    PubMed Central

    Chen, Hui-Ming; Wu, Ming-Tsang

    2017-01-01

    Groundwater pollution from the petrochemical industry causes serious deterioration of soil and groundwater quality and impacts on human health worldwide. However, few studies have examined the effect of residential exposure to petrochemical chlorinated hydrocarbon-contaminated groundwater on renal function impairment in humans. We conducted an ecological study to investigate the two. A polyvinyl chloride (PVC) plant was located in one of the six villages, the study area, in Kaohsiung city of southwestern Taiwan. Based on the direction of groundwater flow and previous groundwater measurements of chlorinated hydrocarbons from Taiwan Environmental Protection Bureau, we divided the six villages into highly-polluted villages, moderately-polluted villages, and a non-polluted village. All inhabitants in those six villages were invited to receive free health examinations between May-June, 2010. In total, 4,432 study subjects ≥18 yrs old were analyzed. Compared to those in the non-polluted village, subjects in highly-polluted villages had 1.89- and 1.46-fold the risk of impaired estimated glomerular filtration rate (eGFR) and proteinuria (95% CI = 1.15–1.85 and 1.09–3.28, respectively) after adjusting for other covariates. Given this relative large sample size, we found that groundwater chlorinated hydrocarbon pollution can cause kidney damage in adults. PMID:28067285

  15. Residential exposure to chlorinated hydrocarbons from groundwater contamination and the impairment of renal function-An ecological study.

    PubMed

    Chen, Hui-Ming; Wu, Ming-Tsang

    2017-01-09

    Groundwater pollution from the petrochemical industry causes serious deterioration of soil and groundwater quality and impacts on human health worldwide. However, few studies have examined the effect of residential exposure to petrochemical chlorinated hydrocarbon-contaminated groundwater on renal function impairment in humans. We conducted an ecological study to investigate the two. A polyvinyl chloride (PVC) plant was located in one of the six villages, the study area, in Kaohsiung city of southwestern Taiwan. Based on the direction of groundwater flow and previous groundwater measurements of chlorinated hydrocarbons from Taiwan Environmental Protection Bureau, we divided the six villages into highly-polluted villages, moderately-polluted villages, and a non-polluted village. All inhabitants in those six villages were invited to receive free health examinations between May-June, 2010. In total, 4,432 study subjects ≥18 yrs old were analyzed. Compared to those in the non-polluted village, subjects in highly-polluted villages had 1.89- and 1.46-fold the risk of impaired estimated glomerular filtration rate (eGFR) and proteinuria (95% CI = 1.15-1.85 and 1.09-3.28, respectively) after adjusting for other covariates. Given this relative large sample size, we found that groundwater chlorinated hydrocarbon pollution can cause kidney damage in adults.

  16. In situ sensing of subsurface contamination--part I: near-infrared spectral characterization of alkanes, aromatics, and chlorinated hydrocarbons.

    PubMed

    Klavarioti, Maria; Kostarelos, Konstantinos; Pourjabbar, Anahita; Ghandehari, Masoud

    2014-05-01

    There is an imperative need for a chemical sensor capable of remote, in situ, long-term monitoring of chemical species at sites containing toxic chemical spills, specifically at chemical waste dumps, landfills, and locations with underground storage tanks. In the current research, a series of experiments were conducted measuring the near-infrared optical absorption of alkanes, aromatics, and chlorinated hydrocarbons. A spectral library was then developed to characterize the optical spectra of liquid hydrocarbons. Near-infrared analysis was chosen due to compatibility with optical fibers. The goal was to differentiate between classes of hydrocarbons and to also discriminate between compounds within a class of similar molecular structures. It was observed that unique absorption spectra can be obtained for each hydrocarbon, and this uniqueness can be used to discriminate between hydrocarbons from different families. Statistical analyses, namely, principal component analysis (PCA) and correlation coefficient (Spearman and Pearson methods), were attempted to match absorption spectra from an unknown hydrocarbon with the database with limited success. An algorithm was subsequently written to identify the characteristic peaks of each hydrocarbon that could be used to match data from an unknown chemical species with the database.

  17. Alterations of phytoplankton assemblages treated with chlorinated hydrocarbons: effects of dominant species sensitivity and initial diversity.

    PubMed

    Bácsi, István; Gonda, Sándor; B-Béres, Viktória; Novák, Zoltán; Nagy, Sándor Alex; Vasas, Gábor

    2015-05-01

    Changes in composition of phytoplankton assemblages due to short-chained chlorinated hydrocarbons (tetrachloroethane, tetrachloroethylene and trichloroethylene) were studied in microcosm experiments with different initial diversities. Diversity decreased further during treatments in the less diverse 2011 summer assemblages, dominated by the euglenid Trachelomonas volvocinopsis (its relative abundance was nearly 70 %). Diversity did not change significantly during treatments in the more diverse 2012 summer assemblages, dominated by cryptomonads (their relative abundance was 40 %). The dominant Trachelomonas volvocinopsis in 2011, due to its insensitivity to the treatment and presumably high competition skills, filled released habitats occurring when sensitive species were not detectable any more. In contrast, cryptomonads were extremely sensitive to the treatments, their abundance decreased under detection limit in the treated assemblages, regardless of diversity conditions. Our results showed that population dynamics of dominant species determine the response to the contamination of the entire community, if these species display high resistance or resilience. If the dominant species was highly sensitive and recovered slowly, compensatory growth of rare species maintained high levels of ecosystem performance.

  18. Source apportionment of chlorinated polycyclic aromatic hydrocarbons associated with ambient particles in a Japanese megacity

    NASA Astrophysics Data System (ADS)

    Kamiya, Yuta; Iijima, Akihiro; Ikemori, Fumikazu; Okuda, Tomoaki; Ohura, Takeshi

    2016-12-01

    Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are novel species of environmental contaminants whose possible sources remain unclear. The occurrence of ClPAHs within total suspended particles (TSP) is compared with weekly air samples at two sites of differing characteristics (industrial and residential) in the megacity of Nagoya, Japan. Samples were collected over 12 months during 2011–2012. All 24 species of targeted ClPAHs were detected at both industrial and residential sites, where mean concentrations of total ClPAHs in TSP were 20.7 and 14.1 pg/m3, respectively. High concentrations at the industrial site were frequently observed during winter, suggesting potent seasonal ClPAH sources there. Positive matrix factorization modeling of particulate ClPAH source identification and apportioning were conducted for datasets including ClPAHs, PAHs, elements and ions, plus elemental carbons in TSP. Eight factors were identified as possible ClPAH sources, with estimates that the dominant one was a specific source of ClPAH emission (31%), followed by traffic (23%), photodegradable and semi-volatile species (18%), long-range transport (11%), and industry and oil combustion (10%). Source contributions of ClPAHs differed substantially from those of PAHs. This suggests specific and/or potent ClPAH sources in the local area, and that the production mechanisms between ClPAHs and PAHs are substantially different.

  19. Structural and dynamical properties of chlorinated hydrocarbons studied with resonant inelastic x-ray scattering

    NASA Astrophysics Data System (ADS)

    Bohinc, R.; Žitnik, M.; Bučar, K.; Kavčič, M.; Carniato, S.; Journel, L.; Guillemin, R.; Marchenko, T.; Kawerk, E.; Simon, M.; Cao, W.

    2016-04-01

    We present a theoretical and experimental study of resonant inelastic x-ray scattering on a large group of chlorinated hydrocarbons: CH3Cl, CH2Cl2, CHCl3, CCl4, CH3CH2Cl, ClCH2CH2Cl, CH3CHCl2, CH3CCl3, C2H2Cl2-iso, C2H2Cl2-cis, C2H2Cl2-trans, and C6H5Cl. Differences in structural and dynamical properties of the molecules generated by diverse chemical environments are observed in the measured Cl(Kα) spectral maps as well as in the Cl(K) total fluorescence yield spectra. The energy position, relative intensity, and the width of the Franck-Condon distribution of low-lying σ∗ and π∗ resonances are extracted by a fitting procedure taking into account the experimental broadening. The theoretical values obtained with the transition potential and Δ Kohn-Sham methods are in good agreement with the experimental parameters indicating subtle differences due to variations in the molecular structure.

  20. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, chlorinated pesticides (DDTs), hexachlorocyclohexane, and hexachlorobenzene residues in smoked seafood.

    PubMed

    Storelli, M M; Stuffler, R Giacominelli; Marcotrigianoi, G O

    2003-06-01

    Smoked seafoods were screened for the presence of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and other organochlorine compounds. Total PAH concentrations ranged from 46.5 ng/g (wet weight) for smoked swordfish to 124.0 ng/g (wet weight) for smoked herring. Among the carcinogenic PAHs, benzo(a)pyrene ranged from undetectable levels for several smoked fish to 0.7 ng/g for Scottish salmon, dibenzo(ah)anthracene was not present in any of the samples analyzed, and benzo(a)anthracene was found in all samples and at particularly high levels in salmon (23.2 ng/g). Benzo(a)pyrene concentrations were below the tolerance limit for all samples. PCB concentrations for the different samples ranged from 2 to 30 ng/g. Chlorinated pesticides (DDTs: p,p'-DDE, p,p'-DDT, o,p'-DDT, p,p'-DDD, and o,p'-DDD) were detected at levels ranging from 0.2 ng/g (wet weight) in bluefin tuna to 17.5 ng/g (wet weight) in salmon. Hexachlorocyclohexane isomers (alphaHCH + betaHCH + gammaHCH) were present in higher amounts in eels (6.5 ng/g) than in the other smoked fish. For 40% of the samples, PCB concentrations exceeded the limit fixed by the European Union, while pesticide levels were below the maximum acceptable limit proposed by the Food and Agriculture Organization.

  1. Contamination of stream fishes with chlorinated hydrocarbons from eggs of Great Lakes salmon

    SciTech Connect

    Merna, J.W.

    1986-01-01

    Pacific salmon Oncorhynchus spp. have been stocked in the Great Lakes where they accumulate body burdens of chlorinated hydrocarbons. The transport of these contaminants to resident communities in spawning streams was studied in two tributaries of Lake Michigan accessible to anadromous spawners and one control tributary blocked to them. No polychlorinated biphenyls (PCBs), DDT, or dieldrin were detected in the sediments or biota of the control stream, or in sediments of the test streams. However, trout Salmo spp. and, to a lesser extent, sculpins Cottus spp. accumulated PCBs and DDT as a result of eating contaminated salmon eggs. Eggs constituted as much as 87% (by weight) of the total stomach contents of trout collected during the salmon spawning season early October to early January. Salmon eggs contained 0.46-9.50 mg PCBs/kg,. and 0.14-1.80 mg DDT/kg. Consumption of eggs varied greatly among individual trout, and there was a strong correlation between numbers of eggs in the stomachs and PCB and DDT concentrations in the fillets.

  2. Chlorinated hydrocarbon residues in Baikal seal (Phoca sibirica) from Lake Baikal: Levels, patterns, and metabolism

    SciTech Connect

    Nakata, H.; Tanabe, S.; Tatsukawa, R.; Amano, M.; Miyazaki, N.; Petrov, A.

    1995-12-31

    Contamination of chlorinated hydrocarbons such as DDTs (DDT and its metabolites), PCBs (polychlorinated biphenyls), CHLs (chlordane compounds) and HCHs (hexachlorocyclohexanes) was assessed in the blubber of Baikal seal (Phoca sibirica) and their fish diet collected from Lake Baikal in 1992. Higher concentrations of DDTs and PCBs were detected, ranging from 4.9 to 160 {micro}g/g and 3.5 to 64 {micro}g/g on a lipid weight basis, respectively, whereas levels of CHLs and HCHs were approximately one or three orders of magnitude lower than those of DDTs and PCBs. The average of DDTs concentrations in adult male Baikal seals were about an order of magnitude higher than those reported for seals in the North Sea around UK and comparable to grey seal in the Baltic Sea, indicating that Baikal seals are categorized in a highly contaminated group. A positive age dependent accumulation of DDTs, PCBs and CHLs was found in male, while a steady-state was observed in female which attributes to the reproductive transfer, mainly lactation, of these chemicals. On the basis of contaminant burdens in adult seals, it was estimated that adult females transfer about 19% and 14% of their DDT and PCB body burdens to their pups during a reproductive process. Based on the data from isomer specific analysis of PCBs, it can be suggested that Baikal seals have higher capacity to metabolize congeners with vicinal H-atoms in meta, para positions than those of marine mammals.

  3. Investigations of the interaction of Spartina alterniflora loisel. and the chlorinated hydrocarbons, the polychlorinated biphenyls

    SciTech Connect

    Mrozek, E. Jr.

    1981-01-01

    Polychlorinated biphenyls (PCB's) are a class of industrial chlorinated hydrocarbons which are toxic to a broad range of organisms, persistent in the environment, and tend to accumulate in estuaries, where they are available to organisms at all trophic levels. Greenhouse and laboratory studies were initiated to characterize the interaction of Spartina alterniflora Loisel, and the PCB's. Particular areas addressed were: (1) uptake, translocation, and accumulation, (2) selectivity of uptake, (3) effects of uptake and/or exposure of PCB's on S. alterniflora growth, and (4) potential for transfer of PCB's from S. alterniflora and marsh substrate to Uca pugnax (fiddler crab). In a greenhouse study it was concluded that S. alterniflora has the capacity to take up, translocate and accumulate /sup 14/C-radioactivity from sand and marsh mud originally treated with /sup 14/C-PCB's. Fiddler crabs (U. pugnax) were exposed to /sup 14/C-PCB's applied to marsh substrate or S. alterniflora plant material which had been grown in the presence of /sup 14/C-PCB's to determine if marsh substrate-to-organism and plant-to-organism PCB transfer was possible. Results indicate that transfer from both sources occurred but that accumulation of /sup 14/C-radioactivity was only observed with crabs exposed to /sup 14/C-PCB treated substrate.

  4. Chlorinated Hydrocarbon Degradation in Plants: Mechanisms and Enhancement of Phytoremediation of Groundwater Contamination

    SciTech Connect

    Stuart Strand

    2004-09-27

    The research objectives for this report are: (1) Transform poplar and other tree species to extend and optimize chlorinated hydrocarbon (CHC) oxidative activities. (2) Determine the mechanisms of CHC oxidation in plants. (3) Isolate the genes responsible for CHC oxidation in plants. We have made significant progress toward an understanding of the biochemical mechanism of CHC transformation native to wild-type poplar. We have identified chloral, trichloroethanol, trichloroacetic acid, and dichloroacetic acid as products of TCE metabolism in poplar plants and in tissue cultures of poplar cells.(Newman et al. 1997; Newman et al. 1999) Use of radioactively labeled TCE showed that once taken up and transformed, most of the TCE was incorporated into plant tissue as a non-volatile, unextractable residue.(Shang et al. 2001; Shang and Gordon 2002) An assay for this transformation was developed and validated using TCE transformation by poplar suspension cells. Using this assay, it was shown that two different activities contribute to the fixation of TCE by poplar cells: one associated with cell walls and insoluble residues, the other associated with a high molecular weight, heat labile fraction of the cell extract, a fixation that was apparently catalyzed by plant enzymes.

  5. Source apportionment of chlorinated polycyclic aromatic hydrocarbons associated with ambient particles in a Japanese megacity

    PubMed Central

    Kamiya, Yuta; Iijima, Akihiro; Ikemori, Fumikazu; Okuda, Tomoaki; Ohura, Takeshi

    2016-01-01

    Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) are novel species of environmental contaminants whose possible sources remain unclear. The occurrence of ClPAHs within total suspended particles (TSP) is compared with weekly air samples at two sites of differing characteristics (industrial and residential) in the megacity of Nagoya, Japan. Samples were collected over 12 months during 2011–2012. All 24 species of targeted ClPAHs were detected at both industrial and residential sites, where mean concentrations of total ClPAHs in TSP were 20.7 and 14.1 pg/m3, respectively. High concentrations at the industrial site were frequently observed during winter, suggesting potent seasonal ClPAH sources there. Positive matrix factorization modeling of particulate ClPAH source identification and apportioning were conducted for datasets including ClPAHs, PAHs, elements and ions, plus elemental carbons in TSP. Eight factors were identified as possible ClPAH sources, with estimates that the dominant one was a specific source of ClPAH emission (31%), followed by traffic (23%), photodegradable and semi-volatile species (18%), long-range transport (11%), and industry and oil combustion (10%). Source contributions of ClPAHs differed substantially from those of PAHs. This suggests specific and/or potent ClPAH sources in the local area, and that the production mechanisms between ClPAHs and PAHs are substantially different. PMID:27922081

  6. Structural and dynamical properties of chlorinated hydrocarbons studied with resonant inelastic x-ray scattering.

    PubMed

    Bohinc, R; Žitnik, M; Bučar, K; Kavčič, M; Carniato, S; Journel, L; Guillemin, R; Marchenko, T; Kawerk, E; Simon, M; Cao, W

    2016-04-07

    We present a theoretical and experimental study of resonant inelastic x-ray scattering on a large group of chlorinated hydrocarbons: CH3Cl, CH2Cl2, CHCl3, CCl4, CH3CH2Cl, ClCH2CH2Cl, CH3CHCl2, CH3CCl3, C2H2Cl2-iso, C2H2Cl2-cis, C2H2Cl2-trans, and C6H5Cl. Differences in structural and dynamical properties of the molecules generated by diverse chemical environments are observed in the measured Cl(K(α)) spectral maps as well as in the Cl(K) total fluorescence yield spectra. The energy position, relative intensity, and the width of the Franck-Condon distribution of low-lying σ* and π* resonances are extracted by a fitting procedure taking into account the experimental broadening. The theoretical values obtained with the transition potential and Δ Kohn-Sham methods are in good agreement with the experimental parameters indicating subtle differences due to variations in the molecular structure.

  7. Gas- and Particle-Phase Products from the Chlorine-Initiated Oxidation of Polycyclic Aromatic Hydrocarbons.

    PubMed

    Riva, Matthieu; Healy, Robert M; Flaud, Pierre-Marie; Perraudin, Emilie; Wenger, John C; Villenave, Eric

    2015-11-12

    The chlorine atom (Cl)-initiated oxidation of three polycyclic aromatic hydrocarbons (PAHs; namely, naphthalene, acenaphthylene, and acenaphthene) was investigated. Experiments were performed in an atmospheric simulation chamber using a proton transfer reaction time-of-flight mass spectrometer (TOF-MS) and an aerosol TOF-MS to characterize the oxidation products in the gas and particle phases, respectively. The major products identified from the reaction of Cl atoms with naphthalene were phthalic anhydride and chloronaphthalene, indicating that H atom abstraction and Cl addition reaction pathways are both important. Acenaphthenone was the principal product arising from reaction of Cl with acenaphthene, while 1,8-naphthalic anhydride, acenaphthenone, acenaphthenequinone, and chloroacenaphthenone were all identified as products of acenaphthylene oxidation, confirming that the cylcopenta-fused ring controls the reactivity of these PAHs toward Cl atoms. Possible reaction mechanisms are proposed for the formation of these products, and favored pathways have been suggested. Large yields of secondary organic aerosol (SOA) were also observed in all experiments, and the major products were found to undergo significant partitioning to the particle-phase. This work suggests that Cl-initiated oxidation could play an important role in SOA formation from PAHs under specific atmospheric conditions where the Cl atom concentration is high, such as the marine boundary layer.

  8. Direct immunofluorescence and enzyme-linked immunosorbent assays for evaluating chlorinated hydrocarbon degrading bacteria

    SciTech Connect

    Brigmon, R.L.; Franck, M.M.; Brey, J.; Fliermans, C.B.; Scott, D.; Lanclos, K.

    1997-06-01

    Immunological procedures were developed to enumerate chlorinated hydrocarbon degrading bacteria. Polyclonal antibodies (Pabs) were produced by immunizing New Zealand white rabbits against 18 contaminant-degrading bacteria. These included methanotrophic and chlorobenzene (CB) degrading species. An enzyme-linked immunosorbent assay (ELISA) was used to test for specificity and sensitivity of the Pabs. Direct fluorescent antibodies (DFAs) were developed with these Pabs against select methanotrophic bacteria isolated from a trichloroethylene (TCE) contaminated landfill at the Savannah River Site (SRS) and cultures from the American Type Culture Collection (ATCC). Analysis of cross reactivity testing data showed some of the Pabs to be group specific while others were species specific. The threshold of sensitivity for the ELISA is 105 bacteria cells/ml. The DFA can detect as few as one bacterium per ml after concentration. Results from the DFA and ELISA techniques for enumeration of methanotrophic bacteria in groundwater were higher but not significantly different (P < 0.05) compared to indirect microbiological techniques such as MPN. These methods provide useful information on in situ community structure and function for bioremediation applications within 1--4 hours of sampling.

  9. Volatile chlorinated hydrocarbons in Antarctic superficial snow sampled during Italian ITASE expeditions.

    PubMed

    Zoccolillo, Lelio; Amendola, Luca; Cafaro, Claudia; Insogna, Susanna

    2007-05-01

    In order to detect the presence of some volatile chlorinated hydrocarbons (VCHCs) and to understand their transport and deposition mechanism, superficial snow was sampled during two Italian ITASE (International Trans Antarctic Scientific Expedition) expeditions: the first traverse was carried out in 1998/1999 from Terra Nova Bay to Dome Concordia; the second traverse was carried out in 2001/2002 through Adélie, George V, Oates and Northern Victoria Lands. Some VCHCs (chloroform; 1,1,1-trichloroethane; tetrachloromethane; 1,1,2-trichloroethylene; tetrachloroethylene) were analysed using a highly sensitive and selective hyphenated technique composed of a purge-and-trap injector coupled to a gas chromatograph with a mass spectrometric detector (PTI-GC-MS) operating in SIM mode. Investigated VCHCs were present in all analysed snow samples with concentration levels of several units, tens, or sometimes hundreds of ng kg(-1). VCHC snow concentration levels remained approximately constant with changing distance from the coast and the comparison between fresh and aged snow did not show any substantial differences; on the basis of this evidence marine aerosol and dry deposition may be rejected as principal VCHC transport and deposition mechanism hypotheses. VCHC concentration levels in Antarctic snow samples were comparable to or greater than those found in snow from temperate zones.

  10. Role of temperature and hydrochloric acid on the formation of chlorinated hydrocarbons and polycyclic aromatic hydrocarbons during combustion of paraffin powder, polymers, and newspaper.

    PubMed

    Takasuga, Takumi; Umetsu, Norihito; Makino, Tetsuya; Tsubota, Katsuya; Sajwan, Kenneth S; Kumar, Kurunthachalam Senthil

    2007-07-01

    Formation of chlorinated hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) were determined using a laboratory-scale incinerator when combusting materials at different temperatures, different concentrations of hydrochloric acid (HCl), and when combusting various types of polymers/newspaper. Polychlorobenzenes (PCBz), polychlorophenols (PCPhs), polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and their toxic equivalency (TEQ) and PAHs were highlighted and reported. Our results imply maximum formation of chlorinated hydrocarbons at 400 degrees C in the following order; PCBz>or=PCPhs>PCDFs>PCDDs>TEQ on a parts-per-billion level. Similarly, a maximum concentration of chlorinated hydrocarbons was noticed with an HCl concentration at 1000 ppm with the presence of paraffin powder in the following order; PAHs>PCBz>or=PCPhs>PCDFs>PCDDs>TEQ an a parts-per-billion level. PAHs were not measured at different temperatures. Elevated PAHs were noticed with different HCl concentrations and paraffin powder combustion (range: 27-32 microg/g). While, different polymers and newspaper combusted, nylon and acrylonitrile butadiene styrene (ABS) produced the maximum hydrogen cyanide (HCN) concentration, concentrations of PCDD/FS, dioxin-like polychlorinated biphenyls (DL-PCBs), and TEQ were in a decreasing order: polyvinylchloride (PVC)

  11. Enhanced utilization of oxidants for in situ chemical oxidation of chlorinated and aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Kang, Namgoo

    Potentially viable strategies were sought for enhanced utilization of potassium permanganate (KMnO4) and Fenton's reagent during in situ chemical oxidation (ISCO). An innovative concept of controlled release of oxidant was introduced and organic-coated, completely or partially microencapsulated KMnO4 (MEPP) particles (874 +/- 377 mum) were created to serve a material that can be specifically targeted to a contaminant source zone. Paraffin wax was employed as the coating material because it is biodegradable, inert to KMnO4, insoluble in water and yet soluble in hydrophobic contaminants such as perchloroethylene (PCE). KMnO4 was released very slowly into water, but the oxidant was rapidly released into PCE. The estimated times for 90% release of the oxidant were 1.6 months, 19.3 years, and 472 years for paraffin wax to KMnO4 mass ratios of 1:1, 2:1 and 5:1, respectively. The MEPP particles preferentially accumulated at the PCE-water interface, and the KMnO4 was rapidly released into PCE (<3 min) as the paraffin wax completely dissolved. These findings suggest that enhanced contact between the target contaminant and the locally high concentrations of KMnO 4 could be achieved at the interfacial region between PCE and water. Fenton's oxidative destruction was investigated for aromatic hydrocarbons (benzene, toluene, ethylbenzene, and o-xylene; BTEX) present as dissolved and adsorbed phases, and chlorinated hydrocarbon (PCE) present mostly as dense non-aqueous phase liquid (DNAPL) (>93% of total PCE mass) in batch reactors (soil: solution = 1 g/L). An enhanced mass removal was observed by combining 300 mM H2O2, 2 mM Fe(III) and 2 mM N-(2-hydroxyethyl)iminodiacetic acid (HEIDA) at near-neutral pH. The PCE degradation was maximal at 600 mM H2O2, 5 mM Fe(III) and 5 mM HEIDA at pH 3. The observed BTEX mass removal rate constants (3.6--7.8 x 10-4 s-1) were compared to the estimated ones (4.1--10.1 x 10-3 s-1) using a semi-quantitative kinetic model. The model sensitivity

  12. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

    NASA Astrophysics Data System (ADS)

    Powell, C. L.; Goltz, M. N.; Agrawal, A.

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  13. Eggshell thinning, chlorinated hydrocarbons, and mercury in inland aquatic bird eggs, 1969 and 1970

    USGS Publications Warehouse

    Faber, R.A.; Hickey, J.J.

    1973-01-01

    In the Upper Great Lakes States, 9 out of 13 species of fish-eating birds were found in 1969-70 to have sustained statistically significant decreases in eggshell thickness since 1946. Maximum changes in a thickness index occurred in great blue herons (-25%), red-breasted mergansers (-23%), common mergansers (-15%). and double-crested cormorants (-15%). Heron eggs taken in Louisiana generally displayed a smaller post-'46 change than herons in the Middle West. On a lipid basis, mean PCB- and DDE- residue levels exceeded 100 ppm in 7 out of 13 species in the Great Lakes States, and in 2 of 7 species in Louisiana, the average DDE: PCB ratios in the two regions being 1.25:1 and 3.9:1, respectively. Individual dieldrin values tended 10 be higher in Louisiana (31.6 and 13.95 ppm in heron species from two different locations), although values reached 10.1 and 9.4 ppm in great blue and black-crowned night herons in Wisconsin. BHC averaged 3.01 and 0.39 ppm in the Lake States and Louisiana, respectively. Of eggs examined for mercury. 29% had levels greater than 0.5 ppm, and 9% greater than 1.0 ppm on a wet-weight basis. Mercury levels in a small sample of eggs from Louisiana were consistently low. The differences in mercury levels between the two regions thus were similar to those found for the chlorinated hydrocarbons. While DDE was a prominent factor for most groups, especially herons, in relation to the eggshell thinning observed, dieldrin was also important to two groups even though DDE was present in much higher amounts. PCB's were also important to mergansers, while mercury was positively correlated with thickness index in grebes and negatively correlated in mergansers.

  14. Assessing breeding potential of peregrine falcons based on chlorinated hydrocarbon concentrations in prey.

    PubMed

    Elliott, J E; Miller, M J; Wilson, L K

    2005-03-01

    Peregrine falcons (Falco peregrinus) now breed successfully in most areas of North America from which they were previously extirpated. The loss during the mid-part of the last century of many of the world's peregrine populations was largely a consequence of impaired reproduction caused by the effects of DDE on eggshell quality and embryo hatchability. Population recovery has been attributed to re-introduction efforts, coupled with regulatory restrictions on the use of organochlorine pesticides. Peregrines have not returned to breed in some areas, such as the Okanagan Valley of British Columbia. That region has been extensively planted in fruit orchards which were treated annually with DDT during the early 1950s to the 1970s. Ongoing contamination of avian species, including potential peregrine prey, inhabiting orchards has been documented. In response to an initiative to release peregrines around the city of Kelowna in the Okanagan Valley, we collected potential peregrine prey species and analyzed whole bodies for chlorinated hydrocarbon residues. We used a simple bioaccumulation model to predict concentrations of DDE in peregrine eggs using concentrations in prey and estimates of dietary makeup as input. Peregrines would be expected to breed successfully only if they fed on a diet primarily of doves. Feeding on as little as 10% of other species such as starlings, robins, gulls and magpies would produce DDE concentrations in peregrine eggs greater than the threshold of 15 mg/kg. We also estimated the critical concentration of DDE in total prey to be about 0.5 mg/kg, one half of the previous most conservative criterion for peregrine prey. Concentrations of dieldrin and PCBs in peregrine prey are less than suggested critical levels.

  15. Chlorinated hydrocarbon pesticides and polychlorinated biphenyls in sediment cores from San Francisco Bay

    USGS Publications Warehouse

    Venkatesan, M.I.; De Leon, R. P.; VanGeen, A.; Luoma, S.N.

    1999-01-01

    Sediment cores of known chronology from Richardson and San Pablo Bays in San Francisco Bay, CA, were analyzed for a suite of chlorinated hydrocarbon pesticides and polychlorinated biphenyls to reconstruct a historic record of inputs. Total DDTs (DDT = 2,4'- and 4,4'-dichlorodiphenyltrichloroethane and the metabolites, 2,4'- and 4,4'-DDE, -DDD) range in concentration from 4-21 ng/g and constitute a major fraction (> 84%) of the total pesticides in the top 70 cm of Richardson Bay sediment. A subsurface maximum corresponds to a peak deposition date of 1969-1974. The first measurable DDT levels are found in sediment deposited in the late 1930's. The higher DDT inventory in the San Pablo relative to the Richardson Bay core probably reflects the greater proximity of San Pablo Bay to agricultural activities in the watershed of the Sacramento and San Joaquin rivers. Total polychlorinated biphenyls (PCBs) occur at comparable levels in the two Bays (< 1-34 ng/g). PCBs are first detected in sediment deposited during the 1930's in Richardson Bay, about a decade earlier than the onset of detectable levels of DDTs. PCB inventories in San Pablo Bay are about a factor of four higher in the last four decades than in Richardson Bay, suggesting a distribution of inputs not as strongly weighed towards the upper reaches of the estuary as DDTs. The shallower subsurface maximum in PCBs compared to DDT in the San Pablo Bay core is consistent with the imposition of drastic source control measures four these constituents in 1970 and 1977 respectively. The observed decline in DDT and PCB levels towards the surface of both cores is consistent with a dramatic drop in the input of these pollutants once the effect of sediment resuspension and mixing is taken into account.

  16. Chlorinated hydrocarbons in coastal lagoons of the pacific coast of Nicaragua.

    PubMed

    Carvalho, F P; Montenegro-Guillen, S; Villeneuve, J; Cattini, C; Bartocci, J; Lacayo, M; Cruz, A

    1999-02-01

    A screening for persistent chlorinated hydrocarbons was carried out in December 1995 in the main coastal lagoons on the Pacific side of Nicaragua, where most of the country's agriculture and pesticide use has been taking place for decades. Results for a wide range of organochlorine pesticides in lagoon sediments show levels that generally were very low in Estero Real, Estero Padre Ramos, and estuary of San Juan del Sur. For example, total DDTs in these lagoons averaged 4.5 +/- 3.4 ng g-1 dry weight, which may be considered a baseline level for the region. Other compounds such as HCHs, BHC, endosulfan, heptachlor, endrin, toxaphene, and aroclors were present in concentrations even lower, generally below 1 ng g-1 dry weight. However, sediments of the Esteros Naranjo-Paso Caballos system at Chinandega district contained pesticide residues in much higher levels, attaining maximum values of 1,420 ng g-1 and 270 ng g-1 dry weight, respectively, for toxaphene and total DDTs. Other compounds such as aroclors, chlordane, endosulfan, and dieldrin were also present in the sediments of this lagoon system, but in lower concentrations. The very high concentrations of toxaphene and DDTs in this lagoon are a result of the intensive use of these pesticides in cotton growing in the district of Chinandega. Due to the long environmental half-lives of these compounds (t(1/2) > 10 years in temperate soils), their concentrations in lagoon sediments will likely remain high for years to come. Based on these results, the development of the new shrimp farming activities in the Pacific coastal lagoons should be restricted to selected areas.

  17. Analytical method development using functionalized polysulfone membranes for the determination of chlorinated hydrocarbons in water.

    PubMed

    Nuhu, Abdulmumin A; Basheer, Chanbasha; Abu-Thabit, Nedal Y; Alhooshani, Khalid; Al-Arfaj, Abdul Rahman

    2011-12-15

    In this study, functionalized polysulfone membrane has been utilized as a sorbent for the extraction of chlorinated hydrocarbons (CHCs) in water samples. Two different functionalized polysulfones (i) phosphonic acid functionalized polysulfone (PPSU-A) with different forms (cross-linked and non cross-linked) membranes and (ii) phosphonic ester functionalized polysulfone (PPSU-E) with different forms (cross-linked and non cross-linked) were evaluated for the extraction of CHCs in water. A 10 ml of spiked water sample was extracted with 50mg piece of the functionalized membrane. After extraction, the membrane was desorbed by organic solvent and the extract was analyzed by gas chromatography-mass spectrometry. Eight CHCs, 1,3,5-trichlorobenzene (1,3,5-TCB), 1,2,3-trichlorobenzene (1,2,3-TCB), 1,1,2,3,4,4-hexachloro-1,3-butadiene (HCBD), 1,2,4-trichloro-3-methylbenzene (TCMB), 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB), pentachlorobenzene (PeCB) and hexachlorobenzene (HCB) were used as model compounds. Experimental parameters such as extraction time, desorption time, types of polymer membrane as well the nature of desorption solvent were optimized. Using optimum extraction conditions calibration curves were linear with coefficients of determination between 0.9954 and 0.9999 over wide range of concentrations (0.05-100 μgl(-1)). The method detection limits (at a signal-to-noise ratio of 3) were in the range of 0.4-3.9 ng l(-1). The proposed method was evaluated for the determination of CHCs in drinking water samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. Site-specific probabilistic ecological risk assessment of a volatile chlorinated hydrocarbon-contaminated tidal estuary.

    PubMed

    Hunt, James; Birch, Gavin; Warne, Michael St J

    2010-05-01

    Groundwater contaminated with volatile chlorinated hydrocarbons (VCHs) was identified as discharging to Penrhyn Estuary, an intertidal embayment of Botany Bay, New South Wales, Australia. A screening-level hazard assessment of surface water in Penrhyn Estuary identified an unacceptable hazard to marine organisms posed by VCHs. Given the limitations of hazard assessments, the present study conducted a higher-tier, quantitative probabilistic risk assessment using the joint probability curve (JPC) method that accounted for variability in exposure and toxicity profiles to quantify risk (delta). Risk was assessed for 24 scenarios, including four areas of the estuary based on three exposure scenarios (low tide, high tide, and both low and high tides) and two toxicity scenarios (chronic no-observed-effect concentrations [NOEC] and 50% effect concentrations [EC50]). Risk (delta) was greater at low tide than at high tide and varied throughout the tidal cycle. Spatial distributions of risk in the estuary were similar using both NOEC and EC50 data. The exposure scenario including data combined from both tides was considered the most accurate representation of the ecological risk in the estuary. When assessing risk using data across both tides, the greatest risk was identified in the Springvale tributary (delta=25%)-closest to the source area-followed by the inner estuary (delta=4%) and the Floodvale tributary (delta=2%), with the lowest risk in the outer estuary (delta=0.1%), farthest from the source area. Going from the screening level ecological risk assessment (ERA) to the probabilistic ERA changed the risk from unacceptable to acceptable in 50% of exposure scenarios in two of the four areas within the estuary. The probabilistic ERA provided a more realistic assessment of risk than the screening-level hazard assessment.

  19. Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies.

    PubMed

    McIntosh, Grant J; Russell, Douglas K

    2013-05-23

    Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems.

  20. Determination of volatile chlorinated hydrocarbons in water samples by static headspace gas chromatography with electron capture detection.

    PubMed

    Li, Tiejun; Guo, Yuanming; Hu, Hongmei; Zhang, Xiaoning; Jin, Yanjian; Zhang, Xiaojun; Zhang, Yurong

    2016-01-01

    A simple, efficient, solvent-free, and commercial readily available approach for determination of five volatile chlorinated hydrocarbons in water samples using the static headspace sampling and gas chromatography with electron capture detection has been described. The proposed static headspace sampling method was initially optimized and the optimum experimental conditions found were 10 mL water sample containing 20% w/v sodium chloride placed in a 20 mL vial and stirred at 50ºC for 20 min. The linearity of the method was in the range of 1.2-240 μg/L for dichloromethane, 0.2-40 μg/L for trichloromethane, 0.005-1 μg/L for perchloromethane, 0.025-5 μg/L for trichloroethylene, and 0.01-2 μg/L for perchloroethylene, with coefficients of determination ranging between 0.9979 and 0.9990. The limits of detection were in the low μg/L level, ranging between 0.001 and 0.3 μg/L. The relative recoveries of spiked five volatile chlorinated hydrocarbons with external calibration method at different concentration levels in pure, tap, sea water of Jiaojiang Estuary, and sea water of waters of Xiaomendao were in the range of 91-116, 96-105, 86-112, and 80-111%, respectively, and with relative standard deviations of 1.9-3.6, 2.3-3.5, 1.5-2.7, and 2.3-3.7% (n = 5), respectively. The performance of the proposed method was compared with traditional liquid-liquid extraction on the real water samples (i.e., pure, tap, and sea water, etc.) and comparable efficiencies were obtained. It is concluded that this method can be successfully applied for the determination of volatile chlorinated hydrocarbons in different water samples.

  1. Assessment of the chlorinated hydrocarbons residues contamination in edible mushrooms from the North-Eastern part of Poland.

    PubMed

    Gałgowska, Michalina; Pietrzak-Fiećko, Renata; Felkner-Poźniakowska, Barbara

    2012-11-01

    The aim of the study was to determine the content of chlorinated hydrocarbon residues in edible mushrooms from the north-eastern part of Poland. Material consisted of two species of fungi: Xerocomus mushrooms (Xerocomus badius), Boletus mushrooms (Boletus edulis). The dried samples (cups and cut-up material) were extracted with Soxhlet method in order to obtain lipid substances. In the fat chlorinated hydrocarbons were determined by Ludwicki et al. (1996) method. The separation and quantitative determination of DDT, DDE, DDD and γ-HCH were conducted with the method of gas chromatography using an electron capture detector - ECD. In all tested samples the presence of γ-HCH, DDT and its metabolites (DDE, DDD) was detected. The higher content of γ-HCH was found in Xerocomus mushrooms (average 0.125 μg/kg of mushrooms); in the Boletus mushrooms -0.11 μg/kg of mushrooms. The content of ΣDDT in cups of Xerocomus mushrooms was more than 2-fold higher than in those of Boletus mushrooms (3.78:1.71 mg/kg of mushrooms). The opposite relationship was observed for cut-up material. The higher concentration of ΣDDT was found in Boletus mushrooms (2.26 mg/kg of mushrooms) while in Xerocomus mushrooms this content was 0.91 mg/kg of mushrooms. Despite the fact that chlorinated hydrocarbons were determined in all samples under study, their contents do not exceed acceptable levels indicating that the consumption of mushrooms does not pose a health risk to consumers from the organochlorine compounds.

  2. Dechlorination of chlorinated hydrocarbons by bimetallic Ni/Fe immobilized on polyethylene glycol-grafted microfiltration membranes under anoxic conditions.

    PubMed

    Parshetti, Ganesh K; Doong, Ruey-an

    2012-01-01

    In this study, the dechlorination of chlorinated hydrocarbons including trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) by bimetallic Ni/Fe nanoparticles immobilized on four different membranes was investigated under anoxic conditions. Effects of several parameters including the nature of membrane, initial concentration, pH value, and reaction temperature on the dechlorination efficiency were examined. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the four membranes using polyethylene glycol as the cross-linker. The agglomeration of Ni/Fe were observed in poly(vinylidene fluoride), Millex GS and mixed cellulose ester membranes, while a relatively uniform distribution of Ni/Fe was found in nylon-66 membrane because of its hydrophilic nature. The immobilized Ni/Fe nanoparticles exhibited good reactivity towards the dechlorination of chlorinated hydrocarbons, and the pseudo-first-order rate constant for TCE dechlorination by Ni/Fe in nylon-66 were 3.7-11.7 times higher than those in other membranes. In addition, the dechlorination efficiency of chlorinated hydrocarbons followed the order TCE>PCE>CT. Ethane was the only end product for TCE and PCE dechlorination, while dichloromethane and methane were found to be the major products for CT dechlorination, clearly indicating the involvement of reactive hydrogen species in dechlorination. In addition, the initial rate constant for TCE dechlorination increased upon increasing initial TCE concentrations and the activation energy for TCE dechlorination by immobilized Ni/Fe was 34.9 kJ mol(-1), showing that the dechlorination of TCE by membrane-supported Ni/Fe nanoparticles is a surface-mediated reaction.

  3. Sediments of salt lakes as a new source of volatile highly chlorinated C1/C2 hydrocarbons

    NASA Astrophysics Data System (ADS)

    Weissflog, L.; Lange, C. A.; Pfennigsdorff, A.; Kotte, K.; Elansky, N.; Lisitzyna, L.; Putz, E.; Krueger, G.

    2005-01-01

    It is shown for the first time that the volatile highly chlorinated C2 hydrocarbons (VCHCs) trichloroethene (TRI; C2HCl3), tetrachloroethene (PER; C2Cl4) and methyl chloroform (MC; C2H3Cl3), but also C1 hydrocarbons tetrachloromethane and chloroform can be naturally formed in the sediment of salt lakes (ssl). Archaic halobacteria appear to play a key role in the microbial formation involved. TRI, PER and MC can be transformed into trichloroacetic acid (TCA) in the atmosphere. TRI and PER can also be metabolised into TCA following uptake by plants. Already considerably phytotoxic by itself, TCA's phytotoxicity is exacerbated if the vegetation concerned is simultaneously exposed to drought-stress. TRI and PER, emitted by these newly identified natural sources, can accelerate desertification in semi-arid and arid climate zones in consequence of the destabilisation of vegetation by its phytotoxic metabolite TCA.

  4. Synergistic degradation of chlorinated hydrocarbons with microorganisms and zero valent iron

    NASA Astrophysics Data System (ADS)

    Schöftner, Philipp; Summer, Dorothea; Leitner, Simon; Watzinger, Andrea; Wimmer, Bernhard; Reichenauer, Thomas

    2016-04-01

    Sites contaminated with chlorinated hydrocarbons (CHC) are located mainly within build-up regions. Therefore in most cases only in-situ technologies without excavation of soil material can be used for remediation. This project examines a novel in-situ remediation method, in which the biotic degradation via bacteria is combined with abiotic degradation via zero-valent iron particles (ZVI). ZVI particles are injected into the aquifer where CHC-molecules are reductively dechlorinated. However Fe0 is also oxidized by reaction with water leading to generation of H2 without any CHC degradation. To achieve biotic degradation often strictly anaerobic strains of the bacteria Dehalococcoides are used. These bacteria can dechlorinate CHC by utilizing H2. By combining these processes the H2, produced during the anaerobic corrosion of Fe0, could be used by bacteria for further CHC degradation. Therefore the amount of used Fe0 and as a consequence also remediation costs could be reduced. Additionally the continuous supply of H2 could make the bacterial degradation more controllable. Different Fe0 particles (nano- and micro-scale) were tested for their perchloroethene (PCE) degradation rate and H2 production rate in microcosms. PCE-degradation rate by different bacterial cultures was investigated in the same microcosm system. In course of these experiments the 13C enrichment factors of the PCE degradation of the different particles and cultures were determined to enable the differentiation of biotic and abiotic degradation. Preliminary results showed, that the nano-scale particles reacted faster with PCE and water than their micro-scaled counterparts. The PCE degradation via micro-scaled particles lead to 13C enrichment factors in the range of -3,6 ‰ ± 0,6 to -9,5 ‰ ± 0,2. With one of the examined bacterial cultures a fast reduction of PCE to ethene was observed. Although PCE and TCE were completely degraded by this culture the metabolites DCE and VC could still be detected

  5. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots.

    PubMed

    Powell, C L; Goltz, M N; Agrawal, A

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~1.9mgL(-1), and initial aqueous [CAH] ~150μgL(-1); cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12±0.01 and 0.59±0.07d(-1), respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Patterns and trends of chlorinated hydrocarbons in nestling bald eagle (Haliaeetus leucocephalus) plasma in British Columbia and Southern California.

    PubMed

    Cesh, Lillian S; Williams, Tony D; Garcelon, David K; Elliott, John E

    2008-10-01

    Patterns and trends of chlorinated hydrocarbons were assessed in bald eagle nestling plasma from sites along the west coast of North America. Eagle plasma was sampled from four areas in southwestern British Columbia (BC), a reference site in northern BC, and from Santa Catalina Island, off the coast of California. Sites were chosen to reflect variation in contaminant exposure due to differing recent and/or historic anthropogenic activities. Santa Catalina Island had significantly greater mean concentrations of p,p'-DDE, 41.3 microg/kg wet weight (ww), than other sites, and Nanaimo/Crofton, BC had the greatest mean concentration of total PCBs, 28.9 microg/kg ww. Contaminant levels measured in 2003 in BC were compared to levels measured in 1993; over that ten year span, concentrations and patterns of chlorinated hydrocarbons have not significantly changed. There were no significant differences in levels of p,p'-DDE or hexachlorobenzene between 1993 and 2003, but significant decreases were found for trans-nonachlor and PCBs at BC sites. Levels of total PCBs and trans-nonachlor in the central Fraser Valley and Nanaimo/Crofton area have significantly decreased. Mean concentrations of p,p'-DDE measured in bald eagle nestling plasma samples in 2003 exceeded published criteria for effects on bald eagle reproduction at Santa Catalina Island and Barkley Sound, more than 30 years since heavy usage restrictions were imposed.

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

    NASA Technical Reports Server (NTRS)

    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.; hide

    2013-01-01

    Four individual sample portions from a single scoop of the Rocknest aeolian deposit were sieved ( 150 m) and delivered to the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatography mass spectrometry analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of 0.01 to 2.3 nanomole.The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N- (tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), a chemical that leaked from a derivatization cup inside SAM.The best candidate for the oxychloride phase in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated species measured by SAM, although other chlorine bearing phases are being considered. Laboratory pyrolysis experiments suggest that reaction of martian chlorine with organic carbon from MTBSTFA can explain the presence of the chloromethanes and a chloromethylpropene also detected by SAM.However, we cannot exclude the possibility that traces of organic carbon of either martian or exogenous origin contributed to some of the chloromethanes measured by SAM. Although the alteration history and exposure age of the Rocknest deposit is unknown, it is possible that oxidative degradation of complex organic matter by ionizing radiation or other chemical processes in Rocknest has occurred.

  8. Ab initio heats of formation for chlorinated hydrocarbons: Allyl chloride, cis- and trans-1-chloropropene, and vinyl chloride

    NASA Astrophysics Data System (ADS)

    Colegrove, Brenda Thies; Thompson, Tyler B.

    1997-01-01

    Ab initio molecular energies at several levels of theory (MP4/6-311G**//MP2/6-31G*, MP4/6-311+G**//MP2/6-31G*,G1, and G2) are used to determine the heats of formation of several chlorinated hydrocarbons (allyl chloride, cis- and trans-1-chloropropene, and vinyl chloride) from atomization and isodesmic reactions. More than one isodesmic reaction was investigated for each molecule. Inconsistencies between the results from isodesmic reactions for a given molecule indicated possible errors in the experimental heats of formation for some of the chlorinated molecules used as references in the isodesmic reactions (in particular 1-chloropropane and 2-chloropropane). To further examine this possibility we did a multivariate regression for the G2 calculated reaction enthalpies for the 30 isodesmic reactions. In the regression, the heats of formation of the hydrocarbons and CH3Cl were fixed at the experimental values. The heats of formation of all the other chlorinated hydrocarbons were varied. The heats of formation determined using this method were: ΔHf298(CH2Cl2)=-22.6 kcal/mole, ΔHf298(CHCl=Cl2)=5.0 kcal/mole, ΔHf298(CCl2=CH2)=-0.2 kcal/mole, ΔHf298(CH2Cl-CH3)=-27.0 kcal/mole, ΔHf298(c-CHCl=CH-CH3)=-3.1 kcal/mole, ΔHf298(t-CHCl=CH-CH3)=-2.8 kcal/mole, ΔHf298(CH2=CClCH3)=-5.4 kcal/mole, ΔHf298(CH2=CH-CH2Cl)=-0.8 kcal/mole, ΔHf298(CH2Cl-CH2-CH3) =-32.2 kcal/mole, ΔHf298(CH3-CHCl-CH3 )=-35.9 kcal/mole. The calculated heats of formation were used to derive the following Benson group enthalpy values: C-(Cl)(H)2(Cd)=-15.6 kcal/mole, Cd-(Cl)(H)=-1.3 kcal/mole, and cis-halogen-alkyl =-0.3 kcal/mole.

  9. IN SITU DESTRUCTION OF CHLORINATED HYDROCARBON COMPOUNDS IN GROUNDWATER USING CATALYTIC REDUCTIVE REDUCTIVE DEHALOGENATION IN A REACTIVE WELL: TESTING AND OPERATIONAL EXPERIENCES. (R825421)

    EPA Science Inventory

    A groundwater treatment technology based on catalytic reductive
    dehalogenation has been developed to efficiently destroy chlorinated
    hydrocarbons in situ using a reactive well approach. The treatment process
    utilizes dissolved H2 as an electron donor, in...

  10. SIMULATION OF PERFORMANCE OF CHLORINE-FREE FLURORINATED ETHERS AND FLUORINATED HYDROCARBONS TO REPLACE CFC-11 AND CFC-114 IN CHILLERS

    EPA Science Inventory

    The paper discusses simulation of the performance of chlorine-free fluorinated ethers and fluorinated hydrocarbons as potential long-term replacements for CFC-11 and -114. Modeling has been done with in-house refrigeration models based on the Carnahan-Starling-DeSantis Equation o...

  11. SIMULATION OF PERFORMANCE OF CHLORINE-FREE FLURORINATED ETHERS AND FLUORINATED HYDROCARBONS TO REPLACE CFC-11 AND CFC-114 IN CHILLERS

    EPA Science Inventory

    The paper discusses simulation of the performance of chlorine-free fluorinated ethers and fluorinated hydrocarbons as potential long-term replacements for CFC-11 and -114. Modeling has been done with in-house refrigeration models based on the Carnahan-Starling-DeSantis Equation o...

  12. Polyethylene as a source of artifacts in the paper chromatography of chlorinated hydrocarbon insecticides

    USGS Publications Warehouse

    Van Valin, C.C.; Kallman, B.J.; O'Donnell, J.J

    1963-01-01

    The introduction of artifacts from vessels, materials, and chemicals is a serious problem in the study of pesticide residues. It is therefore of interest to record findings that polyethylene wash bottles contain substances soluble in organic solvents and reactive with the silver nitrate chromogenic spray commonly employed in the paper chromatographic analysis of chlorinated organic insecticides.

  13. Use of tree rings to investigate the onset of contamination of a shallow aquifer by chlorinated hydrocarbons

    USGS Publications Warehouse

    Yanosky, T.M.; Hansen, B.P.; Schening, M.R.

    2001-01-01

    Oaks (Quercus velutina Lam.) growing over a shallow aquifer contaminated by chlorinated hydrocarbons were studied to determine if it was possible to estimate the approximate year that contamination began. The annual rings of some trees downgradient from the contaminant release site contained elevated concentrations of chloride possibly derived from dechlorination of contaminants. Additionally, a radial-growth decline began in these trees at approximately the same time that chloride became elevated. Growth did not decline in trees that contained smaller concentrations of chloride. The source of elevated chloride and the corresponding reductions in tree growth could not be explained by factors other than contamination. On the basis of tree-ring evidence alone, the release occurred in the late 1960s or early 1970s. Contaminant release at a second location apparently occurred in the mid- to late 1970s, suggesting that the area was used for disposal for at least 5 years and possibly longer. Copyright ?? 2001 Elsevier Science B.V.

  14. Chlorinated hydrocarbon contamination in osprey eggs and nestlings from the Canadian Great Lakes basin, 1991-1995.

    PubMed

    Martin, Pamela A; De Solla, Shane R; Ewins, Peter

    2003-01-01

    Populations of osprey (Pandion haliaetus) in the Great Lakes basin declined dramatically during the 1950s-1970s due largely to adverse effects of persistent chlorinated hydrocarbons, ingested in their fish prey, on eggshell thickness and adult survival. Nevertheless, these contaminants were not measured in osprey tissues during the decades of decline on the Canadian Great Lakes. Between 1991 and 1995, we monitored recovering osprey populations on the Great Lakes, including Georgian Bay and the St. Marys River area on Lake Huron and the St. Lawrence Islands National Park, as well as at two inland sites within the basin. Current OC levels, even from the most contaminated lakes, were typically lower than those associated with reproductive effects. DDE levels in fresh eggs averaged 1.2-2.9 microg/g, well below the 4.2 microg/g level associated with significant eggshell thinning and shell breakage. Nevertheless, a proportion of eggs from all study areas did exceed this level. PCB levels in eggs seldom exceeded 5 microg/g except in one lake of high breeding density in the Kawartha Lakes inland study area, where the mean sum PCB level was 7.1 microg/g and the maximum concentration measured was 26.5 microg/g. On average, mean reproductive output (0.78-2.75 young per occupied nest) of breeding populations in Great Lakes basin study areas exceeded the threshold of 0.8 young thought necessary to maintain stable populations. We concluded that, although eggs and especially nestling plasma, are useful in reflecting local contaminant levels, ospreys are relatively insensitive, at least at the population level, to health effects of current levels of chlorinated hydrocarbons on the Canadian Great Lakes.

  15. Occurrence, profiles, and toxic equivalents of chlorinated and brominated polycyclic aromatic hydrocarbons in E-waste open burning soils.

    PubMed

    Nishimura, Chiya; Horii, Yuichi; Tanaka, Shuhei; Asante, Kwadwo Ansong; Ballesteros, Florencio; Viet, Pham Hung; Itai, Takaaki; Takigami, Hidetaka; Tanabe, Shinsuke; Fujimori, Takashi

    2017-06-01

    We conducted this study to assess the occurrence, profiles, and toxicity of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and brominated polycyclic aromatic hydrocarbons (Br-PAHs) in e-waste open burning soils (EOBS). In this study, concentrations of 15 PAHs, 26 Cl-PAHs and 14 Br-PAHs were analyzed in EOBS samples. We found that e-waste open burning is an important emission source of Cl-PAHs and Br-PAHs as well as PAHs. Concentrations of total Cl-PAHs and Br-PAHs in e-waste open burning soil samples ranged from 21 to 2800 ng/g and from 5.8 to 520 ng/g, respectively. Compared with previous studies, the mean of total Cl-PAH concentrations of the EOBS samples in this study was higher than that of electronic shredder waste, that of bottom ash, and comparable to fly ash from waste incinerators in Korea and Japan. The mean of total Br-PAH concentrations of the EOBS samples was generally three to four orders of magnitude higher than those in incinerator bottom ash and comparable to incinerator fly ash, although the number of Br-PAH congeners measured differed among studies. We also found that the Cl-PAH and Br-PAH profiles were similar among all e-waste open burning soil samples but differed from those in waste incinerator fly ash. The profiles and principal component analysis results suggested a unique mechanism of Cl-PAH and Br-PAH formation in EOBS. In addition, the Cl-PAHs and Br-PAHs showed high toxicities equivalent to PCDD/Fs measured in same EOBS samples when calculated based on their relative potencies to benzo[a]pyrene. Along with chlorinated and brominated dioxins and PAHs, Cl-PAHs and Br-PAHs are important environmental pollutants to investigate in EOBS. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Polynuclear aromatic and chlorinated hydrocarbons in mussels from the coastal zone of Ushuaia, Tierra del Fuego, Argentina.

    PubMed

    Amin, Oscar A; Comoglio, Laura I; Sericano, José L

    2011-03-01

    Mussels (Mytilus edulis chilensis) were collected from 12 coastal locations in Ushuaia Bay, Argentina, and the surrounding area in October 1999 and again in October 2003. Concentrations of polynuclear aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and selected chlorinated pesticides were determined to assess the impact of a fast-growing population in the area. Total PAH concentrations ranged from 2.24 to an extremely high concentration of 2,420 µg/g lipid measured in mussels collected near an oil jetty used to discharge to shore storage tanks. The composition of PAHs in these samples indicates that the source of these compounds inside Ushuaia Bay is predominantly petrogenic, with some pyrogenic background, whereas mostly pyrogenic-related PAHs were evident in areas outside the bay. Total concentrations of PCBs ranged between 12.8 and 8,210 ng/g lipid, with the highest concentration, detected inside Ushuaia harbor, representing a 10-fold increase when compared with historical data. Chlorinated pesticides were detected at comparatively lower concentrations, with 4-4'- 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene being the most common. The aggressive increase in population and related activities observed in the city of Ushuaia over the last two decades might have affected the environmental quality of the local bay. Moreover, the oceanographic and atmospheric conditions existing in Ushuaia Bay and surrounding areas may favor the accumulation and long-term presence of these organic pollutants in all compartments of this fragile environment.

  17. Comparative electrochemical treatments of two chlorinated aliphatic hydrocarbons. Time course of the main reaction by-products.

    PubMed

    Randazzo, Serena; Scialdone, Onofrio; Brillas, Enric; Sirés, Ignasi

    2011-09-15

    Acidic aqueous solutions of the chlorinated aliphatic hydrocarbons 1,2-dichloroethane (DCA) and 1,1,2,2-tetrachloroethane (TCA) have been treated by the electro-Fenton (EF) process. Bulk electrolyses were performed at constant current using a BDD anode and an air diffusion cathode able to generate H(2)O(2) in situ, which reacts with added Fe(2+) to yield OH from Fenton's reaction. At 300 mA, almost total mineralization was achieved at 420 min for solutions containing 4mM of either DCA or TCA. Comparative treatments without Fe(2+) (anodic oxidation) or with a Pt anode led to a poorer mineralization. The better performance of the EF process with BDD is explained by the synergistic action of the oxidizing radicals, BDD(OH) at the anode surface and OH in the bulk, and the minimization of diffusional limitations. The decay of the initial pollutant accomplished with pseudo first-order kinetics. Chloroacetic and dichloroacetic acids were the major by-products during the degradation of DCA and TCA, respectively. Acetic, oxalic and formic acids were also identified. The proposed reaction pathways include oxidative and reductive (cathodic) dechlorination steps. Chlorine was released as Cl(-), being further oxidized to ClO(3)(-) and, mostly, to ClO(4)(-), due to the action of the largely generated BDD(OH) and OH.

  18. Trophodynamic analysis of polychlorinated biphenyl congeners and other chlorinated hydrocarbons in the Lake Ontario ecosystem

    SciTech Connect

    Oliver, B.G.; Niimi, A.J. )

    1988-04-01

    The bioaccumulation of polychlorinated biphenyl (PCB) congeners and some other chlorinated organics in the Lake Ontario ecosystem has been studied. In addition to the classical biomagnification of PCBs and some of the other organics, the chlorine content of the PCBs was observed to increase with trophic level. Most of the differential PCB fractionation seemed to occur at the lower end of the food chain (water to plankton to mysid). At the higher trophic levels (mysid to smelt to salmonid), the PCBs seemed to be distributed as a uniform composition mixture. The bioaccumulation factor of these hydrophobic organics increased linearly with octanol-water partition coefficient of the chemicals at all trophic levels. The environmental bioaccumulation of these chemicals in salmonids was higher than that predicted from bioconcentration from water alone, showing that contaminated food is a major source of these chemical residues in fish.

  19. Chemical induction of tumors in oysters by a mixture of aromatic and chlorinated hydrocarbons, amines and metals

    SciTech Connect

    Gardner, G.R.; Pruell, R.J.; Malcolm, A.R.

    1992-01-01

    Tumors were induced in eastern oysters (Crassostrea virginica) by a mixture of aromatic hydrocarbons, an aromatic amine, polychlorinated biphenyls, chlorinated hydrocarbons, a nitrosoamine and heavy metals. Kidney and enteric tumors developed in oysters following exposure to a mixture containing 3,4-benzopyrene, 1,2-benzanthracene, 2-aminofluorene, N-nitrosodiethylamine, technical chlordane, Aroclors 1242 and 1254, p,p'-DDE, cadmium (CdCl2), chromium (K2CrO4) and lead (Pb(NO3)2). 2-Aminofluorene and N-nitrosodiethylamine, not measured in Black Rock Harbor sediment, were both added at 0.6 and 6.0 micrograms/g dry sediment. A 3% prevalence of low-grade renal and gastrointestinal tumors developed after 30 days in oysters fed water-column suspended sediment particulate spiked with the mixture of chemicals. Disease progression was most advanced in enteric adenomas. Both types are comparable to those produced after 30 days in the same organs by chemically contaminated Black Rock Harbor sediment.

  20. Occurrence and source of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in tidal flats of the Ariake Bay, Japan.

    PubMed

    Sankoda, Kenshi; Kuribayashi, Tomonori; Nomiyama, Kei; Shinohara, Ryota

    2013-07-02

    In this study, we hypothesize that natural photochemical reactions of polycyclic aromatic hydrocarbons (PAHs) in tidal flats are responsible for the occurrence of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs). This study aims to survey the impact of photochemical reactions using a combination of field surveys and lab-scale experiments. Concentrations and profiles of PAHs and Cl-PAHs in road dust and sediments collected from seven tunnels and two watersheds, respectively, were determined. In the lab-scale experiments, anthracene was irradiated with ultraviolet (UV) light under various salinity conditions. No detectable Cl-PAHs were found in the road dust. However, Cl-PAHs were detected in the sediments from 700 to 6.1 × 10(3) pg g(-1) and specifically from downstream sites. 2-Monochloroanthracene (2-Cl-ANT) and 9,10-dichloroanthracene (9,10-di-Cl-ANT) were dominant in the sediments. In the Domen River watershed, the ∑Cl-PAHs and the salinity showed a significant positive correlation (p < 0.01) in the sediments, while such a correlation was not found for PAHs. 2-Cl-ANT, 9-monochloroanthracene, and 9,10-di-Cl-ANT were identified as transformation products in the UV irradiation experiments. Production of these Cl-PAHs was dependent on the solution salinity. These results support our hypothesis, and we conclude that photochemical reactions significantly contribute to the occurrence of Cl-PAHs in the studied tidal flats.

  1. Occurrence of chlorinated and brominated polycyclic aromatic hydrocarbons in surface sediments in Shenzhen, South China and its relationship to urbanization.

    PubMed

    Sun, Jian-Lin; Ni, Hong-Gang; Zeng, Hui

    2011-10-01

    One hundred and fourteen surface sediments were collected from the Maozhou River Watershed in Shenzhen, China from December 2009 to January 2010. Three individual chlorinated polycyclic aromatic hydrocarbons (ClPAHs), six individual brominated polycyclic aromatic hydrocarbons (BrPAHs), and five corresponding parent polycyclic aromatic hydrocarbons (PAHs) were determined. The concentration of 9-chlorophenanthrene was the highest ranging from 0.51-289 ng g(-1) (average, 16.5 ng g(-1)). For BrPAHs, the concentration of 2-bromofluorene was the highest ranging from 0.31-266 ng g(-1) (average, 35.3 ng g(-1)). No correlation was observed between the concentrations of ClPAHs and parent PAHs in surface sediments. In addition, there was no correlation between 1-bromopyrene, 7-bromobenz(a)anthracene and 9,10-dibromoanthracene, and corresponding parent PAHs. However, a significant correlation was found between 9-bromophenanthrene and phenanthrene (p < 0.01), between 9-bromoanthracene and anthracene (p < 0.05), and between 2-bromofluorene and fluorene (p < 0.05). Six fly ash samples collected from one of the municipal domestic waste incineration plants in Shenzhen were also analyzed for source identification. The concentration of 7-bromobenz(a)anthracene was the highest, ranging from 3.21-4.08 ng g(-1). In addition, 2-bromofluorene was not detected in all the fly ash samples. No correlation was found between the concentrations of Cl-/BrPAHs and corresponding parent PAHs in fly ashes. We also examined the relationship between the levels of Cl-/BrPAHs in surface sediments and the urbanization process. Our results suggested the levels of individual Cl-/BrPAHs congeners presented a similar increasing trend with the increasing urbanization level.

  2. Chlorinated hydrocarbons in the marine environment. A report prepared by the Panel on Monitoring Persistent Pesticides in the Marine Environment of the Committee on Oceanography

    USGS Publications Warehouse

    ,; Goldberg, E.D.; Butler, P.; Meier, P.; Menzel, D.; Paulik, G.; Risebrough, R.; Stickel, L.F.

    1971-01-01

    SUMMARY AND RECOMMENDATIONS : The oceans are an ultimate accumulation site for the persistent chlorinated hydrocarbons. As much as 25 percent of the DDT compounds produced to date may have been transferred to the sea. The amount of DDT compounds in the marine biota is estimated to be less than 0.1 percent of total production, yet this amount has produced a demonstrable impact upon the marine environment. Populations of fish-eating birds have experienced reproductive failure and decline. With continued accumulations of persistent chlorinated hydrocarbons in the marine ecosystem, additional species will be threatened. Continued release of these pollutants to the environment can only accelerate the accumulation of unacceptable levels of persistent chlorinated hydrocarbons in the tissues of marine food fish. Certain risks in the utilization of chlorinated hydrocarbons are especially hard to quantify, but they require serious consideration. The rate at which such substances degrade to harmless products in the marine system is unknown; the half-lives of some of the more persistent materials are certainly of the order of years, and perhaps even of decades or centuries. If most of the remaining 75 percent of the persistent chlorinated hydrocarbons is now in reservoirs that will in time transfer their contents to the sea, we may expect an increased level of these substances in marine organisms, despite future improvements of manufacturing practices. In fact, if these compounds degrade with half-lives of decades or longer, there will be no opportunity to redress the consequences. The more the problems are studied, the more unexpected effects are identified. In view of the findings of the past decade, our prediction of the potential hazards of chlorinated hydrocarbons in the marine environment may be vastly underestimated. The Panel makes the following recommendations, which will be developed and expanded in the remainder of the report: ? A massive national effort should be

  3. BIOTRANSFORMATION OF MONOAROMATIC AND CHLORINATED HYDROCARBONS AT AN AVIATION GASOLINE SPILL SITE

    EPA Science Inventory

    A shallow water table aquifer under the U.S. Coast Guard Air Station at Traverse City, MI, has acclimated to the aerobic and anaerobic transformation of monoaromatic hydrocarbons (BTX) released from an aviation gasoline spill. The aquifer also exhibits reductive dechlorination of...

  4. BIOTRANSFORMATION OF MONOAROMATIC AND CHLORINATED HYDROCARBONS AT AN AVIATION GASOLINE SPILL SITE

    EPA Science Inventory

    A shallow water table aquifer under the U.S. Coast Guard Air Station at Traverse City, MI, has acclimated to the aerobic and anaerobic transformation of monoaromatic hydrocarbons (BTX) released from an aviation gasoline spill. The aquifer also exhibits reductive dechlorination of...

  5. TAILORING CATALYSTS FOR HYDRODECHLORINATING CHLORINATED HYDROCARBON CONTAMINANTS IN GROUNDWATER. (R825689C093)

    EPA Science Inventory

    Abstract

    A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...

  6. TAILORING CATALYSTS FOR HYDRODECHLORINATING CHLORINATED HYDROCARBON CONTAMINANTS IN GROUNDWATER. (R825689C078)

    EPA Science Inventory

    Abstract

    A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...

  7. TAILORING CATALYSTS FOR HYDRODECHLORINATING CHLORINATED HYDROCARBON CONTAMINANTS IN GROUNDWATER. (R825689C093)

    EPA Science Inventory

    Abstract

    A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...

  8. TAILORING CATALYSTS FOR HYDRODECHLORINATING CHLORINATED HYDROCARBON CONTAMINANTS IN GROUNDWATER. (R825689C078)

    EPA Science Inventory

    Abstract

    A palladium-on-zeolite catalyst has been optimized for treating groundwater contaminated with halogenated hydrocarbon compounds (HHCs) by hydrodechlorination with dissolved hydrogen. Aqueous sulfite was used as the model poison and the dechlorination of 1,2-di...

  9. Natural attenuation of chlorinated-hydrocarbon contamination at Fort Wainwright, Alaska; a hydrogeochemical and microbiological investigation workplan

    USGS Publications Warehouse

    McCarthy, Kathleen A.; Lilly, Michael R.; Braddock, Joan F.; Hinzman, Larry D.

    1998-01-01

    Natural attenuation processes include biological degradation, by which microorganisms break down contaminants into simpler product compounds; adsorption of contaminants to soil particles, which decreases the mass of contaminants dissolved in ground water; and dispersion, which decreases dissolved contaminant concentrations through dilution. The primary objectives of this study are to (1) assess the degree to which such natural processes are attenuating chlorinated-hydrocarbon contamination in ground water, and (2) evaluate the effects of ground-water/surface-water interactions on natural-attenuation processes in the area of the former East and West Quartermasters Fueling Systems for Fort Wainwright, Alaska. The study will include investigations of the hydrologic, geochemical, and microbiological processes occurring at this site that influence the transport and fate of chlorinated hydrocarbons in ground water. To accomplish these objectives, a data-collection program has been initiated that includes measurements of water-table elevations and the stage of the Chena River; measurements of vertical temperature profiles within the subsurface; characterization of moisture distribution and movement in the unsaturated zone; collection of ground-water samples for determination of both organic and inorganic chemical constituents; and collection of ground-water samples for enumeration of microorganisms and determination of their potential to mineralize contaminants. We will use results from the data-collection program described above to refine our conceptual model of hydrology and contaminant attenuation at this site. Measurements of water-table elevations and river stage will help us to understand the magnitude and direction of ground-water flow and how changes in the stage of the Chena River affect ground-water flow. Because ambient ground water and surface water typically have different temperature characteristics, temperature monitoring will likely provide further insight

  10. Chlorinated hydrocarbon contaminants in feces of river otters from the southern Pacific coast of Canada, 1998-2004.

    PubMed

    Elliott, John E; Guertin, Daniel A; Balke, Jennifer M E

    2008-07-01

    Chlorinated hydrocarbon contaminants in coastal river otters (Lontra canadensis) were evaluated by sampling feces (scats) collected on the south coast of British Columbia, Canada. A broad survey of industrialized areas of the Strait of Georgia region was conducted in 1998, and a subsequent survey of working harbours in 2004. Samples from 1998 were analyzed for polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides, and polychlorinated dioxins (PCDDs) and furans (PCDFs), while in 2004, chemistry was confined to summation operatorPCBs and OC pesticides. Concentrations of OC pesticides were low in both years, with only dichlorodiphenyldichloroethylene (DDE; range: 0.01-2.12 mg/kg lw) and hexachlorocyclobenzene (HCB; range: 0.003-0.25 mg/kg lw) detected in all samples. In 1998, octachlorodibenzo-p-dioxin (OCDD) and other higher chlorinated PCDD/Fs were found in most samples, with OCDD ranging from 120 ng/kg lw in Clayoquot Sound to 19,100 ng/kg lw in a pooled sample from two latrines in Nanaimo. PCBs were present in all samples. In 1998 geometric mean concentrations of the sum of 59 PCB congeners ranged from 0.49 mg/kg lw in Nanaimo to 12.3 mg/kg lw in Victoria Harbour. Six years later, mean summation operatorPCBs remained elevated (geometric mean 9.5 mg/kg lw) in Victoria Harbour. Geometric mean concentrations of summation operatorPCBs from Victoria Harbour in 1998 and 2004 were >9 mg/kg lw, a published adverse effect level for reproduction. At some latrines in both Victoria and Esquimalt Harbours, concentrations of TCDD-toxic equivalents exceeded 1500 ng/kg lw, a value for health effects in otters that we derived using published information. As shown in previous studies, analysis of scats provides an efficient and non-intrusive approach to assessing contaminant threats to otter populations, and to documenting spatial trends in residues.

  11. Evidence for in situ production of chlorinated polycyclic aromatic hydrocarbons on tidal flats: environmental monitoring and laboratory scale experiment.

    PubMed

    Sankoda, Kenshi; Nomiyama, Kei; Yonehara, Takayuki; Kuribayashi, Tomonori; Shinohara, Ryota

    2012-07-01

    This study investigated environmental distributions and production mechanisms of chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in the sediments from some tidal flats located in Asia. Cl-PAHs were found in sediments taken from Arao tidal flat, Kikuchigawa River and Shirakawa River. The range of ∑Cl-PAHs was from 25.5 to 483 pg g(-1) for Kikuchigawa River and Arao tidal flat, respectively. Concentrations of PAHs and Cl-PAHs showed no significant correlations (r=0.134). This result suggests that the origins of these compounds differ. In the identified Cl-PAH isomers, the most abundant Cl-PAH isomer was 9,10-dichloroanthracene (9,10-di-Cl-ANT) in the three sites. In general, concentrations of Cl-ANTs in the coastal environment are about 3-5 orders of magnitude lower than those of anthracene (ANT). However, concentration ratios between Cl-ANTs and ANT (Cl-ANTs/ANT) in the sediments ranged from 4.1% to 24.6%. This result indicated that Cl-PAHs were not generated under industrial processes but the high concentration ratios have resulted from the contribution of photochemical production of Cl-ANTs in the sediments because ANT is known to have high photochemical reactivity. For examining this phenomenon, ANT adsorbed onto glass beads was irradiated with UV under the mimicked field conditions of tidal flats. As a result, it was noticed that, while chlorinated derivatives were negligible in a light-controlled group, production of 2-Cl-ANT, 9-Cl-ANT and 9,10-diCl-ANT on the irradiated surface were found in this study. These results suggest that photochemical reaction of PAHs can be a potential source of the occurrence of Cl-PAHs in the coastal environment.

  12. Utilization of stable carbon isotope in the verification of bioremediation of chlorinated hydrocarbons. Final report, July--December 1995

    SciTech Connect

    DeFlaun, M.F.; Steffan, R.J.; Van de Velde, K.

    1996-10-01

    The overall goal of this work was to test the feasibility of using stable carbon isotope analysis to verify in situ biodegradation of hydrocarbons and chlorinated ethenes under aerobic conditions. Specific objectives were to (1) determine d{sup 13}C values for TCE and the various compounds to be used as co- substrates for TCE degradation; (2) evaluate effects of aerobic biodegradation of co-substrate compounds and TCE on gross fractionation of carbon isotopes as measured in the resulting CO{sub 2}; (3) test the carbon isotope method for its ability to differentiate the source of the CO{sub 2} resulting from aerobic biodegradation; and (4) use samples from an appropriately contaminated bioventing site. Different degrees of fractionation were measured in both pure and mixed cultures for the different compounds tested in this study. Fractionation for toluene was slightly more negative than the starting compound. For JP-4, the fractionation of JP-4 resulted in d{sup 13}C values much more negative than the starting compound. Fractionation for TCE results in d{sup 13}C values more positive, indicating the CO{sub 2} had a higher percentage of {sup 13}C than the source compound. A mixture of toluene and TCE had a d{sup 13}C value intermediate between the two. These results indicate, with the d{sup 13}C values for these co-substrates and chlorinated ethenes sufficiently different, the degradation of one or the other can be determined. When both are being degraded an intermediate value can be obtained.

  13. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and chlorinated pesticides in background air in central Europe - investigating parameters affecting wet scavenging of polycyclic aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Shahpoury, P.; Lammel, G.; Holubová Šmejkalová, A.; Klánová, J.; Přibylová, P.; Váňa, M.

    2014-10-01

    Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and chlorinated pesticides (CPs) were measured in air and precipitation at a background site in central Europe. Σ PAH concentrations in air and rainwater ranged from 0.7 to 327.9 ng m-3 and below analytical method detection limit (< MDL) to 2.1 × 103 ng L-1. The concentrations of PCBs and CPs in rainwater were < MDL. Σ PCB and Σ CP concentrations in air ranged from < MDL to 44.6 and < MDL to 351.7 pg m-3, respectively. The potential relationships between PAH wet scavenging and particulate matter and rainwater properties were investigated. The concentrations of ionic species in particulate matter and rainwater were significantly correlated, highlighting the importance of particle scavenging process. Overall, higher scavenging efficiencies were found for relatively less volatile PAHs, underlining the effect of analyte gas-particle partitioning on scavenging process. The PAH wet scavenging was more effective when the concentrations of ionic species were high. In addition, the elemental and organic carbon contents of the particulate matter were found to influence the PAH scavenging.

  14. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and chlorinated pesticides in background air in central Europe - investigating parameters affecting wet scavenging of polycyclic aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Shahpoury, P.; Lammel, G.; Holubová Šmejkalová, A.; Klánová, J.; Přibylová, P.; Váňa, M.

    2015-02-01

    Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and chlorinated pesticides (CPs) were measured in air and precipitation at a background site in central Europe. ∑ PAH concentrations in air and rainwater ranged from 0.7 to 327.9 ng m-3 and below limit of quantification (< LOQ) to 2.1 × 103 ng L-1. The concentrations of PCBs and CPs in rainwater were < LOQ. ∑ PCB and ∑ CP concentrations in air ranged from < LOQ to 44.6 and < LOQ to 351.7 pg m-3, respectively. The potential relationships between PAH wet scavenging and particulate matter and rainwater properties were investigated. The concentrations of ionic species in particulate matter and rainwater were significantly correlated, highlighting the importance of particle scavenging process. Overall, higher scavenging efficiencies were found for relatively less volatile PAHs, underlining the effect of analyte gas-particle partitioning on scavenging process. The particulate matter removal by rain, and consequently PAH wet scavenging, was more effective when the concentrations of ionic species were high. In addition, the elemental and organic carbon contents of the particulate matter were found to influence the PAH scavenging.

  15. Simulation of ground-water flow and transport of chlorinated hydrocarbons at Graces Quarters, Aberdeen Proving Ground, Maryland

    USGS Publications Warehouse

    Tenbus, Frederick J.; Fleck, William B.

    2001-01-01

    Military activity at Graces Quarters, a former open-air chemical-agent facility at Aberdeen Proving Ground, Maryland, has resulted in ground-water contamination by chlorinated hydrocarbons. As part of a ground-water remediation feasibility study, a three-dimensional model was constructed to simulate transport of four chlorinated hydrocarbons (1,1,2,2-tetrachloroethane, trichloroethene, carbon tetrachloride, and chloroform) that are components of a contaminant plume in the surficial and middle aquifers underlying the east-central part of Graces Quarters. The model was calibrated to steady-state hydraulic head at 58 observation wells and to the concentration of 1,1,2,2-tetrachloroethane in 58 observation wells and 101direct-push probe samples from the mid-1990s. Simulations using the same basic model with minor adjustments were then run for each of the other plume constituents. The error statistics between the simulated and measured concentrations of each of the constituents compared favorably to the error statisticst,1,2,2-tetrachloroethane calibration. Model simulations were used in conjunction with contaminant concentration data to examine the sources and degradation of the plume constituents. It was determined from this that mixed contaminant sources with no ambient degradation was the best approach for simulating multi-species solute transport at the site. Forward simulations were run to show potential solute transport 30 years and 100 years into the future with and without source removal. Although forward simulations are subject to uncertainty, they can be useful for illustrating various aspects of the conceptual model and its implementation. The forward simulation with no source removal indicates that contaminants would spread throughout various parts of the surficial and middle aquifers, with the100-year simulation showing potential discharge areas in either the marshes at the end of the Graces Quarters peninsula or just offshore in the estuaries. The

  16. Bioelectrochemical approach for reductive and oxidative dechlorination of chlorinated aliphatic hydrocarbons (CAHs).

    PubMed

    Lai, Agnese; Aulenta, Federico; Mingazzini, Marina; Palumbo, Maria Teresa; Papini, Marco Petrangeli; Verdini, Roberta; Majone, Mauro

    2017-02-01

    A sequential reductive-oxidative treatment was developed in this study in a continuous-flow bioelectrochemical reactor to address bioremediation of groundwater contaminated by trichloroethene (TCE) and less-chlorinated but still harmful intermediates, such as vinyl chloride. In order to optimize the anodic compartment, whereby the oxygen-driven microbial oxidation of TCE-daughter products occurs, abiotic batch experiments were performed with various anode materials poised at +1.20 V vs. SHE (i.e., graphite rods and titanium mesh anode coated with mixed metal oxides (MMO)) and setups (i.e., electrodes embedded within a bed of silica beads or graphite granule). The MMO anode displayed higher efficiency (>90%) for oxygen generation compared to the graphite electrodes. Additionally, the graphite bed presence adversely affects oxygen generation, likely due to the oxygen scavenging. This effect was completely eliminated by replacing the graphite granules with silica beads. The anodic setups were thereafter verified in a mentioned reactor at an applied TCE loading rate of approximately 20 μM d(-1) and a hydraulic retention time of 1.4 d in each compartment. The cathode consisted of a bed of graphite granules and was potentiostatically controlled at -0.65 V vs. SHE. The best reactor performance in terms of removal efficiency (i.e., >97%), removal rate (i.e., 121.8 ± 2.7 μeq L(-1) d(-1)), and the residual concentration (i.e., 5.03 ± 0.63 μeq L(-1)) of chlorinated contaminants was achieved with the MMO anode placed in a silica bed. Ecotoxicity tests performed with algae confirmed these results by showing progressive toxicity reduction from inlet to cathodic and anodic effluent using this reactor configuration.

  17. Chlorinated hydrocarbons in early life stages of the common snapping turtle (Chelydra serpentina serpentina) from a coastal wetland on Lake Ontario, Canada

    SciTech Connect

    Bishop, C.A.; Lean, D.R.S.; Carey, J.H.; Brooks, R.J.; Ng, P.

    1995-03-01

    To assess intra-clutch variation in contaminant concentrations in eggs, and to investigate the dynamics of chlorinated hydrocarbon accumulation in embryos of the common snapping turtle (Chelydra serpentina), concentrations of p,p{prime}-DDE, hexachlorobenzene, trans-nonachlor, cis-chlordane, and six PCB congeners were measured in eggs, embryos, and hatchlings. Samples were collected from Cootes Paradise, a wetland at the western end of Lake Ontario, Ontario, Canada. The intra-clutch variation in chlorinated hydrocarbon concentrations within four snapping turtle clutches was determined by analyzing the first, last, and middle five eggs oviposited in the nest. The first five eggs had the highest mean concentrations of all chlorinated hydrocarbons, wet weight, and egg diameter. On a lipid weight basis, the first five eggs contained the highest concentration of all compounds except total PCBs and cis-chlordane. The concentration of cis-chlordane was the only parameter measured that was significantly different among the three sets of eggs. At hatching, snapping turtles without yolk sacs contained from 55.2 to 90.5% of the absolute amount of organochlorine compounds measured in the egg at oviposition. Eighteen days after hatching, the body burden of PCBs and pesticides decreased to 45.3 to 62.2% of that in the fresh egg. The accumulation of organochlorine chemicals in embryonic turtles peaked at or just before hatching and then declined thereafter, which is consistent with trends reported in developing sea turtles, fish, and birds.

  18. The historical residue trend of chlorinated hydrocarbons in the Agassiz Ice Cap, Ellesmere I., Canada

    SciTech Connect

    Gregor, D.J.; Peters, A.J.; Backus, S.; Fisher, D.; Zheng, J.

    1995-12-31

    Current detailed measurements of contaminant deposition can not provide a historical perspective except through long term monitoring programs. In the Arctic, ice caps provide an alternative to lake sediments in that the annual snow layers reflect the atmospheric deposition. As a result of the remoteness of the Agassiz Ice Cap (80{degree}49`50``N, 72{degree}56`30``W) and the limited summer melt, annual layers undergo little chemical change, especially after the first summer season, and therefore provide a well defined historical record. PCBs were first measured above detection limit in the core in the late 1950`s. Mean concentration of {Sigma}PCB over the thirty year period is 3.5 ({+-}1.3) ng. L{sup {minus}1}. {Sigma}PCB is dominated by the lower chlorinated congeners with only infrequent detections of congeners with eight or more chlorines. Deposition peaked at 930 ng.m{sup {minus}2}.a{sup {minus}1} in 1967/68 and decreased to 90 ng.m{sup {minus}2}.a{sup {minus}1} in 1980/81. Since 1980/81, deposition has again increased to a local maximum of 850 ng.m{sup {minus}2}.a{sup {minus}1} in 1989/90. PAHs are detectable throughout the sampling period. Only 7 individual PAHs were above the quantification limits including naphthalene (accounting for an overall mean of 88% of the {Sigma}PAH) acenaphthene, fluorene, phenanthrene, fluoranthene, pyrene and chrysene. No PAHs with five or more aromatic rings were observed to be present above the detection limits. The flux of PAHs to the Ice Cap remained relatively constant from 1790 to 1940 at approximately 3 {micro}g.m{sup {minus}2}.a{sup {minus}1}. The period 1940 to 1980 is dominated by a large increase in deposition peaking at 70 {micro}g.m{sup {minus}2}.a{sup {minus}1} in the early 1970`s. The final period, 1980 to 1993 shows a steady increase by a factor of about 2 from a minimum of 10--20 {micro}g.m{sup {minus}2}.a{sup {minus}1}.

  19. Development of a standard reference material containing 22 chlorinated hydrocarbon gases at 1 μmol/mol in nitrogen.

    PubMed

    Li, Ning; Du, Jian; Yang, Jing; Fan, Qiang; Tian, Wen

    2017-09-08

    A gas standard mixture containing 22 chlorinated hydrocarbons in high purity nitrogen was prepared using a two-step weighing method and a gasifying apparatus developed in-house. The concentration of each component was determined using a gas chromatograph with flame ionization detection (GC/FID). Linear regression analysis of every component was performed using the gas standard mixture with concentrations ranging from 1 to 10 μmol/mol, showing the complete gasification of volatile organic compound (VOCs) species in a selected cylinder. Repeatability was also examined to ensure the reliability of the preparation method. In addition, no significant difference was observed between domestic treated and imported treated cylinders, which were conducive to reduction of the cost of raw materials. Moreover, the results of stability testing at different pressures and long-term stability tests indicated that the gas standard at 1 μmol/mol level with relative expanded uncertainties of 5% was stable above 2 MPa for a minimum of 12 months. Finally, a quantity comparison was conducted between the gas standard and a commercial gas standard from Scott Specialty Gases (now Air Liquide America Specialty Gases). The excellent agreement of every species suggested the favorable accuracy of our gas standard. Therefore, this reference material can be applied to routine observation of VOCs and for other purposes.

  20. Identifying sources of chlorinated aliphatic hydrocarbons in a residential area in Italy using the integral pumping test method

    NASA Astrophysics Data System (ADS)

    Alberti, Luca; Lombi, Silvia; Zanini, Andrea

    2011-09-01

    The results of integral pumping tests (IPTs) performed in the city of Fabriano, Italy, are presented. The IPT methodology was developed by the European Union project INCORE, as a tool for groundwater investigation and source localization in contaminated areas. This methodology consists of a multiple-well pumping test in which the wells are positioned along a control plane downstream of suspected contaminant source zones and perpendicular to the mean groundwater flow direction. During the pumping, concentration time series of target contaminants are measured. In Fabriano, two control planes were realized to identify a chlorinated aliphatic hydrocarbon plume, to estimate the mass fluxes and draw up a ranked list of the main contamination sources. A numerical flow model was implemented to support the IPT design and to interpret the results. This study revealed low-level trichloroethylene contamination (concentration below 8 μg/l), tetrachloroethylene contamination (mean concentration up to 500 μg/l) and a mass flow rate of about 300 g/day. Through the application of the IPT method, the mean contaminant concentrations, the spatial distribution of concentration values along the control planes, and the total contaminant mass flow rates were evaluated, and the investigation area was reduced for further and deeper investigation activities.

  1. Impact of carbon, oxygen and sulfur content of microscale zerovalent iron particles on its reactivity towards chlorinated aliphatic hydrocarbons.

    PubMed

    Velimirovic, Milica; Larsson, Per-Olof; Simons, Queenie; Bastiaens, Leen

    2013-11-01

    Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content.

  2. Monitoring the effect of poplar trees on petroleum-hydrocarbon and chlorinated-solvent contaminated ground water

    USGS Publications Warehouse

    Landmeyer, James E.

    2001-01-01

    At contaminated groundwater sites, poplar trees can be used to affect ground-water levels, flow directions, and ultimately total groundwater and contaminant flux to areas downgradient of the trees. The magnitude of the hydrologic changes can be monitored using fundamental concepts of groundwater hydrology, in addition to plant physiology-based approaches, and can be viewed as being almost independent of the contaminant released. The affect of poplar trees on the fate of groundwater contaminants, however, is contaminant dependent. Some petroleum hydrocarbons or chlorinated solvents may be mineralized or transformed to innocuous compounds by rhizospheric bacteria associated with the tree roots, mineralized or transformed by plant tissues in the transpiration stream or leaves after uptake, or passively volatilized and rapidly dispersed or oxidized in the atmosphere. These processes also can be monitored using a combination of physiological- or geochemical-based field or laboratory approaches. When combined, such hydrologic and contaminant monitoring approaches can result in a more accurate assessment of the use of poplar trees to meet regulatory goals at contaminated groundwater sites, verify that these goals continue to be met in the future, and ultimately lead to a consensus on how the performance of plant-based remedial strategies (phytoremediation) is to be assessed.

  3. Comparison of purge and trap GC/MS and purgeable organic chloride analysis for monitoring volatile chlorinated hydrocarbons

    USGS Publications Warehouse

    Barber, Larry B.; Thurman, E. Michael; Takahashi, Yoshi; Noriega, Mary C.

    1992-01-01

    A combined field and laboratory study was conducted to compare purge and trap gas chromatography/mass spectrometry (PT-GC/MS) and purgeable organic chloride (POCl) analysis for measuring volatile chlorinated hydrocarbons (VCH) in ground water. Distilled-water spike and recovery experiments using 10 VCH indicate that at concentrations greater than 1 ??g/l recovery is more than 80 percent for both methods with relative standard deviations of about 10 percent. Ground-water samples were collected from a site on Cape Cod, Massachusetts, where a shallow unconfined aquifer has been contaminated by VCH, and were analyzed by both methods. Results for PT-GC/MS and POCl analysis of the ground-water samples were not significantly different (alpha = 0.05, paired t-test analysis) and indicated little bias between the two methods. Similar conclusions about concentrations and distributions of VCH in the ground-water contamination plume were drawn from the two data sets. However, only PT-GC/MS analysis identified the individual compounds present and determined their concentrations, which was necessary for toxicological and biogeochemical evaluation of the contaminated ground water. POCl analysis was a complimentary method for use with PT-GC/MS analysis for identifying samples with VCH concentrations below the detection limit or with high VCH concentrations that require dilution. Use of POCl as a complimentary monitoring method for PT-GC/MS can result in more efficient use of analytical resources.

  4. Monitoring the effect of poplar trees on petroleum-hydrocarbon and chlorinated-solvent contaminated ground water

    USGS Publications Warehouse

    Landmeyer, J.E.

    2001-01-01

    At contaminated groundwater sites, poplar trees can be used to affect groundwater levels, flow directions, and ultimately total groundwater and contaminant flux to areas downgradient of the trees. The magnitude of the hydrologic changes can be monitored using fundamental concepts of groundwater hydrology, in addition to plant physiology-based approaches, and can be viewed as being almost independent of the contaminant released. The affect of poplar trees on the fate of groundwater contaminants, however, is contaminant dependent. Some petroleum hydrocarbons or chlorinated solvents may be mineralized or transformed to innocuous compounds by rhizospheric bacteria associated with the tree roots, mineralized or transformed by plant tissues in the transpiration stream or leaves after uptake, or passively volatilized and rapidly dispersed or oxidized in the atmosphere. These processes also can be monitored using a combination of physiological- or geochemical-based field or laboratory approaches. When combined, such hydrologic and contaminant monitoring approaches can result in a more accurate assessment of the use of poplar trees to meet regulatory goals at contaminated groundwater sites, verify that these goals continue to be met in the future, and ultimately lead to a consensus on how the performance of plant-based remedial strategies (phytoremediation) is to be assessed.

  5. Modelling of spatial contaminant probabilities of occurrence of chlorinated hydrocarbons in an urban aquifer.

    PubMed

    Greis, Tillman; Helmholz, Kathrin; Schöniger, Hans Matthias; Haarstrick, Andreas

    2012-06-01

    In this study, a 3D urban groundwater model is presented which serves for calculation of multispecies contaminant transport in the subsurface on the regional scale. The total model consists of two submodels, the groundwater flow and reactive transport model, and is validated against field data. The model equations are solved applying finite element method. A sensitivity analysis is carried out to perform parameter identification of flow, transport and reaction processes. Coming from the latter, stochastic variation of flow, transport, and reaction input parameters and Monte Carlo simulation are used in calculating probabilities of pollutant occurrence in the domain. These probabilities could be part of determining future spots of contamination and their measure of damages. Application and validation is exemplarily shown for a contaminated site in Braunschweig (Germany), where a vast plume of chlorinated ethenes pollutes the groundwater. With respect to field application, the methods used for modelling reveal feasible and helpful tools to assess natural attenuation (MNA) and the risk that might be reduced by remediation actions.

  6. Residues in broiler chick tissues from low level feedings of seven chlorinated hydrocarbon insecticides.

    PubMed

    Onley, J H; Giuffrida, L; Watts, R R; Ives, N F; Storherr, R W

    1975-07-01

    Two chlorinated insecticide feeding studies from 1967-1968, using broiler chicks, have been completed. In Study I, lindane, heptachlor epoxide, dieldrin, endrin, methoxychlor, and DDT were fed in combination at 3 levels: 0.05, 0.15, and 0.45 ppm. Data show that, in fat tissues, heptachlor epoxide attained a level approximately 20 times the respective levels in the feed; dieldrin 15 times; endrin 10 times; p,p'-DDT 9 times; lindane 3 times; and o.p'-DDT less than the feeding levels. Of the DDT metabolites, p.p'-DDE and p,p'-DDD, only p,p'-DDE was significant at 3 times the 0.45 ppm feeding level. Endrin ketone, a metabolite of endrin, reached plateau levels approximately equal to feeding levels. All residue levels in liver tissues were less than 0.02 ppm. In Study II, technical chlordane was fed singly at the 0.05, 0.15, and 0.45 ppm levels. Results are tabulated for both total chlordane and for 6 identifiable isomers. Total chlordane in fat tissues attained plateau levels 3-5 times the respective feeding levels. Total chlordane levels in liver and breast tissues were all less than 0.01 ppm.

  7. Secondary aerosol formation from the oxidation of biogenic hydrocarbons by chlorine atoms

    NASA Astrophysics Data System (ADS)

    Cai, Xuyi; Griffin, Robert J.

    2006-07-01

    The chlorine atom (Cl) is a potential oxidant of volatile organic compounds (VOCs) in the atmosphere and is hypothesized to lead to secondary organic aerosol (SOA) formation in coastal and industrialized areas. The purpose of this paper is to test this hypothesis and to quantify the SOA formation potentials of the common monoterpenes α-pinene, β-pinene, and d-limonene when oxidized by Cl in laboratory chamber experiments. Results indicate that the oxidation of these monoterpenes generates significant amounts of aerosol. The SOA yields of α-pinene, β-pinene, and d-limonene in this study are comparable to those when they are oxidized by ozone, by nitrate radical, and in photooxidation scenarios. For aerosol mass up to 30.0 μg m-3, their yields reach approximately 0.20, 0.20, and 0.30, respectively. For d-limonene, data indicate two yield curves that depend on the initial concentration ratio of Cl precursor to d-limonene. It is argued theoretically that multiple SOA yield curves may be common for VOCs, depending on the initial concentration ratio of oxidant to VOC. SOA formation from the three typical monoterpenes when oxidized by Cl in the marine boundary layer, coastal areas, and inland industrialized areas could be a source of organic aerosol in the early morning.

  8. HIgh volume collection of chlorinated hydrocarbons in urban air using three solid adsorbents

    NASA Astrophysics Data System (ADS)

    Billings, W. Neil; Bidleman, Terry F.

    Airborne polychlorinated biphenyls (PCB) and chlorinated pesticides were measured in Columbia, SC; Denver, CO and over a landfill at New Bedford, MA. At each location comparative sampling was carried out using porous polyurethane foam (PPF), Tenax-GC resin and XAD-2 resin. Concentrations of light and heavy PCB (Aroclors 1016 and 1254), p, p'-DDE, chlordane and toxaphene measured using the different adsorbents agreed well, with average relative standard deviations of 11-15%. Hexachlorobenzene (HCB) was poorly collected by PPF, but well retained by the resins. HCB concentrations measured using Tenax and XAD-2 agreed within 6 % average relative standard deviation, and were several times higher than those found using PPF. The breakthrough of Aroclor 1016 on PPF was studied in detail for over 30 field sampling experiments. Penetration of 1016 through a PPF bed depends on total air volume and ambient temperature. Breakthrough from the front to backup traps was best correlated with the temperature-weighted air volume, where the temperature factor was derived from PCB vapor pressures at the ambient sampling temperature and at 20 °C.

  9. Thermal decomposition of selected chlorinated hydrocarbons during gas combustion in fluidized bed

    PubMed Central

    2013-01-01

    Background The process of thermal decomposition of dichloromethane (DCM) and chlorobenzene (MCB) during the combustion in an inert, bubbling fluidized bed, supported by LPG as auxiliary fuel, have been studied. The concentration profiles of C6H5CI, CH2Cl2, CO2, CO, NOx, COCl2, CHCl3, CH3Cl, C2H2, C6H6, CH4 in the flue gases were specified versus mean bed temperature. Results The role of preheating of gaseous mixture in fluidized bed prior to its ignition inside bubbles was identified as important factor for increase the degree of conversion of DCM and MCB in low bed temperature, in comparison to similar process in the tubular reactor. Conclusions Taking into account possible combustion mechanisms, it was identified that autoignition in bubbles rather than flame propagation between bubbles is needed to achieve complete destruction of DCM and MCB. These condition occurs above 900°C causing the degree of conversion of chlorine compounds of 92-100%. PMID:23289764

  10. Headspace solid phase micro extraction GC-ECD determination of volatile organic chlorinated hydrocarbons in soils.

    PubMed

    Pastore, Paolo; Favaro, Gabriella; Badocco, Denis; Lavagnini, Irma

    2005-01-01

    Soil samples were suspended in a suitable aqueous solvent and a solid phase microextraction (SPME) fibre was used to sample the headspace (HS) for five volatile chlorinated compounds (VOX). Their determination was made by GC-ECD technique in the splitless mode. Preliminary studies on the effects of methanol and of the sand/clay ratio on the fibre extraction were made. Four experimental factors, namely, extraction time, extraction temperature, pH and NaCl%, able to affect distribution of the analytes among the four different phases, were varied in suitable ranges. A multivariate approach applied to the face centred cube (FCC) experimental design, was used to try to optimise the overall sample response. The suitable set of factors found for the determination of chloroform, 1,2-dichloroethane, trichloroethylene, 1,1 ,2-trichloroethane, 1,1,2,2-tetrachloroethane, was a compromise among the relevant optimal factor sets of the single analytes. Detection limits of 0.003 ng, 0.022 ng, 0.001 ng, 0.015 ng and 0.002 ng were found respectively for the five cited analytes. The method was successfully used to determine the analyte contents in two real soils sampled in an industrial area.

  11. Organochlorine compounds in Baltic salmon and trout. I. Chlorinated hydrocarbons and chlorophenols 1982

    SciTech Connect

    Vuorinen, P.J.; Paasivirta, J.; Piilola, T.; Surma-Aho, K.; Tarhanen, J.

    1985-01-01

    Polychlorinated hydrocarbons and chlorophenol compounds were analyzed in three populations of Baltic salmon (Salmo salar) and one population of Bothnian Bay trout (Salmo trutta). Muscles, livers an unfertilized eggs were studied and the analysis results treated by standard statistical methods. PCB, DDT residues, HCB and lindan were detected in most, 2,3,6-t-richlorocymene in some samples at levels which are near to the global baseline. Ten chlorophenol compounds were detected, 34DCC at 0-1000 ..mu..g/kg the other 0-100 ..mu..g/kg (fresh weight) levels. Chlorohydrocarbons showed some significant positive correlations with weight, and fat contents of the fish. Significances of the differences between populations and tissues were low or negligible except that the chlorophenols in liver were at clearly higher level than in muscle or eggs.

  12. Reductive dechlorination of chlorinated hydrocarbons as non-aqueous phase liquid (NAPL): preliminary investigation on effects of cement doses.

    PubMed

    Do, Si-Hyun; Batchelor, Bill

    2012-07-15

    The reactivities of various types of iron mixtures to degrade chlorinated hydrocarbons (PCE, TCE and 1,1,1-TCA) in the form of non-aqueous phase liquids were investigated. The iron mixtures included a mixture of Fe(II) and Portland cement (Fe(II)-C), a mixture of Fe(II), Fe(III) and Ca(OH)(2) (Fe(II/III)-L), and a mixture of Fe(II), Fe(III), Ca(OH)(2), and Portland cement (Fe(II/III)-C). When the same amount of Fe(II) was used, Fe(II)-C was more reactive with chlorinated ethylenes (i.e. PCE and TCE) than Fe(II/III)-L. The reductive pathway for high concentrations of total PCE (i.e. above solubility) with Fe(II)-C was determined to be a combination of two-electron transfer, β-elimination and hydrogenolysis. Increasing the cement dose from 5% to 10% in Fe(II)-C did not affect PCE dechlorination rates, but it did favor the β-elimination pathway. In addition, when Fe(II/III)-C with 5%C was used, PCE dechlorination was similar to that by Fe(II)-C, but this mixture did not effectively degrade TCE. A modified second-order kinetic model was developed and shown to appropriately describe degradation of TCE at high concentrations. Fe(II/III)-L effectively degraded high concentrations of 1,1,1-TCA at rates that were similar to those obtained with Fe(II)-C using 10% C. Moreover, both increasing cement doses and the presence of Fe(III) increased dechlorination rates of 1,1,1-TCA, which was mainly through the hydrogenolysis pathway. The reactivity of Fe(II/III)-L was strongly dependent on the target compound (i.e. less reactivity with TCE, more with 1,1,1-TCA). Therefore, Fe(II/III)-L could be a potential mixture for degrading 1,1,1-TCA, but it should be modified to degrade TCE more effectively. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Risk of pancreatic cancer in workers exposed to chlorinated hydrocarbon solvents and related compounds: a meta-analysis.

    PubMed

    Ojajärvi, A; Partanen, T; Ahlbom, A; Boffetta, P; Hakulinen, T; Jourenkova, N; Kauppinen, T; Kogevinas, M; Vainio, H; Weiderpass, E; Wesseling, C

    2001-05-01

    This is a meta-analysis of occupational exposures to chlorinated hydrocarbon (CHC) solvents and pancreatic cancer, based primarily on studies that addressed exposure directly (agent studies) and secondarily on studies that reported data without verification of individual CHC exposures (job title studies), all of which were listed in databases for the period January 1969 to May 1998. Standardized extraction of data and double-checking of consistency of data extraction by five extractors were done. Simple random models estimated meta-relative risks. Suggestive weak excesses were found for trichloroethylene (meta-relative risk (MRR) = 1.24, 95% confidence interval (CI): 0.79, 1.97), polychlorinated biphenyls (MRR = 1.37, 95% CI: 0.56, 3.31), methylene chloride (MRR = 1.42, 95% CI: 0.80, 2.53), and vinyl chloride (MRR = 1.17, 95% CI: 0.71, 1.91) but not for carbon tetrachloride. One study addressed tetrachloroethylene (MRR = 3.08, 95% CI: 0.63, 8.99); another investigated chlorohydrin production (MRR = 4.92, 95% CI: 1.58, 11.4). Exposure-response meta-analyses for trichloroethylene and methylene chloride failed to reveal trends. Job title studies on metal degreasing and dry cleaning revealed significant MRRs (2.0 and 1.4, respectively). Publication bias was unlikely. Confounding may have remained insufficiently controlled. Unless the results are seriously biased by exposure or endpoint misclassification or by confounding, strong causal associations between CHC compounds and pancreatic cancer can be judged unlikely. Interactions between environmental and occupational agents, lifestyle factors, and genetic susceptibility remain a possibility, but the data for this meta-analysis did not address interactions.

  14. Reproductive and morphological condition of wild mink (Mustela vison) and river otters (Lutra canadensis) in relation to chlorinated hydrocarbon contamination.

    PubMed Central

    Harding, L E; Harris, M L; Stephen, C R; Elliott, J E

    1999-01-01

    We assessed chlorinated hydrocarbon contamination of mink and river otters on the Columbia and Fraser River systems of northwestern North America, in relation to morphological measures of condition. We obtained carcasses of mink and river otters from commercial trappers during the winters 1994-1995 and 1995-1996. Necropsies included evaluation of the following biological parameters: sex, body mass and length, age, thymus, heart, liver, lung, spleen, pancreas, kidney, gonad, omentum, adrenal gland and baculum masses, baculum length, and stomach contents. Livers were analyzed, individually or in pools, for residues of organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), dibenzo-p-dioxins, and dibenzofurans. Contaminant levels were relatively low compared to those documented in other North American populations, although they ranged higher than those detected during an earlier survey (1990-1992) of these regional populations. Body condition varied slightly among collection regions, but showed no relationship with contaminant burden. Mink from the upper Fraser River had less fat stores and also had some of the lowest OC contamination levels observed. Similarly, a few individuals with enlarged livers and kidneys had low contaminant levels. Although a few individual animals with gross abnormalities of reproductive systems did not show high levels of contamination, there was a significant negative correlation between total PCB concentrations (as Aroclor 1260) and baculum length in juvenile mink (r = 0.707; p = 0.033; n = 8). The association of juvenile baculum length with eventual reproductive success is unknown, but further characterization of reproductive organ morphology and relationship to contaminants should be undertaken in a larger subset of these populations. Images Figure 1 Figure 2 Figure 3 PMID:9924010

  15. Biochar as a sorbent for chlorinated hydrocarbons - sorption and extraction experiments in single and bi-solute systems

    NASA Astrophysics Data System (ADS)

    Schreiter, I. J.; Wefer-Roehl, A.; Graber, E. R.; Schueth, C.

    2016-12-01

    Biochar (BC) is increasingly deemed a potential sorbent for contaminants in soil and water remediation, and brownfield restoration. In this study, sorption and extraction experiments were performed to assess the potential of three different BCs to sorb and retain the chlorinated hydrocarbons TCE and PCE. BCs studied were produced from wood chips, grain husk, and cattle manure at 450 °C. A commercially available activated carbon (AC) served as a reference. The sorption behaviour was studied in batch experiments in single solute and bi-solute systems. Resulting isotherms were fitted to the Freundlich model. To assess the desorption behaviour, a five step extraction scheme (water at 40°C, water at 80°C, methanol at 50°C, toluene at 50°C, and n-hexane at 50°) was developed utilizing Accelerated Solvent Extraction. Isotherms revealed distinct differences in sorption behaviour depending on BC feedstock. Sorption capacity ranked as follows: wood chip BC > grain husk BC > cattle manure BC for both contaminants. This sequence could be attributable to an increasing specific surface area and a decreasing ash content of the sorbents. It is noteworthy that all three BCs were more effective in adsorbing TCE, which is surprising, given the higher logKOWof PCE. The reverse trend was observed for the AC. In bi-solute experiments, PCE sorbed as good as or stronger than TCE, yet the total mass of sorbed compounds was higher. In contrast, AC showed a significant decrease of TCE sorption. Extraction experiments revealed that for all BCs a large fraction of the contaminants could not be readily desorbed. In all cases, water remobilized < 5 % of the total contaminant mass and up to 70 % could not be extracted by any of the solvents. The findings suggest that BC is a promising sorbent for mixed contaminant systems as it offers a diverse nature of sorption sites and is more effective in long-term stabilization than AC.

  16. Impact of upgrading wastewater treatment plant on the removal of typical methyl, oxygenated, chlorinated and parent polycyclic aromatic hydrocarbons.

    PubMed

    Qiao, Meng; Cao, Wei; Liu, Bochuan; Bai, Yaohui; Qi, Weixiao; Zhao, Xu; Qu, Jiuhui

    2017-12-15

    Wastewater treatment plant (WWTP) secondary effluent is a main source for polycyclic aromatic hydrocarbons (PAHs) and their derivatives (SPAHs) to wastewater receiving rivers in Beijing. The treatment technologies are being upgraded in the WWTPs as the tertiary treatment. To assess the improvement of the removal efficiencies of PAHs and SPAHs after the treatment upgrading, we investigated 16 PAHs and 4 types of SPAHs in the secondary and tertiary treatment process in 5 major WWTPs. Most of the parent PAHs, methyl PAHs, oxygenated PAHs and chlorinated PAHs were detected in the influent, secondary and tertiary effluent. The concentrations of ΣSPAHs (61ng/L-529ng/L) were similar to ΣPAHs (89ng/L-474ng/L), indicating that SPAHs should not be ignored when studying the PAH contamination. ΣPAHs and ΣSPAHs were largely removed by the secondary treatment (45%-82%) and less by the tertiary treatment (0%-24%). The removal efficiencies were lower in the secondary and tertiary treatment in WWTPs than in the lab-scale experiment conducted previously, probably a result of the association of PAHs and SPAHs with dissolved organic matters (DOMs) in wastewater. DOMs might be a limiting factor for the removal of PAHs and SPAHs in WWTPs. The estimated yearly loadings of the total PAHs and SPAHs decreased only 21% in the tertiary effluent compared with the secondary effluent in WWTP1 and 9% in WWTP3. Therefore, the upgrading of WWTPs did not efficiently improve the removal of PAHs and SPAHs. DOMs should be further considered for improving the removal of PAHs, SPAHs and similar contaminants in WWTPs. Copyright © 2017. Published by Elsevier B.V.

  17. In Vitro Transformation of Chlorinated Parabens by the Liver S9 Fraction: Kinetics, Metabolite Identification, and Aryl Hydrocarbon Receptor Agonist Activity.

    PubMed

    Terasaki, Masanori; Wada, Takeshi; Nagashima, Satoshi; Makino, Masakazu; Yasukawa, Hiro

    2016-01-01

    We investigated the kinetics of in vitro transformation of a dichlorinated propyl paraben (2-propyl 3,5-dichloro-4-hydroxybenzoate; Cl2PP) by the rat liver S9 fraction and assessed the aryl hydrocarbon receptor (AhR) agonist activity of the metabolite products identified in HPLC and GC/MS analysis and by metabolite syntheses. The results indicated that the chlorination of Cl2PP reduced its degradation rate by approximately 40-fold. Two hydroxylated metabolite products showed AhR agonist activity of up to 39% of that of the parent Cl2PP when assessed in a yeast (YCM3) reporter gene assay. The determination of the metabolic properties of paraben bioaccumulation presented here provides further information on the value of risk assessments of chlorinated parabens as a means to ensure human health and environmental safety.

  18. Genetic Engineering of Plants to Improve Phytoremediation of Chlorinated Hydrocarbons in Groundwater

    SciTech Connect

    Strand, Stuart E.

    2004-12-01

    I. Mechanism of halogenated hydrocarbon oxidation We are using poplar culture cells to determine the pathway of TCE metabolism. In our earlier work, we found that trichloroethanol (TCEOH) is a major early intermediate. Our studies this year have focused on the steps that follow this toxic intermediate. We did several experiments to track the disappearance of TCEOH after the cells were removed from TCE. We could conclude that TCEOH is not an end-product but is rapidly degraded. Six flasks of poplar liquid suspension cells were exposed to a level of 50 {micro}g/ml TCE for three days. Three of the cultures were subjected to MTBE extractions to quantify the levels of TCEOH produced. The cells of the remaining three cultures were then pelleted and resuspended in fresh medium. After three more days, these were also subjected to MTBE extractions. The samples were analyzed by GC-ECD. After the three days of further metabolism, an average of 91% of the trichloroethanol was gone. When similar experiments were done with intact plants and both free and conjugated TCEOH were quantified, a similar rapid decline in both forms was seen (Shang, 2001). Therefore, it seems probable that similar mechanisms are taking place in both poplar suspension cells and whole poplar plants, so we continued to do our studies with the suspension cells. Metabolism of trichloroethanol may go through trichloroacetic acid (TCAA) prior to dehalogenation. To test this possibility, we exposed cells to TCE and analyzed for TCAA over time. The cultures were analyzed after 4, 5, 6, and 14 days from TCE exposure. We did not detect any significant amount of TCAA above the background in undosed cells. To determine if trichloroethanol itself is directly dehalogenated, we analyzed TCE-exposed cells for the presence of dichloroethanol. Undosed cells did not have any of the DCEOH peak but TCE-dosed cells that produced the highest levels of trichloroethanol did have a small DCEOH peak. Cultures that did not produce

  19. Biochar as a sorbent for chlorinated hydrocarbons - sorption and extraction experiments in single and bi-solute systems

    NASA Astrophysics Data System (ADS)

    Schreiter, Inga J.; Wefer-Roehl, Annette; Graber, Ellen R.; Schüth, Christoph

    2017-04-01

    Biochar (BC) is increasingly deemed a potential sorbent for contaminants in soil and water remediation, and brownfield restoration. In this study, sorption and extraction experiments were performed to assess the potential of three different BCs to sorb and retain the chlorinated hydrocarbons trichloroethylene (TCE) and tetrachloroethylene (PCE). BCs studied were produced from wood chips, grain husk, and cattle manure at 450 °C. A commercially available activated carbon (AC) served as a reference. The sorption behaviour was studied in batch experiments in single solute and bi-solute systems. Resulting isotherms were fitted to the Freundlich model. To assess the desorption behaviour, a five-step extraction scheme (water at 40°C, water at 80°C, methanol at 50°C, toluene at 50°C, and n-hexane at 50°) was developed, utilizing Accelerated Solvent Extraction. Isotherms revealed distinct differences in sorption behaviour depending on BC feedstock. Sorption capacity ranked as follows: wood chip BC > grain husk BC > cattle manure BC for both contaminants. This sequence could be attributable to an increasing specific surface area, an increasing amount of carbon, and a decreasing ash content of the sorbents. It is noteworthy that all three BCs were more effective in adsorbing TCE, which is surprising, given the higher logKow of PCE. The reverse was observed for the AC. Here, sorption is purely driven by the hydrophobicity of the compound rather than sorbent properties. In bi-solute experiments, PCE sorbed as good as or stronger than TCE, yet the total mass of sorbed compounds increased slightly. In contrast, AC showed a significant decrease of TCE sorption and no significant changes in the total mass sorbed. Extraction experiments revealed that for all BCs a large fraction of the contaminants could not be readily desorbed. In all cases, water remobilized < 5 % of the total contaminant mass and up to 70 % could not be extracted by any of the solvents. The findings suggest

  20. Distributions and fate of chlorinated pesticides, biomarkers and polycyclic aromatic hydrocarbons in sediments along a contamination gradient from a point-source in San Francisco Bay, California

    USGS Publications Warehouse

    Pereira, W.E.; Hostettler, F.D.; Rapp, J.B.

    1996-01-01

    The distribution and fate of chlorinated pesticides, biomarkers, and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments along a contamination gradient in the Lauritzen Canal and Richmond Harbor in San Francisco Bay was investigated. Compounds were identified and quantified using gas chromatography-ion trap mass spectrometry. Biomarkers and PAHs were derived primarily from weathered petroleum. DDT was reductively dechlorinated under anoxic conditions to DDD and several minor degradation products, DDMU, DDMS, and DDNU. Under aerobic conditions, DDT was dehydrochlorinated to DDE and DBP. Aerobic degradation of DDT was diminished or inhibited in zones of high concentration, and increased significantly in zones of lower concentration: Other chlorinated pesticides identified in sediment included dieldrin and chlordane isomers. Multivariate analysis of the distributions of the DDTs suggested that there are probably two sources of DDD. In addition, DDE and DDMU are probably formed by similar mechanisms, i.e. dehydrochlorination. A steep concentration gradient existed from the Canal to the Outer Richmond Harbor, but higher levels of DDD than those found in the remainder of the Bay indicated that these contaminants are transported on particulates and colloidal organic matter from this source into San Francisco Bay. Chlorinated pesticides and PAHs may pose a potential problem to biota in San Francisco Bay.

  1. Regional variation of selected polyaromatic and chlorinated hydrocarbons over the South Island of New Zealand, as indicated by their content in Pinus radiata needles.

    PubMed

    Herrmann, R; Baumgartner, I

    1987-01-01

    We analysed needles of Pinus radiata along three transects through the South Island of New Zealand for chlorinated hydrocarbons ( alpha- and gamma-HCH, HCB and PCB) and PAH (fluoranthene, 3,4-benzopyrene, benzo(ghi)perylene and indenopyrene). At rural sites we also collected samples of moss (Wijkia extenuata) and lichens (Usnea sp.) in order to compare the pollutant concentrations within these plants. A principal component analysis confirmed findings from moss and snow studies in Europe that the PAH concentrations vary regionally in the same way. The pattern of the principal component loadings of the chlorinated hydrocarbons reflects their heterogeneous immission and their different chemodynamics. The regional pattern indicates an increase of gamma-HCH from remote areas to those used intensively for agriculture and gardening, followed by a decrease towards the inner city of Christchurch. In contrast, PCB and PAH show their highest levels of contamination in the city. The regional distribution of PAH in Christchurch correlates well with traffic density, and particularly with the pattern of smoke from domestic fires. Our study demonstrates that needles of P. radiata can be better monitors of atmospheric pollution in New Zealand than mosses or lichens.

  2. Chlorinated hydrocarbons and mercury in sediments, red-winged blackbirds (Agelaius phoeniceus) and tree swallows (Tachycineta bicolor) from wetlands in the Great Lakes-St. Lawrence River basin

    SciTech Connect

    Bishop, C.A.; Koster, M.D.; Chek, A.A.; Hussell, D.J.T.; Jock, K.

    1995-03-01

    In 1991, the authors collected red-winged blackbird (Agelauis phoeniceus) eggs and tree swallow (Tachycineta bicolor) eggs and nestlings, and sediment samples from 2 wetland sites in the Great lakes and St. Lawrence River basin. They analyzed for chlorinated hydrocarbons and total mercury and found that biota contained contaminant concentrations which were one to two orders of magnitude above those in sediments. Maximum concentrations of contaminants were found in Akwesasne, St. Lawrence river (PCBs = 18,558.8 ng/g in red-winged blackbird eggs, oxychlordane = 58.8/g and mirex = 40.1 ng/g in tree swallow eggs); Mud Creek, Lake Erie and Cootes Paradise. Despite the migratory habits of red-winged blackbirds and tree swallows, agreement among biota and sediment in geographic variation of contaminant concentrations supports the use of these animals as biomonitors of persistent chemicals. Although chlorinated hydrocarbon concentrations in red-winged blackbird eggs were significantly correlated with sediment contamination, the local nature of the tree swallow chick diet suggests that nestlings would be the best indicator of local contaminant trends.

  3. Implications of treating water containing polynuclear aromatic hydrocarbons with chlorine: a gas chromatographic-mass spectrometric study.

    PubMed Central

    Oyler, A R; Liukkonen, R J; Lukasewycz, M K; Cox, D A; Peake, D A; Carlson, R M

    1982-01-01

    The products of aqueous chlorination reactions of 1-methylnaphthalene, fluorene, dibenzofuran, anthracene, phenanthrene, 1-methylphenanthrene, fluoranthene, and pyrene have been determined. The conditions employed for these reactions approximated those that might be encountered in water treatment facilities. Reactions at pH greater than 6 tended to produce oxygenated products (epoxides, phenols, quinones, etc.), and reactions at pH less than 6 tended to produce both oxygenated (quinones) and chlorinated products. PMID:7151769

  4. The Reaction Specificity of Nanoparticles in Solution: Application to the Reaction of Nanoparticulate Iron and Iron-Bimetallic Compounds with Chlorinated Hydrocarbons and Oxyanions

    SciTech Connect

    2005-06-01

    The prospect for better remediation technologies using nanoparticles of iron, iron oxides, and iron with catalytic metals (i.e., bimetallics) has potentially transformative implications for environmental management of DOE sites across the country. Of particular interest is the potential to avoid undesirable products from the degradation of chlorinated solvents by taking advantage of the potential selectivity of nanoparticles to produce environmentally benign products from CCl{sub 4}. Chlorinated solvents are the most frequently reported subsurface contaminants across the whole DOE complex, and carbon tetrachloride (CCl{sub 4}) is the chlorinated solvent that is of greatest concern at Hanford (U. S. Department Energy 2001). In evaluating technologies that might be used at the site, a critical concern will be that CCl{sub 4} reduction usually occurs predominantly by hydrogenolysis to chloroform (CHCl{sub 3}) and methylene chloride (CH{sub 2}Cl{sub 2}), both of which are nearly as problematic as CCl{sub 4} (National Research Council, 1978). Competing reaction pathways produce the more desirable products carbon monoxide (CO) and/or formate (HCOO{sup -}), and possibly CO{sub 2}, but the proportion of reaction that occurs by these pathways is highly variable. Iron-based metallic and oxide nanoparticles have been shown to have enhanced reactivity towards a variety of chemical species, including chlorinated hydrocarbons and reducible oxyanions. Possibly of greater importance is the ability of nanoparticles to select for specific reaction products, potentially facilitating the formation of more environmentally acceptable products. The purpose of this study is to develop a fundamental understanding of the mechanism responsible for the overall particle reactivity and reaction selectivity of reactive metal and oxide nanoparticles. To achieve this objective the project involves the synthesis (using solution and vacuum synthesis methods) and characterization of well

  5. Effects of p,p'-DDE and some other chlorinated hydrocarbons on the formation of prostaglandins by the avian eggshell gland mucosa.

    PubMed

    Lundholm, C E; Bartonek, M

    1992-01-01

    Some structurally related chlorinated hydrocarbons were investigated for their effects on the production of prostaglandins by the eggshell gland mucosa of ducks and domestic fowl. Formation of PGF2 alpha, PGE2 and TxB2 by homogenates of domestic fowl eggshell gland mucosa was significantly inhibited by in vitro addition of p,p'-DDE, Arochlor 1242 and, to a lesser extent, Arochlor 1260, but not by p,p'-DDT and o,p'-DDE. Comparatively, in duck eggshell gland mucosa homogenates, synthesis of the same prostaglandins was somewhat more sensitive to inhibition by 5 microM p,p'-DDE added in vitro. Eggshell gland mucosa synthesized significantly more PGF2 alpha, PGE2 and TxB2 than did the mucosa of the magnum and isthmus regions of the oviduct. Duck eggshell gland mucosa homogenates synthesized significantly more prostaglandins than similar homogenates from the domestic fowl, and, considering the former synthesis of PGF2 alpha was significantly higher when ducks were slaughtered at 08:00 than at 16:00 hours. In ducks, dietary administration of 40 ppm, p,p'-DDE for 45 days resulted in 21% eggshell thinning compared to the contemporary control values. This treatment also resulted in notable effects in homogenates of the eggshell gland mucosa, as compared to controls: Ca2+ uptake was reduced by 43%, synthesis of PGF2 alpha, PGE2 and TxB2 was reduced by 26%, 38% and 53%, respectively; the Ca content was increased to 145%. The role of p,p'-DDE in inhibiting prostaglandin formation in the eggshell gland is discussed as a mechanism of the eggshell thinning action of this chlorinated hydrocarbon.

  6. Experimental and theoretical studies into the formation of C4-C6 products in partially chlorinated hydrocarbon pyrolysis systems: a probabilistic approach to congener-specific yield predictions.

    PubMed

    McIntosh, Grant J; Russell, Douglas K

    2014-09-25

    This work presents a study of the pyrolytic formation of vinylacetylene and benzene congeners formed from chlorinated hydrocarbon precursors, a complex, multipath polymerization system formed in a monomer-rich environment. (Co-)pyrolyses of dichloro- and trichloroethylene yield a rich array of products, and assuming a single dominant underlying growth mechanism, this (on comparing expected and observed products) allows a number of potentially competing channels to C4 and C6 products to be ruled out. Poor congener/isomer descriptions rule out even-carbon radical routes, and the absence of C3 and C5 products rule out odd-carbon processes. Vinylidenes appear unable to describe the increased reactivity of acetylenes with chlorination noted in our experiments, leaving molecular acetylene dimerization processes and, in C6 systems, the closely related Diels-Alder cyclization as the likely reaction mechanism. The feasibility of these routes is further supported by ab initio calculations. However, some of the most persuasive evidence is provided by congener-specific yield predictions enabled by the construction of a probability tree analogue of kinetic modeling. This approach is relatively quick to construct, provides surprisingly accurate predictions, and may be a very useful tool in screening for important reaction channels in poorly understood congener- or isomer-rich reaction systems.

  7. Levels and trends of PCBs, chlorinated pesticides and petroleum hydrocarbons in mussels from the NW Mediterranean coast: comparison of concentrations in 1973/1974 and 1988/1989.

    PubMed

    Villeneuve, J P; Carvalho, F P; Fowler, S W; Cattini, C

    1999-09-30

    A mussel watch survey was conducted in 1988-1989 along the Mediterranean coast of France and Italy, between Sete and Genoa, in order to assess contamination by organochlorine pesticides, PCBs and petroleum hydrocarbons. Results show concentrations of DDTs (average 130 ng g-1 dry wt.) and PCBs (average 527 ng g-1 dry wt.) higher in coastal areas receiving river discharges and close to large cities. Concentrations of total aliphatics (average 470 micrograms g-1 dry wt.) and PAHs (average 233 micrograms g-1 dry wt.) were generally higher also near large harbours, namely Marseille, Toulon and Genoa. PAHs in mussel samples from Genoa and Monaco were mostly of pyrolytic sources, likely forest fires and exhaust gases from cars, whereas PAHs in other stations were mainly of petrogenic sources. Comparison of chlorinated hydrocarbon concentrations measured in 1988-1989 with those measured in a similar survey carried out at the same sites in 1973-1974, shows that DDTs and PCBs decreased by a factor of approximately 5 in 15 years. This decrease is in agreement with the ban on DDT implemented in 1975 in western Europe and gradual cessation of PCBs production in the 1970s and 1980s. Nevertheless, the residues of these compounds measured in mussels confirm the well-known long persistence of DDTs and PCBs, which are still present in relatively high concentrations in a few areas.

  8. Chlorinated hydrocarbons in livers of American mink (Mustela vison) and river otter (Lutra canadensis) from the Columbia and Fraser River Basins, 1990-1992

    USGS Publications Warehouse

    Elliott, J.E.; Henny, Charles J.; Harris, M.L.; Wilson, L.K.; Norstrom, R.J.

    1999-01-01

    We investigated chlorinated hydrocarbon contaminants in aquatic mustelid species on the Fraser and Columbia Rivers of northwestern North America. Carcasses of river otter (Lutra canadensis) (N=24) and mink (Mustela vison) (N=34) were obtained from commercial trappers during the winters of 1990-91 and 1991a??92. Pooled liver samples were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), including non-ortho congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Most samples contained detectable concentrations of DDE, PCBs, although there was substantial variability in patterns and trends among neighboring samples. Concentrations of DDE were in some mink and several otter samples from the lower Columbia River elevated (to 4700 g/kg wet weight); excluding one mink sample from the Wenatchee area, mean DDE levels generally decreased between 1978a??79 and 1990a??92. PCBs were present in all samples. PCB concentrations in otter livers collected from the lower Columbia were ten-fold lower than measured a decade previously; nevertheless, a sample taken near Portland had a mean concentration of 1500 g/kg, within a range of concentrations associated with reproductive effects in captive mink. Concentrations of 2,3,7,8-TCDD and TCDF were generally below detection limits, except for one otter collected near a pulp mill at Castlegar, on the upper Columbia, with 11 ng TCDD/kg in liver. Elevated concentrations of higher chlorinated PCDD/Fs, probably resulting from use of chlorophenolic wood preservatives, were found in both species; one otter sample from the lower Columbia had 2200 ng OCDD/kg. International TCDD toxic equivalent levels in mink (31 ng/kg) and otter (93 ng/kg) from the lower Columbia River approached toxicity thresholds for effects on reproduction in ranch mink.

  9. Bugs digest chlorinated organics

    SciTech Connect

    Not Available

    1993-02-01

    This article describes a new bioreactor that uses a consortium of aerobic bacteria to biodegrade chlorinated aromatic hydrocarbons. Methanotrophic bacteria are cultivated for their MMO enzyme. After the MMO enzyme breaks down the chlorinated organics by oxidation, non-methanotrophic bacteria consume the byproducts. Pilot-scale testing has demonstrated successful treatment of groundwater containing coal-tar constituents, toluene, trichloroethylene, vinyl chlorides, chlorobenzene, and methyl methacrylate from three Superfund sites.

  10. IR spectroscopic study of Pt-containing zeolites in the hydrodechlorination reaction of C 2 chlorinated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Hannus, I.; Kropok, Zs.; Halász, J.

    2007-05-01

    Some of the chlorinated organic compounds are widely used commercially, because of their advantageous chemical/physical properties or having toxicity for pestiferous living substances. However, emitted into the atmosphere they are responsible for diminishing the ozone layer in the stratosphere. Therefore, a lot of effort is devoted in finding proper solutions to decompose these chemicals in environmentally friendly ways. Platinum on different carriers play very important role in catalytic hydrodechlorination of these compounds. We have found that Pt-containing Y-FAU zeolite is an active catalyst in the hydrodechlorination of trichloroethene. IR spectroscopic experiments showed that the final products are ethane and HCl, and the hydrogen/reactant ratio exerts large influence on the rate of the hydrodechlorination reaction.

  11. Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 2. Experimental and kinetic modeling studies.

    PubMed

    McIntosh, Grant J; Russell, Douglas K

    2013-05-23

    The mechanism of formation of benzene rings during the pyrolysis of dichloro- and trichloroethylenes has been investigated by the method of laser powered homogeneous pyrolysis coupled with product analysis by gas chromatography. Additionally, selected (co)pyrolyses between the chlorinated ethylenes, CH2Cl2, C4Cl4, C4Cl6, and C2H2 have been performed to explicitly probe the roles of 2C3 and C4/C2 reaction pairs in aromatic growth. The presence of odd-carbon products in neat C4Cl6 pyrolyses indicates that 2C3 processes are operative in these systems; however, comparison with product yields from C2HCl3 suggests that C4/C2 processes dominate most other systems. This is further evidenced by an absence of C3 and other odd-carbon species in (co)pyrolyses with dichloromethane which should seed C3-based growth. The reactions of perchlorinated C4 species C4Cl5, C4Cl3, and C4Cl4 with C2Cl2 were subsequently explored through extensive kinetic simulations of the possible reaction pathways based on previous kinetic models and the exhaustive quantum chemical investigations of our preceding work. The experimental and theoretical results strongly suggest that, at moderate temperatures, aromatic ring formation from chlorinated ethylenes normally follows a Diels-Alder coupling of C4 and C2 molecular units followed by internal shifts; the one exception is the C4Cl4 + C2Cl2 system, where steric factors lead to the formation of nonaromatic products. There is little evidence for radical-based routes in these systems.

  12. Transformation of chlorinated hydrocarbons using aquocobalamin or coenzyme F{sub 430} in combination with zero-valent iron

    SciTech Connect

    Morra, M.J.; Borek, V.; Koolpe, J.

    2000-06-01

    More effective methods are necessary for the remediation of soils, sediments, and ground waters contaminated with halogenated organic compounds. The authors objective was to determine the feasibility and utility of using a tetrapyrrole-Fe(0) mixture for reductive dehalogenation of synthetic organic contaminants. Aquocobalamin or coenzyme F{sub 430} was combined with Fe(0) in aqueous systems containing either a single chlorinated compound or mixtures of chlorinated compounds, and substrate disappearance was monitored using gas chromatography-mass spectrometry (GC-MS). Zero-valent iron effectively dehalogenated CCl{sub 4} at low to neutral pH values, while increases in CCl{sub 4} dehalogenation resulting from inclusion of tetrapyrrole catalysts along with Fe(0) occurred only at basic pH values. Rates of CCl{sub 4} disappearance increased with additional aquocobalamin, but reached a maximum and decreased at higher aquocobalamin concentrations. overall dehalogenation rates may thus be a function of Fe(0)'s limited reactive surface area. There was a trend for both tetrapyrrole catalysts to promote the disappearance of halogenated compounds in a mixed substrate containing 20 compounds. Studies with five individual substrates likewise showed trends for increased substrate removal with F{sub 430} beyond that for Fe(0) alone. This increase is most important for compounds such as 1,2-dichloroethane and 1,4-dichlorobenzene that are not readily dehalogenated by Fe(0). Chloride concentrations in the reaction mixtures indicated that reductive dehalogenation was the dominant process responsible for substrate disappearance. Use of a combination of aquocobalamin or coenzyme F{sub 430} and Fe(0) may effectively promote dehalogenation, thus producing fewer products and more complete dehalogenation of the target substrates than can be achieved using only one of the abiotic reductants alone.

  13. An evaluation of the use of an advanced oxidation process to remove chlorinated hydrocarbons from groundwater at the US Department of Energy Kansas City Plant

    SciTech Connect

    Garland, S.B. II; Peyton, G.R.

    1990-10-01

    The Allied-Signal Aerospace Company currently operates a production facility in Kansas City, Missouri, under contract with the US Department of Energy (DOE). Over the years the operation of the DOE Kansas City Plant has resulted in the contamination of groundwater with chlorinated hydrocarbons, including trichloroethene (TCE). One of the plumes of contaminated groundwater, the underground tank farm (UTF) plume, was selected for remediation with an advanced oxidation process (AOP) consisting of simultaneous treatment by ozone (O{sub 3}), ultraviolet (UV) radiation, and hydrogen peroxide (H{sub 2}O{sub 2}). Since the use of AOPs is relatively new for the removal of organics from groundwater, information on design criteria, costs, performance, and operating experience is not well documented in the literature. Therefore, the Oak Ridge National Laboratory (ORNL) was requested to evaluate the treatment process. This report documents the work performed through FY 1989. The results of the initial year of the evaluations, FY 1988, have been published previously, and the evaluation will continue at least through FY 1990. This report first briefly describes the treatment plant and the mechanisms of the treatment process. Next, the methodology and the results from the evaluation are discussed. Finally, conclusions and recommendations are presented. 8 refs., 14 figs., 16 tabs.

  14. Treatability of volatile chlorinated hydrocarbon-contaminated soils of different textures along a vertical profile by mechanical soil aeration: A laboratory test.

    PubMed

    Ma, Yan; Shi, Yi; Hou, Deyi; Zhang, Xi; Chen, Jiaqi; Wang, Zhifen; Xu, Zhu; Li, Fasheng; Du, Xiaoming

    2017-04-01

    Mechanical soil aeration is a simple, effective, and low-cost soil remediation technology that is suitable for sites contaminated with volatile chlorinated hydrocarbons (VCHs). Conventionally, this technique is used to treat the mixed soil of a site without considering the diversity and treatability of different soils within the site. A laboratory test was conducted to evaluate the effectiveness of mechanical soil aeration for remediating soils of different textures (silty, clayey, and sandy soils) along a vertical profile at an abandoned chloro-alkali chemical site in China. The collected soils were artificially contaminated with chloroform (TCM) and trichloroethylene (TCE). Mechanical soil aeration was effective for remediating VCHs (removal efficiency >98%). The volatilization process was described by an exponential kinetic function. In the early stage of treatment (0-7hr), rapid contaminant volatilization followed a pseudo-first order kinetic model. VCH concentrations decreased to low levels and showed a tailing phenomenon with very slow contaminant release after 8hr. Compared with silty and sandy soils, clayey soil has high organic-matter content, a large specific surface area, a high clay fraction, and a complex pore structure. These characteristics substantially influenced the removal process, making it less efficient, more time consuming, and consequently more expensive. Our findings provide a potential basis for optimizing soil remediation strategy in a cost-effective manner. Copyright © 2016. Published by Elsevier B.V.

  15. Low-concentration tailing and subsequent quicklime-enhanced remediation of volatile chlorinated hydrocarbon-contaminated soils by mechanical soil aeration.

    PubMed

    Ma, Yan; Du, Xiaoming; Shi, Yi; Xu, Zhu; Fang, Jidun; Li, Zheng; Li, Fasheng

    2015-02-01

    Mechanical soil aeration has long been regarded as an effective ex-situ remediation technique and as suitable for remediation of large-scale sites contaminated by volatile organic compounds (VOCs) at low cost. However, it has been reported that the removal efficiency of VOCs from soil is relatively low in the late stages of remediation, in association with tailing. Tailing may extend the remediation time required; moreover, it typically results in the presence of contaminants residues at levels far exceeding regulations. In this context, the present study aimed to discuss the tailing that occurs during the process of remediation of soils contaminated artificially with volatile chlorinated hydrocarbons (VCHs) and to assess possible quicklime-enhanced removal mechanisms. The results revealed the following conclusions. First, temperature and aeration rate can be important controls on both the timing of appearance of tailing and the levels of residual contaminants. Furthermore, the addition of quicklime to soil during tailing can reduce the residual concentrations rapidly to below the remedial target values required for site remediation. Finally, mechanical soil aeration can be enhanced using quicklime, which can improve the volatilization of VCHs via increasing soil temperature, reducing soil moisture, and enhancing soil permeability. Our findings give a basic understanding to the elimination of the tailing in the application of mechanical soil aeration, particularly for VOCs-contaminated soils. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Quicklime-induced changes of soil properties: Implications for enhanced remediation of volatile chlorinated hydrocarbon contaminated soils via mechanical soil aeration.

    PubMed

    Ma, Yan; Dong, Binbin; He, Xiaosong; Shi, Yi; Xu, Mingyue; He, Xuwen; Du, Xiaoming; Li, Fasheng

    2017-04-01

    Mechanical soil aeration is used for soil remediation at sites contaminated by volatile organic compounds. However, the effectiveness of the method is limited by low soil temperature, high soil moisture, and high soil viscosity. Combined with mechanical soil aeration, quicklime has a practical application value related to reinforcement remediation and to its action in the remediation of soil contaminated with volatile organic compounds. In this study, the target pollutant was trichloroethylene, which is a volatile chlorinated hydrocarbon pollutant commonly found in contaminated soils. A restoration experiment was carried out, using a set of mechanical soil-aeration simulation tests, by adding quicklime (mass ratios of 3, 10, and 20%) to the contaminated soil. The results clearly indicate that quicklime changed the physical properties of the soil, which affected the environmental behaviour of trichloroethylene in the soil. The addition of CaO increased soil temperature and reduced soil moisture to improve the mass transfer of trichloroethylene. In addition, it improved the macroporous cumulative pore volume and average pore size, which increased soil permeability. As soil pH increased, the clay mineral content in the soils decreased, the cation exchange capacity and the redox potential decreased, and the removal of trichloroethylene from the soil was enhanced to a certain extent. After the addition of quicklime, the functional group COO of soil organic matter could interact with calcium ions, which increased soil polarity and promoted the removal of trichloroethylene. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Effects of tidal operation on pilot-scale horizontal subsurface flow constructed wetland treating sulfate rich wastewater contaminated by chlorinated hydrocarbons.

    PubMed

    Chen, Zhongbing; Vymazal, Jan; Kuschk, Peter

    2017-01-01

    Three different flow regimes were carried out in a pilot-scale horizontal subsurface flow constructed wetland-treating sulfate rich wastewater contaminated with monochlorobenzene (MCB) and perchloroethene (PCE). The three regimes were continuous flow, 7-day cycle discontinuous flow, and 2.5-day cycle discontinuous flow. The results show that intensifying the tidal regime (2.5-day cycle) significantly enhanced MCB removal before 2 m from the inlet and increasing PCE removal efficiency at 0.5 m. The PCE dechlorination process was promoted with tidal operation, especially under the 2.5-day cycle regime, with significant increases of cis-1,2- dichloroethenes (DCEs), vinyl chloride (VC), and ethene, but trans-1,2-DCE was significantly decreased after tidal operation. Due to the high sulfate concentration in the influent, sulfide was observed in pore water up to 20 and 23 mg L(-1) under continuous flow and 7-day cycle regime, respectively. However, sulfide concentrations decreased to less than 4 mg L(-1) under intensified tidal operation (2.5-day cycle). The increase of oxygen concentration in pore water through intensified tidal operation resulted in better MCB removal performance and the successful inhibition of sulfate reduction. In conclusion, intensifying tidal operation is an effective approach for the treatment of chlorinated hydrocarbons and inhibiting sulfide accumulation in horizontal subsurface flow constructed wetland.

  18. Different behavioral effect dose–response profiles in mice exposed to two-carbon chlorinated hydrocarbons: Influence of structural and physical properties

    SciTech Connect

    Umezu, Toyoshi Shibata, Yasuyuki

    2014-09-01

    The present study aimed to clarify whether dose–response profiles of acute behavioral effects of 1,2-dichloroethane (DCE), 1,1,1-trichloroethane (TCE), trichloroethylene (TRIC), and tetrachloroethylene (PERC) differ. A test battery involving 6 behavioral endpoints was applied to evaluate the effects of DCE, TCE, TRIC, and PERC in male ICR strain mice under the same experimental conditions. The behavioral effect dose–response profiles of these compounds differed. Regression analysis was used to evaluate the relationship between the dose–response profiles and structural and physical properties of the compounds. Dose–response profile differences correlated significantly with differences in specific structural and physical properties. These results suggest that differences in specific structural and physical properties of DCE, TCE, TRIC, and PERC are responsible for differences in behavioral effects that lead to a variety of dose–response profiles. - Highlights: • We examine effects of 4 chlorinated hydrocarbons on 6 behavioral endpoints in mice. • The behavioral effect dose–response profiles for the 4 compounds are different. • We utilize regression analysis to clarify probable causes of the different profiles. • The compound's physicochemical properties probably produce the different profiles.

  19. Integrated use of air sparging, soil vapor extraction and pump and treat technologies to remediate chlorinated hydrocarbon contaminated water-bearing units at a HDPE facility

    SciTech Connect

    Sturdivant, R. Jr.; Schramm, W.H.; Bains, F.E.

    1996-09-01

    Disposal practices prior to RCRA caused the release of chlorinated hydrocarbons (CHCs) into the shallow ground water under a temporary pond at the facility. This impact was discovered through a due diligence survey and properly reported to the Louisiana Department of Environmental Quality (LDEQ). Through a phased investigation the company, in cooperation with LDEQ, has determined that the upper three water bearing units have been affected by multiple contaminants forming a DNAPL plume. Remedial actions were proposed to the Agency and implemented with approval during 1994-95. The remedial system includes soil vapor extraction and air sparging for the uppermost zone and pump and treat for contaminated water removal in the second zone. Throughout 1995, the systems efficiency was evaluated and continuous adjustments were made to improve the recovery. A balanced approach to minimize downward movement of contaminants and achieve optimum recovery included: startup of system components, manipulation of recovery rates and installation of additional equipment. Data assimilated over the past year of operation suggests the effective recovery of CHCs. Monitoring of the impacted zones shows a downward trend in contamination levels, however it is evident that control of the impacted zones is incomplete. Proposed alterations to the system include additional recovery wells, pump tests, and continued evaluations to improve the system. Further efforts will be required by the Agency to address the remaining contaminants. This paper will address the implementation of the Corrective Action Program and present the current state of operations and proposed augmentations to improve the system.

  20. California sea lions (Zalophus californianus californianus) have lower chlorinated hydrocarbon contents in northern Baja California, México, than in California, USA.

    PubMed

    Del Toro, Ligeia; Heckel, Gisela; Camacho-Ibar, Víctor F; Schramm, Yolanda

    2006-07-01

    Chlorinated hydrocarbons (CHs) were determined in blubber samples of 18 California sea lions (Zalophus californianus californianus) that stranded dead along Todos Santos Bay, Ensenada, Baja California, México, January 2000-November 2001. Summation operatorDDTs were the dominant group (geometric mean 3.8 microg/g lipid weight), followed by polychlorinated biphenyls ( summation operatorPCBs, 2.96 microg/g), chlordanes (0.12 microg/g) and hexachlorocyclohexanes (0.06 microg/g). The summation operatorDDTs/ summation operatorPCBs ratio was 1.3. We found CH levels more than one order of magnitude lower than those reported for California sea lion samples collected along the California coast, USA, during the same period as our study. This sharp north-south gradient suggests that Z. californianus stranded in Ensenada (most of them males) would probably have foraged during the summer near rookeries 500-1000 km south of Ensenada and the rest of the year migrate northwards, foraging along the Baja California peninsula, including Ensenada, and probably farther north.

  1. Electrical resistivity and induced polarization tomography in identifying the plume of chlorinated hydrocarbons in sedimentary formation: a case study in Rho (Milan - Italy).

    PubMed

    Cardarelli, Ettore; Di Filippo, Gerardina

    2009-09-01

    Resistivity and induced polarization surveying were originally developed for mineral exploration but are now finding new applications in the field of environmental and engineering geophysics. The present article reports the results of a geophysical survey performed with the aim of identifying a plume of chlorinated hydrocarbons in sedimentary formations of the Pandania plain. The tested site is characterized by three sand and gravel aquifers containing a quantity of clay particles which influence the overall bulk resistivity and chargeability. According to data obtained using shallow boreholes, mainly dense non-aqueous phase liquids were found as contaminants in the first and second aquifer. The aforementioned geo-electrical methods were applied in both two- and three-dimensional approaches. Steel and copper electrodes were used in the process of field data acquisition and the results of the survey were compared. The geophysical survey revealed some anomalies that could be explained by the presence of dense non-aqueous phase liquids in the soil medium. The concept of normalized chargeability facilitates the interpretation of detected induced polarization anomalies. The shape of the plume was inferred from maps of resistivity and chargeability to a depth of 25 m below the surface of the ground.

  2. Chlorinated hydrocarbon contaminants in blood of black and turkey vultures from Savannah River Site, South Carolina, USA.

    PubMed

    Senthil Kumar, Kurunthachalam; Bowerman, William W; DeVault, Travis L; Takasuga, Takumi; Rhodes, Olin E; Lehr Brisbin, I; Masunaga, Shigeki

    2003-10-01

    Blood of adult and juvenile black and turkey vultures in the Savannah River Site of South Carolina, USA was analyzed for the presence of 2,3,7,8-chlorine substituted polychlorinated dibenzo-p-dioxins (2,3,7,8-PCDDs), dibenzofurans (2,3,7,8-PCDFs), -dioxin-like and -di-ortho polychlorinated biphenyls. Concentration ranges of 2,3,7,8-PCDD/DFs in blood of black and turkey vultures were 14.2-34.6 and 8.7-56.2 pg/ml wet wt., respectively. Dioxin-like PCBs were in the ranges of 815-4627 and 753-3611 pg/ml wet wt. respectively, in black and turkey vultures. Considerable concentrations of two congeners of di-ortho PCBs were noticed in the ranges of 1415-10325 and 663-7500 pg/ml respectively, in black and turkey vultures. Comparatively, greater toxic equivalency (TEQ) were observed in blood of turkey vultures with the ranges of 3.2-20, whereas black vulture contained 1.8-8.4 pgTEQ/ml wet wt. basis. The species-specific accumulation profiles of PCDD/DFs and dioxin-like PCBs may reflect the different feeding habits, ecology, metabolic capacity and migratory movements of these two scavenging species.

  3. Estimating the in situ sediment-porewater distribution of PAHs and chlorinated aromatic hydrocarbons in anthropogenic impacted sediments

    SciTech Connect

    Hans Peter H. Arp; Gijs D. Breedveld; Gerard Cornelissen

    2009-08-15

    It has become increasingly apparent that the in situ sediment-porewater distribution behavior of organic compounds within anthropogenic impacted sediments is quite diverse, and challenging to generalize. Traditional models based on octanol-water partitioning generally overestimate native porewater concentrations, and modern approaches accounting for multiple carbon fractions, including black carbon, appear sediment specific. To assess the diversity of this sorption behavior, we collected all peer-reviewed total organic carbon (TOC)-normalized in situ sediment-porewater distribution coefficients, K{sub TOC}, for impacted sediments. This entailed several hundreds of data for PAHs, PCBs, PCDD/Fs, and chlorinated benzenes, covering a large variety of sediments, locations, and experimental methods. Compound-specific KTOC could range up to over 3 orders of magnitude. Output from various predictive models for individual carbonaceous phases found in impacted sediments, based on peer-reviewed polyparameter linear free energy relationships (PP-LFERs), Raoult's Law, and the SPARC online-calculator, were tested to see if any of the models could consistently predict literature K{sub TOC} values within a factor of 30 (i.e. about 1.5 orders of magnitude, or half the range of K{sub TOC} values). The Raoult's Law model and coal tar PP-LFER achieved the sought-after accuracy for all tested compound classes, and are recommended for general, regional-scale modeling purposes. As impacted sediment-porewater distribution models are unlikely to get more accurate than this, this review underpins that the only way to accurately obtain accurate porewater concentrations is to measure them directly, and not infer them from sediment concentrations. 86 refs., 2 figs., 3 tabs.

  4. Aqueous chlorination of resorcinol

    USGS Publications Warehouse

    Heasley, V.L.; Burns, M.D.; Kemalyan, N.A.; Mckee, T.C.; Schroeter, H.; Teegarden, B.R.; Whitney, S.E.; Wershaw, R. L.

    1989-01-01

    An investigation of the aqueous chlorination (NaOCl) of resorcinol is reported. The following intermediates were detected in moderate to high yield at different pH values and varying percentages of chlorination: 2-chloro-, 4-chloro-, 2,4-dichloro-, 4,6-dichloro- and 2,4,6-trichlororesorcinol. Only trace amounts of the intermediates were detected when the chlorination was conducted in the presence of phosphate buffer. This result has significant implications since resorcinol in phosphate buffer has been used as a model compound in several recent studies on the formation of chlorinated hydrocarbons during chlorination of drinking water. Relative rates of chlorination were determined for resorcinol and several of the chlorinated resorcinols. Resorcinol was found to chlorinate only three times faster than 2,4,6-trichlororesorcinol. The structure 2,4,6-trichlororesorcinol was established as a monohydrate even after sublimation. A tetrachloro or pentachloro intermediate was not detected, suggesting that the ring-opening step of such an intermediate must be rapid. ?? 1989.

  5. Chlorinated hydrocarbons and biomarkers of exposure in wading birds and fish of the Lower Rio Grande Valley, Texas

    USGS Publications Warehouse

    Wainwright, S.E.; Mora, M.A.; Sericano, J.L.; Thomas, P.

    2001-01-01

    During 1997 we evaluated reproductive success in colonial water birds nesting in the Lower Rio Grande Valley (LRGV), Texas, and correlated success with concentrations of contaminants in eggs. We also measured steroid hormones and gonadosomatic index (GSI) as biomarkers of endocrine effects in common carp (Cyprinus carpio). Nest and fledging success of green herons (Butorides virescens) and great egrets (Ardea alba) were similar to those found in other parts of North America; however, nesting success of black-crowned night-herons (Nycticorax nycticorax) was lower, very likely due to flooding of the nesting area. Except for DDE and toxaphene, all chlorinated pesticides in bird eggs were low and not of concern for negative effects on any of the three species. DDE was highest in green heron eggs and seemed to increase along a geographic gradient from west to east, with eggs from Falcon Reservoir containing low concentrations, and those at Los Indios containing the highest concentrations (approx. 11,000 ng/g WW), near or above the threshold for reproductive impairment. DDE levels in great egrets and black-crowned night-herons were below those that are associated with reproductive impairment. Mean DDE levels in carp at the JAS Farms site were above the threshold level suggested for predator protection. Toxaphene was detected in about 20% of the samples with high levels observed in green heron eggs from Los Indios (mean = 4,402 ng/g WW). These are the highest toxaphene levels reported in bird eggs in the LRGV. Toxaphene levels in fish ranged between 90 and 312 ng/g WW. In general, PCBs in bird eggs and fish tissue were low and at levels not of concern for reproductive effects. The greatest concentrations of testosterone and 11-ketotestosterone were detected in fish from the JAS Farms site, which also had the greatest concentrations of DDE. Increased androgen production and gonad development in fish at this site, relative to Pharr, could be possibly associated with

  6. Chlorinated and parent polycyclic aromatic hydrocarbons in environmental samples from an electronic waste recycling facility and a chemical industrial complex in China.

    PubMed

    Ma, Jing; Horii, Yuichi; Cheng, Jinping; Wang, Wenhua; Wu, Qian; Ohura, Takeshi; Kannan, Kurunthachalam

    2009-02-01

    Chlorinated polycyclic aromatic hydrocarbons (CIPAHs) are a class of halogenated contaminants found in the urban atmosphere; they have toxic potential similar to that of dioxins. Information on the sources of CIPAHs is limited. In this study, concentrations of 20 CIPAHs and 16 parent PAHs were measured in electronic wastes, workshop-floor dust, vegetation, and surface soil collected from the vicinity of an electronic waste (e-waste) recycling facility and in surface soil from a chemical industrial complex (comprising a coke-oven plant, a coal-fired power plant, and a chlor-alkali plant), and agricultural areas in central and eastern China. High concentrations of SigmaCIPAHs were found in floor dust (mean, 103 ng/g dry wt), followed in order of decreasing concentration by leaves (87.5 ng/g drywt), electronic shredder waste (59.1 ng/g dry wt), and soil (26.8 ng/g dry wt) from an e-waste recycling facility in Taizhou. The mean concentration of SigmaCIPAHs in soil from the chemical industrial complex (88 ng/g dry wt) was approximately 3-fold higher than the concentration in soil from e-waste recycling facilities. The soils from e-waste sites and industrial areas contained mean concentrations of SigmaCIPAHs 2 to 3 orders of magnitude higher than the concentrations in agricultural soils (ND-0.76 ng/g), suggesting that e-waste recycling and chlorine-chemical industries are potential emission sources of CIPAHs. The profiles of CIPAHs in soil and dust were similar to a profile that has been reported previously for fly ash from municipal solid waste incinerators (6-CIBaP was the predominant compound), but the profiles in vegetation and electronic shredder waste were different from those found in fly ash. Concentrations of 16 parent PAHs were high (150-49,700 ng/g) in samples collected from the e-waste recycling facility. Significant correlation between SigmaCIPAH and SigmaPAH concentrations suggests that direct chlorination of parent PAHs is the major pathway of formation of

  7. Hepatic microsomal cytochrome p450s and chlorinated hydrocarbons in largha and ribbon seals from Hokkaido, Japan: differential response of seal species to Ah receptor agonist exposure.

    PubMed

    Chiba, Issei; Sakakibara, Akihito; Iwata, T Hisato; Ishizuka, Mayumi; Tanabe, Shinsuke; Akahori, Fumiaki; Kazusaka, Akio; Fujita, Shoichi

    2002-04-01

    From 16 largha seals (Phoca largha) and 15 ribbon seals (Phoca fasciata) in the coastal waters of Hokkaido, Japan, blubber chlorinated hydrocarbon (CHC) levels and hepatic cytochrome P450 (CYP) catalytic activities and their immunochemically detected protein content levels were measured. Concentrations of DDTs (2,2-bis(4-chlorophenyl)-1,1-dichloroethylene,p,p'-DDE; 2,2-bis(4-chlorophenyl)-1,1-dichloroethane, p,p'-DDD; dichlorodiphenyltrichloroethane, p,p'-DDT), polychlorinated biphenyl congeners (PCBs), and chlordane compounds (oxychlordane, chlordanes, and nonachlors) in both species were in the range of 290 to 5,300, 420 to 4,000, and 130 to 1,500 ng/g lipid weight, respectively. Aryl hydrocarbon receptor (AhR) agonists, non-ortho (IUPAC 77 and 126) and mono-ortho (IUPAC 105, 118, and 156) coplanar PCB congeners, were also detected, and the 2,3,7,8-tetrachlordibenzo-p-dioxin (TCDD) toxic equivalents (TEQs) were 4.9 to 120 pg TEQ/g lipid weight. Cross-reactive proteins with polyclonal antibodies against rat CYP1A1 and CYP3A2 were notably detected in seal liver microsomes. Interestingly, a polyclonal antibody against rat CYP2B1 recognized proteins only at trace levels. In largha seals, both levels of alkoxyresorufin- (methoxy-, ethoxy-, pentoxy-, and benzyloxyresorufin) O-dealkylase (AROD) activities and proteins detected by polyclonal antibodies against rat CYP1A1 were significantly correlated with the concentrations of individual coplanar PCB congeners, total TEQs, and total PCBs. Threshold concentrations for TEQs in blubber of the largha seal to induce hepatic CYP1A protein and EROD activity were estimated to be 8.5 and 19 pg TEQ/g fat weight, respectively. In ribbon seals, similar correlations were not detected, although the TEQ levels were not significantly lower than those in largha seals. These results suggest that AROD activity and CYP1A1 protein in the liver of the largha seal could be a biomarker for the exposure to AhR agonists such as coplanar PCB

  8. The inhibitory effect of some chlorinated hydrocarbon pesticides on the ATP-dependent Ca2+ binding of the particulate fraction of the eggshell gland mucosa cells.

    PubMed

    Lundholm, C E; Mathson, K

    1983-05-01

    The pesticide p-p'-DDT and its persistent metabolite p-p'-DDE cause thinning of the eggshells in several species of birds. In earlier investigations on ducks this thinning was found to be associated with a reduction of the ATP-dependent Ca2+ binding to a homogenate of the shell gland mucosal cells by DDE. The activity of a Ca2+-Mg2+-activated ATPase in the homogenate was also decreased on administration of DDE in vivo. We have therefore investigated the in vitro effects of some other chlorinated hydrocarbon pesticides of ecotoxicological interest on the ATP-dependent Ca2+ binding and the Ca2+-Mg2+-activated ATPase activity in a homogenate of the eggshell gland mucosa of the hen and determined the molar concentrations that produced 50% inhibition (=IC50). Several of the investigated compounds, namely toxaphene, chlordane, p-p'-DDD, o-p'-DDE, p-p'-DDT, methoxychlor and PCB (Arochlor 1242), had a similar IC50 to inhibit the Ca2+ binding as p-p'-DDE. Lindane, p-p'-DDA and biphenyl had an IC50 3.3-4 times higher and that of 2.4 D was 13.5 times higher than that of p-p'-DDE. When the IC50 of some of the compounds (p-p'-DDE, PCB, toxaphene, Lindane) was determined that decreased the Ca2+-Mg2+-activated ATPase of the homogenate it was found to be only 18 to 29 per cent of that needed to inhibit the Ca2+ binding by the homogenate. It is therefore probable that some other effect than inhibition of this enzyme is also involved in the Ca2+-binding process and affected by the compounds.

  9. Dynamics of Fe(II), sulphur and phosphate in pilot-scale constructed wetlands treating a sulphate-rich chlorinated hydrocarbon contaminated groundwater.

    PubMed

    Wu, Shubiao; Chen, Zhongbing; Braeckevelt, Mareike; Seeger, Eva M; Dong, Renjie; Kästner, Matthias; Paschke, Heidrun; Hahn, Anja; Kayser, Gernot; Kuschk, Peter

    2012-04-15

    Long-term investigations were carried out in two pilot-scale horizontal subsurface flow constructed wetlands (planted and unplanted) with an iron-rich soil matrix for treating sulphate-rich groundwater which was contaminated with low concentrations of chlorinated hydrocarbons. The temporal and spatial dynamics of pore-water sulphide, Fe(II) and phosphate concentrations in the wetland beds were characterized and the seasonal effects on sulphide production and nitrification inhibition were evaluated. The results demonstrated that the pore-water sulphide concentrations gradually increased from less than 0.2 mg/L in 2005 to annual average concentrations of 15 mg/L in 2010, while the pore-water Fe(II) concentrations decreased from 35.4 mg/L to 0.3 mg/L. From 2005 to 2010, the phosphate removal efficiency declined from 91% to 10% under a relatively constant inflow concentration of 5 mg/L. The pronounced effect of plants was accompanied by a higher sulphate reduction and ammonium oxidation in the planted bed, as compared to the unplanted control. A high tolerance of plants towards sulphide toxicity was observed, which might be due to the detoxification of sulphide by oxygen released by the roots. However, during the period of 2009-2010, the nitrification was negatively impacted by the sulphide production as the reduction in the removal of ammonium from 75% to 42% (with inflow concentration of 55 mg/L) correlated with the increasing mean annual sulphide concentrations. The effect of the detoxification of sulphide and the immobilization of phosphate by the application of the iron-rich soil matrix in the initial years was proven; however, the life-span of this effect should not only be taken into consideration in further design but also in scientific studies.

  10. Simultaneous determination of polycyclic aromatic hydrocarbons and their chlorination by-products in drinking water and the coatings of water pipes by automated solid-phase microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Tillner, Jocelyn; Hollard, Caroline; Bach, Cristina; Rosin, Christophe; Munoz, Jean-François; Dauchy, Xavier

    2013-11-08

    In this study, an automated method for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and their chlorination by-products in drinking water was developed based on online solid-phase microextraction-gas chromatography-mass spectrometry. The main focus was the optimisation of the solid-phase microextraction step. The influence of the agitation rate, type of fibre, desorption time, extraction time, extraction temperature, desorption temperature, and solvent addition was examined. The method was developed and validated using a mixture of 17 PAHs, 11 potential chlorination by-products (chlorinated and oxidised PAHs) and 6 deuterated standards. The limit of quantification was 10 ng/L for all target compounds. The validated method was used to analyse drinking water samples from three different drinking water distribution networks and the presumably coal tar-based pipe coatings of two pipe sections. A number of PAHs were detected in all three networks although individual compositions varied. Several PAH chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also found, their presence correlating closely with that of their respective parent compounds. Their concentrations were always below 100 ng/L. In the coatings, all PAHs targeted were detected although concentrations varied between the two coatings (76-12,635 mg/kg and 12-6295 mg/kg, respectively). A number of chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also detected (from 40 to 985 mg/kg), suggesting that the reaction of PAHs with disinfectant agents takes place in the coatings and not in the water phase after migration. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Comprehensive re-analysis of archived herring gull eggs reconstructs historical temporal trends in chlorinated hydrocarbon contamination in Lake Ontario and Green Bay, Lake Michigan, 1971-1982.

    PubMed

    Norstrom, Ross J; Hebert, Craig E

    2006-08-01

    Herring gull egg homogenates collected between 1971 and 1982 from a colony in central Lake Ontario (Scotch Bonnet Island) and from a colony in central Green Bay, Lake Michigan (Big Sister Island) were archived in the Canadian Wildlife Service Specimen Bank. Pooled samples (N = 10) were exhaustively analyzed in 1993 for a wide range of individual chlorinated hydrocarbon contaminant (CHC) compounds: DDT, mirex and chlordane compounds and metabolites, chlorobenzenes (CBzs), dieldrin, chlorostyrenes (CSs), hexachlorocyclohexanes (HCHs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and 87 PCB congeners, including the TCDD-like non-ortho and mono-ortho congeners. PCBs and DDTs were the dominant residues in eggs from both Lake Ontario (31-242 mg kg(-1) and 9-64 mg kg(-1)) and Green Bay (34-133 mg kg(-1) and 14-91 mg kg(-1)). SigmaPCBs declined by a factor of 4-5 and DDTs a factor of 4-7 at both colonies between 1971 and 1982. Lake Ontario eggs had significantly higher residues of 2,3,7,8-TCDD (0.2-2.0 microg kg(-1)), HCBz (0.1-4.7 mg kg(-1)), OCS (0.03-0.45 mg kg(-1)), three HpCSs (0.13-0.97 mg kg(-1)), mirex and mirex photodegradation products (2.1-9.2 mg kg(-1)) than Green Bay eggs. HCBz levels in Lake Ontario eggs declined a factor of 40, TCDD and chlorostyrenes a factor of 8-10, and mirex a factor of 4 between 1971-1978. Green Bay eggs had slightly higher levels of chlordane-related compounds, dieldrin and beta-HCH than Lake Ontario eggs. There were no consistent or strong trends in residue levels of these pesticides, PCDDs (except TCDD) and PCDFs in either lake, indicating that rates of input and removal of these CHCs in the lakes were much closer in the early 1970s than was the case for the other compounds.

  12. Kinetic Studies of the Cometabolism of 1,4-DIOXANE and Chlorinated Aliphatic Hydrocarbon Mixtures by Rhodococcus Rhodochrous Grown on Isobutane

    NASA Astrophysics Data System (ADS)

    Rolston, H. M.; Semprini, L.; Thankitkul, S.; Azizian, M.; Hyman, M. R.

    2016-12-01

    1,4-dioxane (1,4-D) is a frequently observed groundwater contaminant due to its use as a stabilizer in commercial solvent formulations. In situ bioremediation could potentially provide a large cost savings for treatment of mixtures of chlorinated aliphatic hydrocarbons (CAHs) that include 1,4-D. Aerobic cometabolism is a particularly attractive option, as microorganisms can be stimulated in situ using specific primary substrates. Results will be presented that show the model isobutane-metabolizing bacteria, Rhodococcus rhodochrous (ATCC 21198), has the ability to transform 14-D at high rates and transformation capacities to concentrations below the drinking water screening level of 0.67 µg L-1. Resting cell transformation tests showed 1,4-D and a broad range of CAHs can be cometabolized by ATCC 21198. The maximum transformation rate (kmax) and the half-substrate coefficient (Ks) were determined for isobutane (the growth substrate), 1,4-D, 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethane (1,1-DCA); 1,2-dichloroethane ((1,2-DCA) and 1,1-dichloroethene (1,1-DCE). Of the CAHs tested, 1,1-DCA had the highest kmax, approximately 25% of that for isobutane utilization, while 1,1,1-TCA had the lowest kmax, approximately 2% of isobutane's. 1,4-D was rapidly transformed and had a kmax 25% of that of isobutane. ATCC 21198 effectively transformed mixtures of 1,4-D, 1,1-DCE, 1,2-DCA and 1,1,1-TCA, both in the presence and absence isobutane. Model simulations were performed for the simultaneous cometabolism of 1,4-D and CAH mixtures by ATCC 21198, that included inhibition among the contaminants and isobutane , and terms for a limited transformation capacity. A good match to experimental observations was obtaining using the independently measured rate parameters. Results of model simulations will also be presented using a reactive transport model to evaluate conditions of in situ bioremediation using strain ATCC 21198.

  13. Gamma radiolysis of chlorinated hydrocarbons

    SciTech Connect

    Arbon, R.E.; Mincher, B.J.; Meikrantz, D.H.

    1992-08-01

    This program is the Idaho National Engineering Laboratory (INEL) component of a joint collarborative effort with Lawrence Livermore National Laboratory (LLNL). The purpose of this effort is to demonstrate a viable process for breaking down hazardous halogenated organic wastes to simpler, non-hazardous waste using high energy ionizing radiation. The INEL effort focuses on the use of spent reactor fuel gamma radiation sources to decompose complex wastes such as PCBs. At LLNL, halogenated solvents such as carbon tetrachloride and trichloroethylene are being studied using accelerator radiation sources. The INEL irradiation experiments concentrated on a single PCB congener so that a limited set of decomposition reactions could be studied. The congener 2,2{prime}, 3,3{prime},4,5{prime},6,6{prime} - octachlorobiphenyl was examined following exposure to various gamma doses at the Advanced Test Reactor (AIR) spent fuel pool. The decomposition rates and products in several solvents are discussed. 3 refs.

  14. Gamma radiolysis of chlorinated hydrocarbons

    SciTech Connect

    Arbon, R.E.; Mincher, B.J.; Meikrantz, D.H.

    1992-01-01

    This program is the Idaho National Engineering Laboratory (INEL) component of a joint collarborative effort with Lawrence Livermore National Laboratory (LLNL). The purpose of this effort is to demonstrate a viable process for breaking down hazardous halogenated organic wastes to simpler, non-hazardous waste using high energy ionizing radiation. The INEL effort focuses on the use of spent reactor fuel gamma radiation sources to decompose complex wastes such as PCBs. At LLNL, halogenated solvents such as carbon tetrachloride and trichloroethylene are being studied using accelerator radiation sources. The INEL irradiation experiments concentrated on a single PCB congener so that a limited set of decomposition reactions could be studied. The congener 2,2{prime}, 3,3{prime},4,5{prime},6,6{prime} - octachlorobiphenyl was examined following exposure to various gamma doses at the Advanced Test Reactor (AIR) spent fuel pool. The decomposition rates and products in several solvents are discussed. 3 refs.

  15. Chlorine poisoning

    MedlinePlus

    Chlorine reacts with water in and out of the body to form hydrochloric acid and hypochlorous acid. Both are extremely poisonous. ... chlorine) Throat swelling (may also cause breathing difficulty) ... Severe change in acid level of the blood (pH balance), which leads ...

  16. Characterization of Preferential Ground-Water Seepage From a Chlorinated Hydrocarbon-Contaminated Aquifer to West Branch Canal Creek, Aberdeen Proving Ground, Maryland, 2002-04

    USGS Publications Warehouse

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

    2007-01-01

    Wetlands act as natural transition zones between ground water and surface water, characterized by the complex interdependency of hydrology, chemical and physical properties, and biotic effects. Although field and laboratory demonstrations have shown efficient natural attenuation processes in the non-seep wetland areas and stream bottom sediments of West Branch Canal Creek, chlorinated volatile organic compounds are present in a freshwater tidal creek at Aberdeen Proving Ground, Maryland. Volatile organic compound concentrations in surface water indicate that in some areas of the wetland, preferential flow paths or seeps allow transport of organic compounds from the contaminated sand aquifer to the overlying surface water without undergoing natural attenuation. From 2002 through 2004, the U.S. Geological Survey, in cooperation with the Environmental Conservation and Restoration Division of the U.S. Army Garrison, Aberdeen Proving Ground, characterized preferential ground-water seepage as part of an ongoing investigation of contaminant distribution and natural attenuation processes in wetlands at this site. Seep areas were discrete and spatially consistent during thermal infrared surveys in 2002, 2003, and 2004 throughout West Branch Canal Creek wetlands. In these seep areas, temperature measurements in shallow pore water and sediment more closely resembled those in ground water than those in nearby surface water. Generally, pore water in seep areas contaminated with chlorinated volatile organic compounds had lower methane and greater volatile organic compound concentrations than pore water in non-seep wetland sediments. The volatile organic compounds detected in shallow pore water in seeps were spatially similar to the dominant volatile organic compounds in the underlying Canal Creek aquifer, with both parent and anaerobic daughter compounds detected. Seep locations characterized as focused seeps contained the highest concentrations of chlorinated parent compounds

  17. On the efficiency of the hybrid and the exact second-order sampling formulations of the EnKF: a reality-inspired 3-D test case for estimating biodegradation rates of chlorinated hydrocarbons at the port of Rotterdam

    NASA Astrophysics Data System (ADS)

    Gharamti, Mohamad E.; Valstar, Johan; Janssen, Gijs; Marsman, Annemieke; Hoteit, Ibrahim

    2016-11-01

    This study considers the assimilation problem of subsurface contaminants at the port of Rotterdam in the Netherlands. It involves the estimation of solute concentrations and biodegradation rates of four different chlorinated solvents. We focus on assessing the efficiency of an adaptive hybrid ensemble Kalman filter and optimal interpolation (EnKF-OI) and the exact second-order sampling formulation (EnKFESOS) for mitigating the undersampling of the estimation and observation errors covariances, respectively. A multi-dimensional and multi-species reactive transport model is coupled to simulate the migration of contaminants within a Pleistocene aquifer layer located around 25 m below mean sea level. The biodegradation chain of chlorinated hydrocarbons starting from tetrachloroethene and ending with vinyl chloride is modeled under anaerobic environmental conditions for 5 decades. Yearly pseudo-concentration data are used to condition the forecast concentration and degradation rates in the presence of model and observational errors. Assimilation results demonstrate the robustness of the hybrid EnKF-OI, for accurately calibrating the uncertain biodegradation rates. When implemented serially, the adaptive hybrid EnKF-OI scheme efficiently adjusts the weights of the involved covariances for each individual measurement. The EnKFESOS is shown to maintain the parameter ensemble spread much better leading to more robust estimates of the states and parameters. On average, a well tuned hybrid EnKF-OI and the EnKFESOS respectively suggest around 48 and 21 % improved concentration estimates, as well as around 70 and 23 % improved anaerobic degradation rates, over the standard EnKF. Incorporating large uncertainties in the flow model degrades the accuracy of the estimates of all schemes. Given that the performance of the hybrid EnKF-OI depends on the quality of the background statistics, satisfactory results were obtained only when the uncertainty imposed on the background

  18. Toxic chemicals, including aromatic and chlorinated hydrocarbons and their derivatives, and liver lesions in white croaker (Genyonemus lineatus) from the vicinity of Los Angeles

    SciTech Connect

    Malins, D.C.; McCain, B.B.; Brown, D.W.; Myers, M.S.; Krahn, M.M.; Chan, S.L.

    1987-08-01

    High concentrations of toxic chemicals in sediment and white croaker (Genyonemus lineatus), as well as liver diseases (e.g., carcinomas) in this species, were found in the Los Angeles area. The highest concentrations of aromatic hydrocarbons (AHs) in the sediment were in San Pedro Bay, and the highest concentrations of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) derivatives were in sediment from near the White Point sewer outfall. Concentrations of AHs, polychlorobiphenyls (PCBs), and DDT derivatives were generally higher in food organisms from the croaker's stomach than in sediment. Moreover, croaker from San Pedro Bay and White Point were substantially contaminated with DDT derivatives and metabolites of aromatic compounds, compared to croaker from the Hyperion outfall and Dana Point. The evidence suggest that the observed pathological conditions of the liver were associated with exposure of the croaker to toxic chemicals, which occurred, at least in part, through the ingestion of contaminated food organisms.

  19. Chlorine dioxide

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 00 / 007 TOXICOLOGICAL REVIEW OF CHLORINE DIOXIDE AND CHLORITE ( CAS Nos . 10049 - 04 - 4 and 7758 - 19 - 2 ) In Support of Summary Information on the ( IRIS ) Integrated Risk Information System September 2000 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This docu

  20. Chlorine cyanide

    Integrated Risk Information System (IRIS)

    Chlorine cyanide ; CASRN 506 - 77 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  1. U. S. EPA’S APPROACH FOR CHLORINATED SOLVENTS

    EPA Science Inventory

    The approach for chlorinated solvents is similar to the approach for petroleum hydrocarbons. However, there are more mechanisms of removal, including reductive dechlorination (biotic or abiotic), dehydrochloroelimination (abiotic), and hydrolysis (biotic or abiotic). As a resul...

  2. Chlorinated, brominated, and perfluorinated compounds, polycyclic aromatic hydrocarbons and trace elements in livers of sea otters from California, Washington, and Alaska (USA), and Kamchatka (Russia).

    PubMed

    Kannan, Kurunthachalam; Moon, Hyo-Bang; Yun, Se Hun; Agusa, Tetsuro; Thomas, Nancy J; Tanabe, Shinsuke

    2008-04-01

    Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations.

  3. Reutilization of waste scrap tyre as the immobilization matrix for the enhanced bioremoval of a monoaromatic hydrocarbons, methyl tert-butyl ether, and chlorinated ethenes mixture from water.

    PubMed

    Lu, Qihong; de Toledo, Renata Alves; Xie, Fei; Li, Junhui; Shim, Hojae

    2017-04-01

    BTEX (benzene, toluene, ethylbenzene, ortho-, meta-, and para-xylenes), methyl tert-butyl ether (MTBE), cis-1,2-dichloroethylene (cis-DCE), and trichloroethylene (TCE) are among the major soil and groundwater contaminants frequently co-existing, as a result of their widespread uses. Pseudomonas plecoglossicida was immobilized on waste scrap tyre to remove these contaminants mixture from synthetic contaminated water. The microbial activity was enhanced in the immobilized system, shown by the higher colony forming units (CFUs) (40%), while BTEX were used as growth substrates. The adsorption capacity of tyres toward contaminants reached a maximum within one day, with BTEX (76.3%) and TCE (64.3%) showing the highest sorption removal capacities, followed by cis-DCE (30.0%) and MTBE (11.0%). The adsorption data fitted the Freundlich isotherm with a good linear correlation (0.989-0.999) for the initial contaminants concentration range applied (25-125mg/L). The monoaromatic hydrocarbons were almost completely removed in the immobilized system and the favourable removal efficiencies of 78% and 90% were obtained for cis-DCE and TCE, respectively. The hybrid (biological, immobilization/physical, sorption) system was further evaluated with the contaminants spiked intermittently for the stable performance. The addition of mineral salt medium further enhanced the bioremoval of contaminants by stimulating the microbial growth to some extent.

  4. Chlorinated, brominated, and perfluorinated compounds, polycyclic aromatic hydrocarbons and trace elements in livers of sea otters from California, Washington, and Alaska (USA), and Kamchatka (Russia)

    USGS Publications Warehouse

    Kannan, K.; Moon, H.-B.; Yun, S.-H.; Agusa, T.; Thomas, N.J.; Tanabe, S.

    2008-01-01

    Concentrations of organochlorine pesticides (DDTs, HCHs, and chlordanes), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), perfluorinated compounds (PFCs), and 20 trace elements were determined in livers of 3- to 5-year old stranded sea otters collected from the coastal waters of California, Washington, and Alaska (USA) and from Kamchatka (Russia). Concentrations of organochlorine pesticides, PCBs, and PBDEs were high in sea otters collected from the California coast. Concentrations of DDTs were 10-fold higher in California sea otters than in otters from other locations; PCB concentrations were 5-fold higher, and PBDE concentrations were 2-fold higher, in California sea otters than in otters from other locations. Concentrations of PAHs were higher in sea otters from Prince William Sound than in sea otters from other locations. Concentrations of several trace elements were elevated in sea otters collected from California and Prince William Sound. Elevated concentrations of Mn and Zn in sea otters from California and Prince William Sound were indicative of oxidative stress-related injuries in these two populations. Concentrations of all of the target compounds, including trace elements, that were analyzed in sea otters from Kamchatka were lower than those found from the US coastal locations. ?? The Royal Society of Chemistry.

  5. Chlorine Clues

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This plot shows that levels of the element chlorine rise dramatically in the deeper rocks lining the walls of the crater dubbed 'Endurance.' The data shown here were taken by the Mars Exploration Rover Opportunity's alpha particle X-ray spectrometer at Endurance and 'Eagle Crater,' the site where Opportunity first landed at Meridiani Planum.

    Opportunity has been inching down the walls of Endurance Crater, investigating distinct layers of rock as it goes for clues to Mars' buried past. The various Endurance layers have been informally labeled 'A' through 'F.' Targets within these layers are listed on the graph along with previous targets from Eagle Crater. All the rocks listed here were observed after they had been drilled by the rover's rock abrasion tool.

    The observations indicate that the elements making up the shallow rock layers of Endurance Crater resemble those of Eagle, while the deeper layers of Endurance possess increasingly higher concentrations of the element chlorine.

    Opportunity will continue to roll deeper into Endurance to see if this puzzling trend continues. Scientists hope the new data will help them figure out how the presence of chlorine fits into the history of water at Endurance Crater.

  6. Chlorine Clues

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This plot shows that levels of the element chlorine rise dramatically in the deeper rocks lining the walls of the crater dubbed 'Endurance.' The data shown here were taken by the Mars Exploration Rover Opportunity's alpha particle X-ray spectrometer at Endurance and 'Eagle Crater,' the site where Opportunity first landed at Meridiani Planum.

    Opportunity has been inching down the walls of Endurance Crater, investigating distinct layers of rock as it goes for clues to Mars' buried past. The various Endurance layers have been informally labeled 'A' through 'F.' Targets within these layers are listed on the graph along with previous targets from Eagle Crater. All the rocks listed here were observed after they had been drilled by the rover's rock abrasion tool.

    The observations indicate that the elements making up the shallow rock layers of Endurance Crater resemble those of Eagle, while the deeper layers of Endurance possess increasingly higher concentrations of the element chlorine.

    Opportunity will continue to roll deeper into Endurance to see if this puzzling trend continues. Scientists hope the new data will help them figure out how the presence of chlorine fits into the history of water at Endurance Crater.

  7. The Chlorination Quandary

    ERIC Educational Resources Information Center

    Josephson, Julian

    1978-01-01

    Current use of chlorination technology to disinfect water supplies can cause the production of undesirable products, among them chloroform and chlorobenzene. Alternatives to this methodology include the use of ozone, chlorine dioxide, and bromine chloride in place of chlorine. Presently, the methods are feasible in developed countries only. (MA)

  8. The Chlorination Quandary

    ERIC Educational Resources Information Center

    Josephson, Julian

    1978-01-01

    Current use of chlorination technology to disinfect water supplies can cause the production of undesirable products, among them chloroform and chlorobenzene. Alternatives to this methodology include the use of ozone, chlorine dioxide, and bromine chloride in place of chlorine. Presently, the methods are feasible in developed countries only. (MA)

  9. Biodegration of chlorinated ethenes

    USGS Publications Warehouse

    Bradley, Paul M.; Chapelle, Francis H.

    2010-01-01

    Biodegradation of chlorinated ethenes by naturally occurring or artificially enhanced processes is an important component of current site remediation strategies. At this writing, several microbial mechanisms for chlorinated ethene transformation and degradation have been identified. The purpose of this chapter is to briefly summarize the current understanding of those processes that lead to the biodegradation of chlorinated ethenes.

  10. Water chlorination Vol. 5

    SciTech Connect

    Jolley, R.L.; Bull, R.J.; Davis, W.P.; Katz, S.; Roberts, M.H.

    1985-01-01

    This book describes the significant original contributions in the field of water chlorination of the last three years. It includes chlorination research, developments and alternatives. Issues covered include: water chlorination; risk; epidemiology; carcinogenic and mutagenic effects; toxicology of disinfectants; aquatic models and tumor induction; environmental effects; disinfection; reaction dynamics; chemical methods; drinking water treatment and wastewater treatment.

  11. Bioremediation and phytoremediation: Chlorinated and recalcitrant compounds

    SciTech Connect

    1998-12-31

    Bioremediation and phytoremediation have progressed, especially with regard to the treatment of hydrocarbon-contaminated sites. Sites contaminated with chlorinated and recalcitrant compounds have proven more resistant to these approaches, but exciting progress is being made both in the laboratory and in the field. This book brings together the latest breakthrough thinking and results in bioremediation, with chapters on cometabolic processes, aerobic and anaerobic mechanisms, biological reductive dechlorination processes, bioaugmentation, biomonitoring, and phytoremediation of recalcitrant organic compounds.

  12. Development of compound-specific isotope analysis of stable chlorine in sub-µmol quantities of chlorinated organic substances

    NASA Astrophysics Data System (ADS)

    Holmstrand, H.; Andersson, P.; Gustafsson, O.

    2003-04-01

    Chlorinated hydrocarbons is a common class of substances known to be of high ecotoxicity largely due to their persistence and strongly lipophilic properties. This group of chemicals include the semivolatile compounds dichloro-diphenyl-trichloroethane (DDT) and polychlorinated biphenyls (PCB), which, together with solvents like trichloroethylene (TCE) and perchloroethylene (PCE), are globally present at detectable levels in all natural environments. Recent reports on the possibility of enzymatic synthesis of chlorinated dioxins and furans, illustrate the need for means to distinguish the naturally produced contribution from anthropogenic input to the environment. Shifts in the chlorine isotope composition due to degradation, or synthesis, of a compound are in the order of a few per mil of the initial isotope ratio. The cause of the kinetic isotope effect (KIE) arises from differences in preferential phase distribution of isotopic species. Compound specific isotope analysis (CSIA) of stable chlorine should accordingly provide knowledge relevant to degradation rates, distribution patterns and reaction pathways for organochlorines. Isotope analysis of chlorine, derived from chlorinated hydrocarbons, can be performed using thermal ionisation mass spectrometry (TIMS) with positive ions. This lowers the limit of determination from about 30 μmol Cl for conventional electron ionisation mass spectrometry (EIMS), to less than 0.3 μmol Cl with a precision of 0.25 ppm (1s) for TIMS. Such a decrease by a factor 100 in the requirements of sample size will enable CSIA of sediment samples collected away from the immediate vicinity of strongly contaminated areas. The aim of this study is to develop a functioning sequence for i) sealed tube combustion with CuO of solid phase chlorinated hydrocarbons equivalent to <0.7 μmol Cl, ii) conversion of formed chloride to CsCl by ion exchange chromatography and iii) analysis of chlorine isotopes in TIMS. The described method can open new

  13. TECHNICAL PROTOCOL FOR EVALUATING NATURAL ATTENUATION OF CHLORINATED SOLVENTS IN GROUND WATER

    EPA Science Inventory

    This Protocol is designed to evaluate the fate in ground water of chlorinated aliphatic hydrocarbons and/or fuel hydrocarbons. Documentation of natural attenuation requires detailed site characterization. The data collected under this protocol can be used to compare the relati...

  14. TECHNICAL PROTOCOL FOR EVALUATING NATURAL ATTENUATION OF CHLORINATED SOLVENTS IN GROUND WATER

    EPA Science Inventory

    This Protocol is designed to evaluate the fate in ground water of chlorinated aliphatic hydrocarbons and/or fuel hydrocarbons. Documentation of natural attenuation requires detailed site characterization. The data collected under this protocol can be used to compare the relati...

  15. Inhalation of chlorine gas.

    PubMed Central

    Williams, J. G.

    1997-01-01

    The clinical features of acute chlorine gas inhalation, and its management are reviewed. Current medical views on the chronic effects of an acute overwhelming exposure on lung function (reactive airways dysfunction syndrome), and the more controversial field of lung disease secondary to repeated inhalations of lower concentrations of chlorine gas are discussed. Images Figure PMID:9519180

  16. Water Treatment Technology - Chlorination.

    ERIC Educational Resources Information Center

    Ross-Harrington, Melinda; Kincaid, G. David

    One of twelve water treatment technology units, this student manual on chlorination provides instructional materials for nine competencies. (The twelve units are designed for a continuing education training course for public water supply operators.) The competencies focus on the following areas: purpose and process of chlorination, chlorine…

  17. Water Treatment Technology - Chlorination.

    ERIC Educational Resources Information Center

    Ross-Harrington, Melinda; Kincaid, G. David

    One of twelve water treatment technology units, this student manual on chlorination provides instructional materials for nine competencies. (The twelve units are designed for a continuing education training course for public water supply operators.) The competencies focus on the following areas: purpose and process of chlorination, chlorine…

  18. Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

    NASA Astrophysics Data System (ADS)

    Baker, Angela K.; Sauvage, Carina; Thorenz, Ute R.; van Velthoven, Peter; Oram, David E.; Zahn, Andreas; Brenninkmeijer, Carl A. M.; Williams, Jonathan

    2016-11-01

    The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry.

  19. Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

    PubMed Central

    Baker, Angela K.; Sauvage, Carina; Thorenz, Ute R.; van Velthoven, Peter; Oram, David E.; Zahn, Andreas; Brenninkmeijer, Carl A. M.; Williams, Jonathan

    2016-01-01

    The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry. PMID:27845366

  20. SAM Chlorine Observations at Gale Crater

    NASA Astrophysics Data System (ADS)

    Conrad, P. G.; Farley, K. A.; Vasconcelos, P. M.; Malespin, C.; Franz, H.; McAdam, A.; Sutter, B.; Stern, J. C.; Clark, B. C.; Atreya, S. K.; Mahaffy, P. R.; Martín-Torres, J.; Zorzano, M. P.

    2014-12-01

    The Sample Analysis at Mars investigation has detected Cl-bearing phases of various oxidation states in its thermally evolved gas measurements of both a wind drift deposit of fines and three different rock samples delivered as sieved drill powders to the instrument suite. In addition to HCl (Leshin et al, 2013; Ming et al, 2013) and chlorinated hydrocarbon detections (Glavin et al, 2013; Freissinet et al, in review), oxygen releases consistent with the decomposition of perchlorate salts are also observed. We have also measured chlorine isotope ratios of the four different solid samples, which yielded variable and more negative δ37Cl than typically observed in SNC meteorite analyses. We summarize our chlorine observations in the context of other gases observed in the SAM solid sample analyses, including water, sulfur- and nitrogen-bearing compounds, and REMS observations of Relative Humidity and Temperature, and compare with knowledge of martian chlorine obtained from the SNC meteorites. Finally, we examine the implications of surface/atmosphere Cl interactions and isotopic ratios for the rise and decline of habitable surface environments on Mars. This research was supported by the National Aeronautics and Space Administration (NASA) Mars Science Laboratory mission.

  1. In vitro mutagenicity and genotoxicity study of a number of short-chain chlorinated hydrocarbons using the micronucleus test and the alkaline single cell gel electrophoresis technique (Comet assay) in human lymphocytes: a structure-activity relationship (QSAR) analysis of the genotoxic and cytotoxic potential.

    PubMed

    Tafazoli, M; Baeten, A; Geerlings, P; Kirsch-Volders, M

    1998-03-01

    Using the micronucleus (MN) test and the alkaline single cell gel electrophoresis (Comet) assay, potential mutagenicity (MN formation), genotoxicity (DNA breakage capacity) and cytotoxicity (cell proliferation reduction) of five chlorinated hydrocarbons (carbon tetrachloride, hexachloroethane, 1,2-dichloroethane, 1-chlorohexane and 2,3-dichlorobutane) have been evaluated in isolated human lymphocytes. With the MN test a low but statistically significant mutagenic activity was detected for all tested substances (except 2,3-dichlorobutane) with one out of the two donors and in the presence or absence of an exogenous metabolic activation system (S9 mix). However, at the concentration ranges tested none of the positive compounds induced a clear dose-dependent mutagenic effect. The Comet assay detected a strong DNA damaging effect for 1-chlorohexane, 2,3-dichlorobutane and 1,2-dichloroethane, but not for carbon tetrachloride and hexachloroethane. The influence of metabolism on the genotoxic activity of the chemicals was more clear in the Comet assay than in the MN test. The experimental genotoxicity and cytotoxicity data obtained in this study, together with data on five more related chemicals previously investigated, and their physico-chemical descriptors or electronic parameters have been used for QSAR analysis. The QSAR analysis high-lighted that the toxicity of the tested compounds was influenced by different parameters, like lipophilicity (logP), electron donor ability (charge) and longest carbon-chlorine (LBC-Cl) bond length. In addition, steric parameters, like molar refractivity (MR) and LBC-Cl, and electronic parameters, like ELUMO (energy of the lowest unoccupied molecular orbital, indicating electrophilicity), were predominant factors discriminating genotoxins from non-genotoxins in the presence but not in the absence of S9 mix. Although a limited number of compounds have been examined and cytotoxicity and genotoxicity were identified in two different

  2. Evaluation of the Tenax trap in the Sample Analysis at Mars instrument suite on the Curiosity rover as a potential hydrocarbon source for chlorinated organics detected in Gale Crater

    NASA Astrophysics Data System (ADS)

    Miller, Kristen E.; Kotrc, Benjamin; Summons, Roger E.; Belmahdi, Imene; Buch, Arnaud; Eigenbrode, Jennifer L.; Freissinet, Caroline; Glavin, Daniel P.; Szopa, Cyril

    2015-08-01

    The Sample Analysis at Mars (SAM) instrument suite aboard Curiosity has detected chlorinated organic compounds in Martian sediment samples. The chlorine in these molecules is thought to derive from oxychlorine salts in Martian sediments, but the carbon source remains under investigation. To constrain possible carbon sources, we investigated how the composition and concentration of oxychlorine phases in solid samples affect organic molecules released from the Tenax traps on board SAM. We created Mars analogue soils by spiking olivine sand with calcium perchlorate, magnesium perchlorate, or ferric iron chloride and analyzed the volatiles generated during pyrolysis-gas chromatography-mass spectrometry using commercial instruments operated under SAM-like conditions, with and without a Tenax trap. Benzoic acid, phthalic anhydride, high molecular weight aromatics, and chlorobenzenes are produced from the trap in response to volatiles released during Cl salt pyrolysis. Changes in composition or concentration of oxychlorine phases between samples could thus potentially produce an increase in chlorobenzene, as observed between samples from Rocknest and Cumberland. However, in our experiments benzoic acid, phthalic anhydride, and chlorobenzenes increase in proportion with the amount of HCl sent to the trap, while in Cumberland samples the chlorobenzene increase showed no corresponding increase in HCl. Based on our experiments, the Tenax trap is a possible source of the traces of chlorobenzene observed at Rocknest, John Klein, and Confidence Hills. The order-of-magnitude higher chlorobenzene abundances observed at Cumberland cannot be attributed to the Tenax trap. Furthermore, we found no evidence of significant trap degradation after hundreds of experiments with Cl salt-containing analogue soils.

  3. CHLORINATED SOLVENT PLUME CONTROL

    EPA Science Inventory

    This lecture will cover recent success in controlling and assessing the treatment of shallow ground water plumes of chlorinated solvents, other halogenated organic compounds, and methyl tert-butyl ether (MTBE).

  4. CHLORINATED SOLVENT PLUME CONTROL

    EPA Science Inventory

    This lecture will cover recent success in controlling and assessing the treatment of shallow ground water plumes of chlorinated solvents, other halogenated organic compounds, and methyl tert-butyl ether (MTBE).

  5. Breakpoint chlorination curves of greywater.

    PubMed

    March, J G; Gual, M

    2007-08-01

    A study on chlorination of raw greywater with hypochlorite is reported in this paper. Samples were chlorinated in a variety of conditions, and residual chlorine (Cl2) was measured spectrophotometrically. For each sample, the chlorination curve (chlorine residuals versus chlorine dose) was obtained. Curves showed the typical hump-and-dip profile attributable to the formation and destruction of chloramines. It was observed that, after reactions with strong reductants and chloramines-forming compounds, the remaining organic matter exerted a certain demand of chlorine. The evolution of chlorination curves with addition of ammonia and dodecylbencene sulfonate sodium salt and with dilution of the greywater sample were studied. In addition, chlorination curves at several contact times have been obtained, resulting in slower chlorine decay in the hump zone than in the dip zone. In addition, the decay of coliforms in chlorinated samples was also investigated. It was found that, for a chlorination dosage corresponding to the maximum of the hump zone (average 8.9 mg Cl2/ L), samples were negative in coliforms after 10 to 30 minutes of contact time. After-growth was not observed within 3 days after chlorination. Implications in chlorination treatments of raw greywater can be derived from these results.

  6. [Formation mechanism and chemical safety of nonintentional chemical substances present in chlorinated drinking water and wastewater].

    PubMed

    Onodera, Sukeo

    2010-09-01

    This paper reviews the formation mechanism and chemical safety of nonintentional chemical substances (NICS) present in chlorine-treated water containing organic contaminants. Undesirable compounds, i.e., NICS, may be formed under certain conditions when chlorine reacts with organic matter. The rate and extent of chlorine consumption with organics are strongly dependent on their chemical structures, particularly whether double bonds or sulfur and nitrogen atoms occur in the molecules. Organothiophosphorus pesticides (P=S type) are easily oxidized to their phosphorus compounds (P=O type) in chlorinated water containing HOCl as little as 0.5 mg/l, resulting in an increase in cholinesterase-inhibitory activity. Chlorination of phenols in water also produces a series of highly chlorinated compounds, including chlorophenols, chloroquinones, chlorinated carboxylic acids, and polychlorinated phenoxyphenols (PCPPs). In some of these chloroquinones, 2,6-dichloroalkylsemiquinones exhibit a strong mutagenic response as do positive controls used in the Ames test. 2-phenoxyphenols in these PCPPs are particularly interesting, as they are present in the chlorine-treated phenol solution and they are also precursors (predioxins) of the highly toxic chlorinated dioxins. Polynuclear aromatic hydrocarbons (PAHs) were found to undergo chemical changes due to hypochlorite reactions to give chloro-substituted PAHs, oxygenated (quinones) and hydroxylated (phenols) compounds, but they exhibit a lower mutagenic response. In addition, field work was performed in river water and drinking water to obtain information on chemical distribution and their safety, and the results are compared with those obtained in the model chlorination experiments.

  7. Spatial and temporal variability of inorganic chlorine in Northwestern Europe

    NASA Astrophysics Data System (ADS)

    Sommariva, R.; Hollis, L. D. J.; Baker, A. R.; Ball, S. M.; Bell, T. G.; Cordell, R. L.; Fleming, Z.; Gaget, M.; Yang, M. X.; Monks, P. S.

    2015-12-01

    Chlorine is well known to be a strong oxidant in the atmosphere;chlorine reactivity impacts the formation of tropospheric ozone, theoxidation of methane and non-methane hydrocarbons, and the cycling ofnitrogen, sulphur and mercury. An accurate assessment of the roleplayed by chlorine in tropospheric chemical processes is complicatedby the scarce knowledge of its sources, sinks and distribution.We report observations of inorganic chlorine species (Cl2, ClNO2,particulate chloride) taken over the period 2014-2015 at threedifferent locations in Britain: an urban site a hundred kilometersfrom the ocean (Leicester), a coastal site mostly affected by shiptraffic (Penlee Point, Cornwall) and a coastal site experiencingeither clean air from the North Sea or polluted air from inland(Weybourne, Norfolk).This dataset provides a first look into the geographical distributionand seasonal variability of chlorine in Northwestern Europe: theresults suggest that, during the night, ClNO2 is ubiquitous withconcentrations in the range of hundreds to thousands of pptV at alllocations, whereas Cl2 can be observed only at coastal sites, withconcentrations of a few tens of pptV. The implications of thewidespread presence of these forms of inorganic chlorine for ozoneproduction and, in general, for the oxidative processes in the loweratmosphere are discussed with the help of a wide range of supportingmeasurements.

  8. Review of chlorinated phenols

    SciTech Connect

    Exon, J.H.

    1984-12-01

    The chlorinated phenols are a group of 19 isomers composed of phenol with substituted chlorines. These chemicals are readily soluble in organic solvents but only slightly soluble in water, except for the chlorophenate salts. Chlorophenols with less than 3 chlorines are not used extensively except in the production of higher chlorophenols and chlorophenyloxyacetic acid herbicides. Pentachlorophenol and some tetrachlorophenols are used worldwide, primarily as wood preservatives or fungicides. Residues of chlorophenols have been found worldwide in soil, water and air samples, in food products, and in human and animal tissues and body fluids. Environmental contamination with these chemicals occurs from industrial effluents, agricultural runoff, breakdown of chlorophenyloxyacetic acid herbicides and hexachlorobenzene, and from spontaneous formation following chlorination of water for disinfection and deodorization. The acute toxicity of these chemicals is relatively low and little is known concerning their chronic effects. Chlorophenols have not been shown conclusively to be mutagens, teratogens or carcinogens. However, these compounds may act as promotors or cocarcinogens and the immune system is particularly sensitive to their toxic effects. Transplacental exposure to chlorophenols may result in embryotoxicity and abortion. The major mode of toxic action is as uncouplers of oxidative phosphorylation. The toxicity of chlorophenols decreases with decreasing chlorination. These chemicals are mild hepatotoxins and are stored mainly in hepatic and renal tissues.

  9. Influence of Other Contaminants on Natural Attenuation of Chlorinated Solvents

    SciTech Connect

    Kinsall, B.L.; Palumbo, A.V.; Pfiffner, S.M.; Phelps, T.J.; Salpas, P.

    1999-04-19

    Studies at numerous sites have shown high variability in the degradation rates of chlorinated solvents as measured by microcosm studies with 14C labeled contaminants. The ability of nutrient and carbon additions to stimulate degradation can vary widely. Although some of these variations can be related to the structure of the extant microbial community, the presence of other less refractory contaminants may be critical fctors impacting the rate of chlorocarbon mineralization. Relaatively highe rates of TCE degradation have been observed in the DOE K-25 burial grounds with diverse organic loadings as well as in areas that show evidence for hydrocarbon contamination. Similarly, at other sites where there was TCE in the absence of hydrocarbons or other contaminants, the measured degradation rates have often been found to be very low. At various other sites, the intrasite variability in degradation rates appeared to be related to the presence of hydrocarbon contamination. The highest rates were observed at sites with evidence of hydrocarbons. These observations indicated that the viability of natural attenuation as a remediation option for chlorinated solvents might depend in part on the presence co-contaminants such as hydrocarbons or natural matter.

  10. Hydrodesulfurization of chlorinized coal

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Rohatgi, N. K. (Inventor)

    1983-01-01

    A method of desulfurization is described in which high sulfur coals are desulfurized by low temperature chlorinolysis of coal in liquid media, preferably water, followed by hydrodesulfurization at a temperature above 500 C. The coals are desulfurized to an extent of up to 90% by weight and simultaneously dechlorinated to a chlorine content below 0.1% by weight. The product coals have lower volatiles loss, lower oxygen and nitrogen content and higher fixed carbon than raw coals treated with hydrogen under the same conditions. Heating the chlorinated coal to a temperature above 500 C. in inert gas such as nitrogen results in significantly less desulfurization.

  11. Reaction products of chlorine dioxide.

    PubMed Central

    Stevens, A A

    1982-01-01

    Inspection of the available literature reveals that a detailed investigation of the aqueous organic chemistry of chlorine dioxide and systematic identification of products formed during water disinfection has not been considered. This must be done before an informed assessment can be made of the relative safety of using chlorine dioxide as a disinfectant alternative to chlorine. Although trihalomethanes are generally not formed by the action of chlorine dioxide, the products of chlorine dioxide treatment of organic materials are oxidized species, some of which also contain chlorine. The relative amounts of species types may depend on the amount of chlorine dioxide residual maintained and the concentration and nature of the organic material present in the source water. The trend toward lower concentrations of chlorinated by-products with increasing ClO2 concentration, which was observed with phenols, has not been observed with natural humic materials as measured by the organic halogen parameter. Organic halogen concentrations have been shown to increase with increasing chlorine dioxide dose, but are much lower than those observed when chlorine is applied. Aldehydes have been detected as apparent by-products of chlorine dioxide oxidation reactions in a surface water that is a drinking water source. Some other nonchlorinated products of chlorine dioxide treatment may be quinones and epoxides. The extent of formation of these moieties within the macromolecular humic structure is also still unknown. PMID:7151750

  12. Zeolite-filled PDMS membranes. 1. Sorption of halogenated hydrocarbons

    SciTech Connect

    Vankelecom, I.F.J.; Dotermont, C.; Morobe, M.; Uytterhoeven, J.B.; Vandecasteele, C.

    1997-03-20

    Aiming at a more thorough understanding of the influence of zeolite fillers in PDMS membranes on the pervaporation of chlorinated hydrocarbons from aqueous solutions, the sorption aspect of this separation process was studied. Firstly, the sorption of water and five different chlorinated hydrocarbons was investigated in the zeolite and the polymer separately. Secondly, the composite system was considered and conclusions were drawn concerning interactions at the zeolite-polymer interphase. Finally, the sorption results obtained on the self-synthesized membranes were compared with measurements on commercially available PDMS membranes (GFT). 23 refs., 11 figs., 3 tabs.

  13. Snapping Turtles (Chelydra serpentina) from Canadian Areas of Concern across the southern Laurentian Great Lakes: Chlorinated and brominated hydrocarbon contaminants and metabolites in relation to circulating concentrations of thyroxine and vitamin A.

    PubMed

    Letcher, Robert J; Lu, Zhe; de Solla, Shane R; Sandau, Courtney D; Fernie, Kimberly J

    2015-11-01

    The metabolites of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), as well as other halogenated phenolic contaminants (HPCs) have been shown to have endocrine-disrupting properties, and have been reported with increasing frequency in the blood of wildlife, and mainly in mammals and birds. However, little is known about the persistence, accumulation and distribution of these contaminants in long-lived freshwater reptiles. In the present study, in addition to a large suite of chlorinated and brominated contaminants, metabolites and HPCs, we assessed and compared hydroxylated (OH) PCBs and OH-PBDEs relative to PCBs and PBDEs, respectively, in the plasma of adult male common snapping turtles (Chelydra serpentina). Blood samples were collected from 62 snapping turtles (2001-2004) at 12 wetland sites between the Detroit River and the St. Lawrence River on the Canadian side of the Laurentian Great Lakes of North America. Turtles were sampled from sites designated as Areas of Concern (AOCs) and from a relatively clean reference site in southern Georgian Bay (Tiny Marsh), Lake Huron. Plasma concentrations of Σ46PCB (10-340 ng/g wet weight (ww)) and Σ28OH-PCB (3-83 ng/g ww) were significantly greater (p<0.05) in turtles from the Turkey Creek and Muddy Creek-Wheatley Harbour sites in Lake Erie compared with the reference site turtles. The HPC, pentachlorophenol (PCP), had a mean concentration of 9.6±1.1 ng/g ww. Of the 28 OH-CB congeners screened for, 4-OH-CB187 (42±7 ng/g ww) was the most concentrated of all HPCs measured. Of the 14 OH-BDE congeners examined, four (4'-OH-BDE17, 3-OH-BDE47, 5-OH-BDE47 and 4'-OH-BDE49) were consistently found in all plasma samples. p,p'-DDE was the most concentrated of the 18 organochlorine pesticides (OCPs) examined. The mean concentrations of circulating total thyroxine (TT4), dehydroretinol and retinol in the plasma of the male snapping turtles regardless of sampling site were 5.4±0.3, 81±4.7 and 291±13

  14. Chlorofluorocarbon CFCs, potential alternative HCFCs and HFCs, and related chlorinated compounds: mass spectral study, Part II.

    PubMed

    Reizian-Fouley, A; Dat, Y; Rault, S

    1997-04-01

    In a previous publication, mass spectrometry was applied to the study of several ions formed by dissociative ionization of ethanes, partially substituted with fluorine and chlorine, and to the determination of the fragmentation pattern of each related compound. The aim of the present investigation was to extend this mass spectral study (70 eV and low ionization energy) to a group of closely related analogs, hydrofluorocarbons (HCFCs), HFCs, chlorinated fluorocarbons, and chlorinated hydrocarbons--halogenated methane, ethane, and propane molecules--to make an attempt to predict the relative bond strength and then the behavior--metabolic pathway and tropospheric degradation--of new HCFCs and HFCs.

  15. Chlorine dioxide and hemodialysis

    SciTech Connect

    Smith, R.P. . Dept. of Pharmacology and Toxicology)

    1989-05-01

    Because it has little or no tendency to generate carcinogenic trihalomethanes such as chloroform, chlorine dioxide is an attractive alternative to chlorine for drinking water disinfection. There are, however, concerns about its acute toxicity, and the toxic effects of its by-products, chlorite and chlorate. The human experience with chlorine dioxide in both controlled, prospective studies and in actual use situations in community water supplies have as yet failed to reveal adverse health effects. The EPA has recommended standards of 0.06 mg/L for chlorine dioxide and standards of 0.007 mg/L for chlorite and chlorate in drinking water. Among groups who may be at special risk from oxychlorines in drinking water are patients who must undergro chronic extracorporeal hemodialysis. Although even units for home hemodialysis are supposed to be equipped with devices which effectively remove oxychlorines, there is a always a possibility of operator error or equipment failure. When the equipment is adequately maintained, it is likely that dialysis patients will have more intensive exposures from drinking water than from dialysis fluids despite the much larger volumes of water that are involved in dialysis. This paper discusses a hemodialysis and the standards and effects of oxychlorines. 90 refs., 2 tabs.

  16. Chlorine Dioxide (Gas)

    USDA-ARS?s Scientific Manuscript database

    Chlorine dioxide (ClO2) gas is registered by the U.S. Environmental Protection Agency (EPA) as a sterilant for use in manufacturing, laboratory equipment, medical devices, environmental surfaces, tools and clean rooms. Aqueous ClO2 is registered by the EPA as a surface disinfectant and sanitizer fo...

  17. Impacts of Water Chlorination

    ERIC Educational Resources Information Center

    Environmental Science and Technology, 1976

    1976-01-01

    To learn the consequences of one aspect of technology on man and his surroundings, scientists meeting at the Oak Ridge National Laboratory discussed what is known about the impacts of water chlorination. The conference produced state-of-the-art information about the technology and attempted to summarize all the information on the subject. (BT)

  18. Chlorination of lanthanum oxide.

    PubMed

    Gaviría, Juan P; Navarro, Lucas G; Bohé, Ana E

    2012-03-08

    The reactive system La(2)O(3)(s)-Cl(2)(g) was studied in the temperature range 260-950 °C. The reaction course was followed by thermogravimetry, and the solids involved were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy. The results showed that the reaction leads to the formation of solid LaOCl, and for temperatures above 850 °C, the lanthanum oxychloride is chlorinated, producing LaCl(3)(l). The formation of the oxychloride progresses through a nucleation and growth mechanism, and the kinetic analysis showed that at temperatures below 325 °C the system is under chemical control. The influence of diffusive processes on the kinetics of production of LaOCl was evaluated by studying the effect of the reactive gas flow rate, the mass of the sample, and the chlorine diffusion through the boundary layer surrounding the solid sample. The conversion curves were analyzed and fitted according to the Johnson-Mehl-Avrami description, and the reaction order with respect to the chlorine partial pressure was obtained by varying this partial pressure between 10 and 70 kPa. The rate equation was obtained, which includes the influence of the temperature, chlorine partial pressure, and reaction degree.

  19. Impacts of Water Chlorination

    ERIC Educational Resources Information Center

    Environmental Science and Technology, 1976

    1976-01-01

    To learn the consequences of one aspect of technology on man and his surroundings, scientists meeting at the Oak Ridge National Laboratory discussed what is known about the impacts of water chlorination. The conference produced state-of-the-art information about the technology and attempted to summarize all the information on the subject. (BT)

  20. Effect of chlorination condition and permeability of chlorine species on the chlorination of a polyamide membrane.

    PubMed

    Gu, Joung-Eun; Jun, Byung-Moon; Kwon, Young-Nam

    2012-10-15

    Most studies on membrane chlorination have been investigated in an unpressurized chlorination mode, even if the polyamide membrane was continuously exposed to chlorine under high operating pressure in real water/wastewater treatment plants. In this study, performance changes due to polyamide membrane chlorination were investigated in both pressurized and unpressurized chlorination modes. Chlorination in an unpressurized mode showed a flux increase at high pH and a flux decline at low pH due to the compaction and swelling of the polyamide chains, respectively. On the other hand, chlorination performed in a pressurized mode decreased the water flux in both acidic and alkaline conditions, showing that compaction is overwhelming compared to swelling. The permeability of HOCl, a dominant species at low pH, through the polyamide membrane was pH independent and almost similar to the system recovery, but the permeability of OCl(-), which is dominant at high pH, was maxima at a neutral pH. The different performance behaviors of membranes chlorinated at various pH conditions in the presence or absence of applied pressure could be explained by the permeability of chlorine species and compaction/swelling of polymer chains after chlorination. The effect of membrane chlorination on the chemical property changes at the two different modes was confirmed using attenuated total reflection Fourier transform infrared analysis, and a conceptual model of performance change was proposed to explain the performance discrepancy between the two chlorination modes. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. Chlorine in Lunar Basalts

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Anand, M.; Franchi, I. A.

    2017-01-01

    In the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs, and P, collectively called KREEP, and in its primitive form - urKREEP, [1]), given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO (e.g., [2]). When compared to chondritic meteorites and terrestrial rocks (e.g., [3-4]), lunar samples often display heavy chlorine isotope compositions [5-9]. Boyce et al. [8] found a correlation between delta Cl-37 (sub Ap) and bulk-rock incompatible trace elements (ITEs) in lunar basalts, and used this to propose that early degassing of Cl (likely as metal chlorides) from the LMO led to progressive enrichment in remaining LMO melt in Cl-37over Cl-35- the early degassing model. Barnes et al. [9] suggested that relatively late degassing of chlorine from urKREEP (to yield delta Cl-37 (sub urKREEP greater than +25 per mille) followed by variable mixing between KREEPy melts and mantle cumulates (characterized by delta Cl-370 per mille) could explain the majority of Cl isotope data from igneous lunar samples. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed an in situ study of chlorine isotopes and abundances of volatiles in lunar apatite from a diverse suite of lunar basalts spanning a range of geochemical types.

  2. Process for converting light alkanes to higher hydrocarbons

    DOEpatents

    Noceti, Richard P.; Taylor, Charles E.

    1988-01-01

    A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.

  3. Treatment of spent hydrorefining catalysts by selective chlorination

    SciTech Connect

    Djona, M.; Gaballah, I. |||; Mugica, J.C.; Solozabal, R.

    1995-07-01

    Spent hydrorefining catalysts contain about 5% of CoO and/or NiO, 12% of MoO{sub 3} and up to 10% of V{sub 2}O{sub 5}. They are generally supported by alumina and contain up to 25% of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl{sub 2} + air gas mixture had been investigated. At temperatures lower than 600 C, it was possible to recover more than 90% of nickel and cobalt chlorides, about 99% of the molybdenum and up to 75% of vanadium chlorinated compounds. CoCl{sub 2} and NiCl{sub 2} were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al{sub 2}O{sub 3} could be limited to less than 6%. The scale up of this treatment was successful and a flow-sheet is proposed.

  4. Chlorine Gas Inhalation

    PubMed Central

    White, Carl W.; Martin, James G.

    2010-01-01

    Humans can come into contact with chlorine gas during short-term, high-level exposures due to traffic or rail accidents, spills, or other disasters. By contrast, workplace and public (swimming pools, etc.) exposures are more frequently long-term, low-level exposures, occasionally punctuated by unintentional transient increases. Acute exposures can result in symptoms of acute airway obstruction including wheezing, cough, chest tightness, and/or dyspnea. These findings are fairly nonspecific, and might be present after exposures to a number of inhaled chemical irritants. Clinical signs, including hypoxemia, wheezes, rales, and/or abnormal chest radiographs may be present. More severely affected individuals may suffer acute lung injury (ALI) and/or acute respiratory distress syndrome (ARDS). Up to 1% of exposed individuals die. Humidified oxygen and inhaled β-adrenergic agents are appropriate therapies for victims with respiratory symptoms while assessments are underway. Inhaled bicarbonate and systemic or inhaled glucocorticoids also have been reported anecdotally to be beneficial. Chronic sequelae may include increased airways reactivity, which tends to diminish over time. Airways hyperreactivity may be more of a problem among those survivors that are older, have smoked, and/or have pre-existing chronic lung disease. Individuals suffering from irritant-induced asthma (IIA) due to workplace exposures to chlorine also tend to have similar characteristics, such as airways hyperresponsiveness to methacholine, and to be older and to have smoked. Other workplace studies, however, have indicated that workers exposed to chlorine dioxide/sulfur dioxide have tended to have increased risk for chronic bronchitis and/or recurrent wheezing attacks (one or more episodes) but not asthma, while those exposed to ozone have a greater incidence of asthma. Specific biomarkers for acute and chronic exposures to chlorine gas are currently lacking. Animal models for chlorine gas

  5. [Comparison of the quality and toxicity of wastewater after chlorine and chlorine dioxide disinfections].

    PubMed

    Wang, Li-sha; Zhang, Tong; Hu, Hong-ying

    2005-11-01

    The effects of chlorine and chlorine dioxide disinfections on quality and toxicity of wastewater were compared. The experiment results showed that chlorine disinfection had no obvious effect on wastewater color, while chlorine dioxide disinfection decreased wastewater color observably. The DOC of wastewater did not change much after chlorine and chlorine dioxide disinfections. Chlorine disinfection significantly increased UV230 of wastewater and chlorine dioxide disinfection slightly decreased UV230 of wastewater. When the disinfectants dosage was 30 mg/L, UV230 increased about 0.7 cm(-1) after chlorine disinfection and decreased about 0.05 cm(-1) after chlorine dioxide disinfection. The acute toxicity of wastewater increased with increasing disinfectants dosage for both chlorine and chlorine dioxide disinfections and the acute toxicity after chlorine disinfection is much stronger than that after chlorine dioxide disinfection. The genotoxicity of wastewater increased slightly after chlorine disinfection and decreased slightly after chlorine dioxide disinfection.

  6. The Influence of Nitrogen Oxides on Chlorine Chemistry in Barrow, Alaska

    NASA Astrophysics Data System (ADS)

    McNamara, S. M.; Raso, A. R. W.; Wang, S.; Thanekar, S.; Fuentes, J. D.; Shepson, P. B.; Pratt, K.

    2016-12-01

    Active chlorine chemistry in the springtime Arctic boundary layer impacts the fate of atmospheric pollutants and greenhouse gases. Recent field studies have reported high amounts of molecular chlorine (Cl2), up to 400 parts per trillion (ppt), as well as the presence of chlorinated hydrocarbon oxidation products. However, our knowledge of Arctic chlorine chemistry is limited by a paucity of observations. The presence of nitrogen oxides (NOx) may influence the chlorine chemistry in this region. Here, we report chemical ionization mass spectrometry measurements of Cl2, chlorine monoxide (ClO), nitryl chloride (ClNO2), and dinitrogen pentoxide (N2O5), and NOx measurements at Barrow, AK during March-May 2016. To our knowledge, these data represent the first observations of ClNO2 in the Arctic. While the main source of NOx in a pristine Arctic environment is irradiated snow surfaces, anthropogenic sources can significantly enhance local NOx concentrations. The role of NOx in the activation and temporal trends of the reactive chlorine species are examined using a 0-D photochemical model. The prevalence of chlorine chemistry under elevated nitrogen oxide conditions may have significant impacts on the atmospheric composition in an increasingly polluted Arctic.

  7. Recent developments in enzymatic chlorination.

    PubMed

    Murphy, Cormac D

    2006-04-01

    While the existence of chlorinated natural products has been known for over 100 years, our understanding of the enzymology of biological chlorination reactions has been limited to chloroperoxidases, which are now known not to play a significant role in chlorometabolite biosynthesis. The discoveries of new classes of halogenases, described in this Highlight, have shed new light on the mechanisms of enzymatic chlorination of aromatic and aliphatic compounds.

  8. Apparatus for hydrocarbon extraction

    DOEpatents

    Bohnert, George W.; Verhulst, Galen G.

    2013-03-19

    Systems and methods for hydrocarbon extraction from hydrocarbon-containing material. Such systems and methods relate to extracting hydrocarbon from hydrocarbon-containing material employing a non-aqueous extractant. Additionally, such systems and methods relate to recovering and reusing non-aqueous extractant employed for extracting hydrocarbon from hydrocarbon-containing material.

  9. 21 CFR 177.1610 - Polyethylene, chlorinated.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... chlorinated polyethylene contains a maximum of 60 percent by weight of total chlorine, as determined by ASTM 1method D1303-55 (Reapproved 1979), “Standard Test Method for Total Chlorine in Vinyl Chloride...

  10. A comparison of chlorinated organic material produced by chlorine and chlorine dioxide bleaching

    SciTech Connect

    McKaque, A.B.; Reeve, D.W.

    1995-12-31

    Chlorine and chlorine dioxide react differently with pulp during bleaching and produce different types of organic by-products. The main differences are the large reduction in the amount of AOX (adsorbable organic halogen) in the effluent and EOX (extractable organic halogen) in the pulp. This talk reviews the differences in the amounts and types of chlorinated organic by-products produced by the two different bleaching agents.

  11. Chlorine, Chloramine, Chlorine Dioxide, and Ozone Susceptibility of Mycobacterium avium

    PubMed Central

    Taylor, Robert H.; Falkinham, Joseph O.; Norton, Cheryl D.; LeChevallier, Mark W.

    2000-01-01

    Environmental and patient isolates of Mycobacterium avium were resistant to chlorine, monochloramine, chlorine dioxide, and ozone. For chlorine, the product of the disinfectant concentration (in parts per million) and the time (in minutes) to 99.9% inactivation for five M. avium strains ranged from 51 to 204. Chlorine susceptibility of cells was the same in washed cultures containing aggregates and in reduced aggregate fractions lacking aggregates. Cells of the more slowly growing strains were more resistant to chlorine than were cells of the more rapidly growing strains. Water-grown cells were 10-fold more resistant than medium-grown cells. Disinfectant resistance may be one factor promoting the persistence of M. avium in drinking water. PMID:10742264

  12. Chlorine transfer hose failure.

    PubMed

    Joseph, Giby

    2004-11-11

    On the morning of 14 August 2002, a 1 in. transfer hose used in a rail tank car unloading operation at DPC Enterprises, near Festus, Missouri, catastrophically ruptured and initiated a sequence of events that led to the release of 48,000 pounds of chlorine--a toxic gas--into neighboring areas. The facility repackages bulk dry liquid chlorine into 1 ton containers and 150 pound cylinders for commercial, industrial, and municipal use in the St. Louis metropolitan area. Fortunately, the wind direction on the day of the release limited the effects of the chlorine plume on the surrounding community. However, 63 people sought hospital treatment due to exposure, and hundreds of others were affected by the release (the community was advised to shelter-in-place for 4 h, and traffic was halted on Interstate 55 for 1.5 h). The US Chemical Safety and Hazard Investigation Board (CSB) investigated this incident for the following reasons: This paper presents the lesson-learned from this incident to help prevent similar occurrences. This paper is based on US Chemical Safety and Hazard Investigation Board Report Number 2002-04-I-MO, which was approved by the Board on 1 May 2003. This paper has not been independently approved by the Board and is published for general informational purposes only. Every effort has been made to accurately present the contents of the Board-approved report in this paper. Any material in the paper that did not originate in the Board-approved report is solely the responsibility of the author and does not represent an official finding, conclusion, or position of the Board. A complete copy of the Board investigation report upon which this paper is based is available on the CSB website at "Completed Investigations."

  13. Chlorine analysis by diode laser atomic absorption spectrometry.

    PubMed

    Koch, J; Zybin, A; Niemax, K

    2000-04-01

    The general characteristics of Diode Laser Absorption Spectrometry (DLAAS) in low pressure plasmas particularly with respect to the detection of non-metals are comprehensively recapitulated and discussed. Furthermore, a detector, which is based on DLAAS in a microwave-induced low pressure plasma as an alternative technique for halogene-specific analysis of volatile compounds and polymeric matrices is described. The analytical capability of the technique is demonstrated on the chlorine-specific analysis of ablated polymer fragments as well as gas chromatographically separated hydrocarbons. Since the measurements were carried out by means of a balanced-heterodyne detection scheme, different technical noise contributions, such as laser excess and RAM noise could efficiently be suppressed and the registered absorption was limited only by the principal shot noise. Thus, in the case of the polymer analysis a chlorine-specific absolute detection limit of 10 pg could be achieved. Furthermore, fundamental investigations concerning the influence of hydrocarbons on the dissociation capability of the microwave induced plasma were performed. For this purpose, the carbon-, chlorine- and hydrogen-specific stoichiometry of the compounds were empirically determined. Deviations from the expected proportions were found to be insignificant, implying the possibility of internal standardization relative to the response of a reference sample.

  14. Basic Gas Chlorination Workshop Manual.

    ERIC Educational Resources Information Center

    Ontario Ministry of the Environment, Toronto.

    This manual was developed for use at workshops designed to introduce treatment plant operators to the safe operation and maintenance of gas chlorination systems employing the variable vacuum gas chlorinator. Each of the lessons in this document has clearly stated behavioral objectives to tell the trainee what he should know or do after completing…

  15. Direct Push Optical Screening Tool for High-Resolution, Real-Time Mapping of Chlorinated Solvent DNAPL Architecture

    DTIC Science & Technology

    2016-04-01

    FINAL REPORT Direct Push Optical Screening Tool for High-Resolution, Real- Time Mapping of Chlorinated Solvent DNAPL Architecture ESTCP Project ER...Direct Push Optical Screening Tool for High Resolution, Real-time Mapping of Chlorinated Solvent DNAPL Architecture Murray Einarson Haley...for real-time, high-resolution mapping of petroleum hydrocarbon and coal tar-based NAPL source zones. The objective of this project is to demonstrate

  16. Direct Push Optical Screening Tool for High Resolution, Real-Time Mapping of Chlorinated Solvent DNAPL Architecture

    DTIC Science & Technology

    2016-07-01

    ER-201121) Direct Push Optical Screening Tool for High- Resolution, Real-Time Mapping of Chlorinated Solvent DNAPL Architecture July 2016 This...Report April 2011 - March 2016 Direct Push Optical Screening Tool for High Resolution, Real-time Mapping of Chlorinated Solvent DNAPL Architecture...tools are currently available for real-time, high-resolution mapping of petroleum hydrocarbon and coal tar-based NAPL source zones. The objective of

  17. Accumulation of chlorinated hydrocarbons vapors in pine needles

    SciTech Connect

    Gaggi, C.; Bacci, E.

    1985-01-01

    Needles with different ages from four pines have been analyzed for PCB's, HCB, ..cap alpha..- and ..gamma..-HCH, p,p'DDT and DDE. The accumulation found has been discussed and provisional accumulation rates under actual background condition have been calculated.

  18. Assessment of biological effects of chlorinated hydrocarbons in osprey chicks

    USGS Publications Warehouse

    Elliott, J.E.; Wilson, L.K.; Henny, Charles J.; Trudeau, Suzanne F.; Leighton, Frederick A.; Kennedy, Sean W.; Cheng, Kimberly M.

    2001-01-01

    Osprey (Pandion haliaetus) eggs were collected during 1995 and 1996 at seven sites along the Fraser and Columbia River systems of British Columbia, Canada, and Washington and Oregon, USA. Fifty-four eggs were placed into a laboratory incubator. Thirty-eight of the hatched chicks were sacrificed within 24 h. Hatching success did not differ among sites and therefore between treatment and reference areas. Residual yolk sacs of eggs collected downstream of the large bleached-kraft pulp mill at Castlegar contained greater mean concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD, 2,930 ng/kg lipid) compared with reference sites such as the Nechako River, an upper tributary of the Fraser system (33.7 ng/kg). Total polychlorinated biphenyls (PCBs) in yolk sacs were also higher at Castlegar and in samples from the Columbia River downstream of Portland, Oregon, compared with those from the Nechako River. Concentrations of measured chemicals, including TCDD toxic equivalents (TEQs), total PCBs, p,pa??-dichlorodiphenylethylene (p,pa??-DDE), and other organochlorines were not different in eggs that failed to hatch compared with calculated whole-egg values for hatched eggs. There were significant biochemical responses; a hepatic cytochrome P4501A (CYP1A) cross-reactive protein was detected in all samples tested and correlated positively with ethoxyresorufin o-deethylase (EROD) activity and yolk sac concentrations of TEQs and total PCBs. Tissue concentrations of vitamin A compounds varied among sites and correlated positively with yolk sac concentrations of TEQs and PCBs. Morphological, histological, and other physiological parameters, including chick growth, edema, deformities, and hepatic and renal porphyrin concentrations, neither varied among sites nor showed concentration-related effects.

  19. Bioconcentration of chlorinated aromatic hydrocarbons in aquatic macrophytes

    SciTech Connect

    Gobas, F.A.P.C.; McNeil, E.J.; Lovett-Doust, L.; Haffner, G.D. )

    1991-05-01

    This study reports the bioconcentration and the uptake and elimination kinetics of a series of nonreactive, hydrophobic organic substances in the submerged aquatic macrophyte Myriophyllum spicatum. The tested substances represent a wide range of aqueous solubilities and 1-octanol-water partition coefficients (K{sub OW}). The plant-water bioconcentration factor is shown to follow a linear relationship with the octanol-water partition coefficient for all chemicals, including the superhydrophobic chemicals with log K{sub OW} up to 8.3. The uptake and elimination rate constants tend to follow a biphasic relationship with K{sub OW}. A kinetic model is developed for organic chemical bioconcentration is submerged aquatic macrophyte species. This model is applied to the Detroit River and Lake St. Clair to illustrate the role of aquatic macrophytes in chemical dynamics in aquatic systems.

  20. Assessment of biological effects of chlorinated hydrocarbons in osprey chicks.

    PubMed

    Elliott, J E; Wilson, L K; Henny, C J; Trudeau, S F; Leighton, F A; Kennedy, S W; Cheng, K M

    2001-04-01

    Osprey (Pandion haliaetus) eggs were collected during 1995 and 1996 at seven sites along the Fraser and Columbia River systems of British Columbia, Canada, and Washington and Oregon, USA. Fifty-four eggs were placed into a laboratory incubator. Thirty-eight of the hatched chicks were sacrificed within 24 h. Hatching success did not differ among sites and therefore between treatment and reference areas. Residual yolk sacs of eggs collected downstream of the large bleached-kraft pulp mill at Castlegar contained greater mean concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD, 2,930 ng/kg lipid) compared with reference sites such as the Nechako River, an upper tributary of the Fraser system (33.7 ng/kg). Total polychlorinated biphenyls (PCBs) in yolk sacs were also higher at Castlegar and in samples from the Columbia River downstream of Portland, Oregon, compared with those from the Nechako River. Concentrations of measured chemicals, including TCDD toxic equivalents (TEQs), total PCBs, p,p'-dichlorodiphenylethylene (p,p'-DDE), and other organochlorines were not different in eggs that failed to hatch compared with calculated whole-egg values for hatched eggs. There were significant biochemical responses; a hepatic cytochrome P4501A (CYP1A) cross-reactive protein was detected in all samples tested and correlated positively with ethoxyresorufin o-deethylase (EROD) activity and yolk sac concentrations of TEQs and total PCBs. Tissue concentrations of vitamin A compounds varied among sites and correlated positively with yolk sac concentrations of TEQs and PCBs. Morphological, histological, and other physiological parameters, including chick growth, edema, deformities, and hepatic and renal porphyrin concentrations, neither varied among sites nor showed concentration-related effects.

  1. Anaerobic Degradation of C1 and C2 Chlorinated Hydrocarbons

    DTIC Science & Technology

    1985-12-01

    The reactor was initially seeded with screened (0.25-inch mesh), municipal digester sludge obtained from the Millville Wastewater Treat- V ment...both extremes of the 15-to-20-day range cited above. 95 9 -- -- - - - LO Co ( NJ Cl) 00 Cu z *~ 0 ICD CD *- - a) 0 0O 0 00 Cir W O W co + + a10 9.96

  2. Disinfection kinetics of murine norovirus using chlorine and chlorine dioxide.

    PubMed

    Lim, Mi Young; Kim, Ju-Mi; Ko, Gwangpyo

    2010-05-01

    We determined the disinfection efficiency of chlorine and chlorine dioxide (ClO(2)) using murine norovirus (MNV) and coliphage MS2 as surrogates for human norovirus. Experiments were performed in oxidant demand-free buffer (pH 7.2) at 5 degrees C and 20 degrees C. The extent of virus inactivation by a disinfectant was quantified using three different analytical methods: plaque, short template real-time TaqMan reverse transcriptase-polymerase chain reaction (RT-PCR), and long template RT-PCR assays. Rapid inactivation of MNV by both chlorine and chlorine dioxide was observed by the plaque assay. According to the efficiency factor Hom model, Ct values of 0.314mg/Lmin and 0.247mg/Lmin were required for a 4-log reduction of MNV at 5 degrees C by chlorine and chlorine dioxide, respectively. Lower Ct values were required at 20 degrees C. Both long template and short template RT-PCR assays significantly underestimated the virus inactivation compared to the plaque assay. Our study demonstrates that adequate treatment of water with either chlorine or ClO(2) is likely to effectively control the waterborne transmission of human norovirus.

  3. Determination of polychlorinated biphenyl congeners and chlorinated pesticides in a fish tissue standard reference material.

    PubMed

    Poster, Dianne L; Kucklick, John R; Schantz, Michele M; Porter, Barbara J; Leigh, Stefan D; Wise, Stephen A

    2003-01-01

    The concentrations of a wide range of polychlorinated biphenyl congeners (PCBs) and chlorinated pesticides in a fish tissue Standard Reference Material (SRM) have been determined using multiple methods of analysis. This material, SRM 1946, Lake Superior Fish Tissue, was recently issued by the National Institute of Standards and Technology (NIST) and complements a suite of marine environmental natural-matrix SRMs that are currently available from NIST for the determination of organic contaminants such as aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), PCBs, and chlorinated pesticides. SRM 1946 is a fresh tissue homogenate (frozen) prepared from filleted adult lake trout (Salvelinus namaycush namaycush) collected from the Apostle Islands region of Lake Superior. SRM 1946 has certified and reference concentrations for PCB congeners, including the three non- ortho PCB congeners, and chlorinated pesticides. Certified concentrations are available for 30 PCB congeners and 15 chlorinated pesticides. Reference concentrations are available for 12 PCB congeners and 2 chlorinated pesticides. In addition, SRM 1946 is characterized for additional chemical constituents and properties: fatty acids, extractable fat, methylmercury, total mercury, selected trace elements, proximates, and caloric content. The characterization of chlorinated compounds is described in this paper with an emphasis on the approach used for the certification of the concentrations of PCB congeners and chlorinated pesticides. The PCB congener and chlorinated pesticide data are also compared to concentrations in other marine natural-matrix reference materials available from NIST (fish oil, mussel tissue, whale blubber, and a second fresh frozen fish tissue homogenate prepared from filleted adult lake trout collected from Lake Michigan) and from other organizations such as the National Research Council Canada (ground whole carp), the International Atomic Energy Agency (fish homogenate), and the

  4. [Combined use of active chlorine and coagulants for drinking water purification and disinfection].

    PubMed

    Rakhmanin, Iu A; Zholdakova, Z I; Poliakova, E E; Kir'ianova, L F; Miasnikov, I N; Tul'skaia, E A; Artemova, T Z; Ivanova, L V; Dmitrieva, R A; Doskina, T V

    2004-01-01

    The authors made an experimental study of the efficiency of water purification procedures based on the combined use of active chlorine and coagulants and hygienically evaluated the procedures. The study included the evaluation of water disinfection with various coagulants and active chlorine; the investigation of the processes of production of deleterious organic chlorine compounds; the assessment of the quality of water after its treatment. The coagulants representing aluminum polyoxychloride: RAX-10 (AQUA-AURATE 10) and RAX-18 (AQUA-AURATE 18), and aluminum sulfate, technically pure grade were tested. The treatment of river water with the coagulants RAX-10 and RAX-18, followed by precipitation, filtration, and chlorination under laboratory conditions, was shown to result in water disinfection to the levels complying with the requirements described in SanPiN 2.1.4.1074-01. RAX-18 showed the best disinfecting activity against total and heat-tolerant coliform bacteria, but also to the highly chlorine-resistant microrganisms--the spores of sulfite-reducing Clostridia, phages, and viruses. Since the coagulants have an increased sorptive capacity relative to humus and other organic substances, substitution of primary chlorination for coagulant treatment may induce a reduction in the risk of formation of oncogenically and mutagenically hazardous chlorinated hydrocarbons.

  5. Water chlorination and birth defects.

    PubMed

    Magnus, P; Jaakkola, J J; Skrondal, A; Alexander, J; Becher, G; Krogh, T; Dybing, E

    1999-09-01

    Chlorination of drinking water that contains organic compounds leads to the formation of by-products, some of which have been shown to have mutagenic or carcinogenic effects. As yet, too little is known about the possible teratogenic effects on the human fetus. We linked the Norwegian waterwork registry, containing 1994 data on chlorination practice and color (an indicator for natural organic matter), with the Medical Birth Registry for 1993-1995. The proportion of the population exposed to chlorination and a weighted mean color number in drinking water was computed for each municipality. Among 141,077 births, 2,608 (1.8%) had birth defects. In a comparison between exposed (high color; chlorination) and reference groups (low color; no chlorination), the adjusted odds ratio was 1.14 (0.99-1.31) for any malformation, 1.26 (0.61-2.62) for neural tube defects, and 1.99 (1.10-3.57) for urinary tract defects. This study provides further evidence of the role of chlorination of humic water as a potential cause of birth defects, in a country with relatively low levels of chlorination byproducts.

  6. Free Chlorine and Cyanuric Acid Simulator Application ...

    EPA Pesticide Factsheets

    A web-based application designed to simulate the free chlorine in systems adding free chlorine and cyanuric acid, including the application of Dichlor and Trichlor. A web-based application designed to simulate the free chlorine in systems adding free chlorine and cyanuric acid, including the application of Dichlor and Trichlor.

  7. 46 CFR 151.50-31 - Chlorine.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Chlorine. 151.50-31 Section 151.50-31 Shipping COAST... LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-31 Chlorine. (a) Chlorine barges. Subparts 98.03 and 98.20 of Part 98 of this chapter have been revoked. However, chlorine barges that...

  8. 46 CFR 151.50-31 - Chlorine.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Chlorine. 151.50-31 Section 151.50-31 Shipping COAST... LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-31 Chlorine. (a) Chlorine barges. Subparts 98.03 and 98.20 of Part 98 of this chapter have been revoked. However, chlorine barges that...

  9. 46 CFR 151.50-31 - Chlorine.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Chlorine. 151.50-31 Section 151.50-31 Shipping COAST... LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-31 Chlorine. (a) Chlorine barges. Subparts 98.03 and 98.20 of Part 98 of this chapter have been revoked. However, chlorine barges that...

  10. 21 CFR 173.300 - Chlorine dioxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Chlorine dioxide. 173.300 Section 173.300 Food and... Additives § 173.300 Chlorine dioxide. Chlorine dioxide (CAS Reg. No. 10049-04-4) may be safely used in food... the following methods: (i) Treating an aqueous solution of sodium chlorite with either chlorine gas...

  11. 21 CFR 173.300 - Chlorine dioxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Chlorine dioxide. 173.300 Section 173.300 Food and... Additives § 173.300 Chlorine dioxide. Chlorine dioxide (CAS Reg. No. 10049-04-4) may be safely used in food... the following methods: (i) Treating an aqueous solution of sodium chlorite with either chlorine gas...

  12. 46 CFR 151.50-31 - Chlorine.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Chlorine. 151.50-31 Section 151.50-31 Shipping COAST... LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-31 Chlorine. (a) Chlorine barges. Subparts 98.03 and 98.20 of Part 98 of this chapter have been revoked. However, chlorine barges that...

  13. 46 CFR 151.50-31 - Chlorine.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Chlorine. 151.50-31 Section 151.50-31 Shipping COAST... LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-31 Chlorine. (a) Chlorine barges. Subparts 98.03 and 98.20 of Part 98 of this chapter have been revoked. However, chlorine barges that...

  14. 21 CFR 173.300 - Chlorine dioxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Chlorine dioxide. 173.300 Section 173.300 Food and... Additives § 173.300 Chlorine dioxide. Chlorine dioxide (CAS Reg. No. 10049-04-4) may be safely used in food... the following methods: (i) Treating an aqueous solution of sodium chlorite with either chlorine gas...

  15. 21 CFR 173.300 - Chlorine dioxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Chlorine dioxide. 173.300 Section 173.300 Food and... Additives § 173.300 Chlorine dioxide. Chlorine dioxide (CAS Reg. No. 10049-04-4) may be safely used in food... the following methods: (i) Treating an aqueous solution of sodium chlorite with either chlorine gas...

  16. 40 CFR 704.43 - Chlorinated naphthalenes.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Chlorinated naphthalenes. 704.43... § 704.43 Chlorinated naphthalenes. (a) Definitions—(1) Extent of chlorination means the percent by... means the relative amounts of each isomeric chlorinated naphthalene that composes the chemical substance...

  17. Zebra mussel mortality with chlorine

    SciTech Connect

    Van Benschoten, J.E.; Jensen, J.N.; Harrington, D.; DeGirolamo, D.J.

    1995-05-01

    The rate of mortality of the zebra mussel in response to chlorine is described by a kinetic model that combines a statistical characterization of mussel mortality with a disinfection-type modeling approach. Parameter estimates were made with nine sets of data from experiments conducted in Niagara River water. From the kinetic model, an operational diagram was constructed that describes the time to 95% mortality as a function of chlorine concentration and temperature. Either the model or the diagram can be used to assist utilities in planning chlorination treatments for controlling zebra mussels.

  18. Gaseous, chlorine-free chlorine dioxide for drinking water

    SciTech Connect

    Gordon, G.; Rosenblatt, A.

    1996-11-01

    The benefits of applying chlorine dioxide (ClO{sub 2}) for the oxidative treatment of drinking water are well established. Chlorine dioxide treated finished water typically has substantially lower trihalomethane (THM) levels because ClO{sub 2} will not form chlorinated organic species as a by-product of disinfection. The THMs that are formed are probably due to chlorine from the generator or chlorine used to maintain a post-disinfection residual. An emerging regulatory issue concerning the formation of disinfection by-products (DBPs) is causing the water industry to set standards for the generation and delivery of ClO{sub 2}. The Federal Register (11 February 1994) contains language developed to limit the production of the unwanted inorganic by-products chlorite (ClO{sub 2}{sup -}), chlorate (ClO{sub 3}{sup -}), and bromate (BrO{sub 3}{sup -}) ions by requiring utilities to maintain high (95%) generation efficiencies and by limiting the amount of excess Cl{sub 2} that can be used during the generation process. The efficiency and excess Cl{sub 2} regulations may be problematic for utilities that over-chlorinate to attain chlorine dioxide high yields. Many utilities will have to decide either to reduce the amount of Cl{sub 2} used to react with sodium chlorite (NaClO{sub 2}), thereby increasing the ClO{sub 2}{sup -} residual in finished water, or over-chlorinate to increase yields and surpass the excess Cl{sub 2} limits.

  19. Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

    NASA Technical Reports Server (NTRS)

    Pan, Chenyu; Altemir, David A.; Margrave, John L.; Hauge, Robert H.

    1994-01-01

    Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

  20. Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

    NASA Technical Reports Server (NTRS)

    Pan, Chenyu; Altemir, David A.; Margrave, John L.; Hauge, Robert H.

    1994-01-01

    Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

  1. CHLORINE INACTIVATION OF BACILLUS ENDOSPORES

    EPA Science Inventory

    The possibility of a bioterrorism event resulting in the release of Bacillus anthracis endospores into a drinking water distribution system necessitates research into means by which these endospores can be inactivated. This study was designed to determine the chlorine resistance...

  2. CHLORINE INACTIVATION OF BACILLUS ENDOSPORES

    EPA Science Inventory

    The possibility of a bioterrorism event resulting in the release of Bacillus anthracis endospores into a drinking water distribution system necessitates research into means by which these endospores can be inactivated. This study was designed to determine the chlorine resistance...

  3. EFFECTS OF OZONE, CHLORINE DIOXIDE, CHLORINE, AND MONOCHLORAMINE ON CRYTOSPORIDIUM PARVUM OOCYST VIABILITY

    EPA Science Inventory

    Purified Cryptosporiodium parvum oocysts were exposed to ozone, chlorine dioxide, chlorine, and monochloramine. Excystation and mouse infectivity were compareatively evaluated to assess oocyst viability. Ozone and chlorine dioxide more effectively inactivated oocysts than chlor...

  4. IDENTIFICATION OF NEW DRINKING WATER DISINFECTION BY-PRODUCTS FROM OZONE, CHLORINE DIOXIDE, CHLORAMINE, AND CHLORINE

    EPA Science Inventory

    Due to concern over the potential adverse health effects of trihalomethanes (THMs) and other chlorinated by-products in chlorinated drinking water, alternative disinfection methods are being explored. Ozone, chlorine dioxide, and chloramine are currently popular alternatives to ...

  5. IDENTIFICATION OF NEW DRINKING WATER DISINFECTION BY-PRODUCTS FROM OZONE, CHLORINE DIOXIDE, CHLORAMINE, AND CHLORINE

    EPA Science Inventory

    Due to concern over the potential adverse health effects of trihalomethanes (THMs) and other chlorinated by-products in chlorinated drinking water, alternative disinfection methods are being explored. Ozone, chlorine dioxide, and chloramine are currently popular alternatives to ...

  6. Chlorination of Pyridinium Compounds

    PubMed Central

    Daumer, Kathleen M.; Khan, Ahsan U.; Steinbeck, Marla J.

    2010-01-01

    Reactive oxygen species produced by activated neutrophils and monocytes are thought to be involved in mediating the loss of collagen and other matrix proteins at sites of inflammation. To evaluate their potential to oxidize the pyridinoline (Pyd) cross-links found in collagen types I and II, we reacted hydrogen peroxide (H2O2), hypochlorous acid/hypochlorite (HOCl/OCl−), and singlet oxygen (O2(1Δg)) with the Pyd substitutes, pyridoxamine dihydrochloride and vitamin B6, which share the same chemical structure and spectral properties of Pyd cross-links. Neither H2O2 (125–500 µm) nor O2(1Δg) (10–25 µm) significantly changed the spectral properties of pyridoxamine or vitamin B6. Reaction of HOCl/OCl− (12.5–50 µm) with pyridoxamine at pH 7.2 resulted in a concentration-dependent appearance of two new absorbance peaks and a decrease in fluorescence at 400 nm (excitation 325 nm). The new absorbance peaks correlated with the formation of an N-chloramine and the product of its subsequent reaction with pyridoxamine. In contrast, the extent to which HOCl reacted with vitamin B6, which lacks a primary amine group, was variable at this pH. At lysosomal pH 5.5, Cl2/HOCl/OCl− reacted with both pyridoxamine and vitamin B6. Four of the chlorinated products of this reaction were identified by gas chromatography-mass spectrometry and included 3-chloropyridinium, an aldehyde, and several chlorinated products with disrupted rings. To evaluate the effects of Cl2/HOCl/OCl− on Pyd cross-links in collagen, we exposed bone collagen type I and articular cartilage type II to HOCl. Treatment of either collagen type with HOCl at pH 5.0 or 7.2 resulted in the oxidation of amine groups and, for collagen type II, the specific decrease in Pyd cross-link fluorescence, suggesting that during inflammation both oxidations may be used by neutrophils and monocytes to promote the loss of matrix integrity. PMID:10940296

  7. Cleaning without chlorinated solvents

    NASA Technical Reports Server (NTRS)

    Thompson, L. M.; Simandl, R. F.

    1995-01-01

    Because of health and environmental concerns, many regulations have been passed in recent years regarding the use of chlorinated solvents. The Oak Ridge Y-12 Plant has had an active program to find alternatives for these solvents used in cleaning applications for the past 7 years. During this time frame, the quantity of solvents purchased has been reduced by 92 percent. The program has been a twofold effort. Vapor degreasers used in batch cleaning operations have been replaced by ultrasonic cleaning with aqueous detergent, and other organic solvents have been identified for use in hand-wiping or specialty operations. In order to qualify these alternatives for use, experimentation was conducted on cleaning ability as well as effects on subsequent operations such as welding, painting, and bonding. Cleaning ability was determined using techniques such as x-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) which are capable of examining monolayer levels of contamination on a surface. Solvents have been identified for removal of rust preventative oils, lapping oils, machining coolants, lubricants, greases, and mold releases. Solvents have also been evaluated for cleaning urethane foam spray guns, swelling of urethanes, and swelling of epoxies.

  8. Cleaning without chlorinated solvents

    SciTech Connect

    Thompson, L.M.; Simandl, R.F.

    1994-12-31

    Because of health and environmental concerns, many regulations have been passed in recent years regarding the use of chlorinated solvents. The Oak Ridge Y-12 Plant has had an active program to find alternatives for these solvents used in cleaning applications for the past 7 years. During this time frame, the quantity of solvents purchased has been reduced by 92%. The program has been a twofold effort. Vapor degreasers used in batch cleaning-operations have been replaced by ultrasonic cleaning with aqueous detergent, and other organic solvents have been identified for use in hand-wiping or specialty operations. In order to qualify these alternatives for use, experimentation was conducted on cleaning ability as well as effects on subsequent operations such as welding, painting and bonding. Cleaning ability was determined using techniques such as X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR) which are capable of examining monolayer levels of contamination on a surface. Solvents have been identified for removal of rust preventative oils, lapping oils, machining coolants, lubricants, greases, and mold releases. Solvents have also been evaluated for cleaning urethane foam spray guns, swelling of urethanes and swelling of epoxies.

  9. Chemistry of combined residual chlorination

    SciTech Connect

    Leao, S.F.; Selleck, R.E.

    1982-01-01

    The decay of the combined chlorine residual was investigated in this work. Recent concerns about the formation of undesirable compounds such as chloroform with free residual chlorination have focused attention on the alternative use of combined residual chlorination. This work investigates the applicability of reactions proposed to describe the transformations and decay of the combined residual with time. Sodium hypochlorite was added to buffered solutions of ammonia with the chlorine residual being monitored over periods extending up to 10 days. The reaction was studied at four initial concentrations of hypochlorite of 100, 50, 25 and 10 mg/L as Cl/sub 2/ with molar application ratios of chlorine to ammonia, defined herein as M ratios, of 0.90, 0.50, 0.25 and 0.05 at each hypochlorite dose. Sixty-eight experiments were conducted at the pH of 6.6 and 7.2. The conclusions are: (1) in the absence of free chlorine, the concentration of NH/sub 3/ does not seem to affect the rate of disappearance of the residual other than through the formation of NHCl/sub 2/ by NH/sub 2/Cl hydrolysis; (2) the reaction between NHCl/sub 2/ and NH/sub 4//sup +/ to form NH/sub 2/Cl is either much slower than reported by Gray et. al. or the mechanism is different with a rate limiting step not involving NH/sub 3/ or NH/sub 4//sup +/; (3) a redox reaction in addition to the first-order decomposition of NHCl/sub 2/ appears necessary. Model simulation results indicated that a reaction of the type NH/sub 2/Cl + NHCl/sub 2/ ..-->.. P added to the first-order NHCl/sub 2/ decomposition can explain the results observed except at the higher chlorine doses.

  10. Radio-frequency enhanced decontamination of soils contaminated with halogenated hydrocarbons

    SciTech Connect

    Dev, H.; Bridges, J.; Sresty, G.; Enk, J.; Mshaiel, N.

    1989-02-01

    There has been considerable effort in the development of innovative treatment technologies for the cleanup of sites containing hazardous wastes such as hydrocarbons and chlorinated hydrocarbons. Typical examples of such waste material are: chlorinated solvents, polychlorinated biphenyls, waste aviation fuels, gasoline, etc. The feasibility of treating waste sites containing such materials by in-situ radio frequency heating was established by the study through bench- and pilot-scale experiments. A design for an in-situ field test was developed for the treatment of sites containing solvents and aviation fuel. Cost studies were performed to estimate the treatment cost of a system for the decontamination of sites containing fuels, etc.

  11. Alkaline pretreatment for chlorine removal from high-chlorine rhodochrosite

    NASA Astrophysics Data System (ADS)

    Zhang, Xing-ran; Liu, Zuo-hua; Li, Wen-sheng; Cheng, Ya-ya; Du, Jun; Tao, Chang-yuan

    2016-11-01

    Chloride in manganese ore adversely affects mineral extraction. The mechanisms and the factors that influence an alkali pretreatment to removal chlorine from manganese ore were explored to eliminate hazards posed by chlorine during the electrolysis of manganese. The results showed that sodium carbonate, when used as an alkaline additive, promoted the dissolution of insoluble chloride, enhanced the migration of chloride ions, and effectively stabilized Mn2+. The optimal conditions were a sodium carbonate concentration of 0.45 mol·L-1, a liquid-solid ratio of 5:1 mL·g-1, a reaction time of 1 h, and a temperature of 25°C. The chlorine removal efficiency was greater than 95%, and the ore grade (Mn) was increased by 2.7%.

  12. Effect of moisture, charge size, and chlorine concentration on PCDD/F emissions from simulated open burning of forest biomass

    EPA Science Inventory

    Loblolly pine (Pinus taeda) was combusted at different charge sizes, fuel moisture, and chlorine content to determine the effect on emissions of polychlorinated dibenzo-p-dioxins and polychlorinated diberizofurans (PCDDslFs) as well as co-pollutants CO, PM, and total hydrocarbons...

  13. Effect of moisture, charge size, and chlorine concentration on PCDD/F emissions from simulated open burning of forest biomass

    EPA Science Inventory

    Loblolly pine (Pinus taeda) was combusted at different charge sizes, fuel moisture, and chlorine content to determine the effect on emissions of polychlorinated dibenzo-p-dioxins and polychlorinated diberizofurans (PCDDslFs) as well as co-pollutants CO, PM, and total hydrocarbons...

  14. Field-usable portable analyzer for chlorinated organic compounds

    SciTech Connect

    Buttner, W.J.; Penrose, W.R.; Stetter, J.R.

    1995-10-01

    Transducer Research, Inc. (TRI) has been working with the DOE Morgantown Energy Technology Center to develop a new chemical monitor based on a unique sensor which responds selectively to vapors of chlorinated solvents. We are also developing field applications for the monitor in actual DOE cleanup operations. During the initial phase, prototype instruments were built and field tested. Because of the high degree of selectivity that is obtained, no response was observed with common hydrocarbon organic compounds such as BTX (benzene, toluene, xylene) or POLs (petroleum, oil, lubricants), and in fact, no non-halogen-containing chemical has been identified which induces a measurable response. By the end of the Phase I effort, a finished instrument system was developed and test marketed. This instrument, called the RCL MONITOR, was designed to analyze individual samples or monitor an area with automated repetitive analyses. Vapor levels between 0 and 500 ppm can be determined in 90 s with a lower detection limit of 0.2 ppm using the handportable instrument. In addition to the development of the RCL MONITOR, advanced sampler systems are being developed to: (1) extend the dynamic range of the instrument through autodilution of the vapor and (2) allow chemical analyses to be performed on aqueous samples. When interfaced to the samplers, the RCL MONITOR is capable of measuring chlorinated solvent contamination in the vapor phase up to 5000 ppm and in water and other condensed media from 10 to over 10,000 ppb(wt)--without hydrocarbon and other organic interferences.

  15. Debate over phaseout of chlorine, chlorinated organics continues

    SciTech Connect

    Hileman, B. )

    1993-12-06

    During the past two months, the debate over whether to phase out the use and production of chlorine and chlorinated organics as a broad class of chemicals has continued on a number of fronts. This question was the major focus of discussion at the recent biennial meeting in Windsor Ontario, of the International Joint Commission (IJC)--a binational group that oversees implementation of the Great Lakes Water Quality Agreement. Just prior to the meeting, the governments of the US and Canada presented their views on this issue, and it was the topic most of the speakers discussed during the organized sessions and public hearings. IJC is working on its seventh Biennial Report, which will be completed shortly after the first of the year. The very large comprehensive study on the health and environmental effects of chlorinated organics being prepared by CanTox, a consulting group in Mississauga, Ontario, for CCC and the Chlorine Institute was originally scheduled to be published in June. It is now slated for release sometime in early 1994, and the conference on the health and environmental effects of chlorinated organics that was to be sponsored by CCC and held in September of this year was canceled and has not been rescheduled. The movement to phase out chlorine also may be gathering momentum in Europe. On Oct 15, the 21 nations party to the Barcelona Convention on pollution of the Mediterranean recommended that their governments phase out toxic, persistent, and bioaccumulative substances, especially organohalogens (which include organochlorine), by 2005. This action is similar to proposals made in September 1992 by the Paris Commission, which oversees discharges of pollutants in the northeast Atlantic Ocean.

  16. Photolytic effects in alumina chlorination

    NASA Astrophysics Data System (ADS)

    Soleiman, M. K.; Rao, Y. K.

    1987-06-01

    The temperature dependence of the rate of chlorination of α-alumina with CO/Cl2 gas mixtures exhibits an anomaly, a departure from the normal Arrhenius behavior, in the range 650 to 850°C; it is manifested as a local maximum in the Arrhenius plot at 670°C followed by a local minimum in the range 770 to 850°C. By carefully studying the effect of irradiation of the CO/Cl2 gas mixtures on the rate of chlorination of α-alumina, it is shown that such an anomaly, which has been observed in the chlorination of various metallic oxides, is most likely due to the photochemical formation of phosgene (COCl2) by ambient light incident on the reactant gas mixture during its transport to the main reactor. Phosgene is a better chlorinating agent than a CO/Cl2 mixture. The mechanism of chlorination of α-Al2O3 by CO/Cl2 mixtures subjected to the light emitted by a high-pressure Hg-vapor lamp is elucidated.

  17. Reactions of aqueous chlorine and chlorine dioxide with model food compounds.

    PubMed Central

    Fukayama, M Y; Tan, H; Wheeler, W B; Wei, C I

    1986-01-01

    Chlorine and chlorine dioxide (ClO2), common disinfecting and bleaching chemicals used in the food industry, are potent oxidizing and chlorinating agents. Unfortunately, little is known about the nature of the reactions of chlorine with organic food constituents. This presentation reviews published information concerning the reactions of chlorine gas (Cl2[g]), aqueous chlorine, and ClO2 with model food compounds, the fate of chlorine during the chlorination of specific food products, and the potential toxicity of the reaction products. Fatty acids and their methyl esters react with chlorine with the degree of incorporation corresponding to their degree of unsaturation. Aqueous chlorine oxidizes and chlorinates lipids and amino acids much more readily than ClO2. Several amino acids are highly susceptible to oxidation and chlorination by chlorine compounds. Reactions of chlorine and ClO2 with several food products, including flour and shrimp, have also been characterized. In one model system, 99% of Cl2(g) either reacted with components of flour or was consumed by oxidation/chlorination reactions. The lipids extracted from the chlorinated flour contained significant amounts of chlorine. Exposure of shrimp to hypochlorous acid (HOCl) solution resulted in significant incorporation of chlorine into the edible portion. Although significant quantities of chlorine can be incorporated into specific model compounds and food products, the health risks associated with exposure to chlorinated organic products are unknown. Preliminary studies using the Ames Salmonella/microsome mutagenicity assay indicate that the reaction products from mixtures of aqueous chlorine and various lipids or tryptophan are nonmutagenic. Nevertheless, additional studies are warranted, so that the toxicological significance of these reaction products can be understood more fully. PMID:3545804

  18. Chlorinous flavor perception in drinking water.

    PubMed

    Piriou, P; Mackey, E D; Suffet, I H; Bruchet, A

    2004-01-01

    Chlorinous flavors at the tap are the leading cause of customers' complaints and dissatisfaction with drinking water. To characterize consumer perception and acceptance to chlorinous tastes, extensive taste testing was performed with both trained panelists and average consumers. Taste testing with trained panelists showed that chlorine perception is underestimated by disinfectant flavor thresholds reported in the literature. However, trained panelists significantly overestimate the average consumer's ability to perceive chlorine. In addition, consumer perception seems to be influenced by the chlorination practices of the country they live in. Among water quality characteristics that may influence chlorine perception, temperature was not found to induce any significant change. The influence of total dissolved solids (TDS) on chlorine perception remains unclear and, as reported elsewhere, background tastes such as musty, may significantly impact chlorine threshold.

  19. Chlorine chemistry relevant to urban air pollution

    NASA Astrophysics Data System (ADS)

    Zhang, R.; Zhang, D.; Lei, W.

    2002-05-01

    Reactive chlorine is present in the atmosphere as a consequence of direct emissions and multiphase chemical processes, i.e., from oceanic and terrestrial biogenic emissions, sea-salt production and de-chlorination, biomass burning, and anthropogenic emissions. Recent studies have indicated the importance of anthropogenic sources of chlorine molecules and the related ozone formation in the urban atmosphere. Chlorine radicals react efficiently with atmospheric volatile organic compounds (VOCs) and hence the presence of chlorine radicals significantly enhances the ozone production rate in the urban environments. The talk presents laboratory and theoretical studies of Cl-initiated reactions of VOCs. Implications of related chlorine chemistry and the use of chlorine markers to obtain the atmospheric concentrations of reactive chlorine will be discussed.

  20. 40 CFR 704.43 - Chlorinated naphthalenes.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... weight of chlorine. (2) Import means to import in bulk form or as part of a mixture. (3) Isomeric ratio... the chlorine atom(s) on the naphthalene. (4) Polychlorinated biphenyl means any chemical...

  1. THE ROLE OF CHLORINE IN DIOXIN FORMATION

    EPA Science Inventory

    There is poor correlation between total chlorine in waste streams and formation of polychlorinated dibenzodioxin and polychlorinated dibenzofuran (PCDD/F) during waste combustion. This is because the active chlorine (Cl) species are strongly dependent upon combustion conditions. ...

  2. THE ROLE OF CHLORINE IN DIOXIN FORMATION

    EPA Science Inventory

    There is poor correlation between total chlorine in waste streams and formation of polychlorinated dibenzodioxin and polychlorinated dibenzofuran (PCDD/F) during waste combustion. This is because the active chlorine (Cl) species are strongly dependent upon combustion conditions. ...

  3. Detection of chlorinated aromatic compounds

    DOEpatents

    Ekechukwu, A.A.

    1996-02-06

    A method for making a composition for measuring the concentration of chlorinated aromatic compounds in aqueous fluids, and an optical probe for use with the method are disclosed. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis. 5 figs.

  4. Environmental distribution of chlorinated organic pollutants

    SciTech Connect

    Emmi, F.

    1983-01-01

    A survey of the concentration of PCB's and chlorinated hydrocarbon pesticides in Susquehanna River Basin sediments was performed on samples collected from New York and Pennsylvania in 1976-1979. Highest concentrations were found for PCB's, with median and range of 38 and 13-524 ng/g, respectively. Pesticides had median concentrations ranging from approx.1 ng/g for DDT, DDD, and DDE, to less than 0.1 ng/g for aldrin and dieldrin. Highest concentrations generally were found downstream from industrial centers. Concentrations of PCB's and pesticides were also determined for soil composites collected from six areas of the basin. For several pollutants, the highest levels were found in the Pennsylvania areas, especially the Conestoga River Basin site. The PCB levels were the same (approx.35 ng/g) in all New York soil composites; this was consistent with concentrations predicted from known atmospheric deposition data. Adsorption of atrazine and simazine on model substrates was stuided to elucidate the partitioning of these herbicides on river sediments. Clean sea sand had little affinity for these compounds. Adsorption on illite clay and humic acid-coated sea sand gave relatively large K/sub p/ and K/sub oc/ values compared to the values for river sediments, suggesting that the nature of the sites available for absorbing organic molecules needs further study.

  5. Tolerance of anaerobic bacteria to chlorinated solvents.

    PubMed

    Koenig, Joanna C; Groissmeier, Kathrin D; Manefield, Mike J

    2014-01-01

    The aim of this research was to evaluate the effects of four chlorinated aliphatic hydrocarbons (CAHs), perchloroethene (PCE), carbon tetrachloride (CT), chloroform (CF) and 1,2-dichloroethane (1,2-DCA), on the growth of eight anaerobic bacteria: four fermentative species (Escherichia coli, Klebsiella sp., Clostridium sp. and Paenibacillus sp.) and four respiring species (Pseudomonas aeruginosa, Geobacter sulfurreducens, Shewanella oneidensis and Desulfovibrio vulgaris). Effective concentrations of solvents which inhibited growth rates by 50% (EC50) were determined. The octanol-water partition coefficient or log Po/w of a CAH proved a generally satisfactory measure of its toxicity. Most species tolerated approximately 3-fold and 10-fold higher concentrations of the two relatively more polar CAHs CF and 1,2-DCA, respectively, than the two relatively less polar compounds PCE and CT. EC50 values correlated well with growth rates observed in solvent-free cultures, with fast-growing organisms displaying higher tolerance levels. Overall, fermentative bacteria were more tolerant to CAHs than respiring species, with iron- and sulfate-reducing bacteria in particular appearing highly sensitive to CAHs. These data extend the current understanding of the impact of CAHs on a range of anaerobic bacteria, which will benefit the field of bioremediation.

  6. Colorectal cancers and chlorinated water.

    PubMed

    El-Tawil, Ahmed Mahmoud

    2016-04-15

    Published reports have revealed increased risk of colorectal cancers in people exposed to chlorinated drinking water or chemical derivatives of chlorination. Oestrogen plays a dual positive functions for diminishing the possibilities of such risk by reducing the entrance, and increasing the excretion, of these chemicals. In addition, there are supplementary measures that could be employed in order to reduce this risk further, such as boiling the drinking water, revising the standard concentrations of calcium, magnesium and iron in the public drinking water and prescribing oestrogen in susceptible individuals. Hypo-methylation of genomic DNA could be used as a biological marker for screening for the potential development of colorectal cancers.

  7. Colorectal cancers and chlorinated water

    PubMed Central

    El-Tawil, Ahmed Mahmoud

    2016-01-01

    Published reports have revealed increased risk of colorectal cancers in people exposed to chlorinated drinking water or chemical derivatives of chlorination. Oestrogen plays a dual positive functions for diminishing the possibilities of such risk by reducing the entrance, and increasing the excretion, of these chemicals. In addition, there are supplementary measures that could be employed in order to reduce this risk further, such as boiling the drinking water, revising the standard concentrations of calcium, magnesium and iron in the public drinking water and prescribing oestrogen in susceptible individuals. Hypo-methylation of genomic DNA could be used as a biological marker for screening for the potential development of colorectal cancers. PMID:27096035

  8. The chlorine solar neutrino experiment

    NASA Astrophysics Data System (ADS)

    Rowley, J. K.; Cleveland, B. T.; Davis, R., Jr.

    1985-01-01

    The present consideration of the fourteen years' (1970-1984) results from the Homestake Gold Mine chlorine solar neutrino experiment gives attention to background processes generating Ar-37, as well as the constancy of the Ar-37 production rate. The counter background rates derived from a maximum likelihood treatment are noted to have been variable. The results of the chlorine experiment are clearly different from those of Monte Carlo simulations, with a production rate 3-4 times higher. Solar cycle variations and solar flare effects are also discussed.

  9. Radiolytic dechlorination of chlorinated organics

    NASA Astrophysics Data System (ADS)

    Taghipour, Fariborz; Evans, Greg J.

    1997-02-01

    The radiolytic dechlorination of 12 low molecular weight chlorinated organic compounds present in pulp mill effluent was investigated. For most of these chloro-organic compounds more than 90% dechlorination was obtained for gamma doses up to 20 kGy. Parameters such as the number of chlorine atoms and aqueous solution concentration were found to affect the dechlorination rate. A reaction set was also created to model the behavior of irradiated 0.49-49 mol m -3 chloroform solutions, giving good agreement with experimental results.

  10. Comparison of chlorination and ozonation in treatment of waste water effluents: effects on selected halogenated organic compounds

    SciTech Connect

    Chang, H.

    1983-01-01

    The formation of halogenated hydrocarbons is considered a major drawback in disinfection of waste water using chlorine. The behavior of ozone as an alternative treatment agent was studied by monitoring the generation or destruction of twenty-one volatile halogenated organic compounds that were either proved or suspected products during the chlorination of waste water. The results demonstrated that ozone is preferable to chlorine. While chlorination most of the time resulted in an increase of halogenated compound concentration, ozonation usually diminished the levels of these compounds. Only in one case did ozonation give moderately high production of halogenated organics (tetrachloroethylene). It was found that the behaviors of these oxidizing agents were considerably different in waste water than in carbon filtered water; the chemical reactivities of oxidizing agents may be reinforced in the waste water by certain inorganic species such as trivalent iron.

  11. STABLE CHLORINE ISOTOPE ANALYSIS OF CHLORINATED ORGANIC CONTAMINANTS

    EPA Science Inventory

    The biogeochemical cycling of chlorinated organic contaminants in the environment is often difficult to understand because of the complex distributions of these compounds and variability of sources. To address these issues from an isotopic perspective, we have measured the, 37Cl...

  12. 49 CFR 179.102-2 - Chlorine.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 3 2011-10-01 2011-10-01 false Chlorine. 179.102-2 Section 179.102-2... Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-2 Chlorine. (a) Each tank car used to transport chlorine must comply with all of the following: (1) Tanks must be fabricated from carbon...

  13. 49 CFR 179.102-2 - Chlorine.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Chlorine. 179.102-2 Section 179.102-2... Specifications for Pressure Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-2 Chlorine. (a) Each tank car used to transport chlorine must comply with all of the following: (1) Tanks must...

  14. 21 CFR 173.300 - Chlorine dioxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Chlorine dioxide. 173.300 Section 173.300 Food and... FOOD ADDITIVES PERMITTED IN FOOD FOR HUMAN CONSUMPTION Specific Usage Additives § 173.300 Chlorine dioxide. Chlorine dioxide (CAS Reg. No. 10049-04-4) may be safely used in food in accordance with...

  15. 49 CFR 179.102-2 - Chlorine.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 3 2014-10-01 2014-10-01 false Chlorine. 179.102-2 Section 179.102-2... Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-2 Chlorine. (a) Each tank car used to transport chlorine must comply with all of the following: (1) Tanks must be fabricated from carbon...

  16. 49 CFR 179.102-2 - Chlorine.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 3 2013-10-01 2013-10-01 false Chlorine. 179.102-2 Section 179.102-2... Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-2 Chlorine. (a) Each tank car used to transport chlorine must comply with all of the following: (1) Tanks must be fabricated from carbon...

  17. 49 CFR 179.102-2 - Chlorine.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 3 2012-10-01 2012-10-01 false Chlorine. 179.102-2 Section 179.102-2... Tank Car Tanks (Classes DOT-105, 109, 112, 114 and 120) § 179.102-2 Chlorine. (a) Each tank car used to transport chlorine must comply with all of the following: (1) Tanks must be fabricated from carbon...

  18. 40 CFR 704.45 - Chlorinated terphenyl.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... No. 61788-33-6, comprised of chlorinated ortho-, meta-, and paraterphenyl. (2) Extent of chlorination means the percent by weight of chlorine for each isomer (ortho, meta, and para). (3) Isomeric ratio means the ratios of ortho-, meta-, and parachlorinated terphenyls. (4) Polychlorinated biphenyl means...

  19. BOOSTER CHLORINATION FOR MANAGING DISINFECTANT RESIDUALS

    EPA Science Inventory

    Booster chlorination is an approach to residual maintenance in which chlorine is applied at strategic locations within the distribution system. Situations in which booster chlorination may be most effective for maintaining a residual are explained informally in the context of a ...

  20. Chlorine demand of Savannah River water

    SciTech Connect

    Wilde, E.W.

    1989-01-01

    Savannah River water used for cooling SRS reactors was tested for chlorine demand and the rate of decay for both free and total residual chlorine on seven quarterly dates between 1986 and 1988. Test conditions included chlorine dosages of 1, 3, and 5 mg/l and a variety of contact times ranging from less than 1 minute to one day. Statistically significant differences were detected in the chlorine demand for the seven dates; however, there was no discernible seasonality to the variation. The chlorine demand, amount of combined residual chlorine formed and the persistence of total residual chlorine following a dose of 5 mg/l was significantly greater on one of the seven sampling dates (February, 1988) compared to all of the other dates. These differences could not be attributed to water temperature, pH, ammonia nitrogen concentration, or the amount of rainfall prior to or during the collection of the cooling water. Except as noted above, dissipation of chlorine was similar among the sampling dates. Most reactions of available chlorine with other constituents in the cooking water occurred in the first minute of contact, although measurable total chlorine residuals generally persisted for 24 hours after the dose had been administered. The results of this study indicate that, with occasional exceptions, a chlorine dose of between 3 and 5 mg/l will provide a free chlorine residual of 1 mg/l in Savannah River water. 14 refs., 3 figs., 4 tabs.

  1. BOOSTER CHLORINATION FOR MANAGING DISINFECTANT RESIDUALS

    EPA Science Inventory

    Booster chlorination is an approach to residual maintenance in which chlorine is applied at strategic locations within the distribution system. Situations in which booster chlorination may be most effective for maintaining a residual are explained informally in the context of a ...

  2. 21 CFR 177.1610 - Polyethylene, chlorinated.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyethylene, chlorinated. 177.1610 Section 177... Components of Single and Repeated Use Food Contact Surfaces § 177.1610 Polyethylene, chlorinated. Chlorinated polyethylene identified in this section may be safely used as articles or components of articles that...

  3. 21 CFR 177.1610 - Polyethylene, chlorinated.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Polyethylene, chlorinated. 177.1610 Section 177... Components of Single and Repeated Use Food Contact Surfaces § 177.1610 Polyethylene, chlorinated. Chlorinated polyethylene identified in this section may be safely used as articles or components of articles that...

  4. 21 CFR 177.1610 - Polyethylene, chlorinated.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Polyethylene, chlorinated. 177.1610 Section 177... Components of Single and Repeated Use Food Contact Surfaces § 177.1610 Polyethylene, chlorinated. Chlorinated polyethylene identified in this section may be safely used as articles or components of articles that...

  5. 21 CFR 177.1610 - Polyethylene, chlorinated.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Polyethylene, chlorinated. 177.1610 Section 177... Components of Single and Repeated Use Food Contact Surfaces § 177.1610 Polyethylene, chlorinated. Chlorinated polyethylene identified in this section may be safely used as articles or components of articles that...

  6. An Easy Way To Make Chlorine Water

    NASA Astrophysics Data System (ADS)

    Holmes, L. H., Jr.

    1997-11-01

    Chlorine water can be made easily by mixing hypochlorite and hydrochloric acid. The equilibrium lies toward Cl2 in the reaction HOCl + HCl -> Cl2 + H2O and this can be used to make chlorine water from sodium hypochlorite and hydrochloric acid if the presence of NaCl in the chlorine water does not interfere with its use.

  7. Disinfectants: Chlorine and chlorine dioxide. (Latest citations from the Life Sciences Collection database). Published Search

    SciTech Connect

    Not Available

    1993-05-01

    The bibliography contains citations concerning the antimicrobial properties of chlorine and chlorine dioxide. The use of chlorine for the inactivation of viruses, bacteria, and fungi in wastewater treatment plants is discussed, including the mode of action and factors influencing inactivation. The use of chlorine dioxide as an alternative to chlorine disinfection in swimming pools and water supplies, and possible adverse effects are also discussed. (Contains a minimum of 157 citations and includes a subject term index and title list.)

  8. Enhancement of toxicity and enzyme-repressing activity of p-dioxane by chlorination: stereoselective effects.

    PubMed

    Woo, Y T; Neuburger, B J; Arcos, J C; Argus, M F; Nishiyama, K; Griffin, G W

    1980-01-01

    The acute toxicity of p-dioxane may be enhanced up to 1000-fold by chlorination of the compound. The effect was stereoselective. Of the stereoisomers tested, tetrachloro-p-dioxane, isomer I (2r, 3t, 5t, 6c) was over 80 times more toxic than isomer II (2r, 3c, 5t, 6t). The latter compound was also a potent repressor of hepatic dimethylnitrosamine-demethylase I (DMN-d) and aryl hydrocarbon hydroxylase (AHH).

  9. Chlorine Abundances in Martian Meteorites

    NASA Technical Reports Server (NTRS)

    Bogard, D.D.; Garrison, D.H.; Park, J.

    2009-01-01

    Chlorine measurements made in martian surface rocks by robotic spacecraft typically give Chlorine (Cl) abundances of approximately 0.1-0.8%. In contrast, Cl abundances in martian meteorites appear lower, although data is limited, and martian nakhlites were also subjected to Cl contamination by Mars surface brines. Chlorine abundances reported by one lab for whole rock (WR) samples of Shergotty, ALH77005, and EET79001 range 108-14 ppm, whereas Cl in nakhlites range 73-1900 ppm. Measurements of Cl in various martian weathering phases of nakhlites varied 0.04-4.7% and reveal significant concentration of Cl by martian brines Martian meteorites contain much lower Chlorine than those measured in martian surface rocks and give further confirmation that Cl in these surface rocks was introduced by brines and weathering. It has been argued that Cl is twice as effective as water in lowering the melting point and promoting melting at shallower martian depths, and that significant Cl in the shergottite source region would negate any need for significant water. However, this conclusion was based on experiments that utilized Cl concentrations more analogous to martian surface rocks than to shergottite meteorites, and may not be applicable to shergottites.

  10. Infrared absorption measurements of the kinetics of Cl atom reactions with C{sub 3}H{sub n} (n=4,6) unsaturated hydrocarbons between 300-850 K

    SciTech Connect

    Farrell, J.T.; Pilgrim, J.S.; Taatjes, C.A.

    1997-08-01

    The reaction of chlorine (Cl) atoms with the unsaturated C{sub 3}H{sub n} where n=4,6, hydrocarbons propylene, allene, and methyl acetylene have been uninvestigated as a function of temperature and pressure.

  11. Environmental factors regulating soil organic matter chlorination

    NASA Astrophysics Data System (ADS)

    Svensson, Teresia; Montelius, Malin; Reyier, Henrik; Rietz, Karolina; Karlsson, Susanne; Lindberg, Cecilia; Andersson, Malin; Danielsson, Åsa; Bastviken, David

    2016-04-01

    Natural chlorination of organic matter is common in soils. Despite the widespread abundance of soil chlorinated soil organic matter (SOM), frequently exceeding soil chloride abundance in surface soils, and a common ability of microorganisms to produce chlorinated SOM, we lack fundamental knowledge about dominating processes and organisms responsible for the chlorination. To take one step towards resolving the terrestrial chlorine (Cl) puzzle, this study aims to analyse how environmental factors influence chlorination of SOM. Four factors were chosen for this study: soil moisture (W), nitrogen (N), chloride (Cl) and organic matter quality (C). These factors are all known to be important for soil processes. Laboratory incubations with 36Cl as a Cl tracer were performed in a two soil incubation experiments. It was found that addition of chloride and nitrogen seem to hamper the chlorination. For the C treatment, on the other hand, the results show that chlorination is enhanced by increased availability of labile organic matter (glucose and maltose). Even higher chlorination was observed when nitrogen and water were added in combination with labile organic matter. The effect that more labile organic matter strongly stimulated the chlorination rates was confirmed by the second separate experiment. These results indicate that chlorination was not primarily a way to cut refractory organic matter into digestible molecules, representing one previous hypothesis, but is related with microbial metabolism in other ways that will be further discussed in our presentation.

  12. Chlorine, is there a better alternative?

    PubMed

    Robeck, G G

    1981-04-01

    In brief, the current status of our present knowledge regarding alternatives to free chlorine is as follows: 1. Biocidal Capabilities - Ozone is the most potent biocide of those under consideration. Chlorine dioxide is about on a par with hypochlorous acid, the most efficient form of free residual chlorine. Chlorine dioxide, in contrast to free residual chlorine, increases in efficiency as pH increases above 6. Chloramine is a much weaker biocide than hypochlorite ion, the least inefficient form of free residual chlorine. 2. Health effects - All of the potential alternatives may cause some adverse health effects. Chlorite and chlorate, two of the reaction products of chlorine dioxide, have been shown to cause a subclinical apparently compensated hemolytic anemia in rats. On the other hand, according to very preliminary studies, chlorine and all of the alternatives except chlorine dioxide have been shown to produce reaction products from substances in water that can initiate tumors in mice. Actually, all disinfectants are reactive molecules capable of altering the chemical nature of organic substances present in the water. Thus, the alternative disinfectants question relates to other aspects of water treatment particularly the use of processes for organic precursor removal prior to disinfection. 3. Technology and Economics - The simplest and most economical conversion for many utilities, would be to the use of chloramines and the most difficult and expensive would be to the use of ozone. Conversion to chlorine dioxide would be intermediate in cost.

  13. Detection of chlorinated aromatic compounds

    DOEpatents

    Ekechukwu, Amy A.

    1996-01-01

    A method for making a composition for measuring the concentration of chloated aromatic compounds in aqueous fluids, and an optical probe for use with the method. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis.

  14. Chlorine signal attenuation in concrete.

    PubMed

    Naqvi, A A; Maslehuddin, M; ur-Rehman, Khateeb; Al-Amoudi, O S B

    2015-11-01

    The intensity of prompt gamma-ray was measured at various depths from chlorine-contaminated silica fume (SF) concrete slab concrete specimens using portable neutron generator-based prompt gamma-ray setup. The intensity of 6.11MeV chloride gamma-rays was measured from the chloride contaminated slab at distance of 15.25, 20.25, 25.25, 30.25 and 35.25cm from neutron target in a SF cement concrete slab specimens. Due to attenuation of thermal neutron flux and emitted gamma-ray intensity in SF cement concrete at various depths, the measured intensity of chlorine gamma-rays decreases non-linearly with increasing depth in concrete. A good agreement was noted between the experimental results and the results of Monte Carlo simulation. This study has provided useful experimental data for evaluating the chloride contamination in the SF concrete utilizing gamma-ray attenuation method.

  15. Reactions of aqueous chlorine and chlorine dioxide with model food compounds

    SciTech Connect

    Fukayama, M.Y.; Tan, H.; Wheeler, W.B.; Wei, C.

    1986-11-01

    This presentation reviews published information concerning the reactions of chlorine gas (CL/sub 2/(g)), aqueous chlorine, and ClO/sub 2/ with model food compounds, the fate of chlorine during the chlorination of specific food products, and the potential toxicity of the reaction products. Fatty acids and their methyl esters react with chlorine with the degree of incorporation corresponding to their degree of unsaturation. Aqueous chlorine oxidizes and chlorinates lipids and amino acids much more readily than ClO/sub 2/. Several amino acids are highly susceptible to oxidation and chlorination by chlorine compounds. Reactions of chlorine and ClO/sub 2/ with several food products, including flour and shrimp, have also been characterized. Although significant quantities of chlorine can be incorporated into specific model compounds and food products, the health risks associated with exposure to chlorinated organic products are unknown. Preliminary studies using the Ames Salmonella/microsome mutagenicity assay indicate that the reaction products from mixtures of aqueous chlorine and various lipids or tryptophan are nonmutagenic. Nevertheless, additional studies are warranted, so that the toxicological significance of these reaction products can be understood more fully.

  16. The effect of chlorine and combined chlorine/UV treatment on coliphages in drinking water disinfection.

    PubMed

    Zyara, Alyaa M; Torvinen, Eila; Veijalainen, Anna-Maria; Heinonen-Tanski, Helvi

    2016-08-01

    Chlorine disinfection is a globally used method to ensure the safety of drinking water. However, it has not always been successful against viruses and, therefore, it is important to find new methods to disinfect water. Seventeen different coliphages were isolated from the treated municipal wastewater. These coliphages and MS2 were treated with different dosages of chlorine in drinking water, and a combined chlorine/ultraviolet irradiation treatment for the chlorine-resistant coliphages. Chlorine disinfection with 0.3-0.5 mg/L total chlorine (free Cl-dosage 0.12-0.21 mg/L) for 10 min achieved 2.5-5.7 Log10-reductions for 11 sensitive coliphages. The six most resistant coliphages showed no reduction with these chlorine concentrations. MS2 was intermediate in chlorine resistance, and thus it is not a good indicator for viruses in chlorine disinfection. In the combined treatment total chlorine of 0.05-0.25 mg/L (free Cl-dosage 0.02-0.08 mg/L) and ultraviolet irradiation (14-22 mWs/cm(2)) were more effective than chlorine alone, and 3-5 Log10-reductions were achieved for the chlorine-resistant strains. The chlorination efficiency could be increased by higher dosages and longer contact times, but this could increase the formation of disinfection by-products. Therefore, the combination treatment is a recommended disinfection method.

  17. UV/chlorine process for ammonia removal and disinfection by-product reduction: comparison with chlorination.

    PubMed

    Zhang, Xinran; Li, Weiguang; Blatchley, Ernest R; Wang, Xiaoju; Ren, Pengfei

    2015-01-01

    The combined application of UV irradiation at 254 nm and chlorination (UV/chlorine process) was investigated for ammonia removal in water treatment. The UV/chlorine process led to higher ammonia removal with less chlorine demand, as compared to breakpoint chlorination. Chlorination of NH₃ led to NH₂Cl formation in the first step. The photolysis of NH₂Cl and radical- mediated oxidation of ammonia appeared to represent the main pathways for ammonia removal. The trivalent nitrogen of ammonia was oxidized, presumably by reactions with aminyl radicals and chlorine radicals. Measured products included NO₃⁻and NO₂⁻; it is likely that N₂ and N₂O were also generated. In addition, UV irradiation appeared to have altered the reactivity of NOM toward free chlorine. The UV/chlorine process had lower chlorine demand, less C-DBPs (THMs and HAAs), but more HANs than chlorination. These results indicate that the UV/chlorine process could represent an alternative to conventional breakpoint chlorination for ammonia-containing water, with several advantages in terms of simplicity, short reaction time, and reduced chemical dosage.

  18. Chlorine compounds and stratospheric ozone

    NASA Technical Reports Server (NTRS)

    Cicerone, R. J.; Walters, S.; Stolarski, R. S.

    1975-01-01

    A report by Cicerone et al. (1974) concerned with the potential size of the atmospheric perturbation produced by man-made chlorofluoromethanes is considered, giving attention to a number of errors made in the first investigation and their correction. However, the corrections do not significantly change the results reported. It had been found that chlorine oxides which arise from chlorofluoromethane usage will within 10 or 15 years provide a sink for stratospheric ozone which will dominate the natural sinks for ozone.

  19. Chlorine Abundances in Cool Stars

    NASA Astrophysics Data System (ADS)

    Maas, Zachary; Pilachowski, Catherine A.

    2016-01-01

    We measured the chlorine abundance in 15 evolved giants and one M dwarf in the solar neighborhood. High resolution L-Band spectra were obtained using the Phoenix infrared spectrometer on the Kitt Peak National Observatory Mayall 4m telescope. Chlorine is thought to be primarily produced in explosive oxygen burning but stellar chlorine abundances are virtually unknown. We measured the 35Cl abundance from an HCl feature at 3.69 microns.Analysis of our full sample of giants and dwarfs found the HCl feature is only present in stars with temperatures below 3900K. The [Cl/Fe] abundances in stars with solar metallicity matches the abundance seen in the Sun. Measurements of the [Cl/O] ratio in our sample stars is also consistent with [Cl/O] ratios found in planetary nebulae and H II regions. Our measured abundances are all within one standard deviation, 0.3 dex on average, and are consistent with current chemical evolution models for chlorine in the solar neighborhood. A slight decrease in [Cl/Fe] abundance as [Fe/H] increases may be present and must be verified with future Cl abundances measurements in lower metallicity stars. The average [Cl/Fe] ratio in our sample is -0.07 with a standard deviation of 0.13. An upper limit to the 37Cl isotope abundance in the star RZ Ari, measured from a feature at 3.70 microns, puts a lower limit of 2.5 on the Cl 35/37 isotope ratio for this star. This ratio is consistent with the solar system value of 35/37=3.11.

  20. Microbial based chlorinated ethene destruction

    DOEpatents

    Bagwell, Christopher E [Aiken, SC; Freedman, David L [Clemson, SC; Brigmon, Robin L [North Augusta, SC; Bratt, William B [Atlanta, GA; Wood, Elizabeth A [Marietta, GA

    2009-11-10

    A mixed culture of Dehalococcoides species is provided that has an ability to catalyze the complete dechlorination of polychlorinated ethenes such as PCE, TCE, cDCE, 1,1-DCE and vinyl chloride as well as halogenated ethanes such as 1,2-DCA and EDB. The mixed culture demonstrates the ability to achieve dechlorination even in the presence of high source concentrations of chlorinated ethenes.

  1. Coal desulfurization by aqueous chlorination

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Vasilakos, N.; Corcoran, W. H.; Grohmann, K.; Rohatgi, N. K. (Inventor)

    1982-01-01

    A method of desulfurizing coal is described in which chlorine gas is bubbled through an aqueous slurry of coal at low temperature below 130 degrees C., and at ambient pressure. Chlorinolysis converts both inorganic and organic sulfur components of coal into water soluble compounds which enter the aqueous suspending media. The media is separated after chlorinolysis and the coal dechlorinated at a temperature of from 300 C to 500 C to form a non-caking, low-sulfur coal product.

  2. Determination of ambient air hydrocarbons in 39 US cities

    SciTech Connect

    Seila, R.L.; Lonneman, W.A.

    1988-06-01

    Compliance with the NAAQS for ozone will require the reduction of non-methane organic carbon (NMOC). To this end, speciated hydrocarbons were determined for over 800 ambient air samples from 39 U.S. cities from 1984-1986. Samples were collected in stainless steel spheres on week days from 6 to 9 A.M. during June through September. C2 to C12 hydrocarbons were determined by capillary GC/FID with sample cryogenic preconcentration. The GC retention time identification table consisted of 314 uniquely numbered peaks, of which 97 were specifically named, 214 were identified by type (olefin, paraffin, aromatic). GC-MSD/FID analysis confirmed the identity of 40 peaks and indicated the presence of oxygenated, chlorinated, and fluorinated hydrocarbons in some samples.

  3. IDENTIFICATION OF DRINKING WATER DISINFECTION BY-PRODUCTS FROM OZONE, CHLORINE DIOXIDE, CHLORAMINE, AND CHLORINE

    EPA Science Inventory

    Many drinking water treatment plants are currently using alternative disinfectants to treat drinking water, with ozone, chlorine dioxide, and chloramine being the most popular. However, compared to chlorine, which has been much more widely studied, there is little information abo...

  4. IDENTIFICATION OF DRINKING WATER DISINFECTION BY-PRODUCTS FROM OZONE, CHLORINE DIOXIDE, CHLORAMINE, AND CHLORINE

    EPA Science Inventory

    Many drinking water treatment plants are currently using alternative disinfectants to treat drinking water, with ozone, chlorine dioxide, and chloramine being the most popular. However, compared to chlorine, which has been much more widely studied, there is little information abo...

  5. Observations of interstellar chlorine and phosphorus

    NASA Technical Reports Server (NTRS)

    Jura, M.; York, D. G.

    1978-01-01

    Copernicus observations of interstellar Cl I, Cl II, and P II UV lines toward 10 stars are reported. Column densities are estimated for each species, and upper limits are computed for HCl column densities. Derivation of the gas-phase abundances of chlorine and phosphorus indicates that the averages of both the chlorine and the phosphorus logarithmic abundances relative to hydrogen are between 5.0 and 5.1. It is suggested that interstellar chlorine may be depleted by about a factor of 3 relative to the solar abundance and that interstellar phosphorus is depleted by a factor of 2 to 3. The results are shown to support the prediction that chlorine is ionized in regions containing primarily atomic oxygen and is neutral in regions where there is a significant amount of molecular hydrogen. The photoionization rate of neutral chlorine toward 15 Mon is estimated, and it is concluded that most chlorine is contained within the gas phase.

  6. Observations of interstellar chlorine and phosphorus

    NASA Technical Reports Server (NTRS)

    Jura, M.; York, D. G.

    1978-01-01

    Copernicus observations of interstellar Cl I, Cl II, and P II UV lines toward 10 stars are reported. Column densities are estimated for each species, and upper limits are computed for HCl column densities. Derivation of the gas-phase abundances of chlorine and phosphorus indicates that the averages of both the chlorine and the phosphorus logarithmic abundances relative to hydrogen are between 5.0 and 5.1. It is suggested that interstellar chlorine may be depleted by about a factor of 3 relative to the solar abundance and that interstellar phosphorus is depleted by a factor of 2 to 3. The results are shown to support the prediction that chlorine is ionized in regions containing primarily atomic oxygen and is neutral in regions where there is a significant amount of molecular hydrogen. The photoionization rate of neutral chlorine toward 15 Mon is estimated, and it is concluded that most chlorine is contained within the gas phase.

  7. Decomposition of free chlorine with tertiary ammonium.

    PubMed

    Katano, Hajime; Uematsu, Kohei; Tatsumi, Hirosuke; Tsukatani, Toshihide

    2010-01-01

    The reaction of free chlorine with tertiary ammonium or amine compounds in aqueous solution was studied by the amperometry at a rotating Pt-disk electrode. The amperometric method can be applied to follow the concentration of free chlorine (c(Cl)) even in the presence of chloramine species. By addition of mono- and dibutylammonium to the solution containing free chlorine, the step-like decrease in c(Cl) was observed, indicating the rapid formation of the stable chloramine species. By addition of tributylammonium, the c(Cl) was decreased exponentially to nearly zero even if the free chlorine was present initially in excess. The c(Cl)-t curves can be explained by tributylammonium-species-catalyzed decomposition of free chlorine to chloride ion. The catalytic decomposition was observed also with the tertiary-ammonium-based anion-exchange resins. Furthermore, the anion-exchange resins exhibited the decomposition of not only free chlorine but also chloramines in water.

  8. A kinetics investigation of several reactions involving chlorine containing compounds

    NASA Technical Reports Server (NTRS)

    Davis, D. D.

    1978-01-01

    The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

  9. Toxicity of chlorinated insecticides to quail and pheasants

    USGS Publications Warehouse

    DeWitt, J.B.

    1956-01-01

    'Residues from insecticidal applications of chlorinated hydrocarbons may remain toxic for extended periods. In experiments designed to furnish information on the effects upon quail and pheasants of prolonged feeding upon diets containing small percentages of these compounds, it was shown that aldrin, dieldrin and endrin are cumulative, and that quail are unable to survive after ingesting 5-10 mg./kg, of aldrin, 30-50 mg./kg, of dieldrin, or 6-15 mg./kg, of endrin. Maximum levels (p.p.m.) in the diets permitting survival for extended periods were: DDT, 200; strobane, above 500; aldrin, 0.5; dieldrin, 1.0; endrin, 1.0. Inclusion of these compounds in the diets of breeding quail and pheasants affected hatchability of eggs and viability of chicks, even though the adult birds appeared unaffected.' Detailed figures are given for all points mentioned.

  10. Indoor air: Spatial variations of chlorinated pesticides

    NASA Astrophysics Data System (ADS)

    Anderson, David J.; Hites, Ronald A.

    The concentrations of two classes of chlorinated pesticides were measured in various locations within four homes. The prevalent compounds were chlorinated derivatives of cyclopentadiene which had been used as termiticides. These compounds were found in basement areas at higher concentrations than in upstairs areas of the homes. Another class of chlorinated pesticide was represented by chlorpyrifos; its spatial profile was consistent with its application in upstairs areas.

  11. The Radiothermoluminescence Of The Chlorinated Polyethylene

    NASA Astrophysics Data System (ADS)

    Polizov, Hristo T.

    2007-04-01

    The radiothermoluminescence (RTL) of the high density polyetilene (HDPE) by gamma-irradiation was studied together with the thermally stimulated currents (TSC). The investigation was carried for several kind of samples: pure high density polyethlene and chlorinated high density polyethlene with 7, 28 and 42 per cent chlorine. It has been established, that the intensity of the radiothermoluminescence decreases on the high density polyethylene with the chlorination and the thermally stimulated currents increase as a function of the temperature T has been observed as well that a new phase has been formed in the chlorinated polyethylene with the both methods of the investigation.

  12. Total residual chlorine as a regulatory tool

    SciTech Connect

    Mattice, J.S.; Tsai, S.C.

    1981-01-01

    Inherent in the choice of total residual chlorine (TRC) as a basis for establishing water quality criteria or effluent guidelines for chlorine are assumptions that components of TRC are roughly equivalent in toxicity to aquatic species and that the toxicities of these components are additive. Most of the studies of this assumption involved comparisons of mixtures of residual chlorine components and thus led to conflicting conclusions. In addition, studies designed to avoid the mixture problem omitted one or more of the most likely products of chlorination from the comparison(s). On the other hand, the assumption of additive toxicity of residual chlorine species has largely been ignored. In view of the continuing controversy that focused on the levels of residual chlorine which can be discharged without deleterious impact on receiving waters, it is important that these assumptions be evaluated comprehensively. New data on the toxicities to the mosquitofish, Gambusia affinis, of inorganic monochloramine, inorganic dichloramine, a mixture of these two compounds, and two mixtures with free chlorine are reported. These and other data on the toxicity of residual chlorine species to mosquitofish are then used to examine the questions of toxicity equivalence and additivity of species of residual chlorine. (ERB)

  13. Vanadium-catalyzed chlorination under molecular oxygen.

    PubMed

    Moriuchi, Toshiyuki; Fukui, Yasuhiro; Kato, Satoshi; Kajikawa, Tomomi; Hirao, Toshikazu

    2015-06-01

    A catalytic chlorination of ketones was performed by using a vanadium catalyst in the presence of Bu4NI and AlCl3 under atmospheric molecular oxygen. This catalytic chlorination could be applied to the chlorination of alkenes to give the corresponding vic-dichlorides. AlCl3 was found to serve as both a Lewis acid and a chloride source to induce the facile chlorination. A combination of Bu4NI and AlI3 in the presence of a vanadium catalyst under atmospheric molecular oxygen induced the iodination of ketones.

  14. Reactions of tetracycline antibiotics with chlorine dioxide and free chlorine.

    PubMed

    Wang, Pei; He, Yi-Liang; Huang, Ching-Hua

    2011-02-01

    Tetracyclines (TCs) are a group of widely used antibiotics that have been frequently found in the aquatic environment. The potential reactions of TCs with common water disinfection oxidants such as chlorine dioxide (ClO(2)) and free available chlorine (FAC) have not been studied in depth and are the focus of this study. The oxidation kinetics of tetracycline, oxytetracycline, chlorotetracycline and iso-chlorotetracycline by ClO(2) and FAC are very rapid (with large apparent second-order rate constants k(app) = 2.24 × 10(5)-1.26 × 10(6) M(-1) s(-1) with ClO(2) and k(app) = 1.12 × 10(4)-1.78 × 10(6) M(-1) s(-1) with FAC at pH 7.0) and highly dependent on pH. Species-specific rate constants are obtained by kinetic modeling that incorporates pH-speciation of TCs and the oxidants (for FAC), and reveal that TCs primarily react with ClO(2) and FAC by their unprotonated dimethylamino group and deprotonated phenolic-diketone group. The modest difference in reactivity among the four TCs toward the oxidants is consistent with expectation and can be explained by structural influences on the two reactive moieties. Product evaluation shows that oxidation of TCs by ClO(2) leads to (hydr)oxylation and breakage of TC molecules, while oxidation of TCs by FAC leads to chlorinated and (hydr)oxylated products without any substantial ring breakage. Results of this study indicate that rapid transformation of TCs by oxidants such as ClO(2) and FAC under water and wastewater treatment conditions can be expected.

  15. Bioaccumulation factors for chlorinated benzenes, chlorinated butadienes and hexachloroethane

    SciTech Connect

    Burkhard, L.P.; Sheedy, B.R.; McCauley, D.J.; DeGraeve, G.M.

    1997-08-01

    A field study was performed that measured bioaccumulation factors (BAFs) for chlorinated benzenes, chlorinated butadienes, and hexachloroethane in four species, Fundulus heteroclitus (mummichog), Callinectes sapidus (blue crabs), Brevoortia patronus (gulf menhaden), and Micropoganias undulatus (Atlantic croaker). The measured BAFs were not significantly different among the fishes. The measured BAFs for the C. sapidus were in good agreement with those measured for the fishes except for hexachloroethane (HCE), E- and Z-1,1,2,3,4-pentachlorobuta-1,3-diene (E-and Z-PeCBD), and hexachlorobuta-1,3-diene (HCBD). Their measured BAFs were approximately an order of magnitude smaller than those measured for the fishes. The measured BAFs were also in good agreement with BAFs reported/derived from the literature and to BAFs predicted using two methods of the Environmental Protection Agency (EPA) except for HCE, E- and Z-PeCBD, and HCBD in the C. sapidus. These BAFs were much smaller than the reported/derived and predicted BAFs. The smaller BAFs for HCE, E- and Z-PeCBD, and HCBD were consistent with the metabolism abilities for the C. sapidus, and metabolism processes are believed to be the cause for the smaller BAFs. The predicted BAFs were within a factor of five of the measured BAFs for 90% (n = 48) and 94% (n = 32) using the two methods of the EPA.

  16. Chlorinated aliphatic and aromatic VOC decomposition in air mixture by using electron beam irradiation

    NASA Astrophysics Data System (ADS)

    Chmielewski, A. G.; Sun, Yong-Xia; Bułka, S.; Zimek, Z.

    2004-09-01

    Chlorinated aliphatic and aromatic hydrocarbons, which are emitted from coal power station and waste incinerators, are very harmful to the environment and human health. Recent studies show that chlorinated aliphatic and aromatic hydrocarbons are suspected to be the precursors of dioxin's formation. Dioxin's emission into atmosphere will cause severe environmental problems by ecology contamination. l,4-dichlorobenzene(l,4-DCB) and cis-dichloroethylene( cis-DCE) were chosen as representative chlorinated aromatic and aliphatic compounds, respectively. Their decomposition was investigated by electron beam irradiation. The experiments were carried out "in batch" system. It is found that over 97% cis-DCE is decomposed having an initial concentration of 661 ppm. G-values of cis-DCE decomposition vary from 10 to 28 (molecules/100 eV) for initial concentration of 270-1530 ppm cis-DCE. The decomposition is mainly caused by secondary electron attachment and Cl addition reactions. Comparing with cis-DCE, 1,4-DCB decomposition needs higher absorbed dose. G-value of 1,4-DCB is below 4 molecules/100 eV.

  17. A DFT study of the interaction between large PAHs and atomic chlorine or hydrogen chloride molecule: Toward a modelling of the influence of chlorinated species on the trapping of water by soot

    NASA Astrophysics Data System (ADS)

    Garcia-Fernandez, C.; Radola, B.; Martin-Gondre, L.; Picaud, S.; Rayez, M. T.; Rayez, J. C.; Ouf, F. X.; Rubayo-Soneira, J.

    2017-02-01

    First-principle calculations have been performed to characterize the interaction of chlorinated species (HCl and Cl) with large polycyclic aromatic hydrocarbon (PAH) molecules and radicals. Whereas the characterization of the interaction process on the face of the PAH molecules requires taking into account long-range dispersion interactions in the calculations, trapping at the edge of PAH radicals involves stronger interactions that lead to the dissociation of the HCl molecule. Then, the first steps of water adsorption on the corresponding chlorinated species has been characterized, showing that chlorine may act as an efficient nucleation center for water molecules on such aromatic systems mimicking part of the carbonaceous surfaces that are likely present in soot. These results represent a first but necessary step for a better understanding of soot behavior in industrial or domestic fire situations.

  18. Effects of ozone, chlorine dioxide, chlorine, and monochloramine on Cryptosporidium parvum oocyst viability.

    PubMed Central

    Korich, D G; Mead, J R; Madore, M S; Sinclair, N A; Sterling, C R

    1990-01-01

    Purified Cryptosporidium parvum oocysts were exposed to ozone, chlorine dioxide, chlorine, and monochloramine. Excystation and mouse infectivity were comparatively evaluated to assess oocyst viability. Ozone and chlorine dioxide more effectively inactivated oocysts than chlorine and monochloramine did. Greater than 90% inactivation as measured by infectivity was achieved by treating oocysts with 1 ppm of ozone (1 mg/liter) for 5 min. Exposure to 1.3 ppm of chlorine dioxide yielded 90% inactivation after 1 h, while 80 ppm of chlorine and 80 ppm of monochloramine required approximately 90 min for 90% inactivation. The data indicate that C. parvum oocysts are 30 times more resistant to ozone and 14 times more resistant to chlorine dioxide than Giardia cysts exposed to these disinfectants under the same conditions. With the possible exception of ozone, the use of disinfectants alone should not be expected to inactivate C. parvum oocysts in drinking water. PMID:2339894

  19. Effects of ozone, chlorine dioxide, chlorine, and monochloramine on Cryptosporidium parvum oocyst viability

    SciTech Connect

    Korich, D.G.; Mead, J.R.; Madore, M.S.; Sinclair, N.A.; Sterling, C.R. )

    1990-05-01

    Purified Cryptosporidium parvum oocysts were exposed to ozone, chlorine dioxide, chlorine, and monochloramine. Excystation and mouse infectivity were comparatively evaluated to assess oocyst viability. Ozone and chlorine dioxide more effectively inactivated oocysts than chlorine and monochloramine did. Greater than 90% inactivation as measured by infectivity was achieved by treating oocysts with 1 ppm of ozone (1 mg/liter) for 5 min. Exposure to 1.3 ppm of chlorine dioxide yielded 90% inactivation after 1 h, while 80 ppm of chlorine and 80 ppm of monochloramine required approximately 90 min for 90% inactivation. The data indicate that C. parvum oocysts are 30 times more resistant to ozone and 14 times more resistant to chlorine dioxide than Giardia cysts exposed to these disinfectants under the same conditions. With the possible exception of ozone, the use of disinfectants alone should not be expected to inactivate C. parvum oocysts in drinking water.

  20. Chlorination products: emerging links with allergic diseases.

    PubMed

    Bernard, A

    2007-01-01

    Exposure of the human population to chlorination products has considerably increased during the 20(th) century especially after the 1960s with the development of public and leisure pools. The present article summarizes current knowledge regarding the human exposure to chlorination products and reviews studies suggesting that these chemicals might be involved in the development or exacerbation of allergic diseases. Populations regularly in contact with chlorination products such as swimmers, lifeguards or workers using chlorine as cleaning or bleaching agent show increased risks of allergic diseases or of respiratory disorders frequently associated with allergy. Experimental evidence suggests that chlorination products promote allergic sensitization by compromising the permeability or the immunoregulatory function of epithelial barriers. These findings led to the chlorine hypothesis proposing that the rise of allergic diseases could result less from the declining exposure to microbial agents (the hygiene hypothesis) than from the increasing and largely uncontrolled exposure to products of chlorination, the most widely used method to achieve hygiene in the developed world. Giving the increasing popularity of water recreational areas, there is an obvious need to assess the effects of chlorine-based oxidants on human health and their possible implication in the epidemic of allergic diseases.

  1. Toxicity of chlorine to zebrafish embryos.

    PubMed

    Kent, Michael L; Buchner, Cari; Barton, Carrie; Tanguay, Robert L

    2014-01-16

    Surface disinfection of fertilized fish eggs is widely used in aquaculture to reduce extraovum pathogens that may be released from brood fish during spawning, and this is routinely used in zebrafish Danio rerio research laboratories. Most laboratories use approximately 25 to 50 ppm unbuffered chlorine solution for 5 to 10 min. Treatment of embryos with chlorine has significant germicidal effects for many Gram-negative bacteria, viruses, and trophozoite stages of protozoa, but is less effective against cyst or spore stages of protozoa and certain Mycobacterium spp. Therefore, we evaluated the toxicity of unbuffered and buffered chlorine solutions to embryos exposed at 6 or 24 h post-fertilization (hpf) to determine whether higher concentrations can be used for treating zebrafish embryos. Most of our experiments entailed using an outbred line (5D), with both mortality and malformations as endpoints. We found that 6 hpf embryos consistently were more resistant than 24 hpf embryos to the toxic effects of chlorine. Chlorine is more toxic and germicidal at lower pH, and chlorine causes elevated pH. Consistent with this, we found that unbuffered chlorine solutions (pH ca. 8-9) were less toxic at corresponding concentrations than solutions buffered to pH 7. Based on our findings here, we recommend treating 6 hpf embryos for 10 min and 24 hpf embryos for 5 min with unbuffered chlorine solution at 100 ppm.

  2. 40 CFR 704.43 - Chlorinated naphthalenes.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... CONTROL ACT REPORTING AND RECORDKEEPING REQUIREMENTS Chemical-Specific Reporting and Recordkeeping Rules... means the relative amounts of each isomeric chlorinated naphthalene that composes the chemical substance... the chlorine atom(s) on the naphthalene. (4) Polychlorinated biphenyl means any chemical...

  3. Chemotaxis of Pseudomonas putida toward chlorinated benzoates

    SciTech Connect

    Harwood, C.S.; Parales, R.E.; Dispensa, M. )

    1990-05-01

    The chlorinated aromatic acids 3-chlorobenzoate and 4-chlorobenzoate are chemoattractants for Pseudomonas putida PRS2000. These compounds are detected by a chromosomally encoded chemotactic response to benzoate which is inducible by {beta}-ketoadipate, and intermediate of benzoate catabolism. Plasmid pAC27, encoding enzymes for 3-chlorobenzoate degradation, does not appear to carry genes for chemotaxis toward chlorinated compounds.

  4. Factors Regulating Soil Organic Matter Chlorination

    NASA Astrophysics Data System (ADS)

    Svensson, T.; Gustavsson, M.; Reyier, H.; Rietz, K.; Karlsson, S.; Göransson, C.; Andersson, M.; Öberg, G.; Bastviken, D.

    2013-12-01

    Natural chlorination of organic matter is a common process in various soils. Despite the widespread abundance of soil organic chlorine, knowledge on the processes and regulation of soil organic matter chlorination are modest. The purpose of this study is to elucidate how environmental factors may influence chlorination of organic matter in soil. Four factors were chosen for this study; water content, and nitrogen, organic carbon, and chloride concentrations. The variables are all known in different ways as important for microbes and transformation of chlorine in soil. The soil was collected from 5-15 cm depth in a coniferous forest southeast of Sweden. To test how the selected factors influenced chlorination of organic matter, we used soil laboratory incubations using 36Cl-chloride as a radioisotopic marker. A multivariate factorial design with two levels of i) soil moisture, ii) chloride amendment, iii) nitrogen amendment, and iv) glucose and maltose addition was used to simultaneously test for possible combination effects for all factors. A known radioactivity of 36chloride was added to the soil samples and incubated with four different factor treatments during an incubation period of 15 and 60 days. This presentation will discuss the results of this study including what combination of factors enhanced or hampered chlorination and thereby discuss previous observed variability of organic chlorine and chloride in soil.

  5. Inactivation of Renibacterium salmoninarum by free chlorine

    USGS Publications Warehouse

    Pascho, Ronald J.; Landolt, Marsha L.; Ongerth, Jerry E.

    1995-01-01

    Salmonid fishes contract bacterial kidney disease by vertical or horizontal transmission of the pathogenic bacterium, Renibacterium salmoninarum. Procedures to reduce vertical transmission are under evaluation, but methods are still needed to eliminate sources of waterborne R. salmoninarum. We examined the efficacy of chlorine to inactivate R. salmoninarum. The bacterium was exposed to various levels of chlorine at pH 6, 7, or 8, and at 7.5 °C or 15 °C. At pH 7 and 15 °C, 99% inactivation occurred within 18 s, even at free chlorine concentrations as low as 0.05 mg/l. Chlorine was most effective at neutral or acidic pH, and 15 °C. The inactivation curves for 7.5 °C and pH 7, or 15 °C and pH 8, deviated from first-order kinetics by exhibiting shoulders or a tailing-off effect, suggesting that chlorine and the bacterial cells were not the sole reactants. A plot of the concentration-time (Ct) products for free chlorine at pH 7 and 15 °C produced a line with a slope less than 1, indicating that the duration of exposure was more important than the concentration of free chlorine. These data indicate that R. salmoninarum is very sensitive to chlorine, and that this disinfectant may be appropriate for use in fish hatcheries rearing salmonids affected by bacterial kidney disease.

  6. Bacterial growth with chlorinated methanes.

    PubMed Central

    Leisinger, T; Braus-Stromeyer, S A

    1995-01-01

    Chlorinated methanes are important industrial chemicals and significant environmental pollutants. While the highly chlorinated methanes, trichloromethane and tetrachloromethane, are not productively metabolized by bacteria, chloromethane and dichloromethane are used by both aerobic and anaerobic methylotrophic bacteria as carbon and energy sources. Some of the dehalogenation reactions involved in the utilization of the latter two compounds have been elucidated. In a strictly anaerobic acetogenic bacterium growing with chloromethane, an inducible enzyme forming methyltetrahydrofolate and chloride from chloromethane and tetrahydrofolate catalyzes dehalogenation of the growth substrate. A different mechanism for the nucleophilic displacement of chloride is observed in aerobic methylotrophic bacteria utilizing dichloromethane as the sole carbon and energy source. These organisms possess the enzyme dichloromethane dehalogenase which, in a glutathione-dependent reaction, converts dichloromethane to inorganic chloride and formaldehyde, a central metabolite of methylotrophic growth. Sequence comparisons have shown that bacterial dichloromethane dehalogenases belong to the glutathione S-transferase enzyme family, and within this family to class Theta. The dehalogenation reactions underlying aerobic utilization of chloromethane by a pure culture and anaerobic growth with dichloromethane by an acetogenic mixed culture are not known. It appears that they are based on mechanisms other than nucleophilic attack by tetrahydrofolate or glutathione. PMID:8565906

  7. Hydrocarbon Spectral Database

    National Institute of Standards and Technology Data Gateway

    SRD 115 Hydrocarbon Spectral Database (Web, free access)   All of the rotational spectral lines observed and reported in the open literature for 91 hydrocarbon molecules have been tabulated. The isotopic molecular species, assigned quantum numbers, observed frequency, estimated measurement uncertainty and reference are given for each transition reported.

  8. Oxygenated Derivatives of Hydrocarbons

    USDA-ARS?s Scientific Manuscript database

    For the book entitled “Insect Hydrocarbons: Biology, Biochemistry and Chemical Ecology”, this chapter presents a comprehensive review of the occurrence, structure and function of oxygenated derivatives of hydrocarbons. The book chapter focuses on the occurrence, structural identification and functi...

  9. Recovering hydrocarbons from hydrocarbon-containing vapors

    DOEpatents

    Mirza, Zia I.; Knell, Everett W.; Winter, Bruce L.

    1980-09-30

    Values are recovered from a hydrocarbon-containing vapor by contacting the vapor with quench liquid consisting essentially of hydrocarbons to form a condensate and a vapor residue, the condensate and quench fluid forming a combined liquid stream. The combined liquid stream is mixed with a viscosity-lowering liquid to form a mixed liquid having a viscosity lower than the viscosity of the combined liquid stream to permit easy handling of the combined liquid stream. The quench liquid is a cooled portion of the mixed liquid. Viscosity-lowering liquid is separated from a portion of the mixed liquid and cycled to form additional mixed liquid.

  10. Chlorine

    MedlinePlus

    ... Training Related Bioterrorism Resources Bacillus anthracis (Anthrax) Botulism (Clostridium botulinum toxin) Brucella species (brucellocis) Laboratory Information Surveillance & Investigation Burkholderia mallei (glanders) ...

  11. Subsea hydrocarbon sensor system

    SciTech Connect

    Marosko, R.J.; Warren, W.B.

    1981-08-04

    A hydrocarbon detection system is provided for use in a subsea hydrocarbon production installation which includes production tree assemblies, an electro-hydraulic control module located on the sea floor and remote from the production trees, cable assemblies interconnecting the control module with the production trees through magnetic coupling devices. A pair of inductive elements are electrically coupled by the surrounding sea water. Displacement of the conductive sea water by escaping hydrocarbons affects the coupling between the inductive elements to produce a hydrocarbon-presence-responsive output signal. The inductive elements are resonated within a selected frequency range by capacitors coupled with a primary inductor coil by auxiliary windings on a common core element. An excitation signal sweeps over the selected frequency range at a rate effective to produce a peak detected signal at the resonant frequency. The peak output signal is then monitored to form a control signal functionally related to the presence or absence of hydrocarbons in the sea water.

  12. Plant hydrocarbon recovery process

    SciTech Connect

    Dzadzic, P.M.; Price, M.C.; Shih, C.J.; Weil, T.A.

    1982-01-26

    A process for production and recovery of hydrocarbons from hydrocarbon-containing whole plants in a form suitable for use as chemical feedstocks or as hydrocarbon energy sources which process comprises: (A) pulverizing by grinding or chopping hydrocarbon-containing whole plants selected from the group consisting of euphorbiaceae, apocynaceae, asclepiadaceae, compositae, cactaceae and pinaceae families to a suitable particle size, (B) drying and preheating said particles in a reducing atmosphere under positive pressure (C) passing said particles through a thermal conversion zone containing a reducing atmosphere and with a residence time of 1 second to about 30 minutes at a temperature within the range of from about 200* C. To about 1000* C., (D) separately recovering the condensable vapors as liquids and the noncondensable gases in a condition suitable for use as chemical feedstocks or as hydrocarbon fuels.

  13. Formation of chlorinated lipids post-chlorine gas exposure.

    PubMed

    Ford, David A; Honavar, Jaideep; Albert, Carolyn J; Duerr, Mark A; Oh, Joo Yeun; Doran, Stephen; Matalon, Sadis; Patel, Rakesh P

    2016-08-01

    Exposure to chlorine (Cl2) gas can occur during accidents and intentional release scenarios. However, biomarkers that specifically indicate Cl2 exposure and Cl2-derived products that mediate postexposure toxicity remain unclear. We hypothesized that chlorinated lipids (Cl-lipids) formed by direct reactions between Cl2 gas and plasmalogens serve as both biomarkers and mediators of post-Cl2 gas exposure toxicities. The 2-chloropalmitaldehyde (2-Cl-Pald), 2-chlorostearaldehyde (2-Cl-Sald), and their oxidized products, free- and esterified 2-chloropalmitic acid (2-Cl-PA) and 2-chlorostearic acid were detected in the lungs and plasma of mouse and rat models of Cl2 gas exposure. Levels of Cl-lipids were highest immediately post-Cl2 gas exposure, and then declined over 72 h with levels remaining 20- to 30-fold higher at 24 h compared with baseline. Glutathione adducts of 2-Cl-Pald and 2-Cl-Sald also increased with levels peaking at 4 h in plasma. Notably, 3-chlorotyrosine also increased after Cl2 gas exposure, but returned to baseline within 24 h. Intranasal administration of 2-Cl-PA or 2-Cl-Pald at doses similar to those formed in the lung after Cl2 gas exposure led to increased distal lung permeability and inflammation and systemic endothelial dysfunction characterized by loss of eNOS-dependent vasodilation. These data suggest that Cl-lipids could serve as biomarkers and mediators for Cl2 gas exposure and toxicity. Copyright © 2016 by the American Society for Biochemistry and Molecular Biology, Inc.

  14. The occurrence of chlorine in serpentine minerals

    USGS Publications Warehouse

    Miura, Y.; Rucklidge, J.; Nord, G.L.

    1981-01-01

    Partially serpentinized dunites containing small amounts of Chlorine (< 0.5%) from Dumont, Quebec, and Horoman, Hokkaido, Japan, and one containing less than 0.05% Chlorine from Higashi-Akaishi-Yama, Ehime, Japan have been examined using the electron probe microanalyzer and scanning transmission electron microscope with X-ray analytical capabilities. Chlorine was found together with Si, Mg, Ca and Fe in the serpentine minerals of the Dumont and Hokkaido dunites but not in the Ehime dunite. Chlorine is found associated only with the most finely crystalline facies of the serpentine (grain size less than 10 nm). The Ehime dunite contained no such fine grained serpentine, and was thus effectively chlorine-free, as are the coarser grained serpentines of the other samples. The finegrained chlorine-bearing serpentine also has a much higher concentration of Fe, and can contain smaller amounts of Ca, Ni and Mn than the coarse-grained variety as well as minute awaruite (FeNi3) grains. This fine-grained serpentine probably represents an early stage in the transformation of olivine to serpentine, with chlorine from hydrothermal solutions assisting the necessary chemical changes. The Cl increases the reaction rate by lowering the activation barrier to reaction by the introduction of reaction steps. ?? 1981 Springer-Verlag.

  15. Chlorination of Wastewater, Manual of Practice No. 4.

    ERIC Educational Resources Information Center

    Water Pollution Control Federation, Washington, DC.

    This manual reviews chlorination practices in the treatment and disposal of wastes from the earliest known applications. The application of chlorination for various purposes is described but no attempt has been made to compare chlorination with other methods. Included are chapters on the development and practice of wastewater chlorination,…

  16. Influence of Chlorine Emissions on Ozone Levels in the Troposphere

    EPA Science Inventory

    Chlorine emissions from cooling towers are emitted mainly as hypochlous acid, not as molecular chlorine. Chlorine emissions from cooling towers in electric utilities in the U.S. are estimated to be 4,400 tons per year. Molecular chlorine increases more tropospheric ozone than hyp...

  17. Chlorination of Wastewater, Manual of Practice No. 4.

    ERIC Educational Resources Information Center

    Water Pollution Control Federation, Washington, DC.

    This manual reviews chlorination practices in the treatment and disposal of wastes from the earliest known applications. The application of chlorination for various purposes is described but no attempt has been made to compare chlorination with other methods. Included are chapters on the development and practice of wastewater chlorination,…

  18. Chlorination. Training Module 2.300.2.77.

    ERIC Educational Resources Information Center

    Kirkwood Community Coll., Cedar Rapids, IA.

    This document is an instructional module package prepared in objective form for use by an instructor familiar with chlorine, the reasons for chlorination and safe operation and maintenance of gas chlorine, dry calcium hypochlorite and liquid sodium hypochlorite chlorination systems for water supply and wastewater treatment facilities. Included are…

  19. Influence of Chlorine Emissions on Ozone Levels in the Troposphere

    EPA Science Inventory

    Chlorine emissions from cooling towers are emitted mainly as hypochlous acid, not as molecular chlorine. Chlorine emissions from cooling towers in electric utilities in the U.S. are estimated to be 4,400 tons per year. Molecular chlorine increases more tropospheric ozone than hyp...

  20. Toxicity of chlorine to zebrafish embryos

    PubMed Central

    Kent, Michael L.; Buchner, Cari; Barton, Carrie; Tanguay, Robert L.

    2014-01-01

    Surface disinfection of fertilized fish eggs is widely used in aquaculture to reduce extraovum pathogens that may be released from brood fish during spawning, and this is routinely used in zebrafish (Danio rerio) research laboratories. Most laboratories use approximately 25 – 50 ppm unbuffered chlorine solution for 5 – 10 min. Treatment of embryos with chlorine has significant germicidal effects for many Gram-negative bacteria, viruses, and trophozoite stages of protozoa, it has reduced efficacy against cyst or spore stages of protozoa and certain Mycobacterium spp. Therefore, we evaluated the toxicity of unbufferred and buffered chlorine solution to embryos exposed at 6 or 24 hours post-fertilization (hpf) to determine if higher concentrations can be used for treating zebrafish embryos. Most of our experiments entailed using an outbred line (5D), with both mortality and malformations as endpoints. We found that 6 hpf embryos consistently were more resistant than 24 hpf embryos to the toxic effects of chlorine. Chlorine is more toxic and germicidal at lower pHs, and chlorine causes elevated pH. Consistent with this, we found that unbufferred chlorine solutions (pH ca 8–9) were less toxic at corresponding concentrations than solutions buffered to pH 7. Based on our findings here, we recommend treating 6 hpf embryos for 10 min and 24 hpf for 5 min with unbuffered chlorine solution at 100 ppm. One trial indicated that AB fish, a popular outbred line, are more susceptible to toxicity than 5Ds. This suggests that variability between zebrafish lines occurs, and researchers should evaluate each line or strain under their particular laboratory conditions for selection of the optimum chlorine treatment procedure. PMID:24429474

  1. Efficacy of chlorine dioxide mouthwash against halitosis

    NASA Astrophysics Data System (ADS)

    Bestari, M. D.; Sunarto, H.; Kemal, Y.

    2017-08-01

    To ascertain the effectiveness of using chlorine dioxide mouthwash in addressing halitosis. Forty people were divided equally into the test group (required to gargle with mouthwash containing chlorine dioxide) and the control group (required to gargle with aquadest). The volatile sulfur compound (VSC) and organoleptic scores were measured before gargling and 30 min, 2 h, 4 h, and 6 h after. The Wilcoxon test analysis showed a significant difference (p<0.05) in the mean value of VSC scores between the test group and the control group in four testing periods after gargling. Chlorine dioxide mouthwash is effective in addressing halitosis.

  2. Plasma Processing Of Hydrocarbon

    SciTech Connect

    Grandy, Jon D; Peter C. Kong; Brent A. Detering; Larry D. Zuck

    2007-05-01

    The Idaho National Laboratory (INL) developed several patented plasma technologies for hydrocarbon processing. The INL patents include nonthermal and thermal plasma technologies for direct natural gas to liquid conversion, upgrading low value heavy oil to synthetic light crude, and to convert refinery bottom heavy streams directly to transportation fuel products. Proof of concepts has been demonstrated with bench scale plasma processes and systems to convert heavy and light hydrocarbons to higher market value products. This paper provides an overview of three selected INL patented plasma technologies for hydrocarbon conversion or upgrade.

  3. Hydrocarbon toxicity: A review.

    PubMed

    Tormoehlen, L M; Tekulve, K J; Nañagas, K A

    2014-06-01

    Clinical effects of hydrocarbon exposure have been reported since 1897. These substances are ubiquitous, and their exposures are common. The specific hydrocarbon and route of exposure will determine the clinical effect, and an understanding of this is helpful in the care of the hydrocarbon-exposed patient. To complete a comprehensive review of the literature on hydrocarbon toxicity and summarize the findings. Relevant literature was identified through searches of Medline (PubMed/OVID) and Cochrane Library databases (inclusive of years 1975-2013), as well as from multiple toxicology textbooks. Bibliographies of the identified articles were also reviewed. Search terms included combinations of the following: hydrocarbons, inhalants, encephalopathy, coma, cognitive deficits, inhalant abuse, huffing, sudden sniffing death, toluene, renal tubular acidosis, metabolic acidosis, arrhythmia, dermatitis, and aspiration pneumonitis. All pertinent clinical trials, observational studies, and case reports relevant to hydrocarbon exposure and published in English were reviewed. Chronic, occupational hydrocarbon toxicity was not included. Exposure to hydrocarbons occurs through one of the following routes: inhalation, ingestion with or without aspiration, or dermal exposure. Inhalational abuse is associated with central nervous system depression, metabolic acidosis, and arrhythmia. The exact mechanism of the CNS depression is unknown, but experimental evidence suggests effects on NMDA, dopamine, and GABA receptors. Chronic toluene inhalation causes a non-anion gap metabolic acidosis associated with hypokalemia. Halogenated hydrocarbon abuse can cause a fatal malignant arrhythmia, termed "sudden sniffing death". Individuals who regularly abuse hydrocarbons are more likely to be polysubstance users, exhibit criminal or violent behavior, and develop memory and other cognitive deficits. Heavy, long-term use results in cerebellar dysfunction, encephalopathy, weakness, and dementia

  4. Solvent dewaxing waxy hydrocarbon oils using dewaxing aid

    SciTech Connect

    Komine, K.; Naito, T.; Ohashi, F.; Onodera, T.

    1982-02-16

    In a solvent dewaxing process wherein a waxy hydrocarbon oil is mixed with a dewaxing aid and dewaxing solvent and chilled to form a slurry comprising solid particles of wax and a mixture of dewaxed oil and solvent, the improvement which comprises using a polymeric dewaxing aid comprising a condensation product of naphthalene and chlorinated wax having an average molecular weight ranging from about 20,000 to 500,000 and a molecular weight distribution exceeding the range of from about 10,000 to 1 ,000,000.

  5. Kidney cancer and hydrocarbon exposures among petroleum refinery workers.

    PubMed Central

    Poole, C; Dreyer, N A; Satterfield, M H; Levin, L; Rothman, K J

    1993-01-01

    To evaluate the hypothesis of increased kidney cancer risk after exposure to hydrocarbons, especially those present in gasoline, we conducted a case-control study in a cohort of approximately 100,000 male refinery workers from five petroleum companies. A review of 18,323 death certificates identified 102 kidney cancer cases, to each of whom four controls were matched by refinery location and decade of birth. Work histories, containing an average of 15.7 job assignments per subject, were found for 98% of the cases and 94% of the controls. To each job, industrial hygienists assigned semiquantitative ratings for the intensity and frequency of exposures to three hydrocarbon categories: nonaromatic liquid gasoline distillates, aromatic hydrocarbons, and the more volatile hydrocarbons. Ratings of "present" or "absent" were assigned for seven additional exposures: higher boiling hydrocarbons, polynuclear aromatic hydrocarbons, asbestos, chlorinated solvents, ionizing radiation, and lead. Each exposure had either no association or a weak association with kidney cancer. For the hydrocarbon category of principal a priori interest, the nonaromatic liquid gasoline distillates, the estimated relative risk (RR) for any exposure above refinery background was 1.0 (95% confidence interval [CI] 0.5-1.9). Analyses of cumulative exposures and of exposures in varying time periods before kidney cancer occurrence also produced null or near-null results. In an analysis of the longest job held by each subject (average duration 9.2 years or 40% of the refinery work history), three groups appeared to be at increased risk: laborers (RR = 1.9, 95% CI 1.0-3.9); workers in receipt, storage, and movements (RR = 2.5, 95% CI 0.9-6.6); and unit cleaners (RR = 2.3, 95% CI 0.5-9.9). PMID:8020449

  6. Kidney cancer and hydrocarbon exposures among petroleum refinery workers

    SciTech Connect

    Poole, C.; Dreyer, N.A.; Satterfield, M.H.; Levin, L.

    1993-12-01

    To evaluate the hypothesis of increased kidney cancer risk after exposure to hydrocarbons, especially those present in gasoline, we conducted a case-control study in a cohort of approximately 100,000 male refinery workers from five petroleum companies. A review of 18,323 death certificates identified 102 kidney cancer cases, to each of whom four controls were matched by refinery location and decade of birth. Work histories, containing an average of 15.7 job assignments per subject, were found for 98% of the cases and 94% of the controls. Tb each job, industrial hygienists assigned semiquantitative ratings for the intensity and frequency of exposures to three hydrocarbon categories: nonaromatic liquid gasoline distillates, aromatic hydrocarbons, and the more volatile hydrocarbons. Ratings of {open_quotes}present{close_quotes} or {open_quotes}absent{close_quotes} were assigned for seven additional exposures: higher boiling hydrocarbons, polynuclear aromatic hydrocarbons, asbestos, chlorinated solvents, ionizing radiation, and lead. Each exposure had either no association or a weak association with kidney cancer. For the hydrocarbon category of principal a priori interest, the nonaromatic liquid gasoline distillates, the estimated relative risk (RR) for any exposure above refinery background was 1.0 (95% confidence interval [CI] 0.5-1.9). Analyses of cumulative exposures and of exposures in varying time periods before kidney cancer occurrence also produced null or near-null results. In an analysis of the longest job held by each subject (average duration 9.2 years or 40% of the refiner&y work history), three groups appeared to be at increased risk: laborers (RR = 1.9,95% CI 1.0-3.9); workers in receipt, storage, and movements (RR = 2.5,95% CI 0.9-6.6); and unit cleaners (RR = 2.3, 95% CI 0.5-9.9). 53 refs., 7 tabs.

  7. Chlorine isn't Just for Swimming Pools Anymore... Chlorination of Organic Compounds in the Arctic

    NASA Astrophysics Data System (ADS)

    Han, A.; Raab, T. K.

    2013-12-01

    The cycling of chlorine between its organic and inorganic forms is known to occur in forest soils, but little is known about the generality of this mechanism, which soil components chlorine attaches to, and at what rate chlorination occurs. The study uses peat-rich tundra soils from Barrow, Alaska varying in age since formation of 50 yrs - 5500 yrs BP, and seeks to measure the rate at which organic molecules are chlorinated and to understand what changes those molecules undergo once chlorinated. Soil abundance of chlorine and bromine was estimated in soils of varying age using X-ray fluorescence, and org-Cl levels were measured using pyro-hydrolysis [Table 1]. We considered activity of the enzyme Chloroperoxidase, and data was gathered using absorbance scans of the organic molecule monochlorodimedone to determine whether it had been chlorinated and if so, at what rate. Additional information was gathered from the chlorination of small organic components of the macromolecule lignin, whose constituent molecules make up a large portion of humic materials critical to soil health, through emission scans and fluorescence scans. The results showed that the enzyme chloroperoxidase, which is found in nature and is associated with fungi or bacteria, attaches a chlorine atom to monochlorodimedone and that similar enzymes found in Arctic soils act on it, as well as the lignin model subunits cinnamaldehyde ((2E)-3-phenylprop-2-enal) and naringenin-7-rhamnoglucoside. The results may provide more information on chlorination rates in the Arctic and may contribute to an understanding of how and at what rate chlorine changes form in nature, and answer questions about ozone deterioration or anthropogenic chlorine impact(s) on the environment.Average Halogen Abundance in Arctic Soils xrf=Energy Dispersive X-Ray Fluorescencepyro= TOX Pyro-Hydrolysis

  8. Edge chlorination of hexa-peri-hexabenzocoronene investigated by density functional theory and vibrational spectroscopy.

    PubMed

    Maghsoumi, Ali; Narita, Akimitsu; Dong, Renhao; Feng, Xinliang; Castiglioni, Chiara; Müllen, Klaus; Tommasini, Matteo

    2016-04-28

    We investigate the molecular structure and vibrational properties of perchlorinated hexa-peri-hexabenzocoronene (HBC-Cl) by density functional theory (DFT) calculations and IR and Raman spectroscopy, in comparison to the parent HBC. The theoretical and experimental IR and Raman spectra demonstrated very good agreement, elucidating a number of vibrational modes corresponding to the observed peaks. Compared with the parent HBC, the edge chlorination significantly alters the planarity of the molecule. Nevertheless, the results indicated that such structural distortion does not significantly impair the π-conjugation of such polycyclic aromatic hydrocarbons.

  9. Inactivation of simian rotavirus SA11 by chlorine, chlorine dioxide, and monochloramine.

    PubMed Central

    Berman, D; Hoff, J C

    1984-01-01

    The kinetics of inactivation of simian rotavirus SA11 by chlorine, chlorine dioxide, and monochloramine were studied at 5 degrees C with a purified preparation of single virions and a preparation of cell-associated virions. Inactivation of the virus preparations with chlorine and chlorine dioxide was studied at pH 6 and 10. The monochloramine studies were done at pH 8. With 0.5 mg of chlorine per liter at pH 6, more than 4 logs (99.99%) of the single virions were inactivated in less than 15 s. Both virus preparations were inactivated more rapidly at pH 6 than at pH 10. With chlorine dioxide, however, the opposite was true. Both virus preparations were inactivated more rapidly at pH 10 than at pH 6. With 0.5 mg of chlorine dioxide per liter at pH 10, more than 4 logs of the single-virus preparation were inactivated in less than 15 s. The cell-associated virus was more resistant to inactivation by the three disinfectants than was the preparation of single virions. Chlorine and chlorine dioxide, each at a concentration of 0.5 mg/liter and at pH 6 and 10, respectively, inactivated 99% of both virus preparations within 4 min. Monochloramine at a concentration of 10 mg/liter and at pH 8 required more than 6 h for the same amount of inactivation. Images PMID:6091546

  10. Process for preparing hydrocarbons

    SciTech Connect

    Breuker, J.H.; De H.H.; Kwant, P.B.

    1980-01-15

    A process for preparing light distillate fractions and medicinal oil from heavy hydrocarbon oils comprises two-stage hydrocracking, fractionation distillation and catalytic hydrotreatment of at least part of the fractionation residue.

  11. Behavior of chlorine during coal pyrolysis

    USGS Publications Warehouse

    Shao, D.; Hutchinson, E.J.; Cao, H.; Pan, W.-P.; Chou, C.-L.

    1994-01-01

    The behavior of chlorine in Illinois coals during pyrolysis was evaluated by combined thermo-gravimetry-Fourier transform infrared spectroscopy-ion chromatography (TG-FTIR-IC) techniques. It was found that more than 90% of chlorine in Illinois coals (IBC-103, 105, 106, and 109) was liberated as HCl gas during pyrolysis from 300 to 600??C, with the rate reaching a maximum at 440 ??C. Similarity of the HCl and NH3 release profiles during pyrolysis of IBC-109 supports the hypothesis that the chlorine in coal may be associated with nitrogen and the chlorine is probably bonded to the basic nitrogen sites on the inner walls of coal micropores. ?? 1994 American Chemical Society.

  12. Ozone depletion and chlorine loading potentials

    NASA Technical Reports Server (NTRS)

    Pyle, John A.; Wuebbles, Donald J.; Solomon, Susan; Zvenigorodsky, Sergei; Connell, Peter; Ko, Malcolm K. W.; Fisher, Donald A.; Stordal, Frode; Weisenstein, Debra

    1991-01-01

    The recognition of the roles of chlorine and bromine compounds in ozone depletion has led to the regulation or their source gases. Some source gases are expected to be more damaging to the ozone layer than others, so that scientific guidance regarding their relative impacts is needed for regulatory purposes. Parameters used for this purpose include the steady-state and time-dependent chlorine loading potential (CLP) and the ozone depletion potential (ODP). Chlorine loading potentials depend upon the estimated value and accuracy of atmospheric lifetimes and are subject to significant (approximately 20-50 percent) uncertainties for many gases. Ozone depletion potentials depend on the same factors, as well as the evaluation of the release of reactive chlorine and bromine from each source gas and corresponding ozone destruction within the stratosphere.

  13. Liquid-phase chlorination of perchloroethylene

    SciTech Connect

    Levanova, S.V.; Evstigneev, O.V.; Rodova, R.M.; Berlin, E.R.; Ul'yanov, A.A.

    1988-06-01

    The relationships in the liquid-phase chlorination of perchloroethylene to hexachlorethane in a thermal process and in the presence of an initiator have been studied. The rate constants and the activation parameters of the process have been determined.

  14. Chlorine Salts at the Phoenix Landing Site

    NASA Astrophysics Data System (ADS)

    Hanley, J.; Horgan, B.

    2016-09-01

    Although chlorine salts (perchlorates, chlorides) are known to exist at the Phoenix landing site, their distribution and type have not been positively identified yet. We look for these salts through a novel NIR remote sensing technique.

  15. Innovative Technologies for Chlorinated Solvent Remediation

    NASA Astrophysics Data System (ADS)

    Pennell, Kurt D.; Cápiro, Natalie L.

    2014-07-01

    The following sections are included: * INTRODUCTION * TRADITIONAL REMEDIATION TECHNOLOGIES (1980s) * RESEARCH AND DEVELOPMENT OF INNOVATIVE REMEDIATION TECHNOLOGIES (1990s-2000s) * CURRENT TRENDS IN CHLORINATED SOLVENT REMEDIATION (2010s) * CLOSING THOUGHTS * REFERENCES

  16. Membrane separation of hydrocarbons

    DOEpatents

    Funk, Edward W.; Kulkarni, Sudhir S.; Chang, Y. Alice

    1986-01-01

    Mixtures of heavy oils and light hydrocarbons may be separated by passing the mixture over a polymeric membrane which comprises a polymer capable of maintaining its integrity in the presence of hydrocarbon compounds at temperature ranging from about ambient to about 100.degree. C. and pressures ranging from about 50 to about 1000 psi. The membranes which possess pore sizes ranging from about 10 to about 500 Angstroms are cast from a solvent solution and recovered.

  17. Imidazole catalyzes chlorination by unreactive primary chloramines.

    PubMed

    Roemeling, Margo D; Williams, Jared; Beckman, Joseph S; Hurst, James K

    2015-05-01

    Hypochlorous acid and simple chloramines (RNHCl) are stable biologically derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated--loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case N-α-acetylhistidine chloramine (NAHCl) did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl(+)) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl(+)). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second-order reaction to give 3'-monochloro and 3',5'-dichloro products. Equilibrium constants for the transchlorination reactions HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants on [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl(+); consistent with this interpretation, MeIm markedly catalyzed

  18. Imidazole catalyzes chlorination by unreactive primary chloramines

    PubMed Central

    Roemeling, Margo D.; Williams, Jared; Beckman, Joseph S.; Hurst, James K.

    2015-01-01

    Hypochlorous acid and simple chloramines (RNHCl) are stable biologically-derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated—loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case NAHCl did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl+) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl+). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second order reaction to give 3′-monochloro and 3′,5′-dichloro products. Equilibrium constants for the transchlorination reactions: HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants upon [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl+; consistent with this interpretation, MeIm markedly catalyzed fluorescein chlorination by HOCl

  19. Stratospheric chlorine: Blaming it on nature

    SciTech Connect

    Taube, G.

    1993-06-11

    Much of the bitter public debate over ozone depletion has centered on the claim that chlorofluorocarbons (CFCs) pale into insignificance alongside natural sources of chlorine in the stratosphere. If so, goes the argument, chlorine could not be depleting ozone as atmospheric scientists claim, because the natural sources have been around since time immemorial, and the ozone layer is still there. The claim, put forward in a book by Rogelio Maduro and Ralf Schauerhammer, has since been touted by former Atomic Energy Commissioner Dixy Lee Ray and talk-show host Rush Limbaugh, and it forms the basis of much of the backlash now being felt by atmospheric scientists. The argument is simple: Maduro and Schauerhammer calculate that 600 million tons of chlorine enters the atmosphere annually from seawater, 36 million tons from volcanoes, 8.4 million tons from biomass burning, and 5 million tons from ocean biota. In contrast, CFCs account for a mere 750,000 tons of atmospheric chlorine a year. Besides disputing the numbers, scientists have both theoretical and observational bases for doubting that much of this chlorine is getting into the stratosphere, where it could affect the ozone layer. Linwood Callis of the National Aeronautics and Space Administration's (NASA) Langley Research Center points out one crucial problem with the argument: Chlorine from natural sources is soluble, and so it gets rained out of the lower atmosphere. CFCs, in contrast, are insoluble and inert and thus make it to the stratosphere to release their chlorine. What's more, observations of stratospheric chemistry don't support the idea that natural sources are contributing much to the chlorine there.

  20. Chlorinated and nonchlorinated compounds from the pyrolysis and combustion of polychloroprene.

    PubMed

    Aracil, Ignacio; Font, Rafael; Conesa, Juan A

    2010-06-01

    Thermal decomposition of polychloroprene was studied under inert and oxidative atmospheres at temperatures of 500 and 850 degrees C in a horizontal quartz tubular laboratory reactor in order to determine the products generated. More than two hundred compounds, mainly aromatic hydrocarbons, were identified and quantified, with special focus on chlorinated aromatic compounds, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), chlorobenzenes (CBzs) and chlorophenols (CPhs). The results showed that pyrolysis of polychloroprene at high temperatures leaded to the formation of many aromatic hydrocarbons in high yields. In addition, the yields of total PCDD/Fs in the combustion experiment at 850 degrees C were more than three hundred times higher than those from pyrolysis at the same temperature. Results were also compared with those obtained in a previous work for polyvinyl chloride under similar operating conditions.

  1. Chemistry of saline-water chlorination

    SciTech Connect

    Haag, W.R.

    1981-06-01

    Vast quantities of natural waters are used by power plants for cooling purposes. This water is chlorinated to prevent slime build-up inside the cooling pipes, is circulated through the cooling system, and eventually discharged back into the water body. In order to assess the environmental impact of water chlorination, it is necessary to know what chemical compounds are produced and discharged into the receiving waters. To attack this problem, a review of the present state of knowledge of natural water chlorination chemistry was performed, and some experimental work explained the results of previous workers by showing that chlorine losses at very high doses in seawater are simply the result of chlorate and bromate formation which, however, is negligible at normal doses. The most important chlorine-produced oxidants, along with the relevant chemical reactions, were chosen as a basis for a kinetic model of saline water chlorination chemistry. Kinetic data were compiled in a computer program which simultaneously solves 24 differential equations, one for each species modelled. Estimates were made for the unknown rate constants. A purely predictive model was not possible due to the great variability in the organic demand; however, the model is applicable under a broad variety of conditions (except sunlight), and it provides a reasonably good description of a halamine chemistry under environmental conditions.

  2. New model of chlorine-wall reaction for simulating chlorine concentration in drinking water distribution systems.

    PubMed

    Fisher, Ian; Kastl, George; Sathasivan, Arumugam

    2017-08-30

    Accurate modelling of chlorine concentrations throughout a drinking water system needs sound mathematical descriptions of decay mechanisms in bulk water and at pipe walls. Wall-reaction rates along pipelines in three different systems were calculated from differences between field chlorine profiles and accurately modelled bulk decay. Lined pipes with sufficiently large diameters (>500 mm) and higher chlorine concentrations (>0.5 mg/L) had negligible wall-decay rates, compared with bulk-decay rates. Further downstream, wall-reaction rate consistently increased (peaking around 0.15 mg/dm(2)/h) as chlorine concentration decreased, until mass-transport to the wall was controlling wall reaction. These results contradict wall-reaction models, including those incorporated in the EPANET software, which assume wall decay is of either zero-order (constant decay rate) or first-order (wall-decay rate reduces with chlorine concentration). Instead, results are consistent with facilitation of the wall reaction by biofilm activity, rather than surficial chemical reactions. A new model of wall reaction combines the effect of biofilm activity moderated by chlorine concentration and mass-transport limitation. This wall reaction model, with an accurate bulk chlorine decay model, is essential for sufficiently accurate prediction of chlorine residuals towards the end of distribution systems and therefore control of microbial contamination. Implementing this model in EPANET-MSX (or similar) software enables the accurate chlorine modelling required for improving disinfection strategies in drinking water networks. New insight into the effect of chlorine on biofilm can also assist in controlling biofilm to maintain chlorine residuals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. In situ thermally enhanced biodegradation of petroleum fuel hydrocarbons and halogenated organic solvents

    DOEpatents

    Taylor, R.T.; Jackson, K.J.; Duba, A.G.; Chen, C.I.

    1998-05-19

    An in situ thermally enhanced microbial remediation strategy and a method for the biodegradation of toxic petroleum fuel hydrocarbon and halogenated organic solvent contaminants are described. The method utilizes nonpathogenic, thermophilic bacteria for the thermal biodegradation of toxic and carcinogenic contaminants, such as benzene, toluene, ethylbenzene and xylenes, from fuel leaks and the chlorinated ethenes, such as trichloroethylene, chlorinated ethanes, such as 1,1,1-trichloroethane, and chlorinated methanes, such as chloroform, from past solvent cleaning practices. The method relies on and takes advantage of the pre-existing heated conditions and the array of delivery/recovery wells that are created and in place following primary subsurface contaminant volatilization efforts via thermal approaches, such as dynamic underground steam-electrical heating. 21 figs.

  4. In situ thermally enhanced biodegradation of petroleum fuel hydrocarbons and halogenated organic solvents

    DOEpatents

    Taylor, Robert T.; Jackson, Kenneth J.; Duba, Alfred G.; Chen, Ching-I

    1998-01-01

    An in situ thermally enhanced microbial remediation strategy and a method for the biodegradation of toxic petroleum fuel hydrocarbon and halogenated organic solvent contaminants. The method utilizes nonpathogenic, thermophilic bacteria for the thermal biodegradation of toxic and carcinogenic contaminants, such as benzene, toluene, ethylbenzene and xylenes, from fuel leaks and the chlorinated ethenes, such as trichloroethylene, chlorinated ethanes, such as 1,1,1-trichloroethane, and chlorinated methanes, such as chloroform, from past solvent cleaning practices. The method relies on and takes advantage of the pre-existing heated conditions and the array of delivery/recovery wells that are created and in place following primary subsurface contaminant volatilization efforts via thermal approaches, such as dynamic underground steam-electrical heating.

  5. Chlorine Abundances in Cool Stars

    NASA Astrophysics Data System (ADS)

    Maas, Z. G.; Pilachowski, C. A.; Hinkle, K.

    2016-12-01

    Chlorine abundances are reported in 15 evolved giants and 1 M dwarf in the solar neighborhood. The Cl abundance was measured using the vibration-rotation 1-0 P8 line of H35Cl at 3.69851 μm. The high-resolution L-band spectra were observed using the Phoenix infrared spectrometer on the Kitt Peak Mayall 4 m telescope. The average [35Cl/Fe] abundance in stars with -0.72 < [Fe/H] < 0.20 is [35Cl/Fe] = (-0.10 ± 0.15) dex. The mean difference between the [35Cl/Fe] ratios measured in our stars and chemical evolution model values is (0.16 ± 0.15) dex. The [35Cl/Ca] ratio has an offset of ˜0.35 dex above model predictions, suggesting that chemical evolution models are underproducing Cl at the high metallicity range. Abundances of C, N, O, Si, and Ca were also measured in our spectral region and are consistent with F and G dwarfs. The Cl versus O abundances from our sample match Cl abundances measured in planetary nebula and H ii regions. In one star where both H35Cl and H37Cl could be measured, a 35Cl/37Cl isotope ratio of 2.2 ± 0.4 was found, consistent with values found in the Galactic ISM and predicted chemical evolution models.

  6. Atmospheric reactivity of alcohols, thiols and fluoroalcohols with chlorine atoms

    NASA Astrophysics Data System (ADS)

    Garzon Ruiz, Andres

    Alcohols, thiols and fluoroalcohols are volatile organic compounds (VOCs) which are emitted to the atmosphere from both natural (vegetation, oceans, volcanoes, etc.) and anthropogenic sources (fuels, solvents, wastewater, incinerators, refrigerants, etc.). These pollutants can be eliminated from the troposphere by deposition on the terrestrial surface, direct photolysis or reaction with different tropospheric oxidants. Reactions of VOCs with tropospheric oxidants are involved in the well-known atmospheric phenomenon of photochemical smog or the production of tropospheric ozone. The oxidation of these VOCs in the troposphere is mainly initiated by reaction with OH radicals during the daytime and with NO radicals at night. However, in recent years, the oxidation by chlorine atoms (Cl) has gained great importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments. In general, Cl atoms are much more reactive species than OH and NO; radicals and therefore low concentrations of Cl may compete with OH and NO3 in hydrocarbon oxidation processes. The main source of tropospheric Cl atoms is believed to be the photolysis of chlorine-containing molecules generated by heterogeneous reactions of sea salt aerosols. It has also been proposed that Cl atoms, produced in the photolysis of Cl2 emitted from industrial processes, may enhance hydrocarbon oxidation rates and ozone production in urban environments. In this work, a kinetic, theoretical and mechanistic study of the reaction of several alcohols, thiols, and fluoroalcohols with Cl atoms has been carried out. Pulsed laser photolysis-fluorescence resonance (PLP-RF) technique was used for the kinetic study as a function of temperature and pressure. An environmental chamber-Fourier transform infrared (FTIR) system was also employed in the kinetic studies. Tropospheric lifetimes of these pollutants were estimated using obtained kinetic

  7. Effects of chlorine and chlorine dioxide on human rotavirus infectivity and genome stability.

    PubMed

    Xue, Bin; Jin, Min; Yang, Dong; Guo, Xuan; Chen, Zhaoli; Shen, Zhiqiang; Wang, Xinwei; Qiu, Zhigang; Wang, Jingfeng; Zhang, Bin; Li, Junwen

    2013-06-15

    Despite the health risks posed by waterborne human rotavirus (HRV), little information is available concerning the effectiveness of chlorine or chlorine dioxide (ClO2), two common disinfectants of public water sources, against HRV and their effects on its genome remain poorly understood. This study investigated the effects of chlorine and ClO2 on purified HRV by using cell culture and RT-PCR to assess virus infectivity and genetic integrity, respectively. The disinfection efficacy of ClO2 was found to be higher than that of chlorine. According to the efficiency factor Hom model, Ct value (mg/L min) ranges required for a 4-log reduction of HRV at 20 °C by chlorine and ClO2 were 5.55-5.59 and 1.21-2.47 mg/L min, respectively. Detection of the 11 HRV genome segments revealed that damage to the 1227-2354 bp of the VP4 gene was associated with the disappearance of viral infectivity by chlorine. However, no complete accordance between culturing and RT-PCR assays was observed after treatment of HRV with ClO2. These results collectively indicate that the current practice of chlorine disinfection may be inadequate to manage the risk of waterborne HRV infection, and offer the potential to monitor the infectivity of HRV adapting PCR-based protocols in chlorine disinfection.

  8. Rapeseed lecithin hydroxylation by chlorine replacing with hydroxyl groups in chlorinated phospholipids.

    PubMed

    Górecki, Michał; Sosada, Marian; Boryczka, Monika; Fraś, Pawel; Pasker, Beata

    2012-01-01

    Rapeseed lecithin ethanol soluble fraction (LESF) was hydroxylated with 30% hydrogen peroxide in the presence of acetic acid. The product was compared to the one obtained by method based on nucleophilic substitution reaction of phospholipids chlorine derivatives. In this approach, hydrogen chloride was added to double bonds in unsaturated acyl groups of phospholipids. Next, chlorine was replaced with hydroxyl groups via the alkaline hydrolysis of chlorine derivatives. The surface active properties of the products obtained with the usage of two methods of rapeseed LESF hydroxylation were determined. The minimal surface tension (eta(min), mN/m) and the critical micelle concentration (CMC, g/L) of LESF hydroxylated with hydrogen peroxide (20.2 mN/m, 6.0 g/L) and obtained by chlorine replacing with hydroxyl groups in chlorinated phospholipids (25.0 mN/m, 9.8 g/L) were compared to LESF (31.8 mN/m, 17.8 g/L). Hydroxylated LESF obtained by lecithin chlorination and chlorine replacing with hydroxyl groups in the chlorine derivatives has no peroxides and the good surface active properties. The product as an effective emulsifier can be used in pharmacy and cosmetics.

  9. Bromate ion formation in dark chlorination and ultraviolet/chlorination processes for bromide-containing water.

    PubMed

    Huang, Xin; Gao, Naiyun; Deng, Yang

    2008-01-01

    Bormate (BrO3(-)) is a carcinogenic chemical produced in ozonation or chlorination of bromide-containing water. Although its formation in seawater with or without sunlight has been previously investigated, the formation of bromate in dilute solutions, particularly raw water for water treatment plant, is unknown. In this article, the results of bench scale tests to measure the formation rates of bromate formation in dilute solutions, including de-ionized water and raw water from Yangtze River, were presented in dark chlorination and ultraviolet (UV)/chlorination processes. And the effects of initial pH, initial concentration of NaOCl, and UV light intensity on bromate formation in UV/chlorination of the diluted solutions were investigated. Detectable bromate was formed in dark chlorination of the two water samples with a relatively slow production rate. Under routine disinfecting conditions, the amount of formed bromate is not likely to exceed the national standards (10 microg/L). UV irradiation enhanced the decay of free chlorine, and, simultaneously, 6.6%--32% of Br was oxidized to BrO3(-). And the formation of bromate exhibited three stages: rapid stage, slow stage and plateau. Under the experimental conditions (pH = 4.41--11.07, Ccl2 = 1.23--4.50 mg/L), low pH and high chlorine concentration favored the generation of bromate. High light intensity promoted the production rate of bromate, but decreased its total generation amount due to acceleration of chlorine decomposition.

  10. Effect of UV irradiation on the proportion of organic chloramines in total chlorine in subsequent chlorination.

    PubMed

    Zhang, Tian-Yang; Lin, Yi-Li; Xu, Bin; Xia, Sheng-Ji; Tian, Fu-Xiang; Gao, Nai-Yun

    2016-02-01

    This study investigated the changes of chlorine species and proportion of organic chloramines during the chlorination process after UV irradiation pretreatment in drinking water. It was found that the UV pretreatment could enhance the percentage of organic chloramines by increasing free chlorine consumption in the chlorination of raw waters. The percentage of organic chloramines in total chlorine increased with UV intensity and irradiation time in raw waters. However, for the humic acid synthesized water, the percentage of organic chloramines increased first and then decreased with the increase of UV irradiation time. The value of SUVA declined in both raw and humic acid synthesized waters over the UV irradiation time, which indicated that the decomposition of aromatic organic matter by UV could be a contributor to the increase of free chlorine consumption and organic chloramine proportion. The percentage of organic chloramines during chlorination of raw waters after 30-min UV irradiation pretreatment varied from 20.2% to 41.8%. Total chlorine decreased obviously with the increase of nitrate concentration, but the percentage of organic chloramines increased and was linearly correlated to nitrate concentration.

  11. Chlorine dioxide treatment for zebra mussel control

    SciTech Connect

    Rybarik, D.; Byron, J.; Germer, M.

    1995-06-01

    Chlorine is recognized and commonly used biocide for power plant cooling water and service water treatment programs, including the control of zebra mussels. Chlorine dioxide has recently become a popular method of zebra mussel control because of its economy, safety, environmental acceptability, and effectiveness when compared to other mussel control methods. This control technique was recently demonstrated at Dairyland Power Cooperative`s Alma Generating Station on the east bank of the upper Mississippi River in Alma, Wisconsin. The project was assisted with EPRI Tailored Collaboration Program funds. The Dairyland Power Alam Generating Station consists of five generating units that utilize raw, untreated Mississippi River water for condenser, circulating, and service water supplies. The first units were built in 1947, with the final and largest unit being completed in 1960. Total station generating capacity is 200 MW. Because of recent increases in the zebra mussel density at the station intake, Dairyland Power selected the team of Nalco and Rio Linda to perform a chlorine dioxide treatment of the station`s new water systems to eradicate and control the mussels before their presence created operational difficulties. This paper will present the results of the treatment including treatment theory, design and construction of the treatment system, the method of chlorine dioxide generation, treatment concentration, analytical methods o monitoring chlorine dioxide generation, residuals and trihalomethane (THM) concentrations, protocol for monitoring treatment mortality, and the effects of chlorine dioxide and detoxification on other water chemistry parameters and equipment materials. The goal of this paper is to inform and assist users with establishing consistent and uniform practices for safely utilizing and monitoring chlorine dioxide in the eradication and control of zebra mussels.

  12. Stability and bactericidal activity of chlorine solutions.

    PubMed

    Rutala, W A; Cole, E C; Thomann, C A; Weber, D J

    1998-05-01

    To determine the stability of sodium hypochlorite (diluted household bleach) when stored for 30 days in various types of containers and to determine the efficacy of low concentrations of free available chlorine to inactivate test bacteria. Laboratory-based study. Solutions of standard household bleach were prepared using tap water or sterile distilled water at dilutions of 1:100, 1:50, and 1:5. Chlorine concentrations were measured, and then the solutions were placed into five polyethylene containers and left at room temperature (20 degrees C) under various conditions (translucent containers with light exposure and with or without air; brown opaque container without light or air exposure). Samples for chlorine and pH determinations were taken at time 0 and on days 7, 14, 21, 30, and 40. Bactericidal activity of chlorine solutions was assessed using the Association of Official Analytical Chemists Use-Dilution Method. Test bacteria included Pseudomonas aeruginosa, Staphylococcus aureus, and Salmonella choleraesuis. Chlorine concentrations at 30 days varied from the 40% to 50% range for 1:50 or 1:100 dilutions stored in containers other than closed brown containers to 83% to 85% for the 1:5 dilution stored in closed but non-opaque containers to 97% to 100% for 1:50 or 1:5 solutions stored in closed brown containers. The lowest concentration of sodium hypochlorite solution that reliably inactivated all the test organisms was 100 ppm. These data suggest that chlorine solutions do not need to be prepared fresh daily, as is recommended currently, and the lowest concentration of chlorine that reliably inactivates S aureus, S choleraesuis, and P aeruginosa is 100 ppm.

  13. Water chlorination: An enigma for modern-day environmental chemists

    SciTech Connect

    Johnson, J.D.; Jolley, R.L.

    1987-01-01

    The challenge of modern-day water chlorination is to reap the benefits of chlorine's excellent disinfection efficacy while minimizing its environmental impacts and byproduct toxicity. Chemists, biologists, and engineers need to work together to identify, quantify, and use most effectively the disinfectant forms of chlorine to maximize disinfection, while at the same time they also need to identify, quantify, and minimize the toxic forms of by-products produced by chlorine's reactions with the organic compounds found in water. To the extent that this is possible, we can enjoy the benefits of chlorine disinfection and minimize the human and environmental impacts of chlorination by-products. 22 refs.

  14. Influencing factors and degradation products of antipyrine chlorination in water with free chlorine.

    PubMed

    Cai, Meiquan; Zhang, Liqiu; Qi, Fei; Feng, Li

    2013-01-01

    Owing to its low cost, free chlorine is one of the most common disinfectants for wastewater and drinking water treatment. However, the formation of disinfection byproducts has been found to occur after free chlorine disinfection in recent decades. Antipyrine (ANT), an anti-inflammatory analgesic, has been frequently detected in the aquatic environment. In this work, the removal efficiency of ANT by free chlorine oxidation in ultrapure water was investigated with batch experiments. The influencing factors on the removal of ANT were explored at initial concentrations of ANT from 0.04 to 0.64 mg/L, free chlorine dosage from 0.30 to 1.31 mg/L, and pH from 1.5 to 9.0. The main degradation products were identified by solid phase extraction-gas chromatography-mass spectrometry. The results showed that ANT reacted rapidly with free chlorine in ultrapure water systems and up to 90.6% removal efficiency of ANT was achieved after 25 sec (initial free chlorine 1 mg/L, ANT 0.5 mg/L, pH 7.0). Higher oxidant dosage, lower ANT initial concentration and low pH favor the ANT removal. The main degradation product in ANT chlorination was a monochlorine substitution product (4-chloro-1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one), which can be further chlorinated by free chlorine. In addition, the total organic carbon result indicated that ANT is difficult to be mineralized using chlorine.

  15. Killing of Chlorine-Resistant Bacteria by Chlorine-Bromine Solutions

    PubMed Central

    Farkas-Himsley, H.

    1964-01-01

    The disinfective power of chlorine, bromine, and mixtures of chlorine and bromine at different ratios was compared. The influence of pH was also studied. The experiments were carried out in “purified” water and in natural waters of swimming pools, river, and sea. In the presence of high amounts of nitrogenous growth-promoting material (at neutral pH), bromine was more effective than chlorine; in waters containing low amounts of nitrogenous growth-promoting material, chlorine was found superior. Mixtures of chlorine and bromine at various ratios were found to increase in effectiveness inversely to the percentage of hypobromite generated, down to 10 or 5%. Such effectiveness was found at pH levels of 5.4 to 8.6 in both purified and natural water containing high and low amounts of nitrogenous growth-promoting material. Therefore, the above mixtures seem of practical value for the disinfection of various natural waters. Escherichia coli isolated in the presence of chlorine, either from swimming pools or after deliberate exposure to the halogen, were shown to be chlorine-resistant mutants. Their resistance was maintained for at least nine passages in the absence of the disinfectant, which accounts for the number of passages tested. Chlorine-resistant mutants were not affected by bromine alone but did show a marked sensitivity to low concentrations of bromine active in the presence of chlorine. This was achieved by admixing small amounts of bromide to hypochlorite. A hypothetical model is presented to explain the synergistic sequential block by the two disinfectants. Some chlorine-resistant mutants were found to have changed into relatively slow-growing organisms with a changed phase-sensitivity pattern. Images FIG. 2 PMID:14106934

  16. 78 FR 72633 - Chlorinated Isocyanurates From Spain: Final Results of Antidumping Duty Administrative Review...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-03

    ... International Trade Administration Chlorinated Isocyanurates From Spain: Final Results of Antidumping Duty... chlorinated isocyanurates (chlorinated isos) from Spain.\\1\\ The period of review (``POR'') is June 1, 2011... notice. \\1\\ See Chlorinated Isocyanurates from Spain: Preliminary Results of the Antidumping...

  17. Characterization and Application of a Chlorine Microelectrode for Measuring Monochloramine within a Biofilm

    EPA Science Inventory

    Chlorine microelectrodes with tip sizes of 5-15 μm were developed and used to measure biofilm monochloramine penetration profiles. The chlorine microelectrode showed response to total chlorine, including free chlorine, monochloramine, and dichloramine under various conditions. ...

  18. Characterization and Application of a Chlorine Microelectrode for Measuring Monochloramine within a Biofilm

    EPA Science Inventory

    Chlorine microelectrodes with tip sizes of 5-15 μm were developed and used to measure biofilm monochloramine penetration profiles. The chlorine microelectrode showed response to total chlorine, including free chlorine, monochloramine, and dichloramine under various conditions. ...

  19. Combined remediation technologies: results from field trials at chlorinated solvent impacted sites

    NASA Astrophysics Data System (ADS)

    O'Carroll, D. M.; Chowdhury, A. I.; Lomheim, L.; Boparai, H. K.; Weber, K.; Austrins, L. M.; Edwards, E.; Sleep, B.; de Boer, C. V.; Garcia, A. N.

    2015-12-01

    Non-aqueous phase liquids (NAPLs) are one class of waste liquids often generated from waste mixtures in industrial processes containing surfactants, chlorinated hydrocarbons and other compounds. Chlorinated solvents, a particularly persistent NAPL contaminant, frequently contaminate water sources for decades and are one of the more common contaminants at brownfield and industrialized sites. Although considerable advances in our understanding of the phenomena governing NAPL remediation have been made, and a number of innovative remediation technologies have been developed, existing technologies are rarely able to achieve clean up goals in contaminated aquifers at the completion of remedial activities. The development and pilot scale testing of new and innovative remediation technologies is, therefore, crucial to achieve clean up goals at contaminated sites. Our research group is currently investigating a number of innovative remediation technologies, either individually or as combined remedies. This includes the applicability of nanometals and ISCO (e.g., persulfate) for contaminated site remediation. These technologies can be combined with technologies to enhance amendment delivery (e.g., electrokinetics) or create conditions favorable for enhanced biotic contaminant degradation. This presentation will discuss outcomes from a number of field trials conducted at chlorinated solvent impacted sites by our group with a particular focus on combined remediation technologies.

  20. Reductive dechlorination of chlorinated alkanes and alkenes by iron metal and metal mixtures

    SciTech Connect

    Orth, R.G.; McKenzie, D.E.

    1995-12-31

    Reductive dechlorination using zero valent metals such as iron has seen an increase in interest over the past few years with the extension of iron dechlorination to in-situ treatment of ground water using a process developed by Gillham and O`Hannes in 1994. Earlier applications included the use of metals for water treatment for the degradation of halogenated pesticides. This increased interest is demonstrated by the recent ACS symposium on zero valent metal dechlorination. The work that will be presented involves the reduction of selected chlorinated alkanes and alkenes beginning with chlorobutanes. The position of the chlorines on the carbon chain relative to each other was studied by determining the rates of the dechlorination processes. These studies were carried out in seated batch reactors so that loss of the chlorinated hydrocarbons was minimized and total carbon and chloride mass balances could be obtained. The goal of the studies was to understand the mechanism of the reaction that is believed to follow metal corrosion processes involving two electron transfer reactions.

  1. Superconductivity in aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    Kubozono, Yoshihiro; Goto, Hidenori; Jabuchi, Taihei; Yokoya, Takayoshi; Kambe, Takashi; Sakai, Yusuke; Izumi, Masanari; Zheng, Lu; Hamao, Shino; Nguyen, Huyen L. T.; Sakata, Masafumi; Kagayama, Tomoko; Shimizu, Katsuya

    2015-07-01

    'Aromatic hydrocarbon' implies an organic molecule that satisfies the (4n + 2) π-electron rule and consists of benzene rings. Doping solid aromatic hydrocarbons with metals provides the superconductivity. The first discovery of such superconductivity was made for K-doped picene (Kxpicene, five benzene rings). Its superconducting transition temperatures (Tc's) were 7 and 18 K. Recently, we found a new superconducting Kxpicene phase with a Tc as high as 14 K, so we now know that Kxpicene possesses multiple superconducting phases. Besides Kxpicene, we discovered new superconductors such as Rbxpicene and Caxpicene. A most serious problem is that the shielding fraction is ⩽15% for Kxpicene and Rbxpicene, and it is often ∼1% for other superconductors. Such low shielding fractions have made it difficult to determine the crystal structures of superconducting phases. Nevertheless, many research groups have expended a great deal of effort to make high quality hydrocarbon superconductors in the five years since the discovery of hydrocarbon superconductivity. At the present stage, superconductivity is observed in certain metal-doped aromatic hydrocarbons (picene, phenanthrene and dibenzopentacene), but the shielding fraction remains stubbornly low. The highest priority research area is to prepare aromatic superconductors with a high superconducting volume-fraction. Despite these difficulties, aromatic superconductivity is still a core research target and presents interesting and potentially breakthrough challenges, such as the positive pressure dependence of Tc that is clearly observed in some phases of aromatic hydrocarbon superconductors, suggesting behavior not explained by the standard BCS picture of superconductivity. In this article, we describe the present status of this research field, and discuss its future prospects.

  2. Accumulation of chlorinated benzenes in earthworms

    SciTech Connect

    Beyer, W.N.

    1996-12-31

    Chlorinated benzenes are widespread in the environment. Hexachlorobenzene, pentachlorobenzene and all isomers of dichlorobenzenes, trichlorobenzenes, and tetrachlorobenzenes, have been detected in fish, water, and sediments from the Great Lakes. They probably entered the water as leachates from chemical waste dumps and as effluents from manufacturing. Hexachlorobenzene and pentachlorobenzene are commonly present in Herring gull (Larus argentatus) eggs from the Great Lakes, and some of the isomers of trichlorobenzene and tetrachlorobenzene are occasionally detected at low concentrations. Hexachlorobenzene, which was formerly used as a fungicide, has been the most thoroughly studied chlorinated benzene, and has been detected in many species. Its use as a fungicide in the United States was canceled in 1984. Since about 1975 hexachlorobenzene has been formed mainly in the production of chlorinated solvents. It is highly persistent in the environment and some species are poisoned by hexachlorobenzene at very low chronic dietary exposures. As little as 1 ppm in the diet of mink (Mustela vison) reduced the birth weights of young, and 5 ppm in the diet of Japanese quail (Coturnix coturnix japonica) caused slight liver damage. This paper describes a long-term (26 wk) experiment relating the concentrations of chlorinated benzenes in earthworms to length of exposure and three 8 wk experiments relating concentration to the concentration in soil the soil organic matter content, and the degree of chlorination. 20 refs., 3 figs., 1 tab.

  3. Temporal Decrease in Upper Atmospheric Chlorine

    NASA Technical Reports Server (NTRS)

    Froidevaux, L.; Livesey, N. J.; Read, W. G.; Salawitch, R. J.; Waters, J. W.; Drouin, B.; MacKenzie, I. A.; Pumphrey, H. C.; Bernath, P.; Boone, C.; Nassar, R.; Montzka, S.; Elkins, J.; Cunnold, D.; Waugh, D.

    2006-01-01

    We report a steady decrease in the upper stratospheric and lower mesospheric abundances of hydrogen chloride (HCl) from August 2004 through January 2006, as measured by the Microwave Limb Sounder (MLS) aboard the Aura satellite. For 60(deg)S to 60(deg)N zonal means, the average yearly change in the 0.7 to 0.1 hPa (approx.50 to 65 km) region is -27 +/- 3 pptv/year, or -0.78 +/- 0.08 percent/year. This is consistent with surface abundance decrease rates (about 6 to 7 years earlier) in chlorine source gases. The MLS data confirm that international agreements to reduce global emissions of ozone-depleting industrial gases are leading to global decreases in the total gaseous chlorine burden. Tracking stratospheric HCl variations on a seasonal basis is now possible with MLS data. Inferred stratospheric total chlorine (CITOT) has a value of 3.60 ppbv at the beginning of 2006, with a (2-sigma) accuracy estimate of 7%; the stratospheric chlorine loading has decreased by about 43 pptv in the 18-month period studied here. We discuss the MLS HCl measurements in the context of other satellite-based HCl data, as well as expectations from surface chlorine data. A mean age of air of approx. 5.5 years and an age spectrum width of 2 years or less provide a fairly good fit to the ensemble of measurements.

  4. Chlorine truck attack consequences and mitigation.

    PubMed

    Barrett, Anthony Michael; Adams, Peter J

    2011-08-01

    We develop and apply an integrated modeling system to estimate fatalities from intentional release of 17 tons of chlorine from a tank truck in a generic urban area. A public response model specifies locations and actions of the populace. A chemical source term model predicts initial characteristics of the chlorine vapor and aerosol cloud. An atmospheric dispersion model predicts cloud spreading and movement. A building air exchange model simulates movement of chlorine from outdoors into buildings at each location. A dose-response model translates chlorine exposures into predicted fatalities. Important parameters outside defender control include wind speed, atmospheric stability class, amount of chlorine released, and dose-response model parameters. Without fast and effective defense response, with 2.5 m/sec wind and stability class F, we estimate approximately 4,000 (half within ∼10 minutes) to 30,000 fatalities (half within ∼20 minutes), depending on dose-response model. Although we assume 7% of the population was outdoors, they represent 60-90% of fatalities. Changing weather conditions result in approximately 50-90% lower total fatalities. Measures such as sheltering in place, evacuation, and use of security barriers and cryogenic storage can reduce fatalities, sometimes by 50% or more, depending on response speed and other factors.

  5. Temporal Decrease in Upper Atmospheric Chlorine

    NASA Technical Reports Server (NTRS)

    Froidevaux, L.; Livesey, N. J.; Read, W. G.; Salawitch, R. J.; Waters, J. W.; Drouin, B.; MacKenzie, I. A.; Pumphrey, H. C.; Bernath, P.; Boone, C.; hide

    2006-01-01

    We report a steady decrease in the upper stratospheric and lower mesospheric abundances of hydrogen chloride (HCl) from August 2004 through January 2006, as measured by the Microwave Limb Sounder (MLS) aboard the Aura satellite. For 60(deg)S to 60(deg)N zonal means, the average yearly change in the 0.7 to 0.1 hPa (approx.50 to 65 km) region is -27 +/- 3 pptv/year, or -0.78 +/- 0.08 percent/year. This is consistent with surface abundance decrease rates (about 6 to 7 years earlier) in chlorine source gases. The MLS data confirm that international agreements to reduce global emissions of ozone-depleting industrial gases are leading to global decreases in the total gaseous chlorine burden. Tracking stratospheric HCl variations on a seasonal basis is now possible with MLS data. Inferred stratospheric total chlorine (CITOT) has a value of 3.60 ppbv at the beginning of 2006, with a (2-sigma) accuracy estimate of 7%; the stratospheric chlorine loading has decreased by about 43 pptv in the 18-month period studied here. We discuss the MLS HCl measurements in the context of other satellite-based HCl data, as well as expectations from surface chlorine data. A mean age of air of approx. 5.5 years and an age spectrum width of 2 years or less provide a fairly good fit to the ensemble of measurements.

  6. Chlorination of organophosphorus pesticides in natural waters.

    PubMed

    Acero, Juan L; Benítez, F Javier; Real, Francisco J; González, Manuel

    2008-05-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 degrees C and pH 7 were determined to be 110.9, 0.004 and 191.6 M(-1) s(-1) for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L(-1) was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety.

  7. Hydrocarbon fuel detergent

    SciTech Connect

    Meyer, G.R.; Lyons, W.R.

    1990-01-23

    This patent describes a hydrocarbon fuel composition comprising: a hydrocarbon fuel; and a detergent amount of a detergent comprising an alkenylsuccinimide prepared by reacting an alkenylsuccinic acid or anhydride with a mixture of amines, wherein at least 90 weight percent of the alkenyl substituent is derived from an olefin having a carbon chain of from 10 to 30 carbons or mixtures thereof, and wherein the alkenylsuccinic acid or anhydride is reacted with the mixture of amines at a mole ratio of 0.8 to 1.5 moles of the amines per mole of the alkenylsuccinic acid or anhydride.

  8. Miscellaneous hydrocarbon solvents.

    PubMed

    Bebarta, Vikhyat; DeWitt, Christopher

    2004-08-01

    The solvents discussed in this article are common solvents not categorized as halogenated, aromatic, or botanical. The solvents discussed are categorized into two groups: hydrocarbon mixtures and single agents. The hydrocarbon mixtures discussed are Stoddard solvent, naphtha, and kerosene. The remaining solvents described are n-hexane, methyl n-butyl ketone, dimethylformamide, dimethyl sulfoxide, and butyl mercaptans. Effects common to this group of agents and their unique effects are characterized. Treatment of exposures and toxic effects of these solvents is described, and physiochemical properties and occupational exposure levels are listed.

  9. Quantitative Hydrocarbon Surface Analysis

    NASA Technical Reports Server (NTRS)

    Douglas, Vonnie M.

    2000-01-01

    The elimination of ozone depleting substances, such as carbon tetrachloride, has resulted in the use of new analytical techniques for cleanliness verification and contamination sampling. The last remaining application at Rocketdyne which required a replacement technique was the quantitative analysis of hydrocarbons by infrared spectrometry. This application, which previously utilized carbon tetrachloride, was successfully modified using the SOC-400, a compact portable FTIR manufactured by Surface Optics Corporation. This instrument can quantitatively measure and identify hydrocarbons from solvent flush of hardware as well as directly analyze the surface of metallic components without the use of ozone depleting chemicals. Several sampling accessories are utilized to perform analysis for various applications.

  10. Quantitative Hydrocarbon Surface Analysis

    NASA Technical Reports Server (NTRS)

    Douglas, Vonnie M.

    2000-01-01

    The elimination of ozone depleting substances, such as carbon tetrachloride, has resulted in the use of new analytical techniques for cleanliness verification and contamination sampling. The last remaining application at Rocketdyne which required a replacement technique was the quantitative analysis of hydrocarbons by infrared spectrometry. This application, which previously utilized carbon tetrachloride, was successfully modified using the SOC-400, a compact portable FTIR manufactured by Surface Optics Corporation. This instrument can quantitatively measure and identify hydrocarbons from solvent flush of hardware as well as directly analyze the surface of metallic components without the use of ozone depleting chemicals. Several sampling accessories are utilized to perform analysis for various applications.

  11. Degradability of Chlorinated Solvents in Landfill Environment

    NASA Astrophysics Data System (ADS)

    Wang, J. Y.; Litman, M.

    2002-12-01

    The use of landfills as an in situ remediation system represents a cost-effective alternative for groundwater remediation in the source area. This research was conducted to investigate the intrinsic bioattenuation capacity of the landfill ecosystem for chlorinated aliphatic hydrocarbons (CAHs). This research, using excavated refuse samples, studied how the reductive dechlorination of CAHs is linked to the decomposition of solid waste in landfills. Most research effort in groundwater remediation has focused on the contaminant plumes beneath and downgradient from landfills, while the source area remediation has received increasing attention. Bioreactor landfill and leachate recirculation projects have been planned and implemented by the USEPA and some states. However, the use of bioreactor landfill has primarily been considered only to expedite refuse decomposition. This research provides an understanding of the biological fate of CAHs in landfills, an understanding that can lead to the bioreactor landfill system designed to promote the degradation of pollutants right at the source. The research was conducted in two complementary systems: simulated landfill bioreactors and batch degradation experiment in serum bottles. Refuse samples were excavated from a municipal solid waste landfill located in Wayland, Massachusetts, USA. Bioreactors were designed and operated to facilitate refuse decomposition under landfilling conditions. For each reactor, leachate was collected and recirculated back to the reactor and gas was collected into a gas bag and the methane production rate was monitored. Target CAHs, tetrachloroethene (PCE) and trichloroethene (TCE), were added to selected reactors and maintained at about 20 uM each in leachate. The design is to study the effect of long-term exposure of refuse microorganisms to CAHs on the degradation potential of these chemicals in landfills. Changes of biochemical conditions in bioreactors, including leachate pH, leachate COD, and

  12. Chlorine-rich plasma polymer coating for the prevention of attachment of pathogenic fungal cells onto materials surfaces

    NASA Astrophysics Data System (ADS)

    Lamont-Friedrich, Stephanie J.; Michl, Thomas D.; Giles, Carla; Griesser, Hans J.; Coad, Bryan R.

    2016-07-01

    The attachment of pathogenic fungal cells onto materials surfaces, which is often followed by biofilm formation, causes adverse consequences in a wide range of areas. Here we have investigated the ability of thin film coatings from chlorinated molecules to deter fungal colonization of solid materials by contact killing of fungal cells reaching the surface of the coating. Coatings were deposited onto various substrate materials via plasma polymerization, which is a substrate-independent process widely used for industrial coating applications, using 1,1,2-trichloroethane as the process vapour. XPS surface analysis showed that the coatings were characterized by a highly chlorinated hydrocarbon polymer nature, with only a very small amount of oxygen incorporated. The activity of these coatings against human fungal pathogens was quantified using a recently developed, modified yeast assay and excellent antifungal activity was observed against Candida albicans and Candida glabrata. Plasma polymer surface coatings derived from chlorinated hydrocarbon molecules may therefore offer a promising solution to preventing yeast and mould biofilm formation on materials surfaces, for applications such as air conditioners, biomedical devices, food processing equipment, and others.

  13. Electrochemistry of free chlorine and monochloramine and its relevance to the presence of Pb in drinking water.

    PubMed

    Rajasekharan, Vishnu V; Clark, Brandi N; Boonsalee, Sansanee; Switzer, Jay A

    2007-06-15

    The commonly used disinfectants in drinking water are free chlorine (in the form of HOCl/OCl-) and monochloramine (NH2Cl). While free chlorine reacts with natural organic matter in water to produce chlorinated hydrocarbon byproducts, there is also concern that NH2Cl may react with Pbto produce soluble Pb(II) products--leading to elevated Pb levels in drinking water. In this study, electrochemical methods are used to compare the thermodynamics and kinetics of the reduction of these two disinfectants. The standard reduction potential for NH2Cl/Cl- was estimated to be +1.45 V in acidic media and +0.74 V in alkaline media versus NHE using thermodynamic cycles. The kinetics of electroreduction of the two disinfectants was studied using an Au rotating disk electrode. The exchange current densities estimated from Koutecky-Levich plots were 8.2 x 10(-5) and 4.1 x 10(-5) A/cm2, and by low overpotential experiments were 7.5 +/- 0.3 x 10(-5) and 3.7 +/- 0.4 x 10(-5) A/cm2 for free chlorine and NH2Cl, respectively. The rate constantforthe electrochemical reduction of free chlorine at equilibrium is approximately twice as large as that for the reduction of NH2Cl. Equilibrium potential measurements show that free chlorine will oxidize Pb to PbO2 above pH 1.7, whereas NH2Cl will oxidize Pb to PbO2 only above about pH 9.5, if the total dissolved inorganic carbon (DIC) is 18 ppm. Hence, NH2Cl is not capable of producing a passivating PbO2 layer on Pb, and could lead to elevated levels of dissolved Pb in drinking water.

  14. Separation of chlorinated diastereomers of decarboxy-betacyanins in myeloperoxidase catalyzed chlorinated Beta vulgaris L. extract.

    PubMed

    Wybraniec, Sławomir; Starzak, Karolina; Szneler, Edward; Pietrzkowski, Zbigniew

    2016-11-15

    A comparative chromatographic evaluation of chlorinated decarboxylated betanins and betanidins generated under activity of hypochlorous acid exerted upon these highly antioxidative potent decarboxylated pigments derived from natural sources was performed by LC-DAD-ESI-MS/MS. Comparison of the chromatographic profiles of the chlorinated pigments revealed two different directions of retention changes in relation to the corresponding substrates. Chlorination of all betacyanins that are decarboxylated at carbon C-17 results in an increase of their retention times. In contrast, all other pigments (the non-decarboxylated betacyanins as well as 2-decarboxy- and 15-decarboxy-derivatives) exhibit lower retention after chlorination. During further chromatographic experiments based upon chemical transformation of the related pigments (decarboxylation and deglucosylation), the compounds' structures were confirmed. The elaborated method for determination of chlorinated pigments enabled analysis of a chlorinated red beet root extract that was submitted to the MPO/H2O2/Cl(-) system acting under inflammation-like conditions (pH 5). This indicates a promising possibility for measurement of these chlorinated pigments as indicators of specific inflammatory states wherein betacyanins and decarboxylated betacyanins act as hypochlorite scavengers.

  15. Analysis to differentiate marine chlorine to industrial chlorine in the equatorial region of French Guiana

    NASA Astrophysics Data System (ADS)

    Gobinddass, M. L.; Molinie, J.; Richard, S.; Panechou-Pulcherie, K.; Jeannot, A.; jean-Louis, S.

    2014-12-01

    Marine Chlorine deposition data in French Guiana's east coast and wind speeds influences has been studied here. In 2001 and 2002 an INERIS's studies has shown that monitoring hydrogen chloride emitted by the rocket would be appropriate. Thus, with the help of the French Guiana Space Center, two measurement campaigns (2004-2008) have been implemented by the Regional Observatory Air (ROA). The purpose was to determine the impact of space activities in and around the city of Sinnamary. The ROA has made measurements of chlorine concentration during and outside periods of shooting to assess the chlorine from the rocket boosters of natural background chlorine due to its proximity with the Atlantic Ocean. A method is proposed here to differentiate natural from anthropogenic emissions from chlorine. The use of certain meteorological parameter (wind, humidity, temperature, etc…) will first be discussed for the transportation of chlorine. Then, we will try to classify chlorine dispersion according to the seasons and areas. Finally a comparison with a previous study in Brazil will be made.

  16. Impacts of water quality on chlorine and chlorine dioxide efficacy in natural waters.

    PubMed

    Barbeau, Benoit; Desjardins, Raymond; Mysore, Chandra; Prévost, Michele

    2005-05-01

    The impact of disinfection efficacy in natural waters was evaluated by performing disinfection assays using four untreated surface waters of various qualities and ultra-pure buffered waters as a baseline condition for comparison. Bacillus subtilis spores were spiked in these waters and disinfection assays were conducted at 22 degrees C using either free chlorine or chlorine dioxide. Assays using indigenous aerobic spores were also completed. The inactivation kinetics in natural and ultra-pure buffered waters were not statistically different (at p = 0.05) while using free chlorine, as long as disinfectant decay was taken into account. Filtering natural waters through a 0.45 microm did not improve the sporicidal efficacy of chlorine. For three out of the four waters tested, the efficacy of chlorine dioxide was greater in natural waters compared to that observed in ultra-pure buffered waters. Such results are consistent with previous observations using ultra-pure waters supplemented with NOM-extract from the Suwannee River. Similar to free chlorine results, the impact of filtration (0.45 microm) on the efficacy of chlorine dioxide was not statistically significant.

  17. The effects of low level chlorination and chlorine dioxide on biofouling control in a once-through service water system

    SciTech Connect

    Garrett, W.E. Jr.

    1995-06-01

    Continuous chlorination has been successfully used for the control of Corbicula at a nuclear power plant located on the Chattahoochee River in southeastern Alabama, since 1986. The purpose of this study was to investigate further minimization of chlorine usage and determine if chlorine dioxide is a feasible alternative. Four continuous biocide treatments were evaluated for macro and microfouling control effectiveness, operational feasibility, and environmental acceptability. One semi-continuous chlorination treatment was also evaluated for macrofouling control effectiveness. Higher treatment residuals were possible with chlorine dioxide than with chlorination due to the river discharge limitations. At the levels tested, continuous chlorine dioxide was significantly more effective in providing both macro and microfouling control. Semi-continuous chlorination was just as effective as continuous chlorination for controlling macrofouling. The Corbicula treatment programs that were tested should all provide sufficient control for zebra mussels. Chlorine dioxide was not as cost effective as chlorination for providing macrofouling control. The semi-continuous treatment save 50% on chemical usage and will allow for the simultaneous treatment of two service water systems. Chlorite levels produced during the chlorine dioxide treatments were found to be environmentally acceptable. Levels of trihalomethanes in the chlorinated service water were less than the maximum levels allowed in drinking water.

  18. Comparison of disinfection byproduct formation from chlorine and alternative disinfectants.

    PubMed

    Hua, Guanghui; Reckhow, David A

    2007-04-01

    Seven diverse natural waters were collected and treated in the laboratory under five oxidation scenarios (chlorine, chloramine, both with and without preozonation, and chlorine dioxide). The impact of these disinfectants on the formation of disinfection byproducts was investigated. Results showed that preozonation decreased the formation of trihalomethanes (THMs), haloacetic acids (HAAs) and total organic halogen (TOX) for most waters during postchlorination. A net increase in THMs, HAAs and TOX was observed for a water of low humic content. Either decreases or increases were observed in dihaloacetic acids and unknown TOX (UTOX) as a result of preozonation when used with chloramination. Chloramines and chlorine dioxide produced a higher percentage of UTOX than free chlorine. They also formed more iodoform and total organic iodine (TOI) than free chlorine in the presence of iodide. Free chlorine produced a much higher level of total organic chlorine (TOCl) and bromine (TOBr) than chloramines and chlorine dioxide in the presence of bromide.

  19. Chlorination of Titanium Oxycarbide Produced by Carbothermal Reduction of Rutile

    NASA Astrophysics Data System (ADS)

    Adipuri, Andrew; Zhang, Guangqing; Ostrovski, Oleg

    2008-02-01

    Titanium oxycarbide was produced by carbothermal reduction of rutile. Mixtures of titania and graphite with different carbon to titania molar ratio were pressed into pellets and heated under argon atmosphere at 1450 °C. Titanium oxycarbide was chlorinated in a horizontal tube furnace. Effects of furnace temperature, chlorine partial pressure, gas flow rate, and particle size on the rate and extent of chlorination were examined. The chlorination was ignited at 150 °C to 200 °C. Chlorine partial pressure and gas flow rate strongly affected the chlorination rate, while the effect of particle size was insignificant. Best chlorination results were obtained for titanium oxycarbide produced with carbon to titania molar ratio 2.5, and chlorination was close to 100 pct in 30 minutes.

  20. Study on chlorine removal from mixture of waste plastics.

    PubMed

    Kakuta, Yusuke; Hirano, Katsumi; Sugano, Motoyuki; Mashimo, Kiyoshi

    2008-01-01

    The recycling of waste plastics that include plastics that contain chlorine, such as polyvinyl chloride, is difficult because the chlorine leads to the corrosion of equipment. Then, the dechlorination method of waste plastics containing chlorine (CCWP) that consists of a series of melt process and hot water process was examined. CCWP was put into the melt process with coal tar (HOB) and converter dust (CD) to inhibit the diffusion of the chlorine-containing gas. The results indicated that iron oxide of the principal element of CD combines with chlorine eliminated from CCWP, and forms water-soluble iron chloride on the melt process. HOB dissolves or adsorbs a part of the chlorine during the melt process, and inhibits the diffusion of the chlorine-containing gas. Approximately 98% of the chlorine in the CCWP reacts with CD and forms iron chloride, which can be extracted on the hot water process.

  1. Apparatus and methods for hydrocarbon extraction

    DOEpatents

    Bohnert, George W.; Verhulst, Galen G.

    2016-04-26

    Systems and methods for hydrocarbon extraction from hydrocarbon-containing material. Such systems and methods relate to extracting hydrocarbon from hydrocarbon-containing material employing a non-aqueous extractant. Additionally, such systems and methods relate to recovering and reusing non-aqueous extractant employed for extracting hydrocarbon from hydrocarbon-containing material.

  2. Polycyclic hydrocarbons and cancer

    SciTech Connect

    Gelboin, H.V.P; Ts'o, P.O.P.

    1981-01-01

    This book is Volume 3 of a three-volume series. It discusses polynuclear aromatic hydrocarbons (PAHs) in the marine environment, various PAH dihydrodiols, certain enzyme reactions, carcinogenesis modifications, and tumor promotion. PAH epidemiology for quantifying cigarette smoking and air pollution risks is also covered. (JMT)

  3. Zeroing in on hydrocarbons

    SciTech Connect

    Roest, I.P.B. van der; Brasser, D.J.S.; Wagebaert, A.P.J.; Stam, P.H.

    1997-05-01

    The increasing costs of remediating contaminated sites has stimulated research for cost-reducing techniques in soil investigation and cleanup techniques. MAP Environmental Research has developed a technology using ground penetrating radar in combination with in house developed software to locate and define the extent of hydrocarbon contamination. This article discusses the new technology. 2 figs.

  4. Hydrocarbon options emerge

    SciTech Connect

    Fairley, P.

    1995-11-01

    Europe stole the scene at last week`s International Chlorofluorocarbon (CFC) and Halon Alternatives Conference in Washington as attendees learned more about an accelerating shift to low-cost hydrocarbon refrigerants by European equipment manufacturers. Udo Wenning, representing German refrigerator market leader Bosch-Siemens, told the conference that hydrocarbons-isobutane as refrigerant and cyclopentane to blow the insulating foam-are now used in 90% of German production. Wenning says that in all performance parameters, hydrocarbons match the hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC) replacements favored in the U.S. and Japan and that, unlike HCFCs and HFCs they have low global warming potential. Their Achille`s heel is flammability, Wenning says. American equipment manufacturers aiming to sell a new generation of equipment designed for the new HFC refrigerants sought to amplify concern over flammability at the conference. {open_quotes}In a society as litigious as ours, we do not see a future for flammable refrigerants,{close_quotes} says a representative of air conditioner manufacturer Carrier. Hydrocarbon supporters such as Greenpeace say the risks are mananageable.

  5. Optrode for sensing hydrocarbons

    DOEpatents

    Miller, Holly; Milanovich, Fred P.; Hirschfeld, Tomas B.; Miller, Fred S.

    1988-01-01

    A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon and but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons.

  6. Optrode for sensing hydrocarbons

    DOEpatents

    Miller, Holly; Milanovich, Fred P.; Hirschfeld, Tomas B.; Miller, Fred S.

    1987-01-01

    A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon and but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons.

  7. Optrode for sensing hydrocarbons

    DOEpatents

    Miller, H.; Milanovich, F.P.; Hirschfeld, T.B.; Miller, F.S.

    1987-05-19

    A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons. 6 figs.

  8. Optrode for sensing hydrocarbons

    DOEpatents

    Miller, H.; Milanovich, F.P.; Hirschfeld, T.B.; Miller, F.S.

    1988-09-13

    A two-phase system employing the Fujiwara reaction is provided for the fluorometric detection of halogenated hydrocarbons. A fiber optic is utilized to illuminate a column of pyridine trapped in a capillary tube coaxially attached at one end to the illuminating end of the fiber optic. A strongly alkaline condition necessary for the reaction is maintained by providing a reservoir of alkali in contact with the column of pyridine, the surface of contact being adjacent to the illuminating end of the fiber optic. A semipermeable membrane caps the other end of the capillary tube, the membrane being preferentially permeable to the halogenated hydrocarbon and but preferentially impermeable to water and pyridine. As the halogenated hydrocarbon diffuses through the membrane and into the column of pyridine, fluorescent reaction products are formed. Light propagated by the fiber optic from a light source, excites the fluorescent products. Light from the fluorescence emission is also collected by the same fiber optic and transmitted to a detector. The intensity of the fluorescence gives a measure of the concentration of the halogenated hydrocarbons. 5 figs.

  9. Chlorine: Undergraduate Research on an Element of Controversy

    NASA Astrophysics Data System (ADS)

    Chang, Hasok

    2009-04-01

    If chemical elements were people, chlorine would be a celebrity. Although intrinsically no more or less important than any other element, chlorine has had a knack of making headlines. The genre of "object biography" has been quite successful in popular science recently. We took this opportunity to write a "biographical" study of chlorine. Chlorine's wide range of interesting controversies is well suited for attracting and maintaining the enthusiasm of the diverse range of students we teach in our department.

  10. Diurnal variation of stratospheric chlorine monoxide - A critical test of chlorine chemistry in the ozone layer

    NASA Technical Reports Server (NTRS)

    Solomon, P. M.; De Zafra, R.; Parrish, A.; Barrett, J. W.

    1984-01-01

    Ground-based observations of a mm-wave spectral line at 278 GHz have yielded stratospheric chlorine monoxide column density diurnal variation records which indicate that the mixing ratio and column density of this compound above 30 km are about 20 percent lower than model predictions based on 2.1 parts/billion of total stratospheric chlorine. The observed day-to-night variation is, however, in good agreement with recent model predictions, both confirming the existence of a nighttime reservoir for chlorine and verifying the predicted general rate of its storage and retrieval.

  11. A comparison of the virucidal properties of chlorine, chlorine dioxide, bromine chloride and iodine.

    PubMed Central

    Taylor, G. R.; Butler, M.

    1982-01-01

    Chlorine dioxide, bromine chloride and iodine were compared with chlorine as virucidal agents. Under optimal conditions all disinfectants were effective at low concentrations, but each disinfectant responded differently to acidity and alkalinity. Disinfection by chlorine was impaired by the presence of ammonia, but the other disinfectants retained much of their potency. Disinfection of poliovirus by iodine resulted in structural changes in the virions as seen by electron micrroscopy, but the other disinfectants were able to inactivate poliovirus without causing any apparent structural changes. Images Plate 1 PMID:6290566

  12. Determination of chlorine in silicate rocks

    USGS Publications Warehouse

    Peck, L.C.

    1959-01-01

    In a rapid accurate method for the determination of chlorine in silicate rocks, the rock powder is sintered with a sodium carbonate flux containing zinc oxide and magnesium carbonate. The sinter cake is leached with water, the resulting solution is filtered, and the filtrate is acidified with nitric acid. Chlorine is determined by titrating this solution with mercuric nitrate solution using sodium nitroprusside as the indicator. The titration is made in the dark with a beam of light shining through the solution. The end point of the titration is found by visually comparing the intensity of this beam of light with that of a similar beam of light in a reference solution.

  13. Bromine and Chlorine Go Separate Ways

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This graph shows the relative concentrations of bromine and chlorine at various locations on Earth and Mars. Typically, bromine and chlorine stick together in a fixed ratio, as in martian meteorites and Earth seawater. But sometimes the elements split apart and their relative quantities diverge. This separation is usually caused by evaporation processes, as in the Dead Sea on Earth. On Mars, at Meridiani Planum and Gusev Crater, this split has been observed to an even greater degree than seen on Earth. This puzzling result is currently being further explored by Mars Exploration Rover scientists. Data for the Mars locations were taken by the rover's alpha particle X-ray spectrometer.

  14. Production of chlorine from chloride salts

    DOEpatents

    Rohrmann, Charles A.

    1981-01-01

    A process for converting chloride salts and sulfuric acid to sulfate salts and elemental chlorine is disclosed. A chloride salt and sulfuric acid are combined in a furnace where they react to produce a sulfate salt and hydrogen chloride. Hydrogen chloride from the furnace contacts a molten salt mixture containing an oxygen compound of vanadium, an alkali metal sulfate and an alkali metal pyrosulfate to recover elemental chlorine. In the absence of an oxygen-bearing gas during the contacting, the vanadium is reduced, but is regenerated to its active higher valence state by separately contacting the molten salt mixture with an oxygen-bearing gas.

  15. Bromine and Chlorine Go Separate Ways

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This graph shows the relative concentrations of bromine and chlorine at various locations on Earth and Mars. Typically, bromine and chlorine stick together in a fixed ratio, as in martian meteorites and Earth seawater. But sometimes the elements split apart and their relative quantities diverge. This separation is usually caused by evaporation processes, as in the Dead Sea on Earth. On Mars, at Meridiani Planum and Gusev Crater, this split has been observed to an even greater degree than seen on Earth. This puzzling result is currently being further explored by Mars Exploration Rover scientists. Data for the Mars locations were taken by the rover's alpha particle X-ray spectrometer.

  16. Site-Selective Aliphatic C-H Chlorination Using N-Chloroamides Enables a Synthesis of Chlorolissoclimide.

    PubMed

    Quinn, Ryan K; Könst, Zef A; Michalak, Sharon E; Schmidt, Yvonne; Szklarski, Anne R; Flores, Alex R; Nam, Sangkil; Horne, David A; Vanderwal, Christopher D; Alexanian, Erik J

    2016-01-20

    Methods for the practical, intermolecular functionalization of aliphatic C-H bonds remain a paramount goal of organic synthesis. Free radical alkane chlorination is an important industrial process for the production of small molecule chloroalkanes from simple hydrocarbons, yet applications to fine chemical synthesis are rare. Herein, we report a site-selective chlorination of aliphatic C-H bonds using readily available N-chloroamides and apply this transformation to a synthesis of chlorolissoclimide, a potently cytotoxic labdane diterpenoid. These reactions deliver alkyl chlorides in useful chemical yields with substrate as the limiting reagent. Notably, this approach tolerates substrate unsaturation that normally poses major challenges in chemoselective, aliphatic C-H functionalization. The sterically and electronically dictated site selectivities of the C-H chlorination are among the most selective alkane functionalizations known, providing a unique tool for chemical synthesis. The short synthesis of chlorolissoclimide features a high yielding, gram-scale radical C-H chlorination of sclareolide and a three-step/two-pot process for the introduction of the β-hydroxysuccinimide that is salient to all the lissoclimides and haterumaimides. Preliminary assays indicate that chlorolissoclimide and analogues are moderately active against aggressive melanoma and prostate cancer cell lines.

  17. Hydrocarbonization research: completion report

    SciTech Connect

    Youngblood, E.L.; Cochran, H.D. Jr.; Westmoreland, P.R.; Brown, C.H. Jr.; Oswald, G.E.; Barker, R.E.

    1981-01-01

    Hydrocarbonization is a relatively simple process used for producing oil, substitute natural gas, and char by heating coal under a hydrogen-rich atmosphere. This report describes studies that were performed in a bench-scale hydrocarbonization system at Oak Ridge National Laboratory (ORNL) during the period 1975 to 1978. The results of mock-up studies, coal metering valve and flowmeter development, and supporting work in an atmospheric hydrocarbonization system are also described. Oil, gas, and char yields were determined by hydrocarbonization of coal in a 0.1-m-diam fluidized-bed reactor operated at a pressure of 2170 kPa and at temperatures ranging from 694 to 854 K. The nominal coal feed rate was 4.5 kg/h. Wyodak subbituminous coal was used for most of the experiments. A maximum oil yield of approx. 21% based on moisture- and ash-free (maf) coal was achieved in the temperature range of 810 to 840 K. Recirculating fluidized-bed, uniformly fluidized-bed, and rapid hydropyrolysis reactors were used. A series of operability tests was made with Illinois No. 6 coal to determine whether caking coal could be processed in the recirculating fluidized-bed reactor. These tests were generally unsuccessful because of agglomeration and caking problems; however, these problems were eliminated by the use of chemically pretreated coal. Hydrocarbonization experiments were carried out with Illinois No. 6 coal that had been pretreated with CaO-NaOH, Na/sub 2/CO/sub 3/, and CaO-Na/sub 2/CO/sub 3/. Oil yields of 14, 24, and 21%, respectively, were obtained from the runs with treated coal. Gas and char yield data and the composition of the oil, gas, and char products are presented.

  18. Halogenated volatile organic compounds from the use of chlorine-bleach-containing household products.

    PubMed

    Odabasi, Mustafa

    2008-03-01

    Sodium hypochlorite (NaOCl) and many organic chemicals contained in household cleaning products may react to generate halogenated volatile organic compounds (VOCs). Halogenated VOC emissions from eight different chlorine bleach containing household products (pure and diluted) were investigated by headspace experiments. Chloroform and carbon tetrachloride were the leading compounds along with several halogenated compounds in the headspace of chlorine bleach products. One of the most surprising results was the presence of carbon tetrachloride (a probable human carcinogen and a powerful greenhouse gas that was banned for household use by the U.S. Food and Drug Administration) in very high concentrations (up to 101 mg m(-3)). By mixing surfactants or soap with NaOCl, it was shown that the formation of carbon tetrachloride and several other halogenated VOCs is possible. In addition to quantitatively determined halogenated VOCs (n = 15), several nitrogen-containing (n = 4), chlorinated (n = 10), oxygenated compounds (n = 22), and hydrocarbons (n = 14) were identified in the headspace of bleach products. Among these, 1,1-dichlorobutane and 2-chloro-2-nitropropane were the most abundant chlorinated VOCs, whereas trichloronitromethane and hexachloroethane were the most frequently detected ones. Indoor air halogenated VOC concentrations resulting from the use of four selected household products were also measured before, during, and 30 min after bathroom, kitchen, and floor cleaning applications. Chloroform (2.9-24.6 microg m(-3)) and carbon tetrachloride (0.25-459 microg m(-3)) concentrations significantly increased during the use of bleach containing products. During/ before concentration ratios ranged between 8 and 52 (25 +/- 14, average +/- SD) for chloroform and 1-1170 (146 +/- 367, average +/- SD) for carbon tetrachloride, respectively. These results indicated that the bleach use can be important in terms of inhalation exposure to carbon tetrachloride, chloroform and

  19. 75 FR 61772 - Chlorinated Isocyanurates From China and Spain; Determinations

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-10-06

    ... COMMISSION Chlorinated Isocyanurates From China and Spain; Determinations On the basis of the record \\1... antidumping duty orders on chlorinated isocyanurates from China and Spain would be likely to lead to... antidumping duty order on chlorinated isocyanurates from Spain would not be likely to lead to continuation...

  20. 49 CFR 176.225 - Stowage of chlorine.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Stowage of chlorine. 176.225 Section 176.225 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY... Requirements for Class 2 (Compressed Gas) Materials § 176.225 Stowage of chlorine. Chlorine (UN 1017) must...

  1. 49 CFR 176.225 - Stowage of chlorine.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Stowage of chlorine. 176.225 Section 176.225 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY... Requirements for Class 2 (Compressed Gas) Materials § 176.225 Stowage of chlorine. Chlorine (UN 1017) must...

  2. 49 CFR 176.225 - Stowage of chlorine.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Stowage of chlorine. 176.225 Section 176.225 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY... Requirements for Class 2 (Compressed Gas) Materials § 176.225 Stowage of chlorine. Chlorine (UN 1017) must...

  3. 49 CFR 176.225 - Stowage of chlorine.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Stowage of chlorine. 176.225 Section 176.225 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY... Requirements for Class 2 (Compressed Gas) Materials § 176.225 Stowage of chlorine. Chlorine (UN 1017) must...

  4. 49 CFR 176.225 - Stowage of chlorine.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Stowage of chlorine. 176.225 Section 176.225 Transportation Other Regulations Relating to Transportation PIPELINE AND HAZARDOUS MATERIALS SAFETY... Requirements for Class 2 (Compressed Gas) Materials § 176.225 Stowage of chlorine. Chlorine (UN 1017) must...

  5. Determination of Free Available Chlorine in Denitrified Wastewater Effluent

    DTIC Science & Technology

    1993-01-01

    of chloramines, particularly monochloramine , on the free available chlorine residual measurements made using the DPD method was significant. The...hypochorous acid, hypochlorite ion, and aqueous chlorine, CI.,q)) and combined chlorine ( monochloramine , dichloramine, and nitrogen trichloride) was not...neutral molecule resembling water in structure, it diffuses across cell membranes quite easily. Chloramines, such as monochloramine , are much weaker

  6. EFFECT OF BROMIDE ION ON FORMATION OF HAAS DURING CHLORINATION

    EPA Science Inventory

    loacetic acids (HAAs) during chlorination and he effects of independent variables, including pH, reaction time, and chlorine dosage. Almost all of the indpendent loaetic acids (HAAs) during chlorin...designed to statistically evaluate the influence of bromide ion on the formatio...

  7. EFFECT OF BROMIDE ION ON FORMATION OF HAAS DURING CHLORINATION

    EPA Science Inventory

    loacetic acids (HAAs) during chlorination and he effects of independent variables, including pH, reaction time, and chlorine dosage. Almost all of the indpendent loaetic acids (HAAs) during chlorin...designed to statistically evaluate the influence of bromide ion on the formatio...

  8. Efficiency of Chlorine Dioxide as a Bactericide1

    PubMed Central

    Benarde, Melvin A.; Israel, Bernard M.; Olivieri, Vincent P.; Granstrom, Marvin L.

    1965-01-01

    We found chlorine dioxide to be a more effective disinfectant than chlorine in sewage effluent at pH 8.5. Chlorine dioxide was also found to be a more stable bactericide in relation to pH in the range studied. Images Fig. 1 PMID:5325940

  9. 21 CFR 177.2430 - Polyether resins, chlorinated.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Polyether resins, chlorinated. 177.2430 Section... as Components of Articles Intended for Repeated Use § 177.2430 Polyether resins, chlorinated. Chlorinated polyether resins may be safely used as articles or components of articles intended for repeated...

  10. Mantle hydrocarbons: Abiotic or biotic?

    SciTech Connect

    Sugisaki, Ryuichi; Mimura, Koichi

    1994-06-01

    Analyses of 227 rocks from fifty localities throughout the world showed that mantle derived rocks such as tectonized peridotites in ophiolite sequences (tectonites) and peridotite xenoliths in alkali basalts contain heavier hydrocarbons (n-alkanes), whereas igneous rocks produced by magmas such as gabbro and granite lack them. The occurrence of hydrocarbons indicates that they were not derived either from laboratory contamination or from field contamination; these compounds found in the mantle-derived rocks are called here {open_quotes}mantle hydrocarbons.{close_quotes} The existence of hydrocarbons correlates with petrogenesis. For example, peridotite cumulates produced by magmatic differentiation lack hydrocarbons whereas peridotite xenoliths derived from the mantle contain them. Gas chromatographic-mass spectrometric records of the mantle hydrocarbons resemble those of aliphatics in meteorites and in petroleum. Features of the hydrocarbons are that (a) the mantle hydrocarbons reside mainly along grain boundaries and in fluid inclusions of minerals; (b) heavier isoprenoids such as pristane and phytane are present; and (c) {delta}{sup 13}C of the mantle hydrocarbons is uniform (about {minus}27{per_thousand}). Possible origins for the mantle hydrocarbons are as follows. (1) They were inorganically synthesized by Fischer-Tropsch type reaction in the mantle. (2) They were delivered by meteorites and comets to the early Earth. (3) They were recycled by subduction. The mantle hydrocarbons in the cases of (1) and (2) are abiogenic and those in (3) are mainly biogenic. It appears that hydrocarbons may survive high pressures and temperatures in the mantle, but they are decomposed into lighter hydrocarbon gases such as CH{sub 4} at lower pressures when magmas intrude into the crust; consequently, peridotite cumulates do not contain heavier hydrocarbons but possess hydrocarbon gases up to C{sub 4}H{sub 10}. 76 refs., 5 figs., 3 tabs.

  11. Mantle hydrocarbons: abiotic or biotic?

    PubMed

    Sugisaki, R; Mimura, K

    1994-06-01

    Analyses of 227 rocks from fifty localities throughout the world showed that mantle derived rocks such as tectonized peridotites in ophiolite sequences (tectonites) arid peridotite xenoliths in alkali basalts contain heavier hydrocarbons (n-alkanes), whereas igneous rocks produced by magmas such as gabbro arid granite lack them. The occurrence of hydrocarbons indicates that they were not derived either from laboratory contamination or from held contamination; these compounds found in the mantle-derived rocks are called here "mantle hydrocarbons." The existence of hydrocarbons correlates with petrogenesis. For example, peridotite cumulates produced by magmatic differentiation lack hydrocarbons whereas peridotite xenoliths derived from the mantle contain them. Gas chromatographic-mass spectrometric records of the mantle hydrocarbons resemble those of aliphatics in meteorites and in petroleum. Features of the hydrocarbons are that (a) the mantle hydrocarbons reside mainly along grain boundaries and in fluid inclusions of minerals; (b) heavier isoprenoids such as pristane and phytane are present; and (c) delta 13C of the mantle hydrocarbons is uniform (about -27%). Possible origins for the mantle hydrocarbons are as follows. (1) They were in organically synthesized by Fischer-Tropsch type reaction in the mantle. (2) They were delivered by meteorites and comets to the early Earth. (3) They were recycled by subduction. The mantle hydrocarbons in the cases of (1) and (2) are abiogenic and those in (3) are mainly biogenic. It appears that hydrocarbons may survive high pressures and temperatures in the mantle, but they are decomposed into lighter hydrocarbon gases such as CH4 at lower pressures when magmas intrude into the crust; consequently, peridotite cumulates do not contain heavier hydrocarbons but possess hydrocarbon gases up to C4H10.

  12. Chlorine and carbon isotope measurements can help assessing the effectivenes of a zero valent iron barrier

    NASA Astrophysics Data System (ADS)

    Cretnik, S.; Audi, C.; Bernstein, A.; Palau, J.; Soler, A.; Elsner, M.

    2012-04-01

    Chlorinated aliphatic hydrocarbons (CAH's) such as trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinylchloride (VC) are extensively used in industrial applications. One of the most promising remediation techniques for CAH's in groundwater is their removal via abiotic reductive dechlorination using Zero Valent Iron (ZVI). This is applied for the treatment of contaminated sites by installing permeable reactive barriers (PRB). In this study, isotope fractionation of chlorinated ethylenes in transformation by cast iron has been investigated, because such types of iron are commonly used in PRBs. Batch experiments have been carried out in closed flasks, containing cast iron with aqueous solutions of TCE, cDCE and VC. These substrates and their respective products have been monitored by headspace samplings for their concentration (by GC-FID) and isotope fractionation of carbon and chlorine (by GC-IRMS). A decreasing reactivity trend was observed when compounds contain less chlorine atoms, with differences in rate constants of about one order of magnitude between each of the substances TCE > cDCE > VC. This resulted in the accumulation of products with fewer chlorine atoms. Therefore a similar observation can be expected if degradation in the field is incomplete, for example in the case of aged or improperly designed PRB. Pronounced carbon and chlorine isotope fractionation was measured for each of the compounds, and characteristic dual isotope plots (C, Cl) were obtained for TCE and cDCE. These results may serve as an important reference for the interpretation of isotope data from field sites, since stable isotope fractionation is widely recognized as robust indicator for such pollutant transformations. However, carbon isotope fractionation in a given parent compound may be caused by either abiotic or biotic degradation. In the field, it can therefore be difficult to delineate the contribution of abiotic transformation by PRB in the presence of ongoing

  13. Analysis of hydrocarbon-contaminated groundwater metagenomes as revealed by high-throughput sequencing.

    PubMed

    Abbai, Nathlee S; Pillay, Balakrishna

    2013-07-01

    The tendency for chlorinated aliphatics and aromatic hydrocarbons to accumulate in environments such as groundwater and sediments poses a serious environmental threat. In this study, the metabolic capacity of hydrocarbon (aromatics and chlorinated aliphatics)-contaminated groundwater in the KwaZulu-Natal province of South Africa has been elucidated for the first time by analysis of pyrosequencing data. The taxonomic data revealed that the metagenomes were dominated by the phylum Proteobacteria (mainly Betaproteobacteria). In addition, Flavobacteriales, Sphingobacteria, Burkholderiales, and Rhodocyclales were the predominant orders present in the individual metagenomes. These orders included microorganisms (Flavobacteria, Dechloromonas aromatica RCB, and Azoarcus) involved in the degradation of aromatic compounds and various other hydrocarbons that were present in the groundwater. Although the metabolic reconstruction of the metagenome represented composite cell networks, the information obtained was sufficient to address questions regarding the metabolic potential of the microbial communities and to correlate the data to the contamination profile of the groundwater. Genes involved in the degradation of benzene and benzoate, heavy metal-resistance mechanisms appeared to provide a survival strategy used by the microbial communities. Analysis of the pyrosequencing-derived data revealed that the metagenomes represent complex microbial communities that have adapted to the geochemical conditions of the groundwater as evidenced by the presence of key enzymes/genes conferring resistance to specific contaminants. Thus, pyrosequencing analysis of the metagenomes provided insights into the microbial activities in hydrocarbon-contaminated habitats.

  14. Relative rate studies of the reactions of chlorine atoms with simple alkanes and the chlorinated methanes

    SciTech Connect

    Wingen, L.; Lee, J.J.; Neavyn, R.

    1995-12-01

    The reactions of chlorine atoms with organics are of interest because atomic chlorine is a potential tropospheric oxidant. Relative rate constants for the reaction of pairs of simple alkanes (ethane/propane, ethane/n-butane, and isobutane/n-butane) and the chlorinated methanes (chloromethane, dichloromethane, and chloroform relative to methane) were measured, using the photolysis of Cl{sub 2} as the source of chlorine atoms and following the loss of the organics by GC-FID. The ratios of the relative rate constants were in excellent agreement with the literature except for ethane/n-butane, where our results are approximately 20% lower than recently published values, and for chloroform/methane, where our value is approximately 50% higher than the values recommended by JPL and JPCRD. Our results will be compard to previously published relative rate studies as well as to the results of absolute rate constant studies, and the differences will be discussed.

  15. Microbial degradation of petroleum hydrocarbons.

    PubMed

    Varjani, Sunita J

    2017-01-01

    Petroleum hydrocarbon pollutants are recalcitrant compounds and are classified as priority pollutants. Cleaning up of these pollutants from environment is a real world problem. Bioremediation has become a major method employed in restoration of petroleum hydrocarbon polluted environments that makes use of natural microbial biodegradation activity. Petroleum hydrocarbons utilizing microorganisms are ubiquitously distributed in environment. They naturally biodegrade pollutants and thereby remove them from the environment. Removal of petroleum hydrocarbon pollutants from environment by applying oleophilic microorganisms (individual isolate/consortium of microorganisms) is ecofriendly and economic. Microbial biodegradation of petroleum hydrocarbon pollutants employs the enzyme catalytic activities of microorganisms to enhance the rate of pollutants degradation. This article provides an overview about bioremediation for petroleum hydrocarbon pollutants. It also includes explanation about hydrocarbon metabolism in microorganisms with a special focus on new insights obtained during past couple of years. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Ozone-destroying chlorine tops out

    SciTech Connect

    Kerr, R.A.

    1996-01-05

    This article explores the reality of whether the Montreal Protocol to protect the ozone layer has worked. The prime evidence for the success of the 1987 Protocal is that atmospheric chlorine has peaked and is on the way down. However, there are some concerns that gaps in the existing protocal could slow the recovery.

  17. Thermally dissociated chlorine and bromine molecular jets

    NASA Astrophysics Data System (ADS)

    Frick, J.

    1980-12-01

    High temperature nozzle sources producing thermal dissociation of chlorine and bromine are described. Scattering between molecular potential functions in nonelastic transfer of energy processes and chemical reactions was investigated by molecular beam technique. It is shown that the recombination freezes up faster when the nozzlehole duct is shorter.

  18. Method and apparatus for producing chlorine dioxide

    SciTech Connect

    Santillie, P.W.; Ramras, D.M.

    1984-05-29

    A continuous method and apparatus are described for the efficient production of gaseous chlorine dioxide by the reaction between gaseous sulfur dioxide and an aqueous solution of a metallic chlorate. The chlorate solution and a highly concentrated sulfur dioxide gas are introduced into a packed columnar chamber at closely adjacent locations at the bottom of the chamber so as to flood the chamber and maximize both the contact area and contact time of the two reactants. Throughout the reaction the chamber is subjected to high vacuum imposed by an eductor which exhausts the chlorine dioxide gas and spent reactants. For use of the chlorine dioxide to produce potable water or treat foodstuffs, the chlorine dioxide and spent reactants are exhausted from the chamber separately by respective eductors substantially balanced with respect to each other to impose comparable vacuums upon the chamber. Because of the high efficency of the reaction, substantial heat is generated therefrom which is absorbed by a coolant flowing through a jacket surrounding the chamber. The flow rate of the coolant and flow rate of the reactants into the chamber are porportional due to the dependency of the reactant flow rate on the coolant flow rate.

  19. Chlorinated organic compounds in urban river sediments

    SciTech Connect

    Soma, Y.; Shiraishi, H.; Inaba, K.

    1995-12-31

    Among anthropogenic chemicals, many chlorinated organic compounds have been used as insecticides and detected frequently as contaminants in urban river sediments so far. However, the number and total amount of chemicals produced commercially and used are increasing year by year, though each amount of chemicals is not so high. New types of contaminants in the environment may be detected by the use of newly developed chemicals. Chlorinated organic compounds in the urban river sediments around Tokyo and Kyoto, large cities in Japan, were surveyed and recent trends of contaminants were studied. Contaminants of the river sediments in industrial areas had a variety, but PCB (polychlorinated biphenyls) was detected in common in industrial areas. Concentration of PCB related well to the number of factories on both sides of rivers, although the use of PCB was stopped 20 years ago. In domestic areas, Triclosan (5-chloro-2-(2,4-dichlorophenoxy)-phenol) and Triclocarban (3,4,4{prime}-trichlorocarbanilide)(both are contained in soap or shampoo for fungicides), p-dichlorobenzene (insecticides for wears) and TCEP(tris-chloroethyl phosphate) were detected. EOX(extracted organic halogen) in the sediments was 5 to 10 times of chlorinated organic compounds detected by GC/MS. Major part of organic halogen was suggested to be included in chlorinated organics formed by bleaching or sterilization.

  20. 40 CFR 704.43 - Chlorinated naphthalenes.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... manufacturer's waste contains one or more of the chemical substances identified in paragraph (b) of this... CONTROL ACT REPORTING AND RECORDKEEPING REQUIREMENTS Chemical-Specific Reporting and Recordkeeping Rules... means the relative amounts of each isomeric chlorinated naphthalene that composes the chemical...